Process for separating a mixture of molecular species using crystalline microporous metal sulfide compositions

BACKGROUND OF THE INVENTION
Molecular sieves of the crystalline aluminosilicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synthetic compositions. In general, the crystalline zeolites are formed from corner-sharing AlO.sub.2 and SiO.sub.2 tetrahedra and are characterized by having pore openings of uniform dimensions, having a significant ion-exchange capacity and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without significantly displacing any atoms which make up the permanent crystal structure.
Other crystalline microporous compositions are known which are not zeolitic but which exhibit the ion-exchange and/or adsorption characteristics of the zeolites. These include: (1) a pure silica polymorph, silicalite having a neutral framework containing neither cations nor cation sites as disclosed in the U.S. Pat. No. 4,061,724; 2) crystalline aluminophosphate compositions disclosed in U.S. Pat. No. 4,310,440; 3) silicon substituted aluminophosphates as disclosed in U.S. Pat. No. 4,440,871 and 4) titanium substituted aluminophosphates as disclosed in U.S. Pat. No. 4,500,651.
All of the crystalline molecular sieves described above are based on the oxide of the metal. It would be very desirable to synthesize crystalline microporous materials based on sulfides and selenides. Since sulfur, unlike oxygen, possesses d electron orbitals of low energy, a great flexibility in configuration is available to sulfur in its bonding with other elements. This flexibility should lead to compositions with unique pore structures which should have novel catalytic and electronic properties. Replacement of oxygen with sulfur or selenium should increase the size of the intracrystalline voids and the micropores and therefore increase the size or amount of the occluded species which can be accommodated in the pore.
The prior art shows that a fair amount of work has been done on metal sulfides and selenides. For example, B. Krebs, "Thio-and Seleno-Compounds of Main Group Elements--Novel Inorganic Oligomers and Polmers", Angew. Chem. Int. Ed. Engl. 22 (1983) 113-134, provides a review of main group thio and seleno compounds such as germanium and tin sulfides. Other reports include: of a Cs.sub.2 As.sub.8 S.sub.13 layered compound by W. S. Sheldrick and J. Kaub, Z. Naturforsch. 40b, 571-573 (1985); preparation of thiohydroxo anions of germanium by B. Krebs and H. J. Wallstab, Z. Naturforsch. 36b, 1400-1406 (1981); and preparation of Cs.sub.2 Sb.sub.2 Se.sub.4 by W. S. Sheldrick and J. Kaub, Z. Anorg. Allg. Chem., 536, 114-118 (1986).
However, all the compounds synthesized to date either have a dense structure, a chain, or a layered structure. There is no report of a crystalline three-dimensional microporous metal sulfide or metal selenide. Applicants are the first to synthesize crystalline three-dimensional microporous metal sulfides. Applicants' crystalline metal sulfides have a three-dimensional microporous framework structure of MS.sub.2 units where M is germanium, tin, or a combination thereof. The crystalline composition has the following empirical formula expressed in molar ratios: xR: MA.sub.2.+-.0.2 :zH.sub.2 O, where A is sulfur or selenium, R represents at least one organic templating agent present in the intracrystalline pore system, x has a value of greater than 0 to about 1, and z has a value from 0 to about 4.
Applicants have also been able to synthesize metal sulfide microporous compounds in which some of the germanium or tin atoms have been replaced with one or more metals. Preferred metals may be selected from the group consisting of cobalt, zinc, manganese, iron, nickel, copper, cadmium and gallium. Again, applicants are the first to have synthesized these compounds. Finally, applicants have found that these crystalline three-dimensional microporous composites exhibit adsorption/desorption properties and exhibit fluorescence showing that this new family of compounds have applications in adsorptive separations, as luminescent display materials and as substrates for luminescent sensors or optrodes. These sulfides may also be used as catalysts or catalyst supports in metal sulfide-based catalysts such as hydrogenation, dehydrogenation, dehydration, hydrotreating and syngas conversion reactions.
SUMMARY OF THE INVENTION
This invention relates to a crystalline three-dimensional microporous metal sulfide or metal selenide, a method of preparing the metal sulfide or metal selenide, and a process for separating a mixture of molecular species using the microporous metal sulfide or metal selenide.
Accordingly, one embodiment of the invention is a crystalline composition having a three-dimensional microporous framework structure of MA.sub.2 units, where A is sulfur or selenium and having the empirical formula expressed in molar ratios: xR:MA.sub.2.+-.0.2 :zH.sub.2 O where R represents at least one organic templating agent present in the intracrystalline pore system, x has a value greater than 0 to about 1.0, z has a value of 0 to about 4.0 and M is germanium, tin, or a combination thereof.
One specific embodiment is a metal sulfide having the empirical formula 0.31 TEA: GeS.sub.1.9 :0.39H.sub.2 O where TEA is tetraethylammonium.
Another embodiment of the invention is a crystalline composition having the empirical formula expressed in molar ratios: xR:M.sub.1-y M'.sub.y A.sub.2.+-.0.2 :zH.sub.2 O where y is greater than 0 to about 0.5 and M' is a metal that meets the criteria: (a) occurs in sulfide or selenide minerals of hydrothermal origin; (b) exhibits stable aqueous thiometallate or selenometallate chemistry or forms stable bisulfide or biselenide complexes and (c) gives a minimum framework charge from about 0 to about -1 per metal atom in a M.sub.1-y M'.sub.y A.sub.2.+-.0.2 framework structure.
Another specific embodiment is a metal sulfide having the empirical formula 0.3 TEA:Ge.sub.0.84 Co.sub.0.16 S.sub.2 :1.0 H.sub.2 O.
Yet another embodiment is a process for preparing a crystalline composition having a three-dimensional microporous framework structure of MA.sub.2 units where A is sulfur or selenium and having the empirical formula expressed in molar ratios: xR:MA.sub.2.+-.0.2 :zH.sub.2 O where R represents at least one organic templating agent present in the intracrystalline pore system, x has a value of greater than 0 to about 1, z has a value of 0 to about 4 and M is germanium, tin, or a combination thereof comprising reacting a mixture of the templating agent, an anion, a metal sulfide or metal selenide, and water at a temperature, pressure and time sufficient to form the crystalline composition, the reaction mixture composition expressed in terms of molar ratios is: pRY: (MA.sub.2): mH.sub.2 O where p has a value greater than 0 to about 5, m has a value from about 10 to about 500, and Y is at least one anion present in sufficient quantity to balance the charge on R.
Yet another specific embodiment is a process for preparing a crystalline microporous germanium sulfide comprising forming a reaction mixture of tetraethylammonium bicarbonate, (TEA HCO.sub.3), germanium sulfide (GeS.sub.2) and water in the ratio of 0.53 TEAHCO.sub.3 : GeS.sub.2 : 15H.sub.2 O, heating the mixture at a temperature of 150.degree. C. at autogenous pressure for 23 hours to give a crystalline microporous germanium sulfide having the empirical formula 0.31 TEA: GeS.sub.1.9 :0.39H.sub.2 O.
A further embodiment is a process for preparing a crystalline composition having the empirical formula expressed in molar ratios: xRY:M.sub.1-y M'.sub.y A.sub.2.+-.0.2 :zH.sub.2 O comprising reacting a mixture of the templating agent, an anion, a metal sulfide or selenide and water at a temperature, pressure and time sufficient to form the crystalline composition, the reaction mixture composition expressed in terms of molar ratios is: aRY:MA.sub.2 :cM'X:dH.sub.2 O, where M'X represents a compound of a metal, the metal (M') meeting the criteria a) occurs in sulfide or selenide minerals of hydrothermal origin; b) exhibits stable aqueous thiometallate or selenametallate chemistry or forms stable bisulfide or biselenide complexes and c) gives a minimum framework charge from about 0 to about -1 per metal atom in a M.sub.1-y M'.sub.y A.sub.2.+-.0.2 framework structure, a has a value greater than 0 to about 5, c has a value greater than 0 to about 1, d has a value from about 10 to about 500, and Y is at least one anion present in sufficient quantity to balance the charge on R.
Yet another embodiment is a process for separating a mixture of molecular species having different kinetic diameters comprising contacting the mixture with a crystalline composition having a three-dimensional microporous framework structure of MA.sub.2 units, where A is sulfur or selenium having an intracrystalline pore system and having the empirical formula expressed in molar ratios: xR:MA.sub.2.+-.0.2 :zH.sub.2 O where R represents at least one organic templating agent present in the intracrystalline pore system, x has a value greater than 0 to about 1.0, and z has a value of about 0 to about 4.0 and M is germanium, tin, or a combination thereof, the crystalline composition having pore diameters large enough to adsorb at least one but not all the molecular species of said mixture, the crystalline composition being at least partially activated, whereby at least some molecules of the molecular species whose kinetic diameters are sufficiently small can enter the intracrystalline pore system of the crystalline composition.
Still another embodiment is a process for separating a mixture of molecular species having different degrees of polarity comprising contacting the mixture with a crystalline composition having a three-dimensional microporous framework structure of MA.sub.2 units, where A is sulfur or selenium having an intracrystalline pore system and having the empirical formula expressed in molar ratios: xR:MA.sub.2.+-.0.2 :zH.sub.2 O where R represents at least one organic templating agent present in the intracrystalline pore system, x has a value greater than 0 to about 1.0, and z has a value of about 0 to about 4.0 and M is germanium, tin, or a combination thereof, the crystalline composition having pore diameters large enough to adsorb at least one of the more polar molecular species, the crystalline composition being at least partially activated, whereby at least some molecules of the more polar molecular species are selectively adsorbed into the intracrystalline pore system of the crystalline composition.
Other objects and embodiments will become more apparent after a more detailed description of the invention.
DETAILED DESCRIPTION OF THE INVENTION
As stated, the instant invention relates to crystalline compositions having a three-dimensional microporous structure and a method of preparing the crystalline compositions. The crystalline compositions of the instant invention have a three-dimensional microporous framework structure of MA.sub.2 units and have the empirical formula expressed in molar ratios: xR:MA.sub.2.+-.0.2 : zH.sub.2 O where A is sulfur or selenium, R is at least one organic templating agent (as described in detail below) present in the intracrystalline pore system, M is germanium, tin, or a combination thereof, x has a value of greater than 0 to about 1, preferably from about 0.1 to about 0.6 and especially from about 0.25 to about 0.42, and z has a value of 0 to about 4 and preferably from about 0.2 to about 1.2. It is also within the scope of this invention that part of the germanium or tin may be replaced by other metals to give a crystalline three-dimensional microporous structure having the empirical formula xR:M.sub.1-y M'.sub.y A.sub.2.+-.0.2 :zH.sub.2 O where A, x, R, M and z are as defined above, y has a value greater than 0 to about 0.5 and preferably greater than 0 to about 0.35, and M' is a metal that a) occurs in sulfide or selenide minerals formed from hot aqueous solutions; (b) forms stable aqueous thiometallate or selenometallate compounds or forms stable bisulfide or biselenide complexes and (c) gives a minimum framework charge from about 0 to about -1 per metal atom in a M.sub.1-y M'.sub.y A.sub.2.+-.0.2 framework structure.
By way of further explanation, M' may be selected from those metals which are found in sulfide and/or selenide minerals of hydrothermal origin. (See generally D. J. Vaughan, J. R. Craig, MINERAL CHEMISTRY OF METAL SULFIDES, Cambridge University Press (1978)). By hydrothermal is meant hot aqueous solutions. Thus, hydrothermal origin means minerals formed in or from hot aqueous solutions. In particular those metals which are found in thio and/or selenospinels and in defect structures or superstructures related to sphalerite and wurtzite. Alternatively, those metals which have been experimentally shown to transport as thiometallate anions and/or as bisulfide complexes in aqueous or hydrothermal systems can also be used. The metals must also form stable aqueous thiometallate or selenometallate compounds or alternatively form stable bisulfide or biselenide complexes. By stable is meant that the compounds do not oxidize or react with air or undergo substantial hydrolysis within the time frame of the reaction. These metals are well known to those skilled in the art of chalcogenide chemistry and minerology. Illustrative of the metals which meet the above critera are thallium, silver, lead, mercury, chromium, arsenic, antimony, indium, molybdenum, tungsten, cobalt, zinc, copper, manganese, iron, nickel, cadmium and gallium. Preferred metals may be selected from the group consisting of molybdenum, tungsten, arsenic, antimony, indium, cobalt, zinc, manganese, iron, nickel, copper, cadmium and gallium while especially preferred metals may be selected from the group consisting of cobalt, zinc, manganese, iron, nickel, copper, cadmium and gallium.
The coordination environment of germanium in microporous sulfides and selenides is tetrahedral, which has been confirmed by the X-ray structural solution of a single crystal of the tetrahedral framework material TMA-MnCoGS-2 prepared as in Example 33. In those metallothiogermanates which contain incorporated metals as well as in thiostannates and metallothiostannates, the Sn and incorporated metals may assume 3, 4, 5 or 6 coordination based on the known crystal chemistry of chalcogenide materials.
The metal sulfide compositions are generally synthesized by hydrothermal crystallization for an effective time at an effective pressure and temperature from a reaction mixture containing a metal sulfide, a templating agent, water and an anion. The templating agent is a structure-directing agent and is chosen to be a compound of an element of Group VA of the Periodic Table of the Elements, particularly nitrogen, phosphorous, arsenic and antimony, preferably nitrogen or phosphorus and most preferably nitrogen where such compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms. Particularly preferred compounds for use as templating agents are the amines, quaternary phosphonium compounds and quaternary ammonium compounds, the latter two being represented generally by the formula R.sub.4 Z.sup.+ wherein "Z" is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such as [(C.sub.14 H.sub.32 N.sub.2)(OH).sub.2 ].sub.x wherein "x" has a value of at least 2 are also suitably employed. The mono-, di-and triamines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents can either produce mixtures of the desired metal sulfides or the more strongly directing templating species may control the course of the reaction with the other templating agents serving primarily to establish the pH conditions of the reaction gel. Representative templating agents include: tetramethylammonium ions, tetraethylammonium ions, tetrapropylammonium ions, tetrabutylammonium ions, tetrapentylammonium ions, di-n-propylamine, ethylbutylamine, tripropylamine, triethylamine, triethanolamine, piperidine, cyclohexylamine, 2-methylpyridine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, choline, N,N'-dimethylpiperazine, 1,4-diazabicyclo(2,2,2,)octane, N-methyldiethanolamine, N-methylethanolamine, N-methylpiperidine, 3-methyl-piperidine, N-methylcyclohexylamine, 3-methylpyridine, 4-methylpyridine, quinuc-lidine, N,N'-dimethyl-1,4-diazabicyclo(2,2,2,)octane ion, di-n-butylamine, neopentylamine, di-n-pentylamine, diisopropylamine, t-butylamine, ethylenediamine, pyrrolidine, and 2-imidazolidone. Not every templating agent will direct the formation of every species of metal sulfides, i.e., a single templating agent can, with proper manipulation of the reaction conditions, direct the formation of several metal sulfide compositions, and a given metal sulfide composition can be produced using several different templating agents.
It is also necessary that the reaction mixture contain an anion (Y) selected from the group consisting of bisulfides, sulfides, halides, acetates, sulfates, hydroxides, bicarbonates and mixtures thereof with bicarbonates, bisulfides and hydroxides being preferred. Usually the anion is present as the counter ion of the templating agent, although it may be added in a form separate from the templating agent. For example if the desired templating agent is the tetramethylammonium cation, it may be added as the tetramethylammonium bicarbonate, chloride or hydroxide or as a mixture of tetramethylammonium chloride and sodium bicarbonate. The amount of anion present is the amount necessary to balance the charge on R (templating agent).
The germanium or tin sulfide which is present in the reaction mixture may be either crystalline or amorphous with the amorphous phase preferred.
The selenogermanates and selenostannates may be prepared in a manner similar to the sulfide compositions. Precursors for selenides include GeSe.sub.2 and SnSe.sub.2 . Similar templating systems, such as alkylammonium or arylammonium bicarbonates, biselenides, selenides and hydroxides may be utilized. Thioselenogermanates and thioselenostannates may be prepared by using appropriate combinations of GeS.sub.2, GeSe.sub.2, SnS.sub.2, SnSe.sub.2, along with soluble metal salts if further incorporated elements are desired. As an alternative GeSe.sub.2 and/or SnSe.sub.2 may be digested with alkyl ammonium or aryl ammonium sulfides or bisulfides to produce thioseleno frameworks.
A portion of the germanium or tin framework may be replaced by one or more metals (M') which meet the criteria set forth above. Illustrative of the metals which meet these criteria are thallium, silver, lead, mercury, chromium, arsenic, antimony, indium, molybdenum, tungsten, cobalt, zinc, copper, manganese, iron, nickel, cadmium and gallium. Preferred metals may be selected from the group consisting of molybdenum, tungsten, arsenic, antimony, indium, cobalt, zinc, manganese, iron, nickel, copper, cadmium and gallium, while especially preferred metals may be selected from the group consisting of cobalt, zinc, manganese, iron, nickel, copper, cadmium and gallium.
When one or more of these metals is desired to be present in the final composition, they may be added to the reaction mixture in the form of a water soluble compound. Illustrative of the compounds which can be used are cobalt acetate, zinc acetate, manganese acetate, iron acetate, nickel acetate, copper acetate, cadmium acetate, gallium acetate, chromium acetate, lead acetate, mercury acetate, silver acetate, thallium acetate, cobalt chloride, zinc chloride, manganese chloride, iron chloride, nickel chloride, copper chloride, cadmium chloride, gallium chloride, chromium chloride, indium chloride, mercury chloride, thallium chloride, antimony trichloride, arsenic trichloride, cadmium sulfate and gallium sulfate.
The composition of the reaction mixture will determine the composition of the crystalline product. The composition of the reaction mixture expressed in terms of molar ratios is: pRY:MA.sub.2 :mH.sub.2 O where p has a value greater than 0 to about 5 and preferably from about 0.5 to about 4, m has a value from about 10 to about 500 and preferably from about 10 to about 200, and Y is at least one anion present in sufficient quantity to balance the charge on R. Further, when one or more metal is to be substituted for germanium or tin, the reaction mixture composition is: aRY: MA.sub.2 :cM'X:dH.sub.2 O, where M'X represents a compound of a metal which meets the criteria set forth above, a has a value greater than 0 to about 5 and preferably from about 0.5 to about 4, c has a value greater than 0 to about 1 and preferably greater than 0 to about 0.5 and d has a value from about 10 to about 500 and preferably from about 10 to about 200.
The reaction mixture described above is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between 25.degree. and 250.degree. C. and preferably between 100.degree. and 200.degree. C. for a time of about 2 hours to about 20 days but typically from about 12 hours to about 5 days. The crystalline product which is obtained may be recovered by any convenient method such as centrifugation or filtration. The recovered product is then dried in air. It is also desirable to wash the product with distilled or acidified water prior to drying it.
Because of the use of an aqueous reaction medium, under certain circumstances the resultant product may contain a small fraction of germanium or tin (IV) oxide as the result of hydrolysis. In order to minimize this impurity, it is preferred to add to the reaction mixture from about 5 to 25 percent (as percent of total R) quarternary ammonium or alkylammonium hydrogen sulfide and/or quarternary ammonium or alkylammonium thiogermanate or thiostannate solution.
In some cases it is also desirable to add an alcohol to the slurry as an adjunct space-filling moiety. The alcohol takes the place of some of the alkylammonium or arylammonium templates in the structural voids, and this enhances formation of certain lower charged framework compositions. Illustrative of the alcohols which may be used are isopropanol, t-butanol, n-propanol, sec-butanol and iso-butanol. The amount of alcohol which will be present in the final crystalline composition will vary from about 1 to about 50% of the moles of R present.
As indicated, the crystalline microporous composition has present in the intracrystalline pore system at least one templating agent. A fraction of this templating agent may be removed by heating the metal sulfide or selenide product at a temperature of about 150.degree. to about 300.degree. C. for a time of about 0.5 to about 12 hours. Further, calcination at higher temperatures, e.g., 350.degree. to about 500.degree. C. will completely remove the template. The product which results from calcination at these higher temperatures may be crystalline or may be amorphous with some residual short range order. These calcined materials are useful as catalysts or catalyst supports.
The metal sulfides obtained from the above procedure are crystalline materials as shown by X-ray diffraction and their microporosity has been verified by chemical analysis which shows S/Ge ratios of 1.8 to 2.2 and the presence of large amounts of occluded organic template and water. Additionally, their microporosity has been verified by single crystal diffraction analysis of TMA-MnCoGS-2 which shows that the crystal has a void volume of about 50% and a pore diameter of about 6 .ANG.. Further evidence of the microporosity of these materials is the observation that these materials reversibly adsorb compounds such as CO.sub.2 and H.sub.2 O.
Accordingly, one use of the crystalline materials of this invention is to separate mixtures of molecular species. Prior to use in a separation process, the crystalline materials are activated to remove at least some of any molecular species, e.g., templating agent, which may be present in the intracrystalline pore system as a result of synthesis. This may be accomplished as described above, i.e., by heating.
The crystalline materials of this invention are capable of separating mixtures of molecular species based on the molecular size (kinetic diameters) or on the degree of polarity of the molecular species. When the separation of molecular species is based on molecular size, the crystalline microporous material is chosen in view of the dimensions of its pores such that at least the smallest molecular specie of the mixture can enter the intracrystalline void space while at least the largest specie is excluded. The kinetic diameters of various molecules such as oxygen, nitrogen, carbon dioxide, carbon monoxide are provided in D. W. Breck, ZEOLITE MOLECULAR SIEVES, John Wiley and Sons (1974) p. 636. Thus, it is observed from Example 38 herein that TMA-SnS-1 can be used to separate carbon monoxide from oxygen (kinetic diameter of 3.46 .ANG.).
When the separation is based on degree of polarity, it is generally the case that the more hydrophilic crystalline material of this invention will preferentialy adsorb the more polar molecular species of a mixture having different degrees of polarity even though both molecular species can communicate with the proe system of the crystalline material. For example water, which is more polar, will be preferentially adsorbed over common hydrocarbon molecules such as paraffins, olefins, etc. Thus, the crystalline materials of this invention can be used as dessicants in such adsorption separation/purification processes as natural gas drying, cracked gas drying, etc.
The crystalline materials or compositions of this invention are comprised of neutral or negatively charged three-dimensional frameworks. When the frameworks are negatively charged, their affinity and therefore their selectivity for more polar species will be enhanced. This results in the composition selectively adsorbing the more polar species from a mixture of molecular species. When the microporous three-dimensional framework is neutral, as in a framework of GeA.sub.2 or SnA.sub.2 (A is sulfur or selenium), the selectivity for less polar species will be enhanced, thereby allowing the composition to selectively adsorb the less polar species from a mixture of molecular species. Therefore, a wide variety of molecular species having varying degrees of polarity can be separated by fine tuning the charge on the crystalline material.
If one of the molecular species, e.g., water, is a small impurity, the separation may be effected in the conventional manner by simply passing the stream to be treated through a bed of the particular crystalline material desired. As the operation of the process continues, there develops in the bed a so-called "front" between the material loaded with the impurity, e.g., water, and the material not so loaded. This front moves through the bed in the direction of gas flow. Before the front reaches the downstream end of the bed, the bed is regenerated by cutting off the flow of feed stream and passing through the bed a purge gas which (usually at a temperature of about 50.degree.-150.degree. C.) desorbs the impurity, e.g., water, from the bed. If the purge gas is adsorbed on the bed, this gas can be removed by passing one or two bed volumes of the feed stream through the bed.
If the concentration of one of the species in the mixture is large, e.g., several percents, other conventional techniques, such as pressure swing adsorption (PSA) and thermal swing adsorption may be used. Such techniques are well known to those skilled in the separation art. See, e.g., U.S. Pat. Nos. 4,723,966, 4,589,888, and 4,398,926. For example, a pressure swing adsorption process will operate at a temperature and pressure sufficient to effect the adsorption and desorption of the component or molecular specie which one wants to remove. Typically the temperature is preferably maintained in the range of about -50.degree. to 100.degree. C. and preferably from about 0.degree. to 50.degree. C. The pressure during adsorption can vary from about 0.2 psia (1.4 kPa) to about 1500 psia (10,342 kPa), preferably from about 50 psia (344 kPa) to about 500 psia (3,447 kpa) and more preferably from about 75 psia (517 kPa) to about 350 psia (2,413 kPa). The pressure during desorption is lower than during adsorption and effective to cause desorption of the adsorbed component. The range of this pressure is from about 0.1 torr (1.3 Pa) to 150 psia (1,034 kPa), preferably from about 0.1 torr (1.3 Pa) to 15 psia (103 kPa) and more preferably from about 0.1 torr (1.3 Pa) to about 250 torr (333 Pa). The cyclic process can comprise additional adsorption and regeneration steps as well as intermediate depressurization and purging steps.
The crystalline microporous compositions of the present invention either as synthesized or after calcination can be used as catalysts or catalyst supports in a hydrocarbon conversion process. Hydrocarbon conversion processes are well known in the art and include cracking, hydrocracking, alkylation of both aromatics and isoparaffin, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanation and syngas shift process. Specific reaction conditions and the types of feeds which can be used in these processes are set forth in U.S. Pat. Nos. 4,310,440 and 4,440,871 which are incorporated by reference. Preferred hydrocarbon conversion processes are those in which hydrogen is a component such as hydrotreating or hydrofining, hydrogenation, hydrocracking, hydrodenitrogenation, hydrodesulfurization, etc.
In order to more fully illustrate the variety of species to be derived from the instant invention, the following examples are set forth. It is to be understood that the examples are only by way of illustration and are not intended as an undue limitation on the broad scope of the invention as set forth in the appended claims.
To allow for ready reference, the different structure types of thiogermanates, metallothiogermanates and thiostannates in the following examples have been given arbitrary numbers and acronyms, with the germanium-containing compositions being numbered structure types 1 through 11 and the tin containing compositions being numbered 1 through 4 as in the following examples: TMA-GS-4, where TMA represents the tetramethylammonium template and GS-4 represents the germanium sulfide framework of structure type 4, TMA-CuMnGS-2 represents a TMA template-containing copper manganese germanium sulfide framework of structure type 2, and TMA-SnS-1 represents a TMA template-containing tin sulfide framework with thiostannate structure type 1.
Where the products are subjected to X-ray analysis, the X-ray patterns are obtained using standard X-ray powder diffraction techniques. The radiation source is a high-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K-alpha radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2.degree. (2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2.theta. where .theta. is the Bragg angle as observed on the strip chart. Intensities are determined from the heights of diffraction peaks after subtracting background, "I.sub.o " being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks.
Alternatively, the X-ray patterns are obtained from the copper K-alpha radiation by use of computer based techniques using a Siemens D-500 X-ray powder diffractometer, Siemens Type K-805 X-ray sources, available from Siemens Corporation, Cherry Hill, N.J., with appropriate computer interface.
As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination can impose an uncertainty of about .+-.0.4.degree. on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2 theta values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, s, m, and w which represent very strong, strong, medium, and weak, respectively. In terms of 100 XI/I.sub.o, the above designations are defined as w=0-15; m=15-60; s=60-80 and vs=80-100.
In certain instances the purity of a synthesized product may be assessed with reference to its X-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the X-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.
The crystalline compositions of the instant invention may be characterized by their X-ray powder diffraction patterns and such may have one of the X-ray patterns set forth in the following Tables A through O.
TABLE A______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________6.02-6.05 14.61-14.68 m-vs9.06-9.09 9.73-9.76 s-vs10.07-10.09 8.77-8.78 w-m11.74-11.76 7.52-7.54 m-s13.88-13.89 6.37-6.38 w-m18.38-18.47 4.80-4.83 m______________________________________
TABLE B______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________8.92-9.32 9.50-9.90 s-vs9.26-9.66 9.15-9.55 s-vs12.01-12.51 7.07-7.37 m-s14.35-14.85 5.97-6.17 m-s14.74-15.24 5.81-6.01 m-s28.72-29.52 3.02-3.12 m-s______________________________________
TABLE C______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________10.22-10.69 8.28-8.64 vs11.65-12.37 7.16-7.60 w-m16.77-17.55 5.05-5.29 w-m19.56-20.59 4.31-4.54 m27.62-28.51 3.13-3.23 w-m31.04-32.27 2.77-2.88 w______________________________________
TABLE D______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.15-7.21 12.26-12.37 vs10.43-10.50 8.43-8.48 w10.98-11.05 8.00-8.06 m16.62-16.69 5.31-5.33 m23.02-23.09 3.85-3.86 w27.46-27.55 3.24-3.25 w-m______________________________________
TABLE E______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.04-7.10 12.45-12.56 w-m8.86-8.90 9.94-9.98 vs10.79-10.83 8.17-8.20 w-m11.99-12.03 7.35-7.38 w-m19.42-19.45 4.56-4.57 w-m28.98-29.02 3.03-3.13 w-m______________________________________
TABLE F______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________5.19-5.22 16.94-17.04 vs8.00-8.01 11.04-11.05 w-s8.34-8.42 10.50-10.60 m-s9.83-9.87 8.96-9.00 w-s10.33-10.42 8.49-8.56 m-s12.98-13.04 6.79-6.82 m-s______________________________________
TABLE G______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________6.91-7.31 12.04-12.44 m-s9.58-9.98 8.84-9.24 s-vs 9.94-10.34 8.58-8.88 w-m15.56-16.16 5.49-5.69 m17.89-18.59 4.78-4.94 m27.33-28.13 3.17-3.27 m______________________________________
TABLE H______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________6.22-6.30 14.02-14.22 s-vs8.99-9.07 9.75-9.83 s-vs10.90-10.98 8.06-8.12 m-s11.10-11.31 7.82-7.97 m-s12.50-12.56 7.05-7.08 w-m29.88-29.95 2.98-2.99 m-s______________________________________
TABLE I______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.54-7.94 11.22-11.62 w-m9.34-9.38 9.43-9.47 w-m10.38-10.48 8.44-8.52 vs14.43-14.58 6.08-6.14 w17.53-17.59 5.04-5.06 w-m20.76-20.80 4.27-4.28 w-m______________________________________
TABLE J______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.90-8.03 11.01-11.20 w-m8.64-8.87 9.97-10.23 vs11.74-11.94 7.41-7.54 w17.40-17.74 5.00-5.10 w24.00-24.10 3.69-3.71 w29.27-29.40 3.04-3.05 w______________________________________
TABLE K______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.56-7.69 11.49-11.69 m-s9.00-9.02 9.80-9.83 m-vs11.09-11.10 7.97-7.98 w12.86-12.89 6.87-6.88 m-s15.40-15.45 5.73-5.75 w-s16.03-16.14 5.49-5.53 m-s______________________________________
TABLE L______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.97-8.03 11.02-11.10 vs8.69-8.74 10.11-10.18 w15.76-16.36 5.42-5.62 w-m16.39-16.41 5.40-5.41 w16.84-16.93 5.24-5.26 w24.44-24.46 3.59-3.69 w______________________________________
TABLE M______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________8.83-9.63 9.18-10.01 vs14.15-15.08 5.87-6.26 m-s17.69-19.22 4.62-5.01 w-m21.97-23.45 3.79-4.05 w-m28.69-30.17 2.96-3.08 w-m37.04-38.56 2.33-2.43 w______________________________________
TABLE N______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________11.02-11.42 7.73-8.03 vs12.90-13.50 6.56-6.86 w17.90-18.50 4.79-4.95 m-s21.46-22.26 4.00-4.14 m22.14-22.94 3.89-3.99 m27.84-28.64 3.11-3.21 m-s______________________________________
TABLE O______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.08-7.48 11.94-12.34 vs8.91-9.31 9.50-9.90 w-m10.49-10.89 8.12-8.42 w-m10.82-11.22 7.89-8.19 w12.63-13.23 6.70-7.00 w16.47-17.17 5.17-5.37 w27.32-28.12 3.17-3.27 w______________________________________

EXAMPLE 1
Germanium sulfide was prepared by the following method. A 5 liter three-necked flask was charged with 2 liters of distilled water. To the water was slowly added 100 grams of GeCl.sub.4 with magnetic stirring to give a white slurry. To the slurry was added 2 liters of concentrated reagent grade HCl and about 10 mL of reagent grade concentrated H.sub.2 SO.sub.3 (sulfurous acid). The acidified slurry was vigorously stirred while H.sub.2 S gas was bubbled through at a rate just faster than the mixture could absorb it. The bubbling was continued for a total of 5 hours, at which time no further H.sub.2 S was being absorbed by the slurry.
The solid reaction product, a pearly white fine powder, was recovered by filtration on a medium porosity glass fritted filter, washed with slightly acidified (with HCl) water (2 liters) then methanol (400 mL), and dried under dynamic vacuum (10.sup.-3 torr) overnight. Chemical analysis of the product indicated the presence of 7.5 weight percent Cl, 39.2 weight percent S and 49.1 weight percent Ge, giving a product composition of:
GeS.sub.1.8 Cl.sub.0.31.
EXAMPLE 2
Tetraethylammonium (TEA) bicarbonate was made by bubbling CO.sub.2 gas through 184 grams of 40% aqueous TEAOH until the temperature of the reaction mixture stabilized to room temperature. The resulting solution was diluted to 250.0 mL, giving a 2.0M solution of TEAHCO.sub.3 suitable for use in the following examples where TEAHCO.sub.3 is used. The bicarbonates of all other alkylammonium and quaternary ammonium salts were made in an analogous manner.
EXAMPLE 3
Preparation of TEA-GS-5 (TEA=tetraethylammonium)
A reaction mixture was prepared by combining 8.2 grams of GeS.sub.2 (obtained from the Alfa Chemical Co.) and 15 mL of 2M TEAHCO.sub.3 (from example 2 above). The composition of the reaction mixture was:
0.5TEAHCO.sub.3 :1GeS.sub.2 :14H.sub.2 O.
A portion of the slurry was sealed in a polytetrafluoroethylene (Teflon.TM.) lined stainless steel pressure vessel and digested at 150.degree. C. for 90 hours at autogenous pressure. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. The major phase in the product had a powder diffraction pattern characterized by the data shown in Table 1. The product also contained <50% of cyrstalline GeS.sub.2 starting material impurity.
TABLE 1______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________6.03 14.66 509.06 9.76 2910.06 8.80 611.74 7.54 912.08 7.33 513.90 6.37 418.47 4.80 623.63 3.76 528.02 3.18 3______________________________________
EXAMPLE 4
Preparation of TEA-GS-5
A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1) and 4.0 mL of 2M TEAHCO.sub.3 (made as in Example 2). The composition of the final reaction mixture was:
0.53TEAHCO.sub.3 :1GeS.sub.2 :15H.sub.2 O.
The mixture was momentarily stirred to form a slurry and sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 66 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The major phase in the product had an X-ray powder diffraction pattern represented by the data shown in Table 2. The product also contained minor amounts of GeO.sub.2 and another crystalline impurity.
TABLE 2______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________6.02 14.68 469.06 9.76 10010.07 8.78 3411.74 7.54 4013.88 6.38 1315.75 5.63 1016.33 5.43 616.89 5.25 618.39 4.83 2120.53 4.33 1623.63 3.77 1825.55 3.49 1028.01 3.186 1029.80 2.998 9______________________________________
EXAMPLE 5
a. Preparation of Tetraethylammonium hydrogen sulfide.
In a 1 liter three-necked glass flask equipped with stirbar and gas-tight rubber caps, 368.2 grams of TEAOH was sealed in the flask along with approximately 20 mL of water. Hydrogen sulfide (H.sub.2 S) gas was bubbled through the solution through a stainless steel needle until the solution temperature had stabilized to room temperature. The solution was then diluted to 0.5 liter in a volumetric flask to give a final concentration of 2.0M TEAHS solution.
b. Preparation of Tetraethylammonium-thiogermanate.
A reaction mixture was prepared by combining 50.0 mL of 2M TEAHS (from Example 5a) with 6.8 grams of GeS.sub.2 (from Alfa). The mixture was placed into a Teflon.TM.-lined stainless steel pressure vessel and digested in an oven at 150.degree. C. at autogenous pressure for 44 hours. The product was a yellow solution, a small amount of immiscible yellow liquid on top, and a small amount of white precipitate. The solution was filtered and the immiscible material pumped off under vacuum and then diluted to 250 mL to yield a TEA-thiogermanate reagent which was 0.4M in TEA+ and 0.2M in Ge.
EXAMPLE 6
Preparation of TEA-GS-5.
A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 4.0 mL of 2M TEAHCO.sub.3 (made as in Example 2) and 15.0 mL of TEA-thiogermanate solution (0.2M in Ge; made in Example 3b). The composition of the reaction mixture was:
0.44TEAHCO.sub.3 :0.33TEAHS:1GeS.sub.2 :60H.sub.2 O.
The mixture was placed into a Teflon.TM.-lined stainless steel pressure vessel along with a 0.5 inch Teflon.TM.-covered magnetic stirbar. The mixture was heated in a 100.degree. C. oven and stirred at autogenous pressure for 66 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The X-ray powder diffraction pattern of this product, which contained no crystalline impurities, was characterized by the data shown in Table 3.
TABLE 3______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________6.05 14.61 1009.09 9.73 979.47 9.33 1810.09 8.77 4511.76 7.52 6113.89 6.37 1915.80 5.61 1416.37 5.41 1316.94 5.24 818.34 4.83 2920.44 4.35 621.11 4.21 423.65 3.76 3224.12 3.69 725.50 3.49 625.73 3.46 828.03 3.18 1629.27 3.052 829.84 2.994 930.42 2.938 631.91 2.805 433.62 2.666 635.74 2.512 537.51 2.398 537.98 2.369 548.01 1.895 5______________________________________
EXAMPLE 7
Preparation of TEA-GS-5.
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1) and 4.0 mL of 2M TEAHCO.sub.3 (made as in Example 2). The composition of the final reaction mixture was:
0.53TEAHCO.sub.3 :1GeS.sub.2 :15H.sub.2 O.
The mixture was momentarily stirred to wet the GeS.sub.2 powder, sealed in a Teflon.TM.-lined stainless steel pressure vessel, and then heated in an oven at 150.degree. C. at autogenous pressure for 23 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. A chemical analysis of the product indicated the presence of 15.6 weight percent C, 2.2 weight percent N, 41.2 weight percent Ge, 33.1 weight percent S, 4.2 weight percent H.sub.2 O, and 27.6 weight percent LOI, giving a product composition of:
0.28TEA:GeS.sub.1.8 :0.41H.sub.2 O.
The above product had an X-ray powder diffraction pattern which showed the major product (>90%) to be essentially identical to the TEA-GS-5 product of Examples 3, 4 and 6 along with less than a 10% GeO.sub.2 impurity.
b. A reaction mixture was prepared following the procedure of Example 7A except that the mixture was heated at 100.degree. C. for 18 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. A chemical analysis of the product indicated the presence of 17.3 weight percent C, 2.4 weight percent N, 39.4 weight percent Ge, 33.1 weight percent S, 3.8 weight percent H.sub.2 O, and 30.3 weight percent LOI, giving a product composition of:
0.31TEA:GeS.sub.1.9 :0.39H.sub.2 O.
The above product had an X-ray powder diffraction pattern in which the major phase (>95%) was the TEA-GS-5 product of Example 3 along with a GeO.sub.2 impurity (<5%).
EXAMPLE 8
Preparation of TEA-GS-5
A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (Alfa) and 1.65 grams of 40% TEAOH which had previously been mixed with glacial acetic acid to give a TEA-acetate solution of pH 6-9. The mixture was stirred to wet the GeS.sub.2, sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. for 66 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The X-ray powder diffraction pattern of the product showed the crystalline TEA-GS-5 product of Example 3 as the major phase, with crystalline GeS.sub.2 starting material present as an impurity.
EXAMPLE 9
Preparation of TEA-GS-5
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made according to Example 1), 4 mL of 2M TEAHCO.sub.3 (made according to Example 2) and 1 mL of 1M TEAHS (made by further dilution of 2M TEASH made according to Example 5a). The mixture was stirred to wet the GeS.sub.2 powder, giving a reaction slurry with a final composition of:
0.53TEAHCO.sub.3 :0.06TEASH:1GeS.sub.2 :18H.sub.2 O.
The mixture was sealed in a Teflon.TM. bottle and heated in an oven at 100.degree. C. at autogenous pressure for 66 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The product had an X-ray powder diffraction pattern identical to the TEA-GS-5 product in Example 3, with a minor amount (<5%) of GeO.sub.2 impurity.
b. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 4.0 mL of 2M TEAHCO.sub.3 (made as in Example 2) in which had been dissolved 1.68 grams of TEABr. The mixture was stirred to wet the GeS.sub.2 powder, sealed in a Teflon.TM.-lined stainless steel pressure vessel, and heated in an oven at 100.degree. C. at autogenous pressure for 18 hours. The solid product was recovered by filtration, washed with water, and dried in air at room temperature. The X-ray powder diffraction pattern of the product showed the major phase to be TEA-GS-5 (>85%), along with a minor portion of crystalline GeO.sub.2 impurity.
EXAMPLE 10
Preparation of TMA-GS-4. (TMA=tetramethylammonium)
a. A reaction mixture was prepared by combining 2.0 grams GeS.sub.2 (made as in Example 1), 4.0 mL of 2M TMAHCO.sub.3 (made according to Example 2), and 4.0 mL of H.sub.2 O. The final mixture had the composition:
0.53TMAHCO.sub.3 :1GeS.sub.2 :30H.sub.2 O.
The mixture was stirred momentarily to wet the GeS.sub.2, sealed in a Teflon.TM. bottle and heated in an oven at 100.degree. C. at autogenous pressure for 66 hours. The solid product was recovered by filtration, washed with water, and dried in air at room temperature. The major phase of the product had an X-ray powder diffraction pattern characterized by the data in Table 4. The product also contained minor amounts of crystalline GeO.sub.2 as well as a very poorly crystalline impurity.
TABLE 4______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________9.14 9.68 839.47 9.34 10011.60 7.63 912.27 7.21 3214.58 6.08 1914.95 5.93 1618.38 4.83 1119.02 4.67 1821.52 4.13 822.55 3.94 723.42 3.80 929.12 3.067 2148.68 1.870 14______________________________________
b. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 4.0 mL of 2M TMAHCO.sub.3 (made according to Example 2), and 0.88 grams of TMACl, which was dissolved in the TMAHCO.sub.3 solution before its addition to the GeS.sub.2. The mixture was momentarily stirred to assure wetting of the GeS.sub.2, the final composition being:
0.53TMAHCO.sub.3 :0.53TMACl:1GeS.sub.2 :15H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 162 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. Chemical analysis showed the presence of 10.1 weight percent C, 3.0 weight percent N, 43.9 weight percent Ge, 39.5 weight percent S, 3.3 weight percent H.sub.2 O, and 25.8 weight percent LOI, giving a product composition of:
0.35TMA:GeS.sub.2.0 :0.3H.sub.2 O.
The major product had an X-ray powder diffraction pattern characterized by the data shown in Table 5. The product also contained a small amount (<5%) of GeO.sub.2 impurity.
TABLE 5______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________9.12 9.70 1009.46 9.35 7611.60 7.63 2112.26 7.22 3714.60 6.07 2514.99 5.91 2116.08 5.51 618.34 4.84 718.99 4.67 2321.51 4.13 1922.53 3.95 823.35 3.81 1429.12 3.067 2934.34 2.612 736.36 2.471 545.06 2.012 447.11 1.929 348.63 1.872 1154.54 1.683 3______________________________________
EXAMPLE 11
Preparation of TMA-GS-2
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 4.0 mL of 2M TMAHCO.sub.3 (made according to Example 2) and 0.88 grams of TMACl which was dissolved in the TMAHCO.sub.3 solution before addition to the GeS.sub.2. The final mixture composition was:
0.53TMAHCO.sub.3 :0.53TMACl:1GeS.sub.2 :15H.sub.2 O.
The mixture was momentarily stirred to assure wetting of the GeS.sub.2. The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 66 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. Chemical analysis indicated the presence of 9.0 weight percent C, 2.2 weight percent N, 44.7 weight percent Ge, 39.8 weight percent S, 3.4 weight percent H.sub.2 O, and 20.5 weight percent LOI, giving a product composition of:
0.26TMA:GeS.sub.2.0 :0.31H.sub.2 O.
The major product had an X-ray powder diffraction pattern characterized by the data shown in Table 6. The product also contained a minor amount of GeO.sub.2 and an unidentified crystalline impurity.
TABLE 6______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________10.42 8.49 10011.90 7.44 1813.59 6.51 616.07 5.52 717.12 5.18 819.96 4.45 2228.11 3.175 1129.31 3.047 430.33 2.947 831.44 2.846 8______________________________________
b. A reaction mixture identical to that of Example 11a was formulated and an additional 4 mL of H.sub.2 O was added. The same type of reaction vessel was used, which was heated in an oven at 100.degree. C. at autogenous pressure for 42 hours. The solid product, recovered, washed, and dried as in Example 11a, had an X-ray powder diffraction pattern which showed the major product (>95%) to be the TMA-GS-2 structure of Example 11a. The minor product had an X-ray pattern identifying it as the TMA-GS-4 structure as in Example 10.
EXAMPLE 12
Preparation of DPA-GS-7 (DPA=dipropylamine)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), and 4.0 mL of 2M DPAHCO.sub.3 (made according to Example 2), with momentary stirring to wet the GeS.sub.2. The mixture composition was:
0.53DPAHCO.sub.3 :1GeS.sub.2 :15H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 66 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. Chemical analysis of the product indicated the presence of 15.2 weight percent C, 3.0 weight percent N, 41.0 weight percent Ge, 35.5 weight percent S, 3.5 weight percent H.sub.2 O and 26.1 weight percent LOI, giving a final product composition of:
0.38DPA:GeS.sub.2.0 :0.34H.sub.2 O.
The above product had an X-ray powder diffraction pattern characterized by the data shown in Table 7. A minor amount of GeO.sub.2 impurity was also present.
TABLE 7______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.15 12.37 1009.80 9.02 810.43 8.48 910.98 8.06 2012.87 6.88 716.62 5.33 2418.47 4.80 323.02 3.86 823.17 3.84 723.54 3.78 424.73 3.60 327.46 3.25 1028.07 3.18 733.62 2.665 7______________________________________
b. A reaction mixture was prepared using the same procedure as Example 12a except that 6.0 mL of 2M DPAHCO.sub.3 was used, giving the following reaction mixture composition:
0.8DPAHCO.sub.3 :1GeS.sub.2 :22H.sub.2 O.
The reaction time and temperature was identical to Example 12a. The solid product was recovered by filtration, washed with water, and dried in air at room temperature. An X-ray powder diffraction pattern of the product showed the major component to be the DPA-GS-7 structure of Example 12a, with very minor amounts of GeO.sub.2 and another crystalline impurity.
c. A reaction mixture was prepared in a manner identical to Example 12a except that 2.0 mL of 2M DPAHCO.sub.3 mixed with 2.0 grams of water were mixed with the GeS.sub.2. The reactant composition was:
0.27DPAHCO.sub.3 :1GeS.sub.2 :15H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 90 hours. The solid was recovered by filtration, washed with water, and dried in air at room temperature. X-ray diffraction analysis of the product powder showed the major product to be the DPA-GS-7 structure of Example 12a, along with small amounts of a poorly crystalline impurity and GeO.sub.2.
EXAMPLE 13
Preparation of DPAHCl (dipropylammonium hydrochloride)
A reaction mixture was prepared by placing 101.2 grams of dipropylamine in a glass vessel and cooling it in an ice bath. To the amine there were added 250 mL of 4.0M HCl at a rate so as to keep the reaction mixture temperature below 40.degree. C. The final mixture, once cooled to room temperature, was diluted to 500 mL to give a 2.0M solution of DPAHCl.
EXAMPLE 14
Preparation of DPA-GS-7 (DPA=dipropylamine)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 4.0 mL of 2M DPAHCO.sub.3 (made according to Example 2), and 4.0 mL of 2M DPAHCl (made in Example 13). The final reaction mixture composition was:
0.53DPAHCO.sub.3 :0.53DPAHCl:1GeS.sub.2 :30H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 18 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. A powder X-ray diffraction pattern of the product revealed that the major product was the DPA-GS-7 structure of Example 12a, characterized by the data shown in Table 8. Minor amounts of another crystalline phase and GeO.sub.2 were present as impurities.
TABLE 8______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.21 12.26 1009.87 8.97 710.50 8.43 1011.05 8.00 2012.95 6.84 716.69 5.31 2518.53 4.79 323.09 3.85 923.27 3.82 823.62 3.77 424.81 3.59 327.55 3.24 1328.15 3.17 833.71 2.659 734.63 2.590 3______________________________________
b. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 4.0 mL of 2M DPAHCl, 0.67 grams NaHCO.sub.3, and 2.0 grams of H.sub.2 O. The mixture was stirred momentarily to wet the GeS.sub.2, giving a mixture of final composition:
0.53DPAHCL:0.53NaHCO.sub.3 :1GeS.sub.2 :22H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 66 hours. The solid reaction products were recovered by filtration, washed with water and dried in air at room temperature. An X-ray powder diffraction pattern of the product showed the major product to be the DPA-GS-7 structure of Example 12a, along with a minor amount of GeO.sub.2 impurity.
c. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made in Example 1), 4.0 mL of 2.0M DPAHCl, 0.38 grams of (NH.sub.4).sub.2 CO.sub.3, and 2.0 grams of H.sub.2 O. The mixture was stirred momentarily to wet the GeS.sub.2, giving a mixture of final composition:
0.53DPAHCl:0.27(NH.sub.4).sub.2 CO.sub.3 :1GeS.sub.2 :22H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 66 hours. The solid reaction products were recovered by filtration, washed with water and dried in air at room temperature. An X-ray powder diffraction pattern of the product showed the major product to be the DPA-GS-7 structure of Example 12a, along with a minor amount of GeO.sub.2 impurity.
EXAMPLE 15
Preparation of DPA-GS-8 (DPA=dipropylamine)
a. A reaction mixture was prepared by combining 3.0 grams of GeS.sub.2 (made as in Example 1) and 6.0 mL of 2M DPAHCO.sub.3. The mixture was stirred momentarily to wet the GeS.sub.2, giving a mixture of composition:
0.54DPAHCO.sub.3 :1GeS.sub.2 : 15H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 66 hours, cooled to room temperature and left sealed at room temperature for 500 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. A chemical analysis of the product revealed the presence of 14.1 weight percent C, 2.8 weight percent N, 42.0 weight percent Ge, 33.9 weight percent S, 2.8 weight percent H.sub.2 O and 23.6 weight percent LOI, giving a final product composition of:
0.38DPA:GeS.sub.2.0 :0.24H.sub.2 O.
The X-ray powder diffraction pattern of this product, which also contained a minor amount of GeO.sub.2 impurity was characterized by the data shown in Table 9.
TABLE 9______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.10 12.45 148.90 9.94 10010.83 8.17 1612.03 7.35 1012.78 6.93 914.18 6.25 415.62 5.67 918.50 4.80 319.45 4.56 1221.26 4.18 521.84 4.07 422.57 3.94 323.38 3.81 529.02 3.077 931.29 2.858 331.95 2.801 7______________________________________
b. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 4.0 mL of 2M DPAHCO.sub.3, and 4.0 mL of 2M DPAHCl. The mixture composition was:
0.53DPAHCO.sub.3 :0.53DPAHCl:1GeS.sub.2 :30H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel along with a Teflon.TM. covered magnetic stir-bar and heated in an oven at 100.degree. C. with stirring at autogenous pressure for 42 hours. The solid products were recovered by filtration, washed with water, and dried in air at room temperature. A chemical analysis of the product revealed the presence of 14.3 weight percent C, 2.7 weight percent N, 40.5 weight percent Ge, 35.3 weight percent S, 2.6 weight percent H.sub.2 O and 25.5 weight percent LOI, giving a final product composition of:
0.35DPA:GeS.sub.2.0 :0.26H.sub.2 O.
The X-ray powder diffraction pattern of this product, which also contained a minor amount of GeO.sub.2 impurity was characterized by the data shown in Table 10.
TABLE 10______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.04 12.56 158.86 9.98 10010.79 8.20 2311.99 7.38 1412.75 6.94 1214.16 6.26 415.59 5.69 1018.47 4.80 419.42 4.57 1421.15 4.20 521.79 4.08 522.51 3.95 323.34 3.81 628.98 3.081 1231.25 2.862 331.89 2.806 834.30 2.614 3______________________________________
EXAMPLE 16
Preparation of TPA-GS-6 (TPA=tetrapropylammonium)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1) and 4.8 mL of 1.67M TPAHCO.sub.3 (made according to Example 2). The mixture was stirred momentarily to wet the GeS.sub.2, giving a mixture of composition:
0.53TPAHCO.sub.3 :1GeS.sub.2 :18H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 18 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. A chemical analysis of the product revealed the presence of 19.4 weight percent C, 2.0 weight percent N, 39.0 weight percent Ge, 33.3 weight percent S, 4.3 weight percent H.sub.2 O and 33.7 weight percent LOI, giving a final product composition of:
0.27TPA:GeS.sub.1.9 :0.45H.sub.2 O.
The major component of the product had an X-ray powder diffraction pattern characterized by the data shown in Table 11. A minor amount of GeO.sub.2 impurity (as in Example 7a) was also present.
TABLE 11______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________5.19 17.04 1006.75 13.10 98.00 11.05 568.34 10.60 719.83 9.00 8110.33 8.56 7510.99 8.05 1011.94 7.42 812.43 7.11 1412.98 6.82 3514.63 6.06 4615.49 5.72 3715.94 5.56 2419.52 4.55 1021.50 4.13 1524.48 3.64 1828.70 3.110 629.85 2.993 1230.45 2.935 1231.22 2.865 14______________________________________
b. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 4.8 mL of 1.67M TPAHCO.sub.3, and 1.65 grams of TPABr. The mixture was stirred momentarily to wet the GeS.sub.2, giving a mixture of composition:
0.53TPAHCO.sub.3 :0.27TPABr:1GeS.sub.2 :18H.sub.2 O.
The mixture was sealed in a Teflon .TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 18 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. The above product had an X-ray powder diffraction pattern in which the major phase (>95%) was characterized by the data shown in Table 12. The minor impurity phase present was GeO.sub.2.
TABLE 12______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________5.22 16.94 1008.01 11.05 178.42 10.50 239.87 8.96 2010.42 8.49 5811.93 7.42 412.52 7.07 813.04 6.79 3114.68 6.03 1015.56 5.70 916.00 5.54 619.68 4.51 321.57 4.12 824.57 3.62 428.80 3.100 330.52 2.929 431.11 2.875 3______________________________________
EXAMPLE 17
Preparation of CYC-GS-9. (CYC=cyclohexylamine)
A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1) and 10.0 mL of 1M CYCHCO.sub.3 (made according to Example 2). The mixture was stirred momentarily to wet the GeS.sub.2, giving a mixture composition of:
0.67CYCHO.sub.3 :1GeS.sub.2 :37H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 162 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. A chemical analysis of the product revealed the presence of 15.7 weight percent C, 2.9 weight percent N, 37.2 weight percent Ge, 36.5 weight percent S, 7.3 weight percent H.sub.2 O and 30.1 weight percent LOI, giving a final product composition of:
0.4CYC GeS.sub.2.2 :0.79H.sub.2 O.
The above product had an X-ray powder diffraction pattern characterized by the data shown in Table 13. A minor amount of GeO.sub.2 and another poorly crystalline impurity were also present.
TABLE 13______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.11 12.24 617.99 11.08 79.78 9.04 10010.14 8.73 1812.10 7.31 414.17 6.25 314.71 6.02 415.86 5.59 2016.13 5.50 618.24 4.86 1918.52 4.79 719.62 4.52 320.30 4.37 520.90 4.25 521.52 4.13 324.44 3.64 327.07 3.29 327.73 3.22 2528.66 3.115 329.34 3.044 330.29 2.951 430.49 2.932 633.89 2.645 337.65 2.389 438.43 2.342 3______________________________________
EXAMPLE 18
Preparation of QUI-GS-10. (QUI=quinuclidine)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1) and 8.0 mL of 1M QUIHCO.sub.3 (prepared according to Example 2). The mixture was stirred momentarily to wet the GeS.sub.2, giving a mixture of composition:
0.53QUIHCO.sub.3 :1GeS.sub.2 :30H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 18 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The above product had an X-ray powder diffraction pattern characterized by the data shown in Table 14.
TABLE 14______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________6.22 14.22 1008.99 9.83 8310.90 8.12 4611.10 7.97 4111.28 7.84 3912.50 7.08 2815.61 5.68 1517.63 5.03 2018.81 4.72 4121.30 4.17 824.87 3.58 1426.54 3.36 929.88 2.991 4334.19 2.623 9______________________________________
b. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1) and 12.0 mL of 1M QUIHCO.sub.3. The mixture was stirred momentarily to wet the GeS.sub.2, giving a mixture composition of:
0.8QUIHCO.sub.3 :1GeS.sub.2 :44H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 162 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. Chemical analysis of the product revealed the presence of 19.8 weight percent C, 3.3 weight percent N, 34.9 weight percent Ge, 34.5 weight percent S, 10.2 weight percent H.sub.2 O and 32.4 weight percent LOI, giving a final product composition of:
0.5QUI:GeS.sub.2.2 :1.2H.sub.2 O.
The X-ray powder diffraction pattern of the product was characterized by the data shown in Table 15.
TABLE 15______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________6.30 14.02 649.07 9.75 1009.93 8.91 910.98 8.06 5711.31 7.82 4712.56 7.05 1115.27 5.80 915.89 5.58 1617.69 5.01 1918.92 4.69 2121.26 4.18 525.42 3.50 825.70 3.47 926.64 3.35 629.95 2.984 4034.34 2.611 7______________________________________
EXAMPLE 19
Preparation of SnS.sub.2
A reaction mixture was prepared by combining 70.1 grams of SnCl.sub.4 5H.sub.2 O and 300 grams of H.sub.2 O. A separate solution of 111.4 grams of Na.sub.2 SxH.sub.2 O (43.9% H.sub.2 O) and 300 grams of H.sub.2 O was prepared. The Na.sub.2 S solution was slowly added with stirring to the SnCl.sub.4 solution, until precipitation of SnS.sub.2 ceased, giving a solution of pH 7.6. About 2 mL of concentrated HCl were then added, bringing the final pH to 6.6. The wet golden-brown solid was dehydrated in a dessicator over P.sub.2 O.sub.5.
EXAMPLE 20
Preparation of TMA-SnS-1 (TMA=tetramethylammonium)
a. A reaction mixture was prepared from 1.8 grams of SnS.sub.2 (Alfa), 1.8 grams of TMAOH 5H.sub.2 O (Aldrich), and 5 grams of H.sub.2 O, to give a mixture composition of:
1TMAOH:1SnS.sub.2 :33H.sub.2 O.
The mixture was sealed in a Teflon .TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 15 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The major product exhibited an X-ray diffraction pattern characterized by the data shown in Table 16. At least one other crystalline impurity was present in a minor amount.
TABLE 16______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.74 11.42 59.34 9.47 1110.38 8.52 10012.98 6.82 414.58 6.08 517.53 5.06 618.74 4.73 320.80 4.27 926.01 3.43 431.57 2.834 4______________________________________
b. A reaction mixture was prepared by combining 3.7 grams of SnS.sub.2 (made as in Example 19) and 5.0 mL of 2M TMAHCO.sub.3, giving a mixture composition of:
0.5TMAHCO.sub.3 :1SnS.sub.2 :14H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 65 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. Chemical analysis of the product revealed the presence of 11.3 weight percent C, 3.3 weight percent N, 48.4 weight percent Sn, 27.8 weight percent S, giving a final product composition of:
0.58TMA:SnS.sub.2.1 :0.86H.sub.2 O.
The X-ray powder diffraction pattern of the product was characterized by the data shown in Table 17.
TABLE 17______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________7.74 11.42 149.38 9.43 4110.48 8.44 10013.04 6.79 1314.43 6.14 515.57 5.69 317.14 5.17 317.59 5.04 1618.79 4.72 1120.76 4.28 721.04 4.22 1022.45 3.96 524.05 3.70 526.21 3.40 428.35 3.149 428.68 3.113 529.52 3.026 330.24 2.956 431.58 2.833 432.44 2.760 934.53 2.598 534.85 2.574 436.63 2.453 338.03 2.366 638.94 2.313 947.30 1.922 4______________________________________
EXAMPLE 21
Preparation of TEA-SnS-2.(TEA=tetraethylammonium)
a. A reaction mixture was prepared by combining 1.8 grams of SnS.sub.2 (Alfa) and 10 mL of 2M TEASH (made as in Example 5a), giving a composition of:
2TEASH:1SnS.sub.2 :55H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 64 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The major product exhibited an X-ray diffraction pattern characterized by the data shown in Table 18. At least one other crystalline impurity was present in a minor amount.
TABLE 18______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________5.82 15.18 47.90 11.20 408.64 10.23 10010.86 8.14 311.74 7.54 1314.30 6.19 315.13 5.86 315.91 5.57 517.40 5.10 717.74 5.00 418.15 4.89 418.65 4.76 419.16 4.63 523.73 3.75 524.00 3.71 528.75 3.106 329.27 3.051 3______________________________________
b. A reaction mixture was prepared by combining 3.7 grams of SnS.sub.2 (made as in Example 19) and 5.0 mL of 2M TEAHCO.sub.3, giving a composition of:
0.5TEAHCO.sub.3 :1SnS.sub.2 :14H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 65 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. The major product exhibited an X-ray diffraction pattern characterized by the data shown in Table 19. At least one other crystalline impurity was present in a minor amount.
TABLE 19______________________________________2 .theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________8.03 11.01 138.87 9.97 10011.94 7.41 514.47 6.12 215.42 5.75 316.05 5.52 217.74 5.00 618.36 4.83 318.98 4.68 419.42 4.57 323.85 3.73 324.10 3.69 228.85 3.094 229.40 3.038 2______________________________________
EXAMPLE 22
Preparation of TPA-SnS-3 (TPA=tetrapropylammonium)
a. A reaction mixture was prepared by combining 0.9 grams of SnS.sub.2 (Alfa) and 10.0 mL of 1M TPASH (made as in Example 5a), giving a composition of:
2TPASH:1SnS.sub.2 :110H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 64 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. The major product exhibited an X-ray diffraction pattern characterized by the data shown in Table 20. Minor amounts of two other crystalline phases were present in the product.
TABLE 20______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 7.56 11.69 19 9.00 9.83 2511.10 7.97 712.12 7.30 312.86 6.88 2413.13 6.74 315.40 5.75 816.03 5.53 1617.98 4.93 718.48 4.80 419.48 4.56 527.56 3.24 439.16 2.300 4______________________________________
b. A reaction mixture was prepared by combining 0.6 grams of SnS.sub.2 (made as in Example 19) and 12.0 mL fo TPASH made as in Example 5a), giving a composition of:
3.7TPASH:1SnS.sub.2 :200H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 65 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. The X-ray diffraction pattern of the product was characterized by the data shown in Table 21.
TABLE 21______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 7.69 11.49 30 9.02 9.80 10011.09 7.98 412.11 7.31 512.89 6.87 7413.15 6.73 415.45 5.73 7916.14 5.49 5818.06 4.91 518.74 4.74 1119.36 4.58 1820.13 4.41 520.46 4.34 320.90 4.25 523.24 3.83 524.33 3.66 325.06 3.55 631.05 2.880 531.47 2.842 432.52 2.754 1335.74 2.512 536.51 2.461 437.50 2.398 439.22 2.297 29______________________________________
EXAMPLE 23
Preparation of TPA-SnS-4. TPA=tetrapropylammonium)
a. A reaction mixture was prepared by combining 1.8 grams of SnS.sub.2 (Alfa) and 5.1 grams of TPAOH (40%) and 12 grams of H.sub.2 O, giving a composition of:
1TPAOH:1SnS.sub.2 :84H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 15 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. The major product exhibited an X-ray diffraction pattern characterized by the data shown in Table 22. At least two other crystalline phases were also present as minor components.
TABLE 22______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 7.97 11.10 100 8.69 10.18 810.45 8.47 512.99 6.81 316.06 5.52 1616.39 5.41 816.84 5.26 423.47 3.79 224.44 3.64 429.44 3.033 332.57 2.749 3______________________________________
b. A reaction mixture was prepared by combining 3.7 grams of SnS.sub.2 (made as in Example 19) and 12.0 mL of 1.67M TPAHCO.sub.3 (made as in Example 2), giving a composition of:
1TPAHCO.sub.3 :1SnS.sub.2 :33H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 66 hours followed by standing at room temperature for 1300 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. The X-ray powder diffraction pattern of the product was characterized by the data shown in Table 23.
TABLE 23______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 8.03 11.02 100 8.74 10.11 710.50 8.42 513.04 6.79 414.05 6.30 215.75 5.63 416.06 5.52 916.41 5.40 616.93 5.24 523.41 3.80 324.46 3.64 429.20 3.059 229.47 3.031 3______________________________________
EXAMPLE 24
Preparation of TEA-CoGS-1 (TEA=tetraethylammonium)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.37 grams of cobalt acetate (Co(CH.sub.3 COO).sub.2 4H.sub.2 O, and 6.0 mL of 2M TEAHCO.sub.3 (made according to Example 2.) The mixture was stirred momentarily to wet the GeS.sub.2 and cobalt salt, giving a final mixture composition of:
0.8TEAHCO.sub.3 :1GeS.sub.2 :0.1Co(CH.sub.3 COO)2:22H.sub.2 O
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 18 hours. The solid blue-green reaction product was recovered by filtration, washed with water, and dried in air at room temperature. An elemental analysis of the product revealed the presence of 14.4 weight percent C, 2.2 weight percent N, 31.5 weight percent Ge, 5.0 weight percent Co, 33.6 weight percent S, 9.7 weight percent H.sub.2 O, and 30.0 weight percent LOI, giving a final product composition of:
0.3TEA:Ge.sub.0.84 Co.sub.0.16 S.sub.2.0 1.0H.sub.2 O.
The X-ray powder diffraction pattern of the product was characterized by the data shown in Table 24.
TABLE 24______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 9.43 9.38 10014.83 5.97 5316.42 5.40 418.92 4.69 623.05 3.86 1828.65 3.116 429.75 3.003 1829.89 2.989 1632.95 2.718 433.11 2.706 538.12 2.361 638.34 2.348 538.51 2.336 550.80 1.797 4______________________________________
EXAMPLE 25
Preparation of DPA-CoGS-1 (DPA=dipropylamine)
A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.37 grams of cobalt acetate (Co(CH.sub.3 COO).sub.2 4H.sub.2 O) and 6.0 mL of 2M DPAHCO.sub.3. The mixture was stirred momentarily to wet the GeS.sub.2 and cobalt acetate, giving a final mixture composition of:
0.8DPAHCO.sub.3 :1GeS.sub.2 :0.1Co(CH.sub.3 COO).sub.2 :22H.sub.2 O
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 66 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. An elemental analysis of the product revealed the presence of 13.4 weight percent C, 2.4 weight percent N, 32.7 weight percent Ge, 4.6 weight percent Co, 34.2 weight percent S, 8.4 weight percent H.sub.2 O, and 30.2 weight percent LOI, giving a final product composition of:
0.32DPA:Ge.sub.0.85 Co.sub.0.15 S2.0:0.88H.sub.2 O
The X-ray powder diffraction pattern of the product was characterized by the following data shown in Table 25.
TABLE 25______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 9.34 9.47 10014.77 6.00 3816.19 5.48 318.72 4.74 1020.61 4.31 722.96 3.87 2427.45 3.25 529.77 3.002 2631.99 2.798 232.71 2.738 736.05 2.492 538.06 2.364 938.49 2.339 441.47 2.178 341.84 2.159 547.85 1.901 350.84 1.796 3______________________________________
EXAMPLE 26
Preparation of DIPA-CoGS-1 (DIPA=diisopropylamine)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.37 grams of cobalt acetate (Co(CH.sub.3 COO).sub.2 4H.sub.2 O), and 12.0 mL of 1M DIPAHCO.sub.3, (made as in Example 2). The mixture was stirred momentarily to wet the reagents, giving a final mixture composition of:
0.8DIPAHCO.sub.3 :1GeS.sub.2 :0.1Co(CH.sub.3 COO).sub.2 :44H.sub.2 O
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 42 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. An elemental analysis of the product revealed the presence of 6.2 weight percent C, 12 weight percent N, 32.8 weight percent Ge, 4.2 weight percent Co, 35.5 weight percent S, 6.4 weight percent H.sub.2 O, and 32.7 weight percent LOI, giving a final product composition of
0.16DIPA:Ge.sub.0.86 Co.sub.0.14 S.sub.2.12 :0.68H.sub.2 O
The X-ray powder diffraction pattern of the product, which contained no crystalline impurities, was characterized by the following data shown in Table 26.
TABLE 26______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 9.27 9.54 10014.73 6.02 8716.00 5.54 1018.54 4.79 2122.91 3.88 5927.17 3.28 1729.72 3.006 4831.89 2.807 532.47 2.757 1937.85 2.377 2038.45 2.341 640.94 2.205 546.35 1.959 847.84 1.901 550.77 1.798 651.14 1.786 1553.11 1.724 4______________________________________
EXAMPLE 27
Preparation of TMA-CoGS-1 (TMA=tetramethylammonium)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.37 grams of cobalt acetate (Co(CH.sub.3 COO).sub.3 4H.sub.2 O), and 6.0 mL of 2M TMAHCO.sub.3, (made according to Example 2), and 0.44 grams of TMACl. The TMACl was dissolved in the bicarbonate solution which was then added to the solid ingredients, followed by momentary stirring to wet and mix the reagents, giving a final mixture composition of:
0.8TMHCO.sub.3 :0.27TMACl:1GeS.sub.2 :0.1Co(CH.sub.3 COO).sub.2 :22H.sub.2 O
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 18 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The X-ray powder diffraction pattern of the product was characterized by the following data shown in Table 27. The product also contained a small amount of GeO.sub.2 impurity.
TABLE 27______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 9.20 9.61 10014.63 6.05 3316.17 5.48 318.34 4.84 1722.74 3.91 3126.88 3.32 529.51 3.027 2432.12 2.786 1235.22 2.548 437.55 2.395 838.06 2.365 438.39 2.345 541.88 2.157 347.57 1.911 550.73 1.800 752.37 1.747 455.45 1.657 4______________________________________
EXAMPLE 28
Preparation of TMA-ZnGS-1 (TMA=tetramethylammonium)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.31 grams of zinc acetate (Zn(CH.sub.3 COO).sub.2 2H.sub.2 O), 6.0 mL of 2M TMAHCO.sub.3, (made according to Example 2), and 0.44 grams of TMACl. The TMACl was dissolved in the bicarbonate solution before its addition to the remainder of the reagents. The final mixture was stirred momentarily to wet and combine the reagents, giving a final mixture composition of:
0.8TMAHCO.sub.3 :0.27TMACl:1GeS.sub.2 :22H.sub.2 O.
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 138 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The major phase in the product had an X-ray powder diffraction pattern was characterized by the data shown in Table 28. Minor amounts of at least one other crystalline phase were also present.
TABLE 28______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 9.16 9.66 10014.58 6.07 3316.18 5.48 418.28 4.85 2022.66 3.92 3526.76 3.33 729.42 3.036 2632.02 2.796 1635.12 2.555 537.44 2.402 838.27 2.352 640.63 2.221 347.12 1.929 347.49 1.914 550.58 1.805 852.23 1.751 455.32 1.661 4______________________________________
EXAMPLE 29
Preparation of CYC-ZnGS-1 (CYC =cyclohexylamine)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.31 grams of zinc acetate (Zn(CH.sub.3 COO).sub.2 2O), and O), and 12.0 mL of 1M CYCHCO.sub.3 (made according to Example 2.) The mixture was stirred momentarily to wet the reagents, giving a final mixture composition of:
0.8CYCHCO.sub.3 :1GeS.sub.2 :0.1Zn(CH.sub.3 COO).sub.2 :44H.sub.2 O
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at autogenous pressure for 138 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. An elemental analysis of the product revealed the presence of 13.5 weight percent C, 3.1 weight percent N, 35.4 weight percent Ge, 5.7 weight percent Zn, 36.5 weight percent S, 6.7 weight percent H.sub.2 O, and 23.6 weight percent LOl, giving a product composition of:
0.30CYC:Ge.sub.0.85 Zn.sub.0.15 S.sub.2.0 :0.65H.sub.2 O.
The product had an X-ray powder diffraction pattern characterized by the data shown in Table 29.
TABLE 29______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 9.03 9.79 100 9.90 8.93 1514.40 6.15 3116.04 5.53 417.99 4.93 1322.37 3.97 2526.38 3.38 827.33 3.26 329.04 3.075 2429.36 3.043 531.12 2.874 631.57 2.834 1134.57 2.595 436.95 2.433 737.84 2.378 446.93 1.936 549.96 1.826 451.37 1.779 354.72 1.677 3______________________________________
EXAMPLE 30
Preparation of TEA-MnGS-1 (TEA=tetraethylammonium)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.35 grams of manganese acetate (Mn(CH.sub.3 COO).sub.2 4H.sub.2 O), and 6.0 mL of 2M TEAHCO.sub.3 (made according to Example 2.) The mixture was stirred momentarily to wet the reagents, giving a final mixture composition of:
12TEAHCO.sub.3 :1GeS.sub.2 :0.1Mn(CH.sub.3 COO).sub.2 :22H.sub.2 O
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 18 hours. The solid reaction products were recovered by filtration, washed with water, and dried in air at room temperature. The major component of the product had an X-ray powder diffraction pattern characterized by the data shown in Table 30. A small amount of another crystalline impurity was also present.
TABLE 30______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 9.36 9.45 10014.68 6.03 4016.35 5.42 418.74 4.73 418.92 4.69 422.93 3.88 1123.03 3.86 1129.57 3.021 1129.82 2.996 1138.16 2.358 4______________________________________
EXAMPLE 31
Preparation of TEA-CoMnGS-1 (TEA=tetraethylammonium)
a. A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.18 grams of cobalt acetate (Co(CH.sub.3 COO).sub.2 4H.sub.2 O), and 0.18 grams of manganese acetate (Mn(CH.sub.3 COO).sub.2 4H.sub.2 O), 6.0 mL of 2M TEAHCO3 (made according to Example 2) and 0.84 grams of TEABr. The TEABr was dissolved in the bicarbonate solution, which was then added to the remainder of the reagents and stirred momentarily, giving the composition:
0.8TEAHCO.sub.3 :0.27TEABr:1GeS.sub.2 :0.05Co(CH.sub.3 COO).sub.2 :0.05Mn(CH.sub.3 COO).sub.2 :22H.sub.2 O
The mixture was sealed in a Teflon.sup..TM. -lined stainless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 114 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The X-ray powder diffraction pattern of the product, which contained no crystalline impurities, was characterized by the data shown in Table 31.
TABLE 31______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 9.38 9.43 10014.78 5.99 5516.46 5.38 318.89 4.70 523.01 3.86 1827.79 3.21 328.45 3.14 329.76 3.002 1732.85 2.726 433.10 2.706 437.94 2.371 638.36 2.347 550.72 1.800 4______________________________________
EXAMPLE 32
Preparation of TMA-CuGS-2. (TMA=tetramethylammonium)
A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.3 grams of copper acetate (Cu(CH.sub.3 COO).sub.2.H.sub.2 O), 6.0 mL of 2M TMAHCO.sub.3 (made as in Example 2), and 0.44 grams of TMACl. The mixture was stirred momentarily to wet the reagents, giving a final mixture composition of:
0.8TMAHCO.sub.3 :0.27TMACl:1GeS.sub.2 :0.1Cu(CH.sub.3 COO).sub.2 :22H.sub.2 O
The mixture was sealed in a Teflon .sup..TM. -lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 18 hours. The solid reaction product was recovered by filtration on a 44 micron stainless steel screen and the small amount of amorphous fines were washed away from the product with water. The product was dried in air at room temperature. An elemental analysis of the product revealed the presence of 11.5 weight percent C, 3.1 weight percent N, 39.0 weight percent Ge, 4.4 weight percent Cu, and 39.2 weight percent S, giving a final product composition of:
0.36TMA:Ge.sub.0.89 Cu.sub.0.11 S.sub.2.0
The X-ray powder diffraction pattern of the product, which contained no crystalline impurities, was characterized by the following data shown in Table 32.
TABLE 32______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________10.49 8.43 10012.12 7.30 813.57 6.53 316.05 5.52 517.20 5.16 1119.23 4.62 520.19 4.40 2721.08 4.21 421.96 4.05 924.39 3.65 826.64 3.35 328.02 3.18 1329.35 3.04 829.96 2.98 330.66 2.92 531.25 2.86 531.87 2.81 1432.46 2.76 434.21 2.62 640.54 2.23 541.53 2.17 3______________________________________
EXAMPLE 33
Preparation of TMA-MnCoGS-2. (TMA=tetramethylammonium)
A reaction mixture was prepared by combining 10.0 grams of GeS.sub.2 (made as in Example 1), 0.9 grams of manganese acetate (Mn(CH.sub.3 COO).sub.2.4H.sub.2 O), 0.9 grams of cobalt acetate (Co(CH.sub.3 COO).sub.2 4H.sub.2 O), 30.0 mL of 2M TMAHCO.sub.3 (made as in Example 2), and 2.2 grams of TMACl. The mixture was stirred momentarily to wet the reagents, giving a final mixture composition of:
0.8TMAHCO.sub.3 :0.27TMACl:1GeS.sub.2 :0.05Mn(CH.sub.3 COO).sub.2 :0.05Co(CH.sub.3 COO).sub.2 :22H.sub.2 O
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 18 hours. The solid reaction product was recovered by filtration on a 44 micron stainless steel screen and the small amount of fines were washed away from the product with water. The product was dried in air at room temperature. An elemental analysis of the product revealed the presence of 11.3 weight percent C, 2.9 weight percent N, 39.0 weight percent Ge, 2.6 weight percent Mn, 1.2 weight percent Co, 39.4 weight percent S, 2.2 weight percent H.sub.2 O, and 22.2 weight percent LOI, giving a final product composition of:
0.39TMAGe.sub.0.89 Mn.sub.0.08 Co.sub.0.03 S.sub.2.0 :0.2H.sub.2 O
An X-ray diffraction pattern of the product showed the major product (>95%) to possess an essentially identical diffraction pattern as the TMA-CuGS-2 product in Example 32.
EXAMPLE 34
Preparation of TMA-MnGS-3. (TMA=tetramethylammonium)
A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.72 grams of manganese acetate (Mn(CH.sub.3 COO).sub.2.4H.sub.2 O), 6.0 mL of 2M TMAHCO.sub.3 (made as in Example 2), and 0.44 grams of TMACl. The mixture was stirred momentarily to wet the reagents, giving a final mixture composition of:
0.8TMAHCO.sub.3 :0.27TMACl:1GeS.sub.2 :0.2Mn(CH.sub.3 COO).sub.2 :22H.sub.2 O
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 18 hours. The solid reaction product was recovered by filtration, washed with water and dried in air at room temperature. An elemental analysis of the product revealed the presence of 11.6 weight percent C, 3.0 weight percent N, 35.4 weight percent Ge, 6.3 weight percent Mn, 36.3 weight percent S, 4.5 weight percent H.sub.2 O, and 23.6 weight percent LOI, giving a final product composition of:
0.40TMA:Ge.sub.0.78 Mn.sub.0.22 S.sub.2.0 :0.5H.sub.2 O
An X-ray powder diffraction pattern of the product, which contained no crystalline impurities, was characterized by the following data shown in Table 33.
TABLE 33______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________11.22 7.88 10012.47 7.10 513.20 6.71 818.20 4.87 5018.71 4.74 620.97 4.24 321.86 4.07 2022.54 3.94 2328.24 3.16 5428.91 3.09 429.44 3.03 1031.46 2.84 532.37 2.77 1434.07 2.63 334.65 2.59 736.83 2.44 539.27 2.29 1239.64 2.27 342.62 2.12 747.04 1.93 748.97 1.86 1250.04 1.82 451.00 1.79 551.86 1.76 552.27 1.75 6______________________________________
EXAMPLE 35
Preparation of TMA-FeGS-3. (TMA=tetramethylammonium)
A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (obtained from Alfa Chemical Co.), 0.26 grams of iron acetate (Fe(CH.sub.3 COO).sub.2), 6.0 mL of 2M TMAHCO.sub.3 (made as in Example 2), and 0.44 grams of TMACl. The mixture was stirred momentarily to wet the reagents, giving a final mixture composition of:
0.8TMAHCO.sub.3 :0.27TMACl:1GeS.sub.2 :0.1Fe(CH.sub.3 COO).sub.2 :22H.sub.2 O
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 18 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. An elemental analysis of the product revealed the presence of 11.8 weight percent C, 3.1 weight percent N, 30.7 weight percent Ge, 6.2 weight percent Fe, 36.9 weight percent S, and 7.2 weight percent H.sub.2 O, giving a final product composition of:
0.41TMA:Ge.sub.0.79 Fe.sub.0.21 S.sub.2.0 :0.5H.sub.2 O
An X-ray diffraction pattern of the product, which contains no crystalline impurities, was essentially identical to the diffraction pattern of the TMA-MnGS-3 product in Example 34.
EXAMPLE 36
Preparation of TMA-GaGS-1. (TMA=tetramethylammonium)
A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1), 0.92 grams of gallium sulfate (Ga.sub.2 (SO.sub.4).sub.3 4H.sub.2 O), 8.0 mL of 2M TMAHCO.sub.3 (made as in Example 2), and 0.25 grams of isopropanol. The mixture was stirred momentarily to wet the reagents, giving a final mixture composition of:
1.1TMAHCO.sub.3 :1GeS.sub.2 :0.12Ga.sub.2 (SO.sub.4).sub.3 :0.27i-PrOH:30H.sub.2 O
The mixture was sealed in a Teflon.TM.-lined stainless steel pressure vessel and heated in an oven at 150.degree. C. at autogenous pressure for 100 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The X-ray powder diffraction pattern of the product indicated the presence of approximately 10% crystalline GeO.sub.2 which was accounted for when determining the composition based upon the chemical analysis. An elemental analysis of the product revealed the presence of 7.7 weight percent C, 1.9 weight percent N, 34.9 weight percent Ge, 9.0 weight percent Ga, 33.3 weight percent S, 6.0 weight percent H.sub.2 O, and 18.0 weight percent LOl, giving the following final product composition, assuming (moles Ga) +(moles Ge) =(0.5.times.moles S) in the sulfide framework and any excess Ge (9.2% excess) in the analysis may be attributed to GeO.sub.2 :
0.26 TMA:Ge.sub.0.75 Ga.sub.0.25 S.sub.2.0 :0.64 H.sub.2 O:0.09 GeO.sub.2
An X-ray powder diffraction pattern of the sulfide product was characterized by the following data shown in Table 34.
TABLE 34______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 9.19 9.62 10014.62 6.06 3216.16 5.49 318.42 4.82 1222.75 3.91 2427.00 3.30 529.55 3.02 2232.27 2.77 835.53 2.53 235.98 2.50 237.61 2.39 638.33 2.35 547.61 1.91 550.68 1.80 5______________________________________
EXAMPLE 37
Preparation of EBA-GS-11 (EBA=ethylbutylamine).
A reaction mixture was prepared by combining 2.0 grams of GeS.sub.2 (made as in Example 1) and 6.0 mL of 2 M EBAHCO.sub.3 (made as in Example 2). The mixture was stirred momentarily to wet the reagents, giving a final mixture composition of:
0.8 EBAHCO.sub.3 :1 GeS.sub.2 :22H.sub.2 O
The mixture was sealed in a Teflon .TM.-lined stanless steel pressure vessel and heated in an oven at 100.degree. C. at autogenous pressure for 42 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The X-ray powder diffraction pattern of the product, which contained a minor amount of GeO.sub.2 impurity, was characterized by the following data shown in Table 35.
TABLE 35______________________________________2.theta. d (.ANG.) 100 .times. I/I.sub.o______________________________________ 7.28 12.14 100 8.79 10.06 7 9.11 9.70 16 9.94 8.90 510.69 8.27 1011.02 8.04 912.93 6.85 415.95 5.56 216.82 5.27 1127.72 3.22 528.27 3.16 234.07 2.63 2______________________________________
EXAMPLE 38
Adsorption capacities of TMA-SnS-1 were measured using a mercury-free McBain-Bakr gravimetric adsorption apparatus. The following data were obtained on a sample activated at 150.degree. C.
______________________________________ Kinetic Pressure Wt. % Diameter A Torr Temp. .degree.C. Adsorbed______________________________________CO.sub.2 3.3 300 -78 6.0CO.sub.2 3.3 700 -78 7.3H.sub.2 O 2.65 4.7 24 4.4H.sub.2 O 2.65 20.0 24 7.8______________________________________
The pore size of the activated product is about 3.3 Angstroms, since Ar, which has a kinetic diameter of 3.4 Angstroms, showed no adsorption into the structure at -196.degree. C.
EXAMPLE 39
Luminescence behavior of the compositions TMA-MnGS-2 and TMA-MnZnGS-2 were measured by standard fluorescence techniques. The composition TMA-MnGS-2 was prepared analogously to TMA-CuGS-2 in Example 32, except that 0.38 grams of manganese acetate (Mn(CH.sub.3 COO).sub.2.4H.sub.2 O) was substituted for the copper acetate and the reaction mixture was digested for 114 hr. The composition TMA-MnZnGS-2 was prepared analogously to TMA-MnCoGS-2 in Example 33, except that 0.9 grams of zinc acetate (Zn(CH.sub.3 COO).sub.2.4H.sub.2 O) was substituted for the cobalt acetate. Elemental analyses of the two products gave compositions of
0.38TMA:Ge.sub.0.85 Mn.sub.0.15 S.sub.2.0 :0.17H.sub.2 O, and
0.35TMA:Ge.sub.0.88 Mn.sub.0.07 Zn.sub.0.05 S.sub.2.0 :0.2H.sub.2 O.
X-ray powder diffraction patterns of both compositions showed the major product to possess an essentially identical diffraction pattern as the TMA-CuGS-2 product in Example 32.
Fluorescence was characterized by emission bands between 550 and 670 nm, the most intense of which, at 590 nm, is characteristic of tetrahedral Mn(II). The compositions were excited at both 440 and 355 nm excitation wavelengths, both of which resulted in observed fluorescence. The TMA-MnGS-2 composition displayed fluorescence which was 100 times more intense than the TMA-MnZnGS-2 composition, indicating that the intensity of emission is controllable through adjustment of the product composition.

Number	Name	Date
4061724	Grose et al.	Dec 1977
4101631	Ambrosini et al.	Jul 1978
4310440	Wilson et al.	Jan 1982
4358297	Eberly, Jr.	Nov 1982
4398926	Doshi	Aug 1983
4440871	Lok et al.	Apr 1984
4500651	Lok et al.	Feb 1985
4589888	Hiscock et al.	May 1986
4723966	Fuderer	Feb 1988

	Number	Date	Country
Parent	416170	Oct 1989
Parent	280757	Dec 1988

Process for separating a mixture of molecular species using crystalline microporous metal sulfide compositions

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Continuation in Parts (2)