Patent Grant
10807929
The role of ethylene glycol in society has advanced considerably from the time when shortly after its first synthesis the molecule's properties became the subject of a fierce dispute between two giants of early organic chemistry, Adolphe Wurtz and Hermann Kolbe. In particular, Wurtz and Kolbe disputed ethylene glycol's functionality and chemical formula among the still emerging understanding of alcohol homologs, which were key to Kolbe's greater theories about chemical structure. The laboratory soon became a proxy war of the rising industrial and technical might of the growing rivalry between Germany and France with both countries devoting considerable resources to the scientific investigation and Wurtz's wizardry at chemical synthesis giving France a considerable advantage. The dispute was ended only by resort to arms when Bismarck's German Confederation annexed Wurtz's Alsatian homeland as a result of the Franco-Prussian war and thus, essentially turned an international dispute into a domestic one.
Today, interest in ethylene glycol is more peaceful but all the more competitive because ethylene glycol is one of the most widely produced organic chemicals. Since large scale industrial production of ethylene glycol began on the eve of the First World War, dramatic increases in the use of the internal combustion engine to power automobiles and other vehicles has spurred demand for ethylene glycol as a coolant and antifreeze. Since then, the increase in the production of ethylene glycol has only accelerated, so that by 2017, the estimated worldwide production of ethylene glycol was in excess of 25 billion tons.
Ethylene glycol is typically prepared as one of many of the derivatives of ethylene oxide, and though other production routes are available, most is produced from ethylene oxide in a liquid phase non-catalytic thermal hydration process. Because ethylene oxide reacts with ethylene glycols more readily than it reacts with water it is inevitable that a mixture of monoethylene glycol (MEG), as well as higher glycol coproducts, such as diethylene glycol (DEG), triethylene glycol (TEG) and yet still higher ethylene glycols will be formed. Although these higher glycols have considerable economic value, many producers and plant operators wish to avoid producing them because the end-user market for these products is not as well developed and it may be difficult to find and distribute these higher glycols to industrial consumers who have a need for them.
In order to suppress the reaction between product glycol and ethylene oxide and thereby reduce the formation of these higher glycols, conventional non-catalytic hydration is performed with an amount of water that far exceeds the stoichiometric amount of water for the hydration of ethylene oxide to ethylene glycol, e.g., 15 to 40 moles of water per mole of ethylene oxide. This addition of excess water is effective at balancing the kinetically-favored competing reaction between product glycol and ethylene oxide, which as mentioned above competes with the hydration of ethylene oxide to monoethylene glycol. However, while effective at suppressing the production of higher ethylene glycols, using a large excess of water relative to ethylene oxide presents a problem for the plant operator in removing these large excesses of unreacted water because such removal is energy intensive and requires large-scale evaporation/distillation facilities. Accordingly, there has been intensive research into alternatives to the standard thermal hydration of ethylene oxide for the production of ethylene glycol.
One early example of an alternative to conventional thermal hydration is the homogeneous catalytic hydration of ethylene oxide to monoethylene glycol. The earliest examples of this approach included the homogeneous catalysis of sulfuric acid and their associated salts (see Othmer, D. F. and Thakar, M. S., Glycol Production—Hydration of Ethylene Oxide. Ind. Eng. Chem. 1958, 50, 1235). European Patent No. 0 123 700 described refinements of these earlier generations of acid catalysts by treating them with, e.g., ethylamines to partially neutralize them in the hope of improving the selectivity of the hydration reaction to monoethylene glycol. Since then other salts have been proposed for homogeneous systems, such as quaternary phosphonium salts as described in U.S. Pat. No. 4,160,116 and metallate and bicarbonate salts as described in U.S. Pat. No. 7,683,221. Increasingly creative combinations of organic species such as EDTA and Salen compounds have also been proposed as homogeneous catalysts (see Hal, J. W., Ledford, J. S., and Zhang, X., Catalysis Today 123 (2007), 310-315).
Homogeneous catalyst systems are often utilized in a two-step process for manufacturing ethylene glycol, see e.g., U.S. Pat. No. 4,519,875 in which ethylene oxide is first reacted with carbon dioxide to manufacture ethylene carbonate, which is then hydrolyzed to ethylene glycol, with typically the same catalyst being used in both steps. Following this pioneering patent, continued research has produced incremental refinements in the two-step process. For example, in U.S. Pat. No. 5,763,691, the carbonation reaction is catalyzed in the ethylene oxide absorbate in the presence of a halogenated organic phosphonium salt carbonation catalyst. Additional research has considerably expanded the scope of known catalysts; see for example macrocyclic chelating compounds (“crown ethers”) described in U.S. Pat. No. 7,453,015.
While homogeneous catalysts improved the selectivity of the hydration reaction towards ethylene glycol compared to non-catalytic hydration, homogeneous catalysts have drawbacks that more than offset these improvements. In particular, the glycol product solution contains soluble or suspended homogeneous catalyst—essentially contaminating the product with the catalyst that is detrimental to product quality as well as highly corrosive as, for example, in the case of acid catalysts. Thus, an additional step of separating the homogeneous catalyst from the glycol product solution is necessary increasing the cost and complexity of the process is required. For example, while U.S. Pat. No. 5,763,691 mentioned above seeks to simplify the two-step ethylene glycol manufacturing by reacting the ethylene oxide and carbon dioxide in the absorbate, the patent still requires a separate distillation step for removing the carbonation catalyst.
This process complexity brings with it the additional flaw that it is neither very versatile nor flexible. For example, the process lacks the flexibility to be operated partially catalytically, i.e., in a mixed catalytic and non-catalytic mode—which would allow more higher glycols to be produced should the operator so desire and would also accommodate the plant in case of some logistical or operational upset where it was not capable of operating in a catalytic mode, for example when sufficient catalyst is not available. The two-step hydration process also lacks the versatility to be used both for new plants and revamps. The two-step hydration process can be used only for new plants and cannot be used for revamps because in the case of revamps it would be necessary to remove and replace the entire “back-end,” making such a revamp cost-prohibitive. A drawback of the two-step hydration process is the need to inventory concentrated ethylene oxide (greater than 70% concentration) for the production of the ethylene carbonate intermediate in the first step of the process. The carbonation reaction in the first step is conducted by bubbling carbon dioxide into this concentrated liquid ethylene oxide solution at high temperature and pressure (e.g., greater than 1.6 MPa). The large volume of concentrated ethylene oxide requires considerable additional measures (e.g., the provisioning of liquid cold storage) to prevent reactions or events that could result in ignition, combustion, deflagration, detonation or explosion of any gas stream, but especially those containing higher than typical concentrations of ethylene oxide.
Unsurprisingly, given the aforementioned drawbacks of both non-catalytic and homogeneous catalyzed hydration systems, heterogeneous catalysis using solid or supported catalysts has also been investigated. Those looking for the benefits of higher-selectivity of catalytic hydration without the aforementioned disadvantages have turned their attention toward heterogeneous catalyst systems. Because heterogeneous catalysts are not absorbed into the liquid phase reaction or product solutions, do not contaminate products solutions, do not require a separation step, and facilitate continuous operation of the hydration reactor there has been considerable interest in them.
A variety of solid materials have been proposed as heterogeneous catalysts for hydration. This list include zeolites such as those described by U.S. Pat. No. 3,028,434 as well as amorphous aluminosilicates, solid base and supported acid catalysts such as those disclosed by U.S. Pat. No. 4,165,440. Ion exchange resins have also been proposed with partially amine neutralized sulfonic acid styrene-divinyl benzene resin described in EP 0 123 709; quaternary phosphonium ion exchange resin catalysts, see PCT Publication WO 2000/35840; and strong base ion exchange resins as summarized by U.S. Pat. No. 6,211,419 being among the first ion exchange resins proposed to catalyze the reaction of water and ethylene oxide. More recent publications have expanded the field to wide swaths of anion exchange resins, see e.g., CN Patent No. 1208135.
While strong results have been achieved using heterogeneous ion exchange resin catalysts, there are also certain disadvantages to their use. In particular, ion exchange resin have limited tolerance to heat, so that under typical reaction conditions over long service times the resins experience swelling leading to deactivation. Swelling, which results from internal polymerization within the resin bed and the overall buildup of high molecular weight byproducts, is a serious issue that is the essential limiting factor in the lifespan of an ion exchange resin. Resins typically experience some reversible swelling during operation as they are exposed to solvents; however, through careful management this swelling can be mitigated and the effective life of the ion exchange resin extended. However, exposure of the ion exchange resin to ethylene oxide can cause a more problematic and irreversible swelling of the resin—especially when such exposure occurs at the higher temperatures of the hydration reactor, which as mentioned above may be outside the range of temperatures that the resin can satisfactorily tolerate.
Swelling is not only a problem in itself but can also reduce efficiency and complicate the catalytic hydration process; for example, when the excess swelling requires that the resin be replaced and thus, the catalytic hydration unit in which it is contained taken offline. Various attempts have been made to address these difficulties, including attempts to find resins less prone to swelling under typical operating conditions and in addition developing various process modifications the attempt to either improve performance as well as or in addition to reducing swelling. For example, EP Patent No. 1 828 086 discloses the use of “guard beds” designed to remove impurities that purportedly can cause resin swelling, but such efforts have been ineffectual.
Rather than protecting the resins with a guard bed to attempt to minimize swelling, another more successful approach outlined in PCT Publication WO2008/150338 seeks not to protect the resin but instead facilitate the process of removing the ion exchange resin that has exceeded its usable life by the hitherto unsuggested operation of the catalytic reactor in an upflow mode, which expands the catalyst bed, allows for segregation of the catalyst particles by size and thereby the selective removal of swollen particles. A still further approach is that shown in U.S. Pat. No. 6,160,187, which asserts that reductions in swelling can be obtained under adiabatic reaction conditions and the use of an adiabatic reactor. However, the examples contained in the '187 Patent did not actually demonstrate any improvement in swelling performance of the resins, nor have there been subsequent developments of adiabatic operation, whose development has been neglected.
Accordingly, while there have been several promising developments in individual aspects of heterogeneous catalytic hydration, there remains a considerable need for further improvements of catalytic hydration under adiabatic process conditions.
The present invention relates to a liquid phase process for the production of ethylene glycol comprising: providing a water stream and an aqueous ethylene oxide feed stream; dividing the aqueous ethylene oxide feed stream into at least a first equal proportion and a second equal proportion; combining the first proportion and the water stream to form a first feedstream; feeding the first feedstream into an inlet of a first adiabatic reactor, the inlet of the first adiabatic reactor being at an inlet temperature; reacting the ethylene oxide and water in the presence of a first ion exchange resin catalyst in the first adiabatic reactor to thereby produce a first reactor effluent stream containing water, ethylene glycol, and unreacted ethylene oxide; withdrawing the first reactor effluent stream from an outlet of the first adiabatic reactor; cooling the first reactor effluent stream through a heat-exchanger located downstream of the first adiabatic reactor to the hydration temperature; combining the second proportion and the cooled product stream to form a second feedstream; conveying the second feedstream to an inlet of a second adiabatic reactor, the inlet of the second adiabatic reactor being at the hydrolysis temperature; reacting ethylene oxide and water contained in the second feedstream in the presence of a second ion exchange resin catalyst in the second adiabatic reactor to thereby produce a second reactor effluent stream containing water, ethylene glycol, and unreacted ethylene oxide; wherein the first adiabatic reactor and the second adiabatic reactor each contain an ion exchange resin catalyst in a fixed catalyst bed and the outlet temperature is higher than the inlet temperature.
The foregoing summary, as well as the following detailed description of preferred embodiments of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there is shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown. In the drawings:
All parts, percentages and ratios used herein are expressed by volume unless otherwise specified. All pressures are absolute. All documents cited herein are incorporated by reference.
By “water” it is meant any kind of water suitable for use in chemical and petrochemical processing, including deionized, demineralized, industrial, potable and distilled water. Condensate of steam and condensate obtained from the dehydration and evaporation section of the glycol manufacture process may also be used.
By the present invention, an improved adiabatic catalytic hydration process has been developed in which catalyst swelling is reduced, process flexibility is considerably improved, and the process is configured such that it can be advantageously employed to revamp a non-catalytic process to a catalytic one. A particular advantage of the present invention is that a series of adiabatic reactors are used with injection of fresh aqueous ethylene oxide solution to each adiabatic reactor. Conventionally, the non-catalytic hydration reaction is carried out in a single adiabatic reactor without regard to the outlet, or maximum temperature of the reactor. Such operation could pose particular hazards for the ion exchange resins of the present invention since temperatures outside the temperature range designated for such resins can increase swelling and reduce catalyst life as discussed above.
Rather than use these single-stage adiabatic reactors and the disadvantages which accompany them (such as high temperature in the presence of the catalyst), the present invention instead makes use of multi-stage adiabatic reactors arranged in series with external inter-stage cooling and injection of fresh aqueous ethylene oxide solution to each stage. Since no heat is removed in the adiabatic reactor, the temperature of the effluent exceeds the temperature of the feed, and the heat of reaction must be removed from the effluent by a coolant after each stage. This is particularly important to prevent the aforementioned resin swelling and to prevent excessive non-catalytic reaction of product glycols with ethylene oxide to higher glycols. Further, the conventional non-catalytic adiabatic reactor cannot advantageously be configured to have multiple reactor stages in series with injection of fresh aqueous ethylene oxide solution. In such a configuration the introduction of fresh ethylene oxide to a reactor effluent stream containing an appreciable concentration of product glycols would cause the excessive reaction of product glycols to undesirable higher glycols. In the present invention, these problems are addressed by providing a catalytic hydration reaction section with two or more adiabatic reactors in series, inter-stage cooling between each reactor, and injection of fresh aqueous ethylene oxide solution to each reactor. The inter-stage cooling removes the heat of reaction of the effluent, reducing its temperature so that it may be combined with fresh aqueous ethylene oxide solution for the next successive reactor stage. The present invention makes use of both the cooled effluent temperature from each inter-stage cooler and the proportion of fresh aqueous ethylene oxide injection to each reactor to control the maximum temperature in each reactor within a range desirable for catalyst life and performance. Moreover, from a process perspective cooling by external inter-stage heat exchangers is easier, more efficient, and less complicated than configuring the appropriate duty for internal reactor cooling, and can be adjusted to absorb normal fluctuations in the process while maintaining the performance of the catalytic reactors. Thus, the use of a series of adiabatic reactors such as this present invention improves process versatility and allows for a revamping or retrofitting of a conventional non-catalytic hydration process into a catalytic one, as will be described in greater detail below.
In the present invention these benefits are achieved while still preserving the high selectivity of preceding catalytic hydration systems to monoethylene glycol. In each adiabatic reactor bed, ethylene oxide and water react in the presence of a heterogeneous catalyst (such as ion-exchange resin) to form monoethylene glycol with at least 98% of the ethylene oxide converted into monoethylene glycol, with only small percentages being converted into higher glycols like diethylene glycol or triethylene glycol.
Thus, by the present invention an improved process scheme has been developed that includes a catalytic hydration reaction section containing adiabatic reactors in series, which maintains low resin swelling and excellent selectivity while also reducing process complexity and increasing versatility.
This catalytic hydration reaction section (also “reaction section”) prepared according to the present invention as described above is shown as 25 in
Any suitable means for generating this liquid feed stream which is highly enriched with ethylene oxide is applicable to the present inventive process for catalytically producing ethylene glycol. One suitable means for doing this is the direct two-stage flash absorber-stripper section shown in
Ethylene oxide is produced by continuously contacting an oxygen-containing gas with an olefin, preferably ethylene, in the presence of an ethylene oxide (“epoxidation”) catalyst (described in greater detail below). Oxygen may be supplied to the reaction in substantially pure molecular form or in a mixture such as air. By way of example, typical reactant feed mixtures under operating conditions may contain from about 0.5% to about 45%, preferably about 5% to about 30% of ethylene and from about 3% to about 15% oxygen, with the balance comprising comparatively inert materials including such substances as carbon dioxide, water, inert gases, other hydrocarbons, and the reaction moderators described herein. Non-limiting examples of inert gases include nitrogen, argon, helium and mixtures thereof. Non-limiting examples of the other hydrocarbons include methane, ethane, propane and mixtures thereof. Carbon dioxide and water are byproducts of the epoxidation process as well as common contaminants in the feed gases. Both have adverse effects on the catalyst, so the concentrations of these components are usually kept at a minimum.
Also present in the reaction, as previously mentioned, are one or more reaction moderators, non-limiting examples of which include organic halogen-containing compounds such as C1 to C8 halohydrocarbons; especially preferred are chloride-containing moderators such as methyl chloride, ethyl chloride, ethylene dichloride, vinyl chloride or mixtures thereof. Controlling chloride concentration level is particularly important with rhenium-containing catalysts.
As mentioned above, a usual method for the ethylene epoxidation process comprises the vapor-phase oxidation of ethylene with molecular oxygen, in the presence of an epoxidation catalyst, in a fixed-bed tubular reactor. Conventional, commercial fixed-bed ethylene-oxide reactors are typically in the form of a plurality of parallel elongated tubes (in a suitable shell) approximately 0.7 to 2.7 inches O.D. and 0.5 to 2.5 inches I.D. and 15-53 feet long, each filled and packed with catalyst. The reaction feed mixture (described above) is introduced into these tubes, and the resulting reactor effluent gas contains ethylene oxide, un-used reactants, and byproducts.
For purposes of illustration only, the following are conditions that are often used in current commercial ethylene oxide reactor units: a gas hourly space velocity (GHSV) of 1500-10,000 h−1, a reactor inlet pressure of 150-400 psig, a coolant temperature of 180-315° C., an oxygen conversion level of 10-60%, and an EO production rate (work rate) of 7-20 lbs. EO/cu.ft. catalyst/hr. The feed composition in the reactor inlet after the completion of start-up and during normal operation typically comprises (by volume %) 1-40% ethylene, 3-12% O2; 0.3% to 20%, preferably 0.3 to 5%, more preferably 0.3 to 1% of CO2; 0-3% ethane, an amount of one or more chloride moderators, which are described herein; and the balance of the feed being comprised of argon, methane, nitrogen or mixtures thereof.
Typical operating conditions for the ethylene epoxidation process involve temperatures in the range from about 180° C. to about 330° C., and preferably, from about 200° C. to about 325° C., and more preferably from about 225° C. to about 280° C. The operating pressure may vary from about atmospheric pressure to about 30 atmospheres, depending on the mass velocity and productivity desired. Higher pressures may be employed within the scope of the invention. Residence times in commercial-scale reactors are generally on the order of about 2 to about 20 seconds.
In
As mentioned above, the absorber 9 is directly and permanently affixed to the top surface of the flash drum 5, by for example, welding. The absorber 9 is affixed to the flash drum 5 in the same manner as a still-column and reboiler configuration well-known to those skilled in the art. More specifically, the absorber 9 is affixed to the flash drum 5 along the longitudinal axis of the flash drum 5 but is preferably fixed at the midpoint of the longitudinal axis. The cross-section of the absorber 9 matches the shape of the opening in the flash drum 5 over which the absorber 9 is affixed and which allows communication between the flash drum 5 and the absorber 9. The cross-section of the absorber and the shape of the opening in the flash drum 5 have the same matching shape and that shape may be any shape between a circle and an ellipse, between an eccentricity of 0 and an eccentricity of 1. The opening in the flash drum 5 and the absorber 9 are aligned so that the center of the opening is collinear with the center of the absorber 9. Configuring the opening in the flash drum 5 and the shape of the absorber 9 and their respective alignments ensures that there is proper fluid communication between these two elements. The absorber 9 is preferably welded flush to the inner diameter of the opening made in the flash drum 5 so that the outer diameter of the absorber 9 is flush with the diameter of the opening in the flash drum 5.
In order to ensure the balance between flashing the more volatile “light” solutes while maintaining high solubility of ethylene oxide in the rich cycle water, the pressure in the flash drum 5 is maintained at about 0.1 MPa to about 0.3 MPa and the pressure in the absorber 9 to which there is direct communication is just slightly lower than the pressure in the flash drum 5. The temperature of the gases at the top of the absorber 9 is from about 30° C. to about 45° C., while the temperature in the flash drum 5 is from about 50° C. to about 60° C.
The overhead components of the absorber 9 are returned through conduit 12 to the upstream reaction section (not shown) as possible recycle to the reactor. The rich cycle water flows as liquid bottoms from the flash drum 5 through pump 14 and through optional heat exchanger 20 (which preheats the stream) and to the stripper 15. The pressure in the stripper 15 in maintained by control of the back pressure provided by the vapor vent from vent condenser 19. The temperature in the stripper 15 overhead is to be from about 25° C. to about 40° C. and the stripper 15 bottoms is about 120° C. to about 160° C. The rich cycle water stream can be preheated in heat exchanger 20 to reduce the duty necessary to operate the stripper 15. The pressure in the stripper 15 is maintained within a range of about 0.2 MPa to about 0.6 MPa. The stripper 15 may also utilize a steam ejector system well-known to those skilled in the art, with steam supplied from either: (1) steam generated elsewhere in the ethylene oxide production facility or (2) medium- or high-pressure steam supplied externally/OSBL; or a combination of these two sources.
The pressurized stripper-overhead stream flows through conduit 30 to the reaction section 25 as shown in
Under these circumstances of streams having a higher than typical ethylene oxide concentration, operators will continue to maintain appropriate safety standards that are always observed when producing, handling or storing ethylene oxide. As always, measures must be taken to prevent reactions or events that could result in ignition, combustion, deflagration, detonation or explosion of any gas stream, but especially those containing higher than typical concentrations of ethylene oxide. Accordingly, to prevent such events relief devices may be used to relieve or reduce undesirable pressure built-up in the process, reaction, or separation systems or elsewhere in the ethylene oxide plant both upstream and downstream of what is illustrated. The separation in the stripper 15 is so effective that nearly all of the ethylene oxide in the rich cycle water that enters the stripper 15 is successfully separated and recovered from the rich cycle water and leaves the stripper 15 as net liquid overhead stream while only a very small portion of EO leaves the stripper 15 elsewhere.
The pressurized stripper-overhead stream made in stripper 15 flows at elevated pressure through conduit 30 from the stripper section 1 to the reaction section 25 as shown in
As discussed above, such inter-stage cooling is necessary because the reaction of water with ethylene oxide is highly exothermic, so is it necessary to remove the heat of reaction from the product or outlet streams when the reaction occurs in adiabatic reactor as in the present invention to avoid excessive reactor bed temperature rise that can compromise the life of temperature sensitive catalyst such as ion-exchange resins. This differs from isothermal conditions where the heat of reaction is removed directly from the reactor. Maintaining the ion exchange resin catalyst at temperatures that the resin can tolerate is of course critical to reduce swelling, prevent degradation and maximize catalyst life. If operated properly the adiabatic temperature rise can be controlled to a level which maintains both good performance and life.
Lastly, positioned down-stream of the reactor train 22 is a conventional non-catalytic adiabatic pipe reactor 26 (this reactor of course contains no catalyst).
As the pressurized stripper overhead stream flows through conduit 30 into the reactor section, it is divided into equal proportions among the four reactors in series; then the first equal proportion of highly concentrated ethylene oxide stream is mixed with a source of water 36 (previously heated in a heat exchanger 35), in a mixing device, e.g., a static mixer, to create a dilute aqueous ethylene oxide feed stream 37. Stream 36 is heated in a heat exchanger 35 in order to bring mixed stream 37 to a temperature of between 50° C. and 90° C.
Also present is a water stream 36. The water stream 36 may be taken from any source of water, including OSBL, but preferably is taken from another section in the ethylene oxide/ethylene glycol plant. For example, the water may come from the recovery condensed water from ethylene glycol evaporation section of the plant—specifically the water may be condensed from the overhead vapor of one or more of the evaporators in the evaporation section.
When taken together, the water stream 36 and pressurized stripper overhead stream flowing through conduit 30 form the combined diluted feed stream to the reactor train 22. This combined feed stream will have a stoichiometric excess of water to ethylene oxide than is necessary for the hydration of ethylene oxide to ethylene glycol, however, the amount of this excess is considerably lower than the excess amount used in the prior art. Accordingly in the present invention the combined streams 40 and 36 have a molar ratio of water:ethylene oxide mole ratio of about 5:1 to about 15:1, preferably about 7:1 to about 12:1. And thus, because the combined overall feed stream contains less water, the final reactor train product stream 88 will also have correspondingly lower amounts of water that need to be removed from the product, as described below.
The aqueous ethylene oxide contained in stripper product liquid stream 40 is divided into four approximately equal streams 57, 61, 64, and 67, each of these streams containing approximately equal molar amounts of water and ethylene oxide. Of these, stream 57 is combined with water stream 36 (after being heated in heat exchanger 35) to form the feed stream 37 to reactor 38 so that the molar ratio of water:ethylene oxide in feed stream 37 is about 40:1 to about 10:1, preferably about 30:1 to about 20:1. This is a considerable improvement over conventional operation of catalytic and non-catalytic hydration. By co-feeding stream 57 along with the water stream 36 to the first reactor 38 and then co-feeding the other equal portions (61, 64, 67) of the aqueous ethylene oxide feed stream 40 with reactor effluent (70, 73, 76) a high diluted water:ethylene oxide ratio in the feed stream to each reactor can be obtained while simultaneously maintaining a lower overall water:ethylene oxide ratio in the product stream 88 at the end of the reactor section which is fed to the evaporators for water removal. Thus, the reaction of ethylene oxide and water is catalyzed in the presence of ion exchange resin and at a significant excess of water to ethylene oxide. This encourages selectivity to monoethylene glycol production and suppression of higher glycol homolog formation—there is thus a benefit of both effects. And yet this is maintained while having a final product that is much more concentrated in ethylene glycol and thus requires far less energy in the evaporation section. For example in the present invention the final product of the reactor section, the combined reactor product 88, may have a water:ethylene glycol ratio of 10:1 or even lower while by contrast in a conventional plant the glycol reactor effluent sent to the evaporation section has a water:ethylene oxide mole ratio of about 25:1, thus reducing the amount of heat duty necessary for evaporation of the excess water by a factor of at least 2.5. A significant advantage of the present invention is that the water:ethylene oxide mole ratio can be adjusted and optimized as necessary and desired for catalyst and energy usage, ethylene oxide availability, and product yield requirement.
Having illustrated the overall operational scheme of the reactor section and the benefits of the present invention, the process of the present invention will now be described in further detail with continued reference to
As mentioned above, streams 57 and 36 are combined to form the feed stream 37 to the first reactor and thus, the catalyst bed outlet temperature of reactor 38 is regulated by controlling the heating of the water stream 36 in the exchanger 35, which will in turn control the inlet temperature of the stream 37. The catalyst bed outlet temperature in the successive series reactors 40, 46, and 52 is each regulated with the use of exchangers 39, 43, and 49, respectively, used to cool the feed stream to each reactor.
Regulating temperature and pressure are important parts of the process of the present invention. The hydration reaction in the present invention is carried out as a liquid phase process. In the present invention by “liquid phase process” it is meant that the feed streams supplied to the reactor, the reactor product or reactor effluent streams, and the reactants inside the reactor are maintained in the liquid phase. Accordingly, the temperature and pressure in each reactor is such that as the streams are supplied to and enter into each reactor, they are maintained in the liquid phase. The temperature and pressure in each reactor is thus regulated to maintain the contents of the reactor in a liquid phase. The choice of temperature is largely determined by the considerations of the aforementioned paragraphs. Thus given the temperature ranges, below, in the present invention with the reactor contents being in liquid form, the pressure will be between about 0.5 MPa to about 1.5 MPa, preferably 0.8 MPa to 1.2 MPa.
In selecting the temperature, two competing requirements must be balanced. First, the temperature of the inlet in the present invention must be sufficiently high to drive the hydration reaction of ethylene oxide so that the conversion of ethylene oxide to monoethylene glycol is complete or nearly complete. Specifically, by “complete”, “nearly complete”, or “completion” it is meant the conversion percentage of ethylene oxide to monoethyelene glycol should be about at least 97%, preferably at least about 99%. Thus, the temperature at the inlet to reactors 38, 40, 46, and 52 must be within the range of about 50° C. to about 90° C., preferably within the range of about 70° C. to about 85° C. However, the temperature in the reactor (and consequently at the reactor outlet) should not be too high because, as mentioned above, a significantly high temperature increase inside the reactor causes swelling and degradation of the ion exchange resin. High temperatures in the reactor are the result of the exothermic hydration reaction and so to moderate any temperature increase this heat of reaction must be removed. In such applications, adiabatic reactors have considerably fewer process complications but have the disadvantage that they do not remove the heat of reaction. Accordingly, in the present invention it has been discovered that the temperature rise can nonetheless be at least partially moderated by the superabundant water in each reactor which acts as a heat sink. Thus, while one goal of the present invention is to reduce the amount of water used in the production of ethylene glycol, nonetheless at least a minimum amount of water is necessary to moderate the temperature increase in the reactors arising from the exothermic reaction. As described above, both of these goals are met in the present invention by dividing the aqueous ethylene oxide feed stream 40 into four equal portions 57, 61, 64, and 67 and co-feeding (“stage feeding” terminology can also be used) them to form the feed streams to reactors 38, 40, 46, 52. With this inventive configuration a high water:ethylene oxide ratio is obtained inside each reactor moderating the exotherm so that at the outlet of each reactor the temperature is between about 85° C. to about 120° C., preferably between about 100° C. to about 110° C.
Despite the success of the present invention at moderating the temperature rise in the reactor it may nonetheless be necessary to reduce the reactor effluent temperature still further until reaching the acceptable inlet temperature range mentioned above. In order to do this streams 70, 73, and 76 are passed through heat exchangers 39, 43, and 49, respectively. This presents an opportunity for heat integration as a flow stream (not pictured) from outside the reaction section may be heated in any of heat exchangers 39, 43, and 49 by indirect heat exchange with the reactor effluent from one or more of the series reactors.
As noted above, at higher temperatures there is nearly complete conversion of ethylene oxide to monoethylene glycol—at lower inlet temperatures not all of the ethylene glycol will react and detectable amounts of ethylene oxide will appear and remained unreacted (“break through”) in the reactor effluent. In certain situations it may be desired to reduce the inlet temperature in order to reduce the ethylene oxide conversion to allow for more ethylene oxide breakthrough—when for example it is desired to extend the life of the ion exchange resin catalyst or in other situations, as described below.
In addition to the above-mentioned parameters and operating conditions, other factors that may be considered when operating the process include but are not limited to: reactor and process configuration, the conversion rate and selectivity of the ion exchange resin catalyst, and reactants flow rate (LHSV). This unique reactor configuration allows flexibility in choosing reactor operating parameters that best suits plant operation targets in terms of catalyst and energy usage, ethylene oxide availability, and product yield requirement. In addition, the preparation of the highly concentrated ethylene oxide liquid feed stream 40 that feeds the present invention reduces considerably the number of steps required in the epoxidation process section, when compared to conventional commercial plants that require more steps because of the need for more dilute aqueous ethylene oxide and high temperatures for the conventional non-catalyzed thermal hydrolysis.
With the aforesaid considerations in mind, feed stream 37, at an appropriate temperature, enters reactor 38 where the ethylene oxide reacts with water in the presence of an ion exchange resin catalyst or catalyst bed to form monoethylene glycol. In the adiabatic reactors of the present invention, e.g., reactor 38, mixing ethylene oxide with hot dilution water to achieve the appropriate temperature in the presence of the catalyst results in the hydration of ethylene oxide that is highly selective to monoethylene glycol so that at least about 95%, preferably at least about 98% of the ethylene oxide that is converted is to monoethylene glycol with only small percentages being converted into higher glycols like diethylene glycol or triethylene glycol. So for example with respect to reactor 38 on a molar basis the number of moles of monoethylene glycol in the reactor effluent 70 will approximate the number of moles of ethylene oxide in the feedstream 38. In addition to the monoethylene glycol product, each effluent of the reactors in the present invention contains water (the excess unreacted water for use in the next reactor), monoethylene glycol and trace quantities of other components including ethylene oxide and higher glycol homologs.
Despite the pressure drop across the length of reactor 38, there is sufficient pressure differential between reactor 38 and 40 for the first reactor effluent 70 to pass through heat exchanger 39, where it is cooled and then the first reactor effluent is combined with stream 61 to form a second feedstream 81 which enters reactor 40 as in reactor 38 the ethylene oxide reacts with water at a high selectivity and conversion rate so that substantially all of the ethylene oxide is reacted with a stoichiometric amount of water to product monoethylene glycol at the aforementioned conversion percentages. The second reactor effluent, which like the first reactor effluent contains unreacted water, monoethylene glycol and the trace components mentioned above, travels by pressure differential through heat exchanger 43. Essentially the only difference between the first reactor effluent 70 and the second reactor effluent 73 is that the latter contains more monoethylene glycol because it contains the amount of monoethylene glycol that is produced in both reactors 38 and 40. Reactors 46 and 52 and their associated streams are operated in the same manner as 38 and 40 with the second reactor effluent 73 cooled in heat exchanger 43 and combined with equal portion 64 of the aqueous concentrated ethylene oxide feed stream 40 to form the third feedstream 75 which reacts in the presence of a third ion exchange resin catalyst bed in the third reactor 46 to form a third reactor effluent 76. The third reactor effluent 76 cooled in heat exchanger 49 and combined with equal portion 67 to form a fourth feedstream 77, which reacts in the presence of a fourth ion exchange resin catalyst bed in the fourth reactor 52 to form a fourth reactor effluent 79, each effluent becoming successively more enriched in monoethylene glycol as described above.
In addition to the previously described reactor train 22 encompassing the four down-flow, fixed-bed series reactors, the reactor section 25 also includes a conventional pipe reactor 26 to which the fourth reactor effluent 79 may be supplied to after being heated in heat exchanger 55. In the present invention this pipe reactor 26 is configured and operated to provide hitherto unknown levels of versatility and operability to a catalytic hydration process scheme, which shall now be described in more detail.
First, in addition to increasing the conversion and selectivity of the reaction of ethylene oxide and water to MEG, the present invention may also be operated and configured to increase the versatility and adaptability of the hydration process by allowing the process operator to make di- and triethylene glycol. This can be done by physically bypassing one or more of the catalytic reactors 38, 40, 46, 52 (this bypass itself is not illustrated) and thereby removing the one or more catalytic reactors from the circulation of the feedstream. The ethylene oxide that “breaks through” that remains unreacted after by-passing one or more of the aforementioned catalyst reactors is sent to the non-catalytic pipe reactor 26 for thermal conversion of ethylene oxide and water to ethylene glycol. As the pipe reactor 26 is non-catalytic and relies entirely on thermal conversion the fourth reactor effluent 79 is preheated in heat exchanger 55 to arrive within the effective temperature range for non-catalytic hydration of ethylene oxide into monoethyelene glycol—preferably the inlet temperature of the pipe reactor 26 is from about 130° C. to about 160° C.
Of course this non-catalytic thermal conversion is significantly less selective to MEG, with substantial amounts of higher glycols relative to MEG such as DEG and TEG also produced so that by increasing the amount of ethylene oxide that is converted into ethylene glycol in the pipe reactor, the combined reactor product 88 contains less MEG and more DEG and TEG than would be produced if only the catalytic reactors in the reaction section 22 were being used. This provides the operator a versatile and flexible process for ethylene glycol production as the output of mono-, di- and triethylene glycol product may be adjusted by the operator to meet demand. In a limiting case, all four series reactors are bypassed so that only the final non-catalytic pipe reactor 26 is left and all hydration will occur in this reactor—thus converting the catalytic process into a non-catalytic one. Alternatively, the catalytic train 22 adds flexibility to decrease utility consumption in the plant while still maintaining a fixed monoethylene glycol production, compared to the same production in a plant employing non-catalyzed EO hydrolysis. If about half of the production of ethylene glycol is made in the catalytic reactors 38 and 40 of reactor train 22 (with reactors 46 and 42 bypassed), and the balance is made in the pipe thermal reactor 26, the plant product distribution obtained will be similar to a conventional non-catalytic thermal hydrolysis process, but with the advantage of running the plant at an approximately 20% lower molar ratio of water:ethylene oxide, resulting in significant utility savings in glycol evaporation.
Alternatively, rather than physically bypassing the reactors, a “temperature bypass” can be effected by reducing the inlet temperature to one or more of the series reactors as low as desired to reduce the reaction between the ethylene oxide and water and reducing the amount of monoethylene glycol made in the reactors, meaning more unreacted ethylene oxide “breakthrough” is seen in the outlets of the catalytic reactors. This ethylene oxide is then converted to ethylene glycol in the pipe reactor as set forth above.
The pipe reactor may also function in a “finishing” role. Even when the train of reactors 22 is operating within normal catalytic efficiency as designed to maximize the conversion of ethylene oxide to ethylene glycol, nonetheless a small amount of unreacted ethylene oxide will remain unreacted through all four reactors in train 22 and this ethylene oxide will “breakthrough” in the fourth reactor effluent 79. In the present invention train 26 is preferably operated so that the concentration of ethylene oxide in the fourth reactor effluent 79 will be no greater than about 1 mol %. This remaining ethylene oxide can then be converted to monoethylene glycol in the pipe reactor 26.
Finally, the pipe reactor 26 can also be used as a stand-by reactor in situations where one or more of the catalytic reactors malfunctions or has to be otherwise removed from service because of exhaustion, a blockage in the resin bed or nozzle or some other difficulty commonly observed in operation of ion exchange resin beds. When this happens the malfunctioning catalytic reactor must be taken out of service. This means that there will be excess unconverted ethylene oxide in the reaction section 22 which is undesirable. This excess ethylene oxide breakthrough can be converted into ethylene glycol in the pipe reactor 26. Thus, the presence of the pipe reactor 26 in the present prevention provides considerable flexibility and operability for the process operator. Unlike in the prior art where the inability to replace or repair the ion exchange resin catalyst or reactor is a serious disadvantage of solid/heterogeneous catalytic systems, in the present invention reactors may be taken offline for such repair without interrupting operation.
While four reactors and three heat exchangers are shown in the reactor section of
The primary drawbacks of more reactors is cost and complexity including the additional capital cost of reactors, pumps, exchangers and other equipment as well as the operating costs of larger volumes of ion exchange resin catalyst as well as additional piping, instrumentation and operational complexity.
The alkylene glycol in the combined reactor product 88 can then be recovered by a multi-effect evaporator or vacuum distillation, or any other suitable means known to those skilled in the art. Recovery techniques can be combined for different stages in the recovery. For example, the multi-effect evaporator can be used to remove water from the reactor effluent while vacuum distillation can be used for glycol drying. Indeed, it is one of the benefits of the present invention that in the post-glycol reaction section of the plant, complexity can be reduced because the amount of heat duty necessary for evaporation of the excess water has been reduced as noted above and as detailed in the example, below. Thus, while prior art plants often incorporate evaporation systems having several effects or stages (see e.g., EP No. 2121646 B1) the present invention requires fewer number of stages.
As discussed above, the present invention may involve one or more ion exchange resin catalysts. Ion exchange resins have a polymer matrix which contain on the surface ion exchanging sites populated by ionic functional groups. Ion exchange resins are typically differentiated between cationic or anionic exchange resins, although other types of ion exchange resins are also available. For a more comprehensive description of cation- and anion-exchange resins see, de Dardel, F. and Arden, T. V. Ion Exchangers in Ullman's Encyclopedia of Industrial Chemistry (2005).
Suitable polymer matrices for the ion exchange resin catalysts include a polystyrene matrix, a polyacrylic matrix, a polyalkylamine resin as well as other polymeric materials. Preferably, the polymer matrix is cross-linked with divenylbenzene to a sufficient degree to increase the operating capacity while also not increasing the density of the ion exchange material to such an extent that the ion exchange material becomes too physically hard and too chemically resistant to chemical treatment. Preferably the matrix is a styrene, divenylbenzene co-polymer.
Fixed to sites on the polymer matrices described above are ionic stationary groups that determine whether the resin functions as a cationic or anionic ion exchange resin. In solutions, the positive or negative charge of the stationary groups is compensated for by ions of opposite charge which are referred to herein as the functional group.
Strongly acidic cationic ion exchange resins typically include sulfonic groups as stationary groups in turn attached to a styrene-divenylbenzene polymer matrix. Examples of strongly acidic sulfonic cation-exchange resins include Amberlite IR 120, Dowex HCR, Lewatit S 100, and Amberlyst 15, among others.
Cationic ion exchange resins may also include the resin material that is the copolymer obtained by the addition polymerization of an acrylic or methacrylic acid and divinylbeneze such as disclosed in U.S. Pat. No. 3,957,698. Other suitable polymer materials for cationic exchange resins include the resin matrix formed when polyvinylpyridine resin cross-linked with divenylbenzene. Such materials are available under the Reillex HPQ trademark. Sulfonated phenolic polymer resins are also suitable cationic ion exchange resins.
Weakly acidic cationic ion exchange resins typically include carboxylic groups as stationary groups. Examples of weakly acidic cation-exchange resins include Amberlite IRC 86, Dowex Mac-3, Lewatit CNP, among others.
As used herein in the present invention, strongly basic anionic exchange resins contain quaternary ammonium stationary groups. These are further divided into Type I, made by the reaction of trimethylamine with the styrene-divenylbenzene copolymer after chloromethylation, and Type II obtained by the reaction of the styrene-divenylbenzene copolymer with dimethylethanolamine. Suitable examples of such Type I resins include Lewatit MP 500 available from Lanxess, and Amberlyst 26 and Amberlite IRA 402, and IRA 410 available from Dow. Suitable examples of strongly basic Type II resins include, e.g., Purolite A510S (Purolite Corporation).
Weakly basic anion exchange resins typically include polyacryclic resins provided with stationary groups by reaction with a polyfunctional amine to result in anion exchange resins such as the tertiary ammonium weakly basic Amberlite IRA 67 and Amberlyst 21 resins (available from Dow). It should be especially noted that this ion exchange resin can be then be further treated with chloromethane or dimethyl sulfate to give a quaternary amine strongly basic Type I resin Amberlite IRA 458 resin (Dow). Weakly basic anion exchange resins may also include a free base group as the stationary group such as the Amberlite IRA-67 resin (Dow).
In a particular embodiment of the present invention the strongly basic anionic exchange resin contains a “linking” group of 3-7 linking atoms, preferably 3-5 carbon atoms between the quaternary ammonium stationary group and the benzene group of the polymer matrix/material. An example of such a linking chain in a strong base resin is illustrated in U.S. Pat. No. 5,945,568 and was produced under the name Diaion TSA1200 (Mitsubishi Chemical). As specified in the '568 patent the linking group which links the quaternary ammonium stationary group to the benzene group of the polymer matrix is not particularly limited as long as it is sufficiently long. Suitable examples of the linking group are an alkylene group or an alkyleneoxyalkylene group. A preferred example for use in the present invention is an anion exchange resin which comprises, as the substrate, a polymer of a vinyl aromatic compound and which has a structure such that a quaternary ammonium group is bonded to the aromatic group via a linking group having a chain length of at least 3.
Without being limited by theory it is believed that in the present invention this linking group prevents the nucleophilic attack on the ammonium stationary group from the benzene ring which otherwise would lead to accelerated deactivation and degradation of the ion exchange resin catalyst and reduced stability and catalyst life.
A variety of ions are suitable for use as the functional group in anionic resins of the present invention and may be selected from the group including bicarbonate, carbonate, hydroxide, bisulfite, carboxylate, citrate, and metalate, and molybdate anions. These functional groups may be used with any of the stationary groups and resin material identified above.
In the present invention it is preferred that the ion exchange resin catalyst is from the group of type I strongly basic anion exchange resins, more preferably type I strongly basic anion exchange resins with a bicarbonate or monocitrate functional group, and most preferably type I strongly basic anion exchange resins with a bicarbonate or monocitrate functional group with a linking group.
In addition to the ion exchange materials specified above, any other suitable cationic or anionic exchange resin may be used such as the cation- and anion-exchange resins set forth above in de Dardel, F. and Arden, T. V. 2008, Ion Exchanger, in Ullman's Encyclopedia of Industrial Chemistry.
In addition to the aforementioned ion exchange material it is also possible to use a combination of a homogeneous and heterogeneous catalyst—for example a solid catalyst on which is adsorbed a soluble metallic catalyst. In this case, first a solid catalyst having a metallic catalyst adsorbed on it is prepared. Then, during the liquid-phase hydration reaction described above, the metallic catalyst is desorbed from the solid catalyst and can effectively catalyze the reaction. The metallic catalyst must then be separated from the reaction products and can be reused for re-adsorbing on to the solid catalyst. The solid catalyst in this case can be an ion exchange resin.
The above paragraphs concern the selection of suitable ion exchange resin catalysts for use in the catalytic reactors of the present invention. With respect to the operation of the ion exchange resin-containing catalytic reactors, in
As can probably be surmised, in up-flow operation the feedstream travels in a direction from the bottom of the reactor upwards. In PCT Publication No. WO2008/150338A1 increased stability and operational life of ion exchange resin in up-flow operational mode was reported. In the present invention with liquid-phase reactants and a solid catalyst up-flow operation may provide a modest amount of bed fluidization during up-flow operation which increases the void fraction between adjacent resin particles allowing for the reduction of the inhomogeneities and contaminates that otherwise become embedded and trapped in the catalyst bed during down-flow operation and degrade catalyst performance. U.S. Pat. No. 6,160,187 has previously disparaged up-flow operation of catalytic reactors because the resulting bed fluidization purportedly causes greater catalyst attrition and reduced monoethylene glycol selectivity due to axial mixing. However, it has been discovered in the present invention that in the liquid phase process of the present invention these criticisms are not realistic because they are more likely to occur in gas/solid catalyst systems where there are much higher velocities, a greater difference in densities (between the gas reactant and solid catalyst compared to a liquid reactant and solid catalyst), and thus a much greater bed expansion than in the present liquid/solid catalyst system of our invention. Thus, up-flow operation remains a suitable mode of operation in the present invention.
Silver-Based Epoxidation Catalyst
The silver-based epoxidation catalyst includes a support, and at least a catalytically effective amount of silver or a silver-containing compound; also optionally present is a promoting amount of rhenium or a rhenium-containing compound; also optionally present is a promoting amount of one or more alkali metals or alkali-metal-containing compounds. The support employed in this invention may be selected from a large number of solid, refractory supports that may be porous and may provide the preferred pore structure. Alumina is well known to be useful as a catalyst support for the epoxidation of an olefin and is the preferred support.
Regardless of the character of the support used, it is usually shaped into particles, chunks, pieces, pellets, rings, spheres, wagon wheels, cross-partitioned hollow cylinders, and the like, of a size suitable for employment in a fixed-bed epoxidation reactor. The support particles will preferably have equivalent diameters in the range from about 3 mm to about 12 mm, and more preferably in the range from about 5 mm to about 10 mm. (Equivalent diameter is the diameter of a sphere having the same external surface (i.e., neglecting surface within the pores of the particle) to volume ratio as the support particles being employed.) Suitable supports are available from Saint-Gobain Norpro Co., Sud Chemie AG, Noritake Co., CeramTec AG, and Industrie Bitossi S.p.A. Without being limited to the specific compositions and formulations contained therein, further information on support compositions and methods for making supports may be found in U.S. Patent Publication No. 2007/0037991.
In order to produce a catalyst for the oxidation of an olefin to an olefin oxide, a support having the above characteristics is then provided with a catalytically effective amount of silver on its surface. In one embodiment, the catalytic effective amount of silver is from 10% by weight to 45% by weight. The catalyst is prepared by impregnating the support with a silver compound, complex or salt dissolved in a suitable solvent sufficient to cause deposition of a silver-precursor compound onto the support. Preferably, an aqueous silver solution is used.
A promoting amount of a rhenium component, which may be a rhenium-containing compound or a rhenium-containing complex may also be deposited on the support, either prior to, coincidentally with, or subsequent to the deposition of the silver. The rhenium promoter may be present in an amount from about 0.001 wt. % to about 1 wt. %, preferably from about 0.005 wt. % to about 0.5 wt. %, and more preferably from about 0.01 wt. % to about 0.1 wt. % based on the weight of the total catalyst including the support, expressed as the rhenium metal.
Other components which may also be deposited on the support either prior to, coincidentally with, or subsequent to the deposition of the silver and rhenium are promoting amounts of an alkali metal or mixtures of two or more alkali metals, as well as optional promoting amounts of a Group IIA alkaline earth metal component or mixtures of two or more Group IIA alkaline earth metal components, and/or a transition metal component or mixtures of two or more transition metal components, all of which may be in the form of metal ions, metal compounds, metal complexes and/or metal salts dissolved in an appropriate solvent. The support may be impregnated at the same time or in separate steps with the various catalyst promoters. The particular combination of support, silver, alkali metal promoter(s), rhenium component, and optional additional promoter(s) of the instant invention will provide an improvement in one or more catalytic properties over the same combination of silver and support and none, or only one of the promoters.
As used herein the term “promoting amount” of a certain component of the catalyst refers to an amount of that component that works effectively to improve the catalytic performance of the catalyst when compared to a catalyst that does not contain that component. The exact concentrations employed, of course, will depend on, among other factors, the desired silver content, the nature of the support, the viscosity of the liquid, and solubility of the particular compound used to deliver the promoter into the impregnating solution. Examples of catalytic properties include, inter alia, operability (resistance to runaway), selectivity, activity, conversion, stability and yield. It is understood by one skilled in the art that one or more of the individual catalytic properties may be enhanced by the “promoting amount” while other catalytic properties may or may not be enhanced or may even be diminished.
Suitable alkali metal promoters may be selected from lithium, sodium, potassium, rubidium, cesium or combinations thereof, with cesium being preferred, and combinations of cesium with other alkali metals being especially preferred. The amount of alkali metal deposited or present on the support is to be a promoting amount. Preferably, the amount ranges from about 10 ppm to about 3000 ppm, more preferably from about 15 ppm to about 2000 ppm, and even more preferably from about 20 ppm to about 1500 ppm, and as especially preferred from about 50 ppm to about 1000 ppm by weight of the total catalyst, measured as the metal.
Suitable alkaline earth metal promoters comprise elements from Group IIA of the Periodic Table of the Elements, which may be beryllium, magnesium, calcium, strontium, and barium or combinations thereof. Suitable transition metal promoters may comprise elements from Groups IVA, VA, VIA, VIIA and VIIIA of the Periodic Table of the Elements, and combinations thereof.
The amount of alkaline earth metal promoter(s) and/or transition metal promoter(s) deposited on the support is a promoting amount. The transition metal promoter may typically be present in an amount from about 0.1 micromoles per gram to about 10 micromoles per gram, preferably from about 0.2 micromoles per gram to about 5 micromoles per gram.
The silver solution used to impregnate the support may also comprise an optional solvent or a complexing/solubilizing agent such as are known in the art. A wide variety of solvents or complexing/solubilizing agents may be employed to solubilize silver to the desired concentration in the impregnating medium. Useful complexing/solubilizing agents include amines, ammonia, oxalic acid, lactic acid and combinations thereof. Amines include an alkylene diamine having from 1 to 5 carbon atoms. In one preferred embodiment, the solution comprises an aqueous solution of silver oxalate and ethylene diamine. The complexing/solubilizing agent may be present in the impregnating solution in an amount from about 0.1 to about 5.0 moles per mole of silver, preferably from about 0.2 to about 4.0 moles, and more preferably from about 0.3 to about 3.0 moles for each mole of silver.
When a solvent is used, it may be an organic solvent or water, and may be polar or substantially or totally non-polar. In general, the solvent should have sufficient solvating power to solubilize the solution components. At the same time, it is preferred that the solvent be chosen to avoid having an undue influence on or interaction with the solvated promoters. Organic-based solvents which have 1 to about 8 carbon atoms per molecule are preferred. Mixtures of several organic solvents or mixtures of organic solvent(s) with water may be used, provided that such mixed solvents function as desired herein.
The concentration of silver in the impregnating solution is typically in the range from about 0.1% by weight up to the maximum solubility afforded by the particular solvent/solubilizing agent combination employed. It is generally very suitable to employ solutions containing from 0.5% to about 45% by weight of silver, with concentrations from 5 to 35% by weight of silver being preferred.
Impregnation of the selected support is achieved using any of the conventional methods; for example, excess solution impregnation, incipient wetness impregnation, spray coating, etc. Typically, the support material is placed in contact with the silver-containing solution until a sufficient amount of the solution is absorbed by the support. Preferably the quantity of the silver-containing solution used to impregnate the porous support is no more than is necessary to fill the pores of the support. A single impregnation or a series of impregnations, with or without intermediate drying, may be used, depending, in part, on the concentration of the silver component in the solution. Impregnation procedures are described, for example, in U.S. Pat. Nos. 4,761,394, 4,766,105, 4,908,343, 5,057,481, 5,187,140, 5,102,848, 5,011,807, 5,099,041 and 5,407,888. Known prior procedures of pre-deposition, co-deposition and post-deposition of various the promoters can be employed.
After impregnation of the support with the silver-containing compound, i.e., a silver precursor, a rhenium component, an alkali metal component, and the optional other promoters, the impregnated support is calcined for a time sufficient to convert the silver containing compound to an active silver species and to remove the volatile components from the impregnated support to result in a catalyst precursor. The calcination may be accomplished by heating the impregnated support, preferably at a gradual rate, to a temperature in the range from about 200° C. to about 600° C. at a pressure in the range from about 0.05 to about 3.5 MPa. In general, the higher the temperature, the shorter the required heating period. A wide range of heating periods have been suggested in the art; e.g., U.S. Pat. No. 3,563,914 discloses heating for less than 300 seconds, and U.S. Pat. No. 3,702,259 discloses heating from 2 to 8 hours at a temperature of from 100° C. to 375° C., usually for duration of from about 0.5 to about 8 hours. However, it is only important that the heating time be correlated with the temperature such that substantially all of the contained silver is converted to the active silver species. Continuous or step-wise heating may be used for this purpose.
During calcination, the impregnated support may be exposed to a gas atmosphere comprising an inert gas or a mixture of an inert gas with from about 10 ppm to 21% by volume of an oxygen-containing oxidizing component. For purposes of this invention, an inert gas is defined as a gas that does not substantially react with the catalyst or catalyst precursor under the conditions chosen for the calcination. Further information on catalyst manufacture may be found in the aforementioned U.S. Patent Publication No. 2007/0037991.
For purposes of illustration only, the following are conditions that are often used in current commercial ethylene oxide reactor units: a gas hourly space velocity (GHSV) of 1500-10,000 h−1, a reactor inlet pressure of 1 Mpa to 3 MPa, a coolant temperature of 180-315° C., an oxygen conversion level of 10-60%, and an EO production rate (work rate) of 100-350 kg EO/m3 catalyst/hr and a change in ethylene oxide concentration, AEO, of from about 1.5% to about 4.5%. The feed composition in the reactor inlet after the completion of start-up and during normal operation typically comprises (by volume %) 1-40% ethylene, 3-12% O2; 0.2% to 10%, preferably 0.2% to 6%, more preferably 0.2% to 5% of CO2; 0-5% ethane, an amount of one or more chloride moderators, which are described herein; and the balance of the feed being comprised of argon, methane, nitrogen or mixtures thereof.
The invention will now be described in more detail with respect to the following non-limiting examples.
A process for preparing ethylene glycol according to the prior art is simulated with use of a single, non-catalytic tubular/pipe reactor. In the process a feedstream is fed to the reactor from which is taken the reactor effluent, with the table below giving values in kilograms per hour:
As used above, “WEOR” is the molar ratio of water to ethylene oxide. This prior art process produces ethylene glycol at good conversation rates but uses a large excess of water—which must then be removed from the ethylene glycol product making the process significantly more energy intensive than the process according to the present invention as will be discussed below.
A process for preparing ethylene glycol according to the present invention is simulated according to
As shown in
As can be seen in the table above, water and ethylene oxide are provided to the process at a molar ratio of 10:1 (combination of Streams A and B)—which is much lower than prior art process, for example that shown in Example 1, above. However, by dividing the input streams into multiple streams fed to multiple reactors as specified by the present invention, much higher water to ethylene oxide ratios are obtained in each reactor—as shown above the molar ratio of water to ethylene oxide in the streams entering the reactor is approximately 32:1 in each case. This high WEOR not only improves the selectivity and conversion of ethylene oxide to MEG (as shown above conversion to MEG in this simulation was at 99%) but it also helps moderate the temperature rise in each reactor reducing the amount of cooling necessary in the interstage heat exchangers and reducing the high temperatures that could potentially damage the ion exchange resin catalyst.
Furthermore, as mentioned above, the use of lower WEOR in the process prepared according to the present invention results in considerable energy savings compared to the prior art. In this simulation of the process according to the present invention (Example 2) and the simulation of the comparative prior art process (Example 1) the final evaporation load was:
Thus, the prior art process has an evaporator load that is 2.5 times higher that of the present invention.
It will be appreciated by those skilled in the art that changes could be made to the embodiments of the liquid phase process described above without departing from the broad inventive concept thereof. It is understood therefore that this invention is not limited to the particular embodiments or configurations or compositions disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.
The present invention claims the benefit of U.S. Provisional Patent Application No. 62/664,603 filed Apr. 30, 2018, the entire content and disclosure of which is incorporated herein by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3028434 | Weisz et al. | Apr 1962 | A |
| 3563914 | Wattimena | Feb 1971 | A |
| 3702259 | Nielsen | Nov 1972 | A |
| 3867113 | Foster et al. | Feb 1975 | A |
| 3957698 | Hatch | May 1976 | A |
| 4160116 | Mieno et al. | Jul 1979 | A |
| 4165440 | Kim | Aug 1979 | A |
| 4519875 | Becker et al. | May 1985 | A |
| 4761394 | Lauritzen | Aug 1988 | A |
| 4766105 | Lauritzen | Aug 1988 | A |
| 4778567 | Kakimoto et al. | Oct 1988 | A |
| 4875909 | Kakimoto et al. | Oct 1989 | A |
| 4908343 | Bhasin | Mar 1990 | A |
| 5011807 | Hayden et al. | Apr 1991 | A |
| 5057481 | Bhasin | Oct 1991 | A |
| 5099041 | Hayden et al. | Mar 1992 | A |
| 5102848 | Soo et al. | Apr 1992 | A |
| 5187140 | Thorsteinson et al. | Feb 1993 | A |
| 5407888 | Herzog et al. | Apr 1995 | A |
| 5763691 | Kawabe et al. | Jun 1998 | A |
| 5945568 | Nagata et al. | Aug 1999 | A |
| 6160187 | Strickler | Dec 2000 | A |
| 6211419 | Strickler et al. | Apr 2001 | B1 |
| 7453015 | Van Kruchten et al. | Nov 2008 | B2 |
| 7663005 | Crudge et al. | Feb 2010 | B2 |
| 7683221 | Powell et al. | Mar 2010 | B2 |
| 8183400 | Szul et al. | May 2012 | B2 |
| 20020082456 | Van Kruchten et al. | Jun 2002 | A1 |
| 20050119510 | Boons et al. | Jun 2005 | A1 |
| 20060161026 | Van Kruchten | Jul 2006 | A1 |
| 20060183927 | Billig | Aug 2006 | A1 |
| 20070037991 | Rizkalla | Feb 2007 | A1 |
| 20170298035 | Olthof | Oct 2017 | A1 |
| Number | Date | Country |
|---|---|---|
| 1208135 | Feb 1999 | CN |
| 103709001 | Apr 2014 | CN |
| 104974115 | Oct 2015 | CN |
| 0123700 | Nov 1984 | EP |
| 0123709 | Nov 1984 | EP |
| 1828086 | Oct 2009 | EP |
| 2121646 | Feb 2011 | EP |
| 2010528113 | Aug 2010 | JP |
| 0035840 | Jun 2000 | WO |
| 2006072766 | Jul 2006 | WO |
| 2008150338 | Dec 2008 | WO |
| 2009105252 | Aug 2009 | WO |
| 2017178418 | Oct 2017 | WO |
| Entry |
|---|
| International Search Report dated Aug. 12, 2019, received in International Application No. PCT/US2019/029830. |
| International Search Report dated Aug. 13, 2019, received in International Application No. PCT/US2019/029820. |
| International Search Report dated Aug. 13, 2019, received in International Application No. PCT/US2019/029818. |
| International Search Report dated Aug. 16, 2019, received in International Application No. PCT/US2019/029825. |
| Shvets, V. F., et al., “The Model of Catalytic Reactor of Ethylene Glycol Production”, Organic Process Research & Development, Published on web Nov. 2, 2005, pp. 768-773, vol. 9, No. 6. |
| Office Action dated Nov. 25, 2019 received in U.S. Appl. No. 16/398,975. |
| Office Action dated Dec. 13, 2019 received in U.S. Appl. No. 16/399,045. |
| Othmer, D. F., et al., “Glycol Production—Hydration of Ethylene Oxide”, Industrial and Engineering Chemistry, Sep. 1958, pp. 1235-1244, vol. 50, No. 9. |
| Van Hal, J. W., et al., “Investigation of three types of catalysts for the hydration of ethylene oxide (EO) to monoethylene glycol (MEG)”, Catalysis Today, Available online Mar. 19, 2007, pp. 310-315, 123. |
| Number | Date | Country | |
|---|---|---|---|
| 20190330134 A1 | Oct 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62664603 | Apr 2018 | US |
