Iron oxides with a higher degree of refining

Abstract

Iron oxides are upgraded by calcining at from 700 to 1200° C.

Description

DESCRIPTION

[0001] The present invention relates to a process for upgrading iron oxide, which comprises calcining iron oxide at not less than 700° C.

[0002] EP-A-1 027 928 describes a catalyst, especially for dehydrogenation of ethylbenzene to styrene, which is prepared using an iron oxide obtained by spray roasting an iron salt solution, especially hydrochloric acid iron solutions (Ruthner process). The disadvantage of such iron oxides is their high residual chloride content.

[0003] EP-A-797 481 discloses iron oxides as a starting material for catalysts, especially for dehydrogenation of ethylbenzene to styrene, which are restructured by mixing with a further metal compound and subsequent calcination and which have very small BET surface areas. The disadvantage of such a restructuring is the contamination of the iron oxide by the metal compound added.

[0004] JP-A-61-72601 discloses a fluidized bed process for cracking heavy hydrocarbons into lighter hydrocarbons using a pulverulent catalyst prepared by slurrying up an iron oxide powder with water,. spray drying and finally calcining at temperatures between 1200 and 1600° C. Disadvantages of this process are the immense cost and inconvenience and the high calcination temperatures.

[0005] EP-A-827 488 describes a process for reducing the residual chloride content in iron oxides, especially in iron oxides generated by spray roasting hydrochloric acid pickling wastes, by mixing the iron oxide with a hydrated metal compound and subsequent calcination. The disadvantage of this process is its cost and inconvenience.

[0006] U.S. Pat. No. 4,134,858 discloses roasting iron oxide at 800° C. before using it to prepare styrene catalysts. However, any residual chloride content in the iron oxide cannot be sufficiently lowered by this method.

[0007] U.S. Pat. No. 2,414,585 discloses precalcining iron oxide for preparing dehydrogenation catalysts. The iron oxide obtained is said to have a BET surface area of <8 m2/g and preferably of about 4 m2/g. Such catalysts leave a lot to be desired.

[0008] It is an object of the present invention to remedy the aforementioned disadvantages.

[0009] We have found that this object is achieved by a novel and improved process for upgrading iron oxide, which comprises calcining iron oxides at from 700 to 2500° C. The invention further provides novel iron oxides and their use as catalysts, and for the preparation of catalysts, especially for the preparation of catalysts for dehydrogenation of ethylbenzene to styrene.

[0010] The process of the invention can be carried out as follows:

[0011] The upgrading of the present invention may be applied to any iron oxide, but is preferably applied to iron oxides generated by working up hydrochloric acid waste liquids from steel pickling, for example, especially iron oxides generated by spray roasting hydrochloric acid pickling wastes (Ruthner process).

[0012] The iron oxide may be subjected to a batch operated or preferably continuous calcination at from 700 to 1200° C., preferably at from 840 to 1150° C., particularly preferably at from 850 to 1100° C., especially at from 860 to 1000° C., or generally from 0.1 to 24 h, preferably from 0.25 to 10 h, particularly preferably from 0.3 to 5 h, especially from 0.5 to 1.5 h, without pretreatment, i.e., for example without mechanical pretreatment, and preferably dry, i.e., without prior treatment with water, an acid or base or some other material. Useful calcination apparatus includes all known ovens. The calcination can be carried out batchwise, for example in muffle furnaces, or continuously, for example in rotary tube ovens or in belt calciners. Preference is given to continuous processes. The calcination can be carried out at just one temperature or in stages at various temperatures or in the form of a continuous temperature ramp. When the calcination is carried out in rotary tubes, the rotary tube should be equipped with tappers which prevent sticking of the iron oxide to the wall of the rotary tube and ensure continuous transportation of the iron oxide. Advantageously, the calcination is carried out in smooth rotary tubes without internal fitments, and the residence time can be adjusted via the speed of rotation, the feed speed and the inclination of the rotary tube. The calcination is further advantageously carried out under a gas stream, for example nitrogen or air, in order that chlorine compounds being released may be expelled and advantageously removed in a downstream off-gas scrub. The chloride content is advantageously reducible in a stationary bed, i.e., for example in the course of calcination in a muffle furnace or on a belt calciner. When a calcination is carried out in a moving bed, for example in a rotary tube, comparatively somewhat higher temperatures can be required to reduce the chloride content than in a stationary bed, and this can lead to a comparatively further reduced BET surface area. Depending on the preferred ratio of chloride content and BET surface area, it can therefore be advantageous to operate selectively with a stationary bed or with a moving bed.

[0013] However, small amounts of water, acids, bases or organic compounds may be added, provided this does not adversely affect the properties of the upgraded iron oxide compared to a dry upgrading process. Preference is given to calcining commercially available iron oxide without any pretreatment whatever.

[0014] Useful iron oxides for the upgrading according to the invention include all iron oxides, regardless of how obtained. Natural, preferably industrially produced and also commercially available iron oxides are suitable, especially iron oxides generated by working up hydrochloric acid pickling wastes. These iron oxides may contain impurities, for example a residual chloride content and/or compounds of titanium, manganese, aluminum, chromium, phosphorus, zinc, copper, molybdenum, tungsten, silicon, nickel, magnesium, potassium, sodium, cobalt, vanadium, zirconium, niobium, sulfur, lanthanum, lead, tin and/or calcium. Of particular suitability are iron oxides which are generated by spray roasting hydrochloric acid pickling wastes in the steel industry and are present as Fe2O3 having a residual chloride content in the range from 0 to 10 000 ppm, preferably in the range from 50 to 5000 ppm and particularly preferably in the range from 500 to 2000 ppm, usually in the hematite crystal form and in a BET surface area of typically from 3 to 5 m2/g.

[0015] Iron oxides upgraded according to the invention generally have a residual chloride content of less than 400 ppm, preferably less than 300 ppm and particularly preferably less than 250 ppm, especially less than 200 ppm. The average particle size, determined by laser diffraction as hereinbelow described, is generally more than 5 μm, i.e., from 5.1 to 200 μm, preferably from 8 to 100 μm, particularly preferably from 10 to 80 μm and very particularly preferably from 12 to 30 μm, and the fines fraction having particle sizes of less than 1 μm is generally less than. 15% by weight, preferably less than 10% by weight, particularly preferably less than 5% by weight. The BET surface area of the iron oxides treated according to the invention is generally in the range from 0.4 to 5 m2/g, preferably in the range from 0.4 to 3.5 m2/g, particularly preferably in the range from 0.5 to 3 m2/g and especially in the range from 0.6 to 2.5 m2/g, very particularly preferably in the range from 0.7 to 2 m2/g. The iron oxides treated according to the invention generally have a hematite structure. They are useful for a whole series of industrial applications such as pharmaceuticals, cosmetics, magnetic tape coatings, chemical reactions, catalysts or for preparing catalysts, especially for preparing catalysts for dehydrogenation of ethylbenzene to styrene.

[0016] The industrial production of styrene by dehydrogenation of ethylbenzene can be effected by isothermal processes or by adiabatic processes. The isothermal process is generally operated at from 450 to 700° C., preferably from 520 to 650° C., in the gas phase with addition of water vapor at from 0.1 to 5 bar, preferably from 0.2 to 2 bar, particularly preferably from 0.3 to 1 bar, especially from 0.4 to 0.9 bar. The adiabatic process is generally operated at from 450 to 700° C., preferably from 520 to 650° C., in the gas phase with addition of water vapor at from 0.1 to 2 bar, preferably from 0.2 to 1 bar, particularly preferably from 0.3 to 0.9 bar, especially from 0.4 to 0.8 bar. Catalysts for the dehydrogenation of ethylbenzene to styrene can be regenerated by means of water vapor.

[0017] Catalysts for the dehydrogenation of ethylbenzene to styrene generally contain iron oxide and an alkali metal compound, for example potassium oxide. Such catalysts generally further contain a number of promoters. Promoters described include for example compounds of calcium, magnesium, cerium, molybdenum, tungsten, chromium and titanium. The catalysts may be prepared using compounds of the promoters that will be present in the ready-produced catalyst or compounds which during the production process convert into compounds that are present in the ready-produced catalyst. The materials used may also include assistants to improve the processibility, the mechanical strength or the pore structure. Examples of such assistants include potato starch, cellulose, stearic acid, graphite or Portland cement. The materials used can be mixed directly in a mixer, kneader or preferably a muller. They can also be slurried up into a sprayable mix and be spray dried to form a powder. Th materials used are preferably processed in a muller or kneader in the presence of water to form an extrudable mass. The ultrasonic bath (100% setting) was started up and, following a dispersion time of 5 min, the measurement was carried out under continuing ultrasonication. Specific BET surface areas were determined according to DIN 66133 and pore volumes and average pore radii according to DIN 66131.

INVENTIVE EXAMPLE 1

[0018] 2 kg of HP type iron oxide from Thyssen-Krupp were heated to 900° C. in a muffle furnace, left in the oven at this temperature for 1 h and subsequently allowed to cool down with the oven.

INVENTIVE EXAMPLE 2

[0019] Inventive example 1 was repeated at 800° C.

INVENTIVE EXAMPLE 3

[0020] Inventive example 1 was repeated at 850° C.

INVENTIVE EXAMPLE 4

[0021] Inventive example 1 was repeated at 950° C.

INVENTIVE EXAMPLE 5

[0022] 20 g of HP type iron oxide from Thyssen-Krupp were heated to 900° C. in a quartz glass rotary tube under an air stream, maintained therein at 900° C. for 1 h and then allowed to cool down therein.

INVENTIVE EXAMPLE 6

[0023] Inventive example 5 was repeated, except that the iron oxide was maintained at 900° C. for 2 h.

INVENTIVE EXAMPLE 7

[0024] The iron oxide was continuously calcined under an air stream in a rotary tube. The rotary tube was equipped with three tappers. The wall temperature of the rotary tube was 970° C. and the residence time of the iron oxide was about one hour.

[0025] The physical properties of the inventively pretreated iron oxides of inventive examples 1 to 7 are summarized in table 1 and compared therein with those of the nonupgraded iron oxide.

INVENTIVE EXAMPLE 8

[0026] A spray slurry prepared by suspending 420 g of potassium carbonate (potash), 516 g of cerium carbonate hydrate (40% by weight cerium content), 74 g of ammonium heptamolybdate, 70 g of calcium hydroxide (white chalk hydrate), 55 g of magnesite and 1880 g of the iron oxide upgraded according to inventive example 1 in 4.5 liters of water was sprayed to form a powder which was pasted up with sufficient water (about 500 ml) in the presence of starch in a kneader to form an extrudable mass which was extruded into strands 3 mm in diameter. The strands were then dried at 120° C., broken to a length of about 0.8 mm and finally calcined in a rotary tube at 875° C. for 1 h.

INVENTIVE EXAMPLE 9

[0027] 415 ml of a catalyst of inventive example 2 were tested in an externally heated tubular reactor 3 cm in internal diameter under the conditions reported in table 3.

COMPARATIVE EXAMPLE A

[0028] A catalyst was prepared similarly to inventive example 8 except that the upgraded iron oxide of inventive example 1 was replaced by nonupgraded iron oxide (HP type from Thyssen-Krupp).

COMPARATIVE EXAMPLE B

[0029] 415 ml of the catalyst of comparative example A were tested similarly to inventive example 3 in the same reactor under the same conditions. The results are summarized in table 3.

TABLE 1
Properties of a commercially available iron oxide
prepared by the Ruthner process (type HP from
Thyssen-Krupp) and of iron oxides prepared therefrom by
the upgrading according to the invention from inventive
examples 1 to 7.
			Fines less	BET
	Residual	Average	than	surface
	chloride	particle size	1 mm	area
Iron oxide	[ppm]	[μm]	[% by weight]	[m2/g]
Untreated HP type	1400	11	15	4.3
(Thyssen-Krupp)
Inventive example 1	66	19	2	1.4
Inventive example 2	240	15	2.5	2.1
Inventive example 3	110	18	1.7	1.8
Inventive example 4	19	22	1	1.1
Inventive example 5	230	—	—	1.6
Inventive example 6	190	—	—	0.7
Inventive example 7	190	13	1.9	0.9

[0030]

TAB. 2
Comparison of physical properties of the catalyst of
inventive example 2, prepared using an iron oxide
upgraded according to the invention, and of the catalyst
of comparative example A, prepared according to the
prior art.
	BET		Average	Cut
	surface area	Pore volume	pore diameter	resistance
	[m2/g]	[ml/g]	[μm]	[N]
Inventive	1.3	0.27	1.28	64
example 8
Comparative	2.9	0.25	0.39	51
example A

[0031]

TABLE 3
Comparison of conversion and selectivity for
dehydrogenation of ethylbenzene to styrene using an
inventive catalyst (inventive example 3) and a prior art
catalyst (comparative example B).
				Inventive	Comparative
	Pres-			example 9	example B
	sure	Steam/EB	Tempera-	EB conversion	EB conversion
LHSV	abs.	ratio	ture	(styrene	(styrene
[h−1]	[bar]	[kg/kg]	[° C.]	selectivity)	selectivity)
0.85	0.5	1.4	590	70.2% (96.2%)	68.3% (96.1%)
0.85	0.5	1.4	570	54.5% (97.2%)	53.9% (97.2%)
0.45	0.5	1.5	550	46.7% (97.4%)	45.7% (97.2%)
0.45	0.4	1.1	550	46.2% (97.9%)	41.5% (97.9%)

Claims

1. A process for upgrading an iron oxide, which comprises generating said iron oxide by spray roasting hydrochloric acid pickling wastes from the steel industry, and calcining said iron oxide without any other process steps or the addition of other substances at from 840 to 1150° C.

2. A process as claimed in claim 1, wherein said iron oxide is calcined at from 850 to 1000° C.

3. Iron oxide upgraded as claimed in claim 1 or 2, characterized by a residual chloride content of less than 400 ppm.

4. Iron oxide as claimed in claim 3, characterized by an average particle size of more than 5 μm and a particle size fraction of less than 1 μm of less than 15% by weight.

5. Iron oxide as claimed in claim 3, characterized by a chloride content of less than 200 ppm.

6. The use of iron oxide as claimed in claim 3 as a catalyst or for preparing catalysts.

7. The use of iron oxide as claimed in claim 3 for preparing catalysts for dehydrogenating ethylbenzene to styrene.

8. A catalyst prepared using an iron oxide as claimed in claims 3 to 5.

9. A catalyst as claimed in claim 8, comprising from 20 to 80% by weight of iron oxide, from 5 to 40% by weight of potassium compound, reckoned as potassium oxide, and optionally further promoters selected from the compounds of calcium, magnesium, cerium or molybdenum.

10. A catalyst as claimed in claim 8, prepared using an iron oxide comprising an average pore diameter of more than 0.6 μm.

11. A catalyst as claimed in claim 8, prepared using an iron oxide having a BET surface area of from 0.4 to 5 m2/g.

12. A catalyst as claimed in claim 8, characterized by a chloride content of less than 500 ppm.

13. A catalyst as set forth in claim 8, characterized by a chloride content of less than 200 ppm.

14. A process for dehydrogenating ethylbenzene to give styrene at from 450 to 700° C. and a pressure of from 0.1 to 5 bar, which comprises employing a catalyst as claimed in any of claims 8 to 13.