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    • 专利摘要:
    Catalyst for reducing carbon monoxide by means of hydrogen so as to obtain a mixture consisting substantially of C1-C4-hydrocarbons. The catalyst is made by precipitating a salt of a hydrocyanic acid of the general formula MeIMeII(CN)x, separating and drying the salt so precipitated and forming it. In the formula, the cationic component Me I stands for at least one of the elements Ce, Cu, Co, Ni, Fe, Mn, Zn, Ag and K or a mixture of these elements, or for Ca or Mg in admixture with (NH)4; the anionic component MeII stands for at least one of the elements Cu, Co, Ni, Fe, Mn, Zn and Ag or a mixture of these elements; and x stands for the sum of the metal valencies; MeI and MeII are not permitted to stand for iron alone, or for a mixture of iron with copper.
    公开号:SU884555A3
    申请号:SU772546250
    申请日:1977-11-25
    公开日:1981-11-23
    发明作者:Фогт Вильхельм；Кох Юрген；Глазер Херманн
    申请人:Хехст Аг(Фирма)；
    IPC主号:
    专利说明:

    (5) METHOD FOR PRODUCING A CATALYST FOR RESTORING CARBON OXIDE WITH HYDROGEN
    one
    The invention relates to a method for producing a catalyst for reducing carbon monoxide with hydrogen to form mixtures of hydrocarbons having generally from 1 to 4 carbon atoms.
    Ethylene is one of the most important lower hydrocarbons used on a large scale in the chemical industry as a starting material for the production of many secondary products.
    In view of the significant need for ethylene, it is of interest to use to obtain this product from other raw materials other than oil. As such, a source of raw material can be considered water vapor released when 20 carbon is reacted with water at high temperature with water gas.
    Catalytic hydrogenation of carbon monoxide leads to the formation of hydrocarbons of a number of olefins and paraffins in different ratios, depending on
    bridges from the used catalysts and reaction conditions.
    When CO is hydrogenated using iron or mixtures of iron / copper as a catalyst, as opposed to cobalt catalysts, olefin formation is accelerated and the methane fraction is reduced. Known catalysts are so-called precipitated catalysts. To obtain them, the metals are dissolved in nitric acid and their salts are quickly precipitated in a hot state with a solution of an alkaline carbonate. After precipitation, the precipitate is filtered, washed with water, dried on, crushed and sieved. Recovery of the sifted material is performed by treatment with hydrogen or synthesis gas at and at a pressure of 10 at til.
    However, manufactured by this method. Iron or iron-oxide catalysts, from the point of view of their catalytic efficiency in the hydrogenation of CO, are unsatisfactory in that the proportion of Cn-S hydrocarbons, especially hydrocarbons, in the reaction gas is too small, i.e. Catalysts for the formation of lower olefinic hydrocarbons are not selective enough. The closest to the proposed technical essence and the achieved effect is a method of producing a catalyst for reducing carbon monoxide with hydrogen, BKJOK iron and / or copper as an active component, by treating a hydrocyanic acid salt of the general formula Meg Med (CM), where Mej is iron and / or copper; Me, is iron, X 1-, hydrogen or a mixture of hydrogen and carbon monoxide in a molar ratio of from 3: 1 to 1: 2 at 280-350 ° C and dav. Lenia from 4 to ZP abs. . A disadvantage of the known method of catalyst preparation is the low activity of the catalyst obtained. So, for example, the fraction of C2 hydrocarbons in the reaction when carbon monoxide is reduced by hydrogen in a molar ratio of 1: 2 at and 9.5 at. Is 2.8-3, I vol. % The purpose of the invention is the preparation of a catalyst with increased activity. The purpose is achieved by the fact that the method of producing a catalyst for reducing carbon monoxide with hydrogen, including iron and / or copper as an active component, by treating a hydrocyanic acid salt of the general formula Meg (CN), tde Mej and Me ,, are metals, X is the ligand number of the complex, hydrogen or a mixture of hydrogen and carbon oxide in a molar ratio of from 3: 1 to 1: 2 at a temperature of 28 and pressure from to ZOab.a as a salt of hydrocyanic acid is Compound of the indicated general formula, in which in case e is manganese, Me copper, and in the case of Metz iron, Me-ja) silver, or zinc, or cobalt, or manganese, or b) mixtures of copper with 54 iron and nickel, or copper with cerium, or copper with cobalt, or copper with manganese under the condition x equal to 1 to 15, or c) a mixture of silver with cerium or silver with iron, provided either d) a mixture of calcium or magnesium with NH. provided . A distinctive feature of the invention is the use as a salt of hydrocyanic acid of a compound of the above formula, in which in the case of Metz manganese, copper, and in the case of Me. - iron Mejp- a) silver or zinc, or cobalt, or manganese, or b) a mixture of copper with iron and nickel, or copper with cerium, or copper with cobalt, or copper with manganese under the condition x equal to from 1 to 15, or c) a mixture of se-. ribs with cerium or silver with iron, provided either d) a mixture of calcium or magnesium with NH4. provided . The proposed method for producing a catalyst allows one to obtain a catalyst with increased activity compared to a catalyst prepared in a known manner. For example, the fraction of hydrocarbons Cj in the reaction gas, when carbon monoxide is reduced by hydrogen in a molar ratio of 1: 2 at 350-4 ° C and a pressure of 9.3 at, is 3.63%, 08 vol. In its appearance, the catalyst may have The grain or tablet form or catalyst may be supported on a carrier, such as alumina, silicic acid, infusible earth, asbestos, fiberglass, clay minerals, pumice or activated carbon. In the case of molding a catalyst with a carrier, the proportion of catalytically effective components on the carrier material is about 1-95 wt., Pre-. property weight., in terms of the total weight of the catalytically effective components and carrier substances. The application of the catalysts prepared by the proposed method to a carrier can be carried out by precipitating the salts of cyanic acid in an aqueous suspension of the carrier. The mixture of precipitated salt and carrier is separated, dried, washed and subjected to thermal decomposition at the required temperature. But it is also possible to impregnate the formed carriers, firstly, the carrier is impregnated with an aqueous solution of a hydrocyanic acid salt, then the impregnated carrier is dried and then exposed to the carrier with an aqueous precipitant solution or vice versa. Another embodiment consists in dry mixing the active component with the carrier. The catalyst may be used to catalytically hydrogenate carbon monoxide with hydrogen gas to form hydrocarbon mixtures, mainly with - carbon atoms. Hydrogenation can be carried out in such a way that a gas mixture of hydrogen and carbon monoxide in a molar ratio of 3: 1 to 1: 2 at a temperature of about 150-500 ° C and, if necessary, at pressures up to 100 atm in an amount of about 100-3000 Nl gas per 1 liter of catalyst per hour is passed through the catalyst and hydrocarbons with 1-carbon atoms are separated from the exhaust gas. A predominantly gas mixture with a molar ratio of Hij to CO as 2: 1 to 1: 1 at a temperature of 250 to and at a pressure of from 1 to 30 atm in an amount of from 100 to 2000 nl of gas per liter of catalyst per hour is passed through the catalyst. The proposed catalyst is technically progressive, since it is prepared in an economical manner and, with the conversion of carbon monoxide with hydrogen to form hydrocarbon mixtures, has a relatively high selectivity. Example 1. (, 7 g of Ce (NO. |). And 116 g of CU (N0 i). O is dissolved in 1 l of water and then the solution is mixed with vigorous stirring (and at 60 ° C is introduced into the solution from, 7 g Fe (CN) f, .Zonor in 1 liter of water. The precipitate formed is aspirated and washed with 1.5 liters of water in 100 ml parts each. The precipitate, which in sum corresponds to the composition of Ce4Cu (tFe (CN) (, -, 5, dried at-C, the solid mass is crushed to a particle size of 1.6-2.5 mm. After 30 g of the product prepared in this way, p 3 "0-350 ° C, and at a pressure of 20 atm, a gas mixture of 50 vol% H is passed through, and 50 o6,% CO. The outlet gas rate is constantly 25 nl / h. The reaction gas contains pressed 11.25 OBD SNd 2, vol.% C, j, H ,, 1.18 vol. CftHg, 1.7 vol% CjH and 0.3 vol.% CjHg. Additionally from the separator located behind the reactor after 10 h works get b, g unidentified oil. Example 2. Ce4Cu 5i tFe (CN) g39 Analogously to example 1, a solution of 52.05 g of Ce (MOe) s - bNoor + 87.0 g of Cu (NOft) Q ЗН / з О in 1 l of water is combined with a solution of N g K (CN) 3HrtO in 1 l of water and the precipitate formed is sucked off, washed, dried and crushed. After 30 g of the obtained product, a gas mixture of 50 vol.% Hjj and 50 o6.% CO is passed at 315 C and at 30 at. The outlet gas had a speed of 33 nl / h and contained 11.7 rpm. CH, 2; 7 vol. C / jH, 1.38% by volume CftHjj, 78% by volume , and 0.52% vol. CjHg. After 30 hours of operation, an additional 60 g of high boiling hydrocarbons are obtained. Example 3- Ci 1.5 ire (CN) b. To a solution of 0.5 mol K 4 Ge (CM) (, in 1 liter of water is mixed with a solution of 0.75 mol CuSO and 0.25 mol Co (NO) ij. After the suction of the formed precipitate and thorough washing with water the still wet filter cake is mixed in a laboratory blender with 125 g of asbestos and 125 g of fine silicic acid, then dried and pressed into tablets with a diameter of 3 mm. The total composition of the filter cake corresponds approximately to the formula Cu ;, Co (j5 Fe {CM) b2 .. tO g tablets are loaded into the reactor and then treated at 320 ° C and at 10 atm with gaseous hydrogen. The catalyst was tested at a pressure of 7 atm and at 300–310 ° C by passing the CO – XH mixture (1: 1). A constant amount of 25 nl / h of the reaction gas contained 11.5 vol. of CH4, 2.86 vol., 0.7% by volume, 2, Ti o6,% CzN4, and 0.31% v / v pressure, at a temperature of 290 ° C and with a quantity of exhaust gas of 10 nl / h, the exhaust gas contained 9.38% by volume of CH ., 2.0ob. СЛН ,, 0.32 obL C.N., 1.37% by volume of CjH and 1; 37% by volume. Example A. CuFej / 3 f Jf / 3 Fe (CN) Solution of 211 , 2 g of K4 Fe (CN) b in 1 l of water are mixed with vigorous stirring with 2 l of aqueous pacTsopaj which contained 137.3 g of CuS04, 93.2 g of ReOc.7H and 51.2 g of NiSO 7Hi2p. The precipitate formed is filtered off with suction and washed with water, and the filtered precipitate, which in total corresponds to the formula GRESNA, is mixed with 125 g of asbestos and 125 g of silicic acid, dried and pressed into tablets. 40 g of these tablets are loaded into the reactor and treated for 2 hours with a stream of HI at 320 ° C and at a pressure of 10 at. When passing a gas mixture of H / and CO in a volume ratio of 1: 1 through the mass of tablets at 10 atm and at C, the exhaust gas at the time of selection of 10 nl / h contained 13.6 vol. CHi, 0.81-06.%., 2.56 OBD C „H, 1.61% by volume and 0.35 OBD SaNb. OOb. La (CN) (Example 5. Co) A solution of 1/5 mol K4.tFe (CN) b3 in 0.8 l of water is combined with a solution that contains 2/5 mol Co (N03) l in 0 , 5 liters of water. The precipitated precipitate is sucked off, thoroughly washed with 1.5 l of water, to which 0.2 mol of Co (KOZ) was added to the washing solution, and then mixed with 50 g of asbestos and 50 g of silicic acid, the mixture is dried and The subsequent processing of the tablets was 9 tons, analogously to Example 4, at 280 ° C, with 12.32% by volume contained in the reaction mixture: CH4, 1.66% by volume C / IH, 0.96% by volume 0.55 VL CjHg. High-boiling condensates turned out in 55 hours in an amount of 36 g. Example 6. Гее (СК) Analogously to example 1 from Fe (NOa) n, Ni (N0-1) and K rFeCCN) receive complex cyanide with the total composition .i fFe (CN)} and pass through the latter as in example 1 the gas mixture from JI and Hjji. The exhaust reaction gas contained 32.8 vol. СН4, 0.06 vol.% С (Н4, 3, vol.% CQHj 1.47 vol.%, 1.05 o6.%. In addition, 10 g of liquid hydrocarbons are obtained within 20 hours. Example 7. MnjlFeCCNyo v In the same way as 1 from aqueous solutions of 0.3 mol MnSO and 0.2 mol. (CN) 3 a precipitate is obtained with a total composition (CN), and the next one is washed, dried and crushed. 30 g of the product thus obtained is passed at 310 s and j at a gas mixture of CO and HQ. in a volume ratio of 1: 1. The amount of gas withdrawn from the apparatus was constantly 10 nl / h and contained 6.76 vol.t eH4, 0.52% by volume СЛН, 1, 96 OBD C 1.68% by volume, 77% by volume, R and mep 8. Cu 5 Po5Ue (C) .P. Transformation 0.2 mol. K fFelCN). 0.03 mol CuSO.- and 0.1 mol H / jO in an aqueous solution, a precipitate is obtained with a total composition of Fe (CN) J. Subsequent treatment of the precipitate is carried out analogously to example 7. The reaction gas removed contained 8, obd CH4, 2.0 vol.% C2H4, 1.3 vol.% , 3.8 about .; and 0.9 vol. Within 62 hours, an additional 25.5 g of liquid hydrocarbons were obtained. Example 9. Cu jMio jrFeCCM). kQ g of the complex salt described in example 3 of the formula Cu jNijj g-rFe (CN) (|, J is loaded with a gas mixture of CO and I 12 in a volume ratio of 1: 1 at and at, the exhaust gas exhaust quantity being constant 25 nl / h. The reaction gas contained 17.78 vol., O, O vol.,% C2.H4, 2.2 vol., 0.35 vol. CjHj, and 0.91 vol., Formation of oily higher hydrocarbons not observed. Example 10. Cuj rCo (CN) g, 32 The precipitate obtained by transformation (CH) b with copper acetate in an aqueous solution is processed as tablets in example 3 into tablets and after 40 g of tablets is passed gas a mixture of CO and H (j (1: 0 at an at a pressure of 10 at. The exhaust gas was continuously withdrawn at a rate of 10 l / h, with 16 vol. SNL contained in the gas stream, 0.16 vol. 0, 63% by volume 1.70% by volume and 0.32% by volume CjHg. Higher liquid hydrocarbons were obtained in 13 hours in an amount of 2.1g. Example 11. AdaGSo (CM) b, Deposition (CM) bZ using AgNO3 in dilute aqueous acetic acid solution get a complex salt with the total composition AgjECoCCN). The precipitate as described in Example 3 is tabletted with asbestos and silicic acid, and 40 g of these tablets are loaded with a gas mixture of 10 at and 320 ° C. The amount of waste gas was constantly 10 nl / h. moreover, the gas contained 12.3 OBD CH, 0.05% by volume, 1.06% by volume. , 0.35 about. CjH, and 0.49 OBD CjHg. Example 12. (CN)} The complex salt obtained by precipitating K4CMn {CN) J with an ammonia solution Cuj-; salts are loaded, under the conditions described in example 11, with a gas mixture of CO and Hrj. The exhaust gas contained 1.6 OBD, SNd, 0.3 vol.% CqH ,, O, OBD, 0.3 vol.% CjH, and 0.12 OBD CjHg. Liquid higher hydrocarbons were not formed. PRI me R 13. (CN) fe3 8 a solution of 0.2 mol (€ N) fe in 1 liter of water is mixed with 1 liter of an aqueous solution which contained Q, k mol of MnS04. A white precipitated precipitate, which consisted of a total of Mnf tFeiCN), is sucked off, washed, and as described in Example 5f, after mixing with asbestos and silicic acid, it is tableted. After 50 ml of the preformed product is passed at 315 C and at i atm a gas mixture of 50 vol. CO and 50 OBD Hft. The amount of exhaust gas was 10 nl / h. The reaction gas contained j, / vol. CH4. 1.76 about. , 0.72 OBD, 2.59 vol.% CjHfc and 0.2t vol. CgHg. Until iHo. Over 100 hours of work, 28.3 g of hydrocarbons were obtained. N, p and me r lit. Mg (NH4) 5.lFe (CNU Compound aqueous solutions that contain stoichiometric amounts of MgCl (j, ammonium chloride, and potassium ferrocyanide) produce an ammonium ammonium ferrocyanide. After drying the complex salt, 10 g of a substance with a grain size of 2 mm at 320 ° C are introduced into the reactor and at 20 atm, a gas mixture of CO and Hij is charged in a volume ratio of 1: 1. With a constant amount of exhaust gas of 20 nl / h, the reaction gas contained 15.9 vol% CH /, 0.5 o & amp.%: C (4 2.35 vol. L, 0.3 vol., And 0.77 vol.%. Additionally, 1 $ g of higher hydrocarbons were obtained in 22 hours. Example 15. Sa KN4U1Gge (SM)) Similarly, Calcium ammonium ferrocyanide and complex salt are obtained under the conditions of treatment with a CO / HQ gas mixture as described in example It. The amount of 20 nl withdrawn / reaction gas contained 11.2 OBD CH4., 1.02 vol.% ScND, 0.95 OBD Co.N 10 0.77 vol. and 0.3 OL CaHg. Additionally, 19.6 g of liquid hydrocarbons were obtained in 27 hours Example 16. Znj tFe (CN) b. Reaction 0.6 mol ZnS047H ( 0 s O mol (CN) b in an aqueous solution that contained 279 g of SiOj Ketien, jxFx) precipitate a total composition of Zn3rFe (CS) 2Q - “SiO 27 g of the mixture is placed in a gas mixture (COvHj l :) at 9.5 at at and with an exhaust gas quantity of 15 nl / The following gas composition was obtained: 8.0 vol.% CH, 1.6 vol.% Cj, H,., k vol% V SLH and higher hydrocarbons. Example 17. Ag4rFe (CN) 63. From the aqueous solution of K4.Fe (CN) (with the addition of AgNQJ, the complex role of the total composition (C4) b3) is precipitated, the latter is washed with water and, after mixing asbestos and silicic acid, pressed into tablets with a diameter of 3 mm. 15 g of a preformed product are introduced into the reactor and react with a gas mixture of CO and -H. 2 in a volume ratio of 1: 1 at and at 20 at. Waste in the amount of Ju nl / h waste. This gas contained 10.71% by volume of CH., 0.7% by volume. C, 1.9 OBD 1.71 ob. C ,, Hfe and 0.5 vol. C, Hg. Example 18. (C) bl. The transformation of cerium nitrate (ill), AdE1) and K4lFe ChJ) in an aqueous solution gives a precipitate of the total composition of CeAD Fe (CN) b - After washing and drying the precipitate during the latter, it is crushed into particles of 1-2.5 mm in size. By passing a gas mixture of 33 vol. CO and 67% by volume of Hp after 30 g of product particles at and 10 atm the exhaust gas removed in the amount of 15 nl / h contained 11.9% by volume of CH4, 2.62% by volume. Sa.N4, 0.6 about. SzN, 1.25 OBD CjH and 0.25 OBD. .. Example 19.) 6. 0.5 mol of precipitation obtained with precipitation with a total composition of tFe (CN) b3 is mixed with 250 g of alumina called Condea NG and then 30 g of granules with a size of 1.5-2.5 mm are granulated, loaded into the reactor at 320 ° C and 20 atoms react with a gas mixture of 50 vol.% CO and 50 vol.%. Nl Released in the amount of 30 nl / h, the reaction gas contained 1 vol. CH4., 0.99 OBD Cfi.H ,, 32 OBD. 2,0k vol.% CjH Ig I 1,18 vol. . Additionally, 25 g of higher liquid hydrocarbons were obtained during 26 hours of operation. Example 20. Ad2ReGRE (SC) ЗЗ. The precipitate obtained according to example 19 is mixed with asbestos and silicic acid, and the mixture is pressed into tablets with a diameter of 3 mm. It is admixed to 0.5 mol of KgrfetFe (CH} bl 125 g of asbestos and 125 g of silicic acid. 30 g of the tableted product is reacted at 320 ° С and at 20 atm with a gas mixture of CO and H j in a volume ratio of 1: 1. the amount of 30 nl / h the reaction mixture contained 10.62 o6.t CHA, 2, volume 1.95 vol.1 C5.Hi, 2.52 vol L SzNb and 0.67 vol.1 I. During 18 hours of operation 6.8 g of higher 9RDFODE carbon were obtained. Formula of the invention. A method for preparing a catalyst for reducing carbon monoxide with hydrogen, including iron and / or honey as an active component, by treating a salt of hydrogen cyanide to acids of the general formula Me5.Me; (CNJfe x 12 where and Metz are metals, X is the ligand number of the complex, hydrogen or a mixture of hydrogen and carbon monoxide in molar with a ratio from 3 J1 to 1: 2 at a temperature from 280 to and under pressure from up to 30 abs.atm, characterized in that, in order to obtain a catalyst with increased activity, as a salt of hydrocyanic acid, a compound of the indicated general formula is used, in which in case of Me "is manganese, Me (- copper, and in the case of Me" - iron. He, a) silver or cobalt or manganese, or b) a mixture of copper with iron and nickel, or copper with cerium or copper with manganese with x: 1 to 15, or c) a mixture of silver with cerium or silver with delese provided either d) a mixture of calcium or magnesium with YAND provided. Sources of information taken into account in the examination 1.Winnakker-Weingrarthner. Chemical technology, t.Organicheskaya technology, 1 ed. Karl Hauser, Munich, 1952, p. 780-803. 2.Patent of the USSR in case No. 2 09352, cl. B 01 J 23/70, 1976 (orotype).
    权利要求:
    Claims (2)
    [1]
    Claim
    A method of producing a catalyst for the reduction of carbon monoxide with hydrogen •, including iron and / or copper as an active component, by treating a salt of hydrocyanic acid of the general formula
    884555. 12 where M · And Mets are metals, x is the ligand number of the complex, with hydrogen or a mixture of hydrogen and carbon monoxide in a molar ratio of 3: 1 to 1: 2 at a temperature of 280 to 350 ° C and a pressure of 4 to 30 abs .atm of m and n sistent in that, in order to obtain enhanced activity of catalyst v.kachestve hydrocyanic acid salt is used, the compound of the general formula in which m in the case of Ne - manganese, Me (- copper, and in the case of Me ( ( - iron, Mw [- a) silver or zinc g or cobalt ( or manganese, or b) a mixture of copper with iron and nickel or copper with cerium ^ or copper with manganese under condition x equal to from 1 to 15, either c) silver or silver x = 1, or d) magnesium with NND at Sources used
    Me x [Me and (CN) fc ] x ♦ mixtures of silver with deleuze with a mixture of calcium provided x = 1. information taken into account during the examination
    1. Winnaker-Weingrärtner. Chemical Technology, vol. Organic Technology 1, ed. Karl Hauser, Munich. 1952, p. 780-803.
    [2]
    2. USSR patent for hare Ν '2409352, 30 cells. In 01 J 23/70, 1976 (orototype).
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE729290C|1936-02-26|1942-12-15|Ig Farbenindustrie Ag|Process for converting carbon monoxide and hydrogen|
    US2234246A|1937-12-09|1941-03-11|Celanese Corp|Metallic composition|
    FR1011662A|1949-02-26|1952-06-25|Ruhrchemie Ag|Process for obtaining carbon monoxide hydrogenation products with a high content of oxygen compounds|
    US2767202A|1952-01-30|1956-10-16|Ruhrchemie Ag|Catalytic hydrogenation of carbon monoxides|
    US2753367A|1952-07-09|1956-07-03|Ruhrchemie Ag|Catalytic hydrogenation of carbon monoxide|
    NL7414755A|1973-11-20|1975-05-22|Basf Ag|PROCEDURE FOR ETHYNYLATION.|
    DE2546587C3|1975-10-17|1978-05-03|Hoechst Ag, 6000 Frankfurt|Catalyst for the reduction of carbon monoxide|US4394298A|1980-01-10|1983-07-19|Phillips Petroleum Company|Hydrogenation catalyst|
    US4670476A|1983-12-20|1987-06-02|Exxon Research And Engineering Company|Manganese-spinel catalysts in CO/H2 olefin synthesis|
    US4604375A|1983-12-20|1986-08-05|Exxon Research And Engineering Co.|Manganese-spinel catalysts in CO/H2 olefin synthesis|
    US4618597A|1983-12-20|1986-10-21|Exxon Research And Engineering Company|High surface area dual promoted iron/managanese spinel compositions|
    US4588705A|1984-08-10|1986-05-13|Exxon Research And Engineering Co.|Method for preparing dual colloid compositions|
    CA1250565A|1984-08-10|1989-02-28|Michael A. Richard|Method for preparing dual colloid catalystcompositions|
    US4639431A|1985-07-11|1987-01-27|Exxon Research And Engineering Company|Catalysts in Fischer-Tropsch process for producing olefins|
    US4657885A|1985-07-11|1987-04-14|Exxon Research And Engineering Company|Cerium promoted Fischer-Tropsch catalysts|
    US4613722A|1985-07-25|1986-09-23|Phillips Petroleum Company|Dehydrogenation of C3 and C4 hydrocarbons over an iron-based catalyst|
    US5504118A|1986-05-08|1996-04-02|Rentech, Inc.|Process for the production of hydrocarbons|
    US4762817A|1986-11-03|1988-08-09|Union Carbide Corporation|Aldehyde hydrogenation catalyst|
    US4876402A|1986-11-03|1989-10-24|Union Carbide Chemicals And Plastics Company Inc.|Improved aldehyde hydrogenation process|
    US5032570A|1987-08-04|1991-07-16|Hitachi Metals, Ltd.|Method for producing ceramic superconducting material using intermediate products|
    US5198592A|1987-12-11|1993-03-30|Engelhard De Meern B.V.|Hydrogenolysis reaction and catalyst suitable therefor|
    GB9005964D0|1990-03-16|1990-05-09|Shell Int Research|Catalyst preparation process|
    GB9015193D0|1990-07-10|1990-08-29|Shell Int Research|Catalysts and catalysts precursors suitable for hydrocarbon synthesis|
    US20020019309A1|1999-10-15|2002-02-14|Lapidus Albert L?Apos;Vovich|Process for the preparation of high activity carbon monoxide hydrogenation catalysts; the catalyst compositions, use of the catalysts for conducting such reactions, and the products of such reactions|
    JP4773116B2|2005-03-24|2011-09-14|新日本製鐵株式会社|Method for producing catalyst for producing hydrocarbons from synthesis gas, and method for producing hydrocarbons from synthesis gas using the catalyst|
    JP6948057B2|2017-08-30|2021-10-13|公立大学法人大阪|Organophosphorus compound decomposition catalyst|
    CN113453798A|2019-02-28|2021-09-28|埃克森美孚化学专利公司|Catalyst composition and precursor, process for preparing the same and process for converting synthesis gas|
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    申请号 | 申请日 | 专利标题
    DE19762653985|DE2653985A1|1976-11-27|1976-11-27|CATALYST FOR REDUCING CARBON MONOXIDE WITH HYDROGEN|
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