GB2025252A - Preparation of Methanol Synthesis Catalyst - Google Patents
Preparation of Methanol Synthesis Catalyst Download PDFInfo
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- GB2025252A GB2025252A GB7924732A GB7924732A GB2025252A GB 2025252 A GB2025252 A GB 2025252A GB 7924732 A GB7924732 A GB 7924732A GB 7924732 A GB7924732 A GB 7924732A GB 2025252 A GB2025252 A GB 2025252A
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- United Kingdom
- Prior art keywords
- catalyst
- weight
- manganese
- aqueous solution
- solution
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 6
- 150000002823 nitrates Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 150000002697 manganese compounds Chemical class 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical class [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 10
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017610 Cu(NO3) Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical class CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical class [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- DNNLEMIRRGUGOZ-UHFFFAOYSA-N oxygen(2-);thorium(4+) Chemical class [O-2].[O-2].[Th+4] DNNLEMIRRGUGOZ-UHFFFAOYSA-N 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A methanol synthesis catalyst containing 20-50 wt% cupric oxide, 15-60 wt% zinc oxide, 5-35 wt% alumina or chromia and 0.2-7.0 wt. The manganese oxide is prepared by calcining fine precipitates obtained by addition of sodium hydroxide or carbonate to aqueous solutions of the metal nitrates at an elevated temperature to give a pH of 8-9, where at least two components are coprecipitated, and manganese is introduced either by coprecipitation of its nitrate or by subsequently impregnating the calcined precipitate.
Description
SPECIFICATION
Copper-containing Catalyst
This invention relates to a method of preparing a copper-containing catalyst for use in synthesizing methanol.
Previously proposed catalysts for use in the synthesis of methanol may be divided into two basic groups, viz. zinc-chromic catalysts used in high-temperature/h igh-pressu re processes, and copper-containing catalysts having application in low-temperature/lowpressure processes.
The method described in Polish Patent
Specification No. 34000 relates to the preparation of high-activated catalyst for synthesis of methanol, obtained by heating to boiling a mixture of solutions of cupric, zinc and aluminium nitrates or acetates to precipitate hydroxides using soda lye, the rates of mixing, adding and concentration of the lye being so selected that local higher strength of the lye is prevented, and adding such an amount thereof that the alkalinity of solution after the precipitation is 0.08--0.15 N, whereupon the precipitate is rinsed with water until 0.005 N alkalinity is obtained, filtered and dried.
German Patent Specification No. 2.302.658 describes a method of preparing a catalyst used for the synthesis of methanol, which comprises obtaining a first precipitate containing compounds thermally decomposable to oxides, said compounds having at least one bivalent metal and one triavlent metal, the oxides of which are capable of forming spinel-type mixed oxides, and obtaining a second precipitate containing cupric compounds thermally decomposable to oxides, and then mixing both the precipitates together.
The method given above is laborious to conduct, because of the many steps required for preparing three independant solutions from which, after retaining a proper sequence of operation, two precipitates are obtained and then combined to be subjected to homogenization, filtering, drying and calcinating. The so prepared catalyst contains at least 20% of Zn/Al spines.
According to the Czechoslovakian Patent
Specification No.164273, a catalyst contains 30-80 wt. % of copper, 10-50 wt. % of zinc, 10-50 wt. % of manganese and 1-25 wt. % of vanadium. Polish Patent Application No. P 1 99644 relates to a catalyst having, apart from chromium, zinc, aluminium, magnesium, nickel, cerium, titanium, thorium oxides, additionally a perrhenic acid salt in the form of ammonium salt or metal salt, wherein the metal is selected from the groups II to IV of the periodic classification.
Using these catalyst may result in the formation of undesirable by-products such as paraffins, higher alcohols and ethers during the preparation of methanol. Besides, a methanation reaction is initiated by these catalyst that is particularly dangerous in production of methanol.
The method of German Patent Specification No. 1.965.007 involves the preparation of a catalyst from basic zinc carbonate and basic copper carbonate. The compound catalyst comprises a combination of zinc oxide, cupric oxide and alumina prepared from a homogeneous water dispersion of these oxides by removing water and drying the product obtained. The weight ratio of zinc oxide of cupric oxide with regard to the metal varies from 0.5 Zn:1 Cu to 3
Zn:1 Cu, and alumina content in the compound is 5 to 45 wt. % basing on the weight of dried compound. Homogeneity in qualitative composition of the catalyst is not secured by such procedure thus resulting in different activity of catalyst from different batches.
The catalysts mentioned above have similar technological properties and yield, but the requirements made for industrial catalysts are not met entirely.
Cupic catalysts, especially those containing more than 50 wt. % of CuO, are susceptible to a rapid deactivation process because of their low thermostability. Besides, they are subject to poisoning with such elements as S, Cl, Fe, Ni.
Cupric catalysts lose their catalytic properties irreversibly when a temperature of 3000C is exceeded.
An object of the invention is to obviate or mitigate the aforesaid disadvantages.
As a result of studies on the practical chemistry of catalysts for synthesizing methanol, it has been found that rapid deactivation of cupric catalysts is caused by high content of cupric oxide e.g. 5070 wt. % in the known catalysts.
During catalytic reduction, the cupric oxide is almost completely reduced to metallic copper together witn releasing a great amount of heat resulting in local overheating and thus, because of recrystallization, decreasing catalyst life.
According to the present invention there is provided a method of preparing a catalyst for the synthesis of methanol, comprising calcining fine precipitates obtained by addition of sufficient sodium hydroxide or carbonate to aqueous solutions of the nitrates of copper II, zinc and ether aluminium of chromium to an elevated temperature to give a pH of from 8 to 9, in which at least two of the carbonates are coprecipitated from an aqueous solution of the nitrates of both, said method including the step of introducing manganese by adding the nitrate thereof to the aqueous nitrate solution so as one of or as a third component of an aqueous solution so as to obtain the manganese in the said coprecipitate or by impregnating the calcinate with an aqueous solution of a manganese compound decomposable to manganese oxide, and oxidising the impregnated catalyst, the consitution of the catalyst, obtained by selection of appropriate proportions of the metal compounds aforesaid, being from 20 to 50% by weight of cupric oxide, from 1 5 to 60% by weight of zinc oxide, from 5 to 35% by weight of alumina or chromia, and from 0.2 to 7.0% be weight of manganese oxide.
Thus there is provided a method of preparing a cupric catalyst from solutions of cupric nitrate, zinc nitrate, aluminium nitrate or chromium and manganese ntirates by simultaneous coprecipitation at elevated temperature by means of at least two components as sodium carbonate or sodium hydroxide simultaneously the temperature of the nitrate and precipitating solutions being the same and amounting from 800C to 1000C the concentration of the precipitating solution 5-10 wt. % and of the solution of nitrates 10--1 5 wt. %
referring to all the nitrates by the final pH kept
between 8-9. After rinsing to neutral reaction, the precipitate is dried at temperature of from
270 to 3000C, granulated with addition of 2% of graphite and, optionally, manganese is introduced
into the catalytic system in the form of aqueous solution of permanganic acid of concentration 2-4 wt. % or aqueous solution of manganese acetate of concentration 2-1 0 wt. % whereupon it is dired and tableted.
During preparation of the cupric catalyst, the proportioning rate of the precipitating solution is also of some importance. It has been found that the most preferable rate of precipitation is 30
50 I/h, which assures that very fine-crystalline deposits of carbonates or hydroxides are obtained, thus increasing the catalyst activity.
Observation of all the desiderata mentioned above ensures that a catalyst having proper activity and size of cupric oxide crystallites is obtained.
Manganese introduced as a component into the catalytic composition in an amount of 0.2-7 wt. % greatly improves thermostability and life of the catalyst.
The content of manganese introduced into the catalytic system has been found to control the size of catalyst crystallites. With increasing magnanese content the size of cupric oxide crystallites increases, however, introducing manganese in the form of aqueous solutions of permanganic acid or manganese acetate during the granulation of the catalyst ensures that the finest cupric oxide crstallites in size from 50 to 70 can be obtained.
Example I
241.6 g of Cu(NO3)2.3H2O; 397.8 g of Zn(NO3)2.6H2O, and 401.4 g of Al(NO3)3.9H2O were dissolved in 6940 ml of distilled water, then heated to a temperature of 95C1 000C at continuous mixing.
A solution of 450 g of Na2CO3 in 2550 ml of distilled water was heated to a temperature of 90-1 000C and then poured into the solution of cupric nitrate, zinc nitrate and aluminium nitrate over a period of 5 minutes. A blue-green deposit was precipitated and pH of the resulting mixture was 8.5. The precipitate was rinsed with hot distilled water until pH of the washings was about 7.0
After decanting the last portion of water, the precipitate was filtered off, dried at temperature of 11 00C and calcined at 3000C to decompose the carbonates to oxides. The calcined deposit was powdered, mixed with 2 wt. % of graphite and granulated with 119 g of 2.85 wt. % of aqueous solution of permanganic acid to obtain a material of suitable forming properties.
After the granules had been dried at 1 1 OOC, the catalyst was tableted. Pellets in dimension of 5x5 mm and a mean crushing strength of 200 kg/cm2 were obtained.
The composition of the catalyst was as follows: wt. % CuO 32.4
ZnO 44.3 At203 22.3
MnO2 1,0
This corresponds to the following gram-atomic ration: Cu1O Zn133 Awl10,7 MnO.3 The CuO crystaliites were 50 A in size.
Example II
A method of preparing the catalyst is similar to that in Example I, excpet that co-precipitation from the solution of cupric, zinc, aluminium and manganese ntirates were performed with 10% solution of NaOH to introduce manganese into the catalytic system.
Composition of the obtained catalyst was: wt. % CuO 30.3
Zno 44.2 At203 20.4
MnO 5.1
This corresponds to the following gram-atomic ratio; CurO On,4.3 Ai10.s mn,9 Mean crushing strength and bulk density were 250 kg/cm2 and 1.4 kg/dcm3, respectively.
The size of CuO crystallites was 1 50 .
Example Ill
A method of preparing the catalyst is similar to that in Example I, but the manganese was introduced in the from of aqueous solution of manganese acetate into the catalytic system during granulation of the catalyst. A solution of
Na2CO3 was used as precipitating agent which was slowly proportioned, as in Example I into the solution of cupric, zinc and aluminium nitrates.
The final pH was 9.0.
Composition of the catalyst obtained was follows: wt. % CuO 25
ZnO 50 At203 23
MnO 2
This corresponds to the following gram-atomic ratio: Cu,O Zn19,5 Al 14A Mn,, The average crusming strength was 230 kg/cm2, CuO crystallites size 60 , and the bulk density 1.3 kg/dcm3.
Example IV
364.5 g of Cu(NO3)2.3H 0 416 9 g of Zn(NO3)2.6H2O, and 31 5.9 g of Cr(NO3)3.9H20 were dissolved in 7350 ml of distilled H2O, then heated to a temperature of 95-1 000C while constantly agitating. Also 10% sodium carbonate solution was prepared and heated to a temperature 900 to 1000C, the solution of sodium carbonate being poured into the solution of cupric, zinc and chromium nitrates over 3 minutes.A deposit of blue-green colour was precipitated, and the pH of the resulting mixture was 8.9 The precipitate was rinsed with hot distilled water until the washings had a pH of 7.0
After decanting the last portion of water, the precipitate was filtered off, then dried at the temperature of 11 00C and calcined at 3000C to decompose the carbonates to oxides. The calcined material was crushed, mixed with 2 wt.
% of graphite and granulated. 20.7 g of
Mn(C2H302)2.4H20 were dissolved in an amount of water adequate to obtain a mix of good granule forming properties.
After drying the granules at a temperature of 11 00C, the catalyst was tableted. Pellets in size of 5x5 mm and means crushing strength of 150 kg/cm2 were obtained.
The catalyst composition was as follows: wt. % CuO 40
ZnO 38.0 Cr2O3 20.0
MnO 2.0 which corresponds to the following gram-atomic ratio:
Cu10 Zn9,3 Cry,2 MnO.s6 The CuO crystallites were 70 A in size.
Claims (14)
1. A method of preparing a catalyst for the synthesis of methanol, comprising calcining fine precipitates obtained by addition of sufficient sodium hydroxide or carbonate to aqueous solutions of the nitrates of copper II, zinc and ether aluminium of chromium at an elevated temperature to give a pH of from 8 to 9, in which at least two of the carbonates are co-precipitated from an aqueous solution of the nitrates of both, said method including the step of introducing manganese by adding the nitrate thereof to the aqueous solution as one of or as a third component of an aqueous solution so as to obtain the manganese in the said coprecipitate or by impregnating the calcinate with an aqueous solution of a manganese compound decomposable to manganese oxide, and oxidising the impregnated catalyst, the constitution of the catalyst, obtained by selection of appropriate proportions of the metal compounds aforesaid, being from 20 to 50% by weight of cupric oxide, from 1 5 to 60% by weight of zinc oxide, from 5 to 35% by weight of alumina or chromia, and from 0.2 to 7.0% by weight of manganese oxide.
2. A method according to claim 1, in which the precipitation is effected at a temperature of from 80to 1100C.
3. A method according to claim 1 or 2, in which the total concentration of metal nitrates in aqueous solution is from 10 to 15% by weight.
4. A method according to claim 1 or 2 or 3, in which the concentration of the sodium hydroxide or carbonate is from 5 to 15% by weight.
5. A method according to claim 4 in which the sodium hydroxide or carbonate is added to the metal nitrate solution at a rate of from 30 to 50 litres per hour.
6. A method according to any preceding claim, in which the precipitated hydroxides or carbonates are rinsed with water to neutral reaction.
7. A method according to any preceding claim, in which the calcined catalyst is mixed with graphite and granulated.
8. A method according to claim 7, in which the catalyst is mixed with 2% by weight of graphite.
9. A method according to any preceding claim, in which the calcined catalyst is impregnated with a solution of permanganic acid or manganese acetate.
10. A method according to claim 9, in which the said solution is of concentration from 2 to 10% by weight.
11. A method according to claim 9 or claim 10, in which the impregnated catalyst is formed into pellets and dried.
12. A method of preparing a methanol synthesis catalyst according to any one of
Examples I to IV hereinbefore.
13. A method of preparing a methanol synthesis catalyst according to claim 1, substantially as hereinbefore described.
14. A methanol synthesis catalyst whenever prepared by the method claimed in any of claims 1 to 13.
1 5. A method according to any preceding claim wherein the calcination is effected at a temperature of from 270 to 3000C
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL1978208466A PL120574B1 (en) | 1978-07-15 | 1978-07-15 | Method of manufacture of copper catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2025252A true GB2025252A (en) | 1980-01-23 |
| GB2025252B GB2025252B (en) | 1982-12-22 |
Family
ID=19990607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7924732A Expired GB2025252B (en) | 1978-07-15 | 1979-07-16 | Preparation of methanol synthesis catalyst |
Country Status (7)
| Country | Link |
|---|---|
| DD (1) | DD145093A5 (en) |
| DE (1) | DE2928435A1 (en) |
| GB (1) | GB2025252B (en) |
| PL (1) | PL120574B1 (en) |
| RO (1) | RO76535A (en) |
| SU (1) | SU1126205A3 (en) |
| YU (1) | YU146279A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788175A (en) * | 1985-08-30 | 1988-11-29 | Imperial Chemical Industries Plc | Catalyst |
| EP0482753A2 (en) * | 1990-09-18 | 1992-04-29 | Csir | Methanol synthesis catalyst |
| EP0548920A1 (en) * | 1991-12-23 | 1993-06-30 | Süd-Chemie Ag | Process for the production of high alcohols by catalytic hydrogenation of alkyl esters of carboxylic acids |
| EP0552463A1 (en) * | 1991-12-13 | 1993-07-28 | Süd-Chemie Ag | Chromium-free catalyst for the selective hydrogenation of organic compounds |
| CN1048917C (en) * | 1994-10-20 | 2000-02-02 | 中国科学院山西煤炭化学研究所 | Method for preparing high-activity methylated copper-zinc/alumina catalyst with metal surfactant by phase transfer |
| EP2364209A4 (en) * | 2008-11-10 | 2012-12-05 | Basf Corp | Copper catalyst for dehydrogenation application |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3005550A1 (en) * | 1980-02-14 | 1981-08-20 | Süd-Chemie AG, 8000 München | METHOD FOR PRODUCING OLEFINS |
| RU2500470C1 (en) * | 2012-11-20 | 2013-12-10 | Открытое акционерное общество "Ангарский завод катализаторов и органического синтеза" (ОАО "АЗКиОС") | Method of preparing catalyst for methanol synthesis and carbon monooxide conversion |
-
1978
- 1978-07-15 PL PL1978208466A patent/PL120574B1/en unknown
-
1979
- 1979-06-21 YU YU01462/79A patent/YU146279A/en unknown
- 1979-07-09 SU SU792784398A patent/SU1126205A3/en active
- 1979-07-12 DD DD79214298A patent/DD145093A5/en unknown
- 1979-07-13 DE DE19792928435 patent/DE2928435A1/en not_active Withdrawn
- 1979-07-14 RO RO7998165A patent/RO76535A/en unknown
- 1979-07-16 GB GB7924732A patent/GB2025252B/en not_active Expired
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788175A (en) * | 1985-08-30 | 1988-11-29 | Imperial Chemical Industries Plc | Catalyst |
| EP0482753A2 (en) * | 1990-09-18 | 1992-04-29 | Csir | Methanol synthesis catalyst |
| EP0482753A3 (en) * | 1990-09-18 | 1992-08-05 | Csir | Methanol synthesis catalyst |
| US5254520A (en) * | 1990-09-18 | 1993-10-19 | Csir | Catalyst for the synthesis of methanol |
| EP0552463A1 (en) * | 1991-12-13 | 1993-07-28 | Süd-Chemie Ag | Chromium-free catalyst for the selective hydrogenation of organic compounds |
| US5403962A (en) * | 1991-12-13 | 1995-04-04 | Sud-Chemie Ag | Chromium-free catalyst for the hydrogenation of organic compounds |
| EP0548920A1 (en) * | 1991-12-23 | 1993-06-30 | Süd-Chemie Ag | Process for the production of high alcohols by catalytic hydrogenation of alkyl esters of carboxylic acids |
| US5386066A (en) * | 1991-12-23 | 1995-01-31 | Sud-Chemie Ag | Catalyst and process for hydrogenation of carboxylic acid alkyl esters to higher alcohols |
| CN1048917C (en) * | 1994-10-20 | 2000-02-02 | 中国科学院山西煤炭化学研究所 | Method for preparing high-activity methylated copper-zinc/alumina catalyst with metal surfactant by phase transfer |
| EP2364209A4 (en) * | 2008-11-10 | 2012-12-05 | Basf Corp | Copper catalyst for dehydrogenation application |
| EP3243566A1 (en) * | 2008-11-10 | 2017-11-15 | BASF Corporation | Copper catalyst for dehydrogenation application |
Also Published As
| Publication number | Publication date |
|---|---|
| PL208466A1 (en) | 1980-03-10 |
| YU146279A (en) | 1982-08-31 |
| DE2928435A1 (en) | 1980-01-24 |
| SU1126205A3 (en) | 1984-11-23 |
| DD145093A5 (en) | 1980-11-19 |
| RO76535A (en) | 1981-04-30 |
| GB2025252B (en) | 1982-12-22 |
| PL120574B1 (en) | 1982-03-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |