EP3554690A1 - Tableted catalyst for methanol synthesis having increased mechanical stability - Google Patents
Tableted catalyst for methanol synthesis having increased mechanical stabilityInfo
- Publication number
- EP3554690A1 EP3554690A1 EP17842317.4A EP17842317A EP3554690A1 EP 3554690 A1 EP3554690 A1 EP 3554690A1 EP 17842317 A EP17842317 A EP 17842317A EP 3554690 A1 EP3554690 A1 EP 3554690A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- calcium aluminate
- range
- mixture
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- 238000000465 moulding Methods 0.000 claims description 16
- 238000007669 thermal treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002459 porosimetry Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 239000011575 calcium Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- -1 oxides Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical group Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 229910002535 CuZn Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013462 industrial intermediate Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910001700 katoite Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001374 small-angle light scattering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/80—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 zinc, cadmium or mercury
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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
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- B01J2219/30211—Egg, ovoid or ellipse
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
Definitions
- Suitable catalysts are systems based on copper and zinc. These are usually in the form of tablets, extrudates or granules.
- No. 7,084,312 describes the preparation of catalysts based on copper, zinc and aluminum, for which an oxidic mixture of copper, zinc and aluminum with metallic copper, a cement or a mixture of both materials mixed and formed into tablets.
- the catalyst is used for the hydrogenation of organic
- the Caiciumaluminat can be subjected to a thermal treatment (calcination) before use as a binder material. This takes place at a temperature between 100 and 500 ° C, preferably between 150 and 400 ° C and more preferably between 200 and 300 ° C instead.
- the catalysts prepared by the process according to the invention in tablet form have a lateral compressive strength of 50 to 300 N, preferably 100 to 250 N, particularly preferably 150 to 250 N in the oxide state.
- the tablets produced by tabletting have a diameter in the range of 5 to 7 mm, a height in the range of 3 to 5 mm and a lateral compressive strength in the range of 160 to 220 N.
- Hydrogen-nitrogen mixture is typically in the range of 1 to 4% by volume.
- the reduction takes place, for example, at a temperature in the range from 150 ° C. to 450 ° C., in particular in the range from 180 ° C. to 300 ° C., preferably in the range from 190 ° C. to 290 ° C., particularly preferably at approximately 250 ° C.
- Hexadecane 2-ethyl-hexanol, propylene glycol and mixtures thereof, especially iso-decanol.
- a thin oxide layer having a thickness of, for example, 0.5 to 50 nm, preferably 1 to 20 nm, more preferably 1 to 10 nm at the surface of the Catalyst is formed which protects the shaped catalyst body from further oxidation.
- Reduction may occur ex situ or in situ in the reaction plant in which the
- the active copper surface of the reduced shaped catalyst body is between 20 m 2 / g and 50 m 2 / g, preferably between 20 m 2 / g and 40 m 2 / g, particularly preferably between 25 m 2 / g and 36 m 2 / g ,
- the catalyst obtainable by the process according to the invention preferably has a BET surface area in the range from 70 to 150 m 2 / g, in particular from 75 to 140 m 2 / g and particularly preferably from 80 to 120 m 2 / g.
- the pore volume of the shaped catalyst body according to the invention is between 150 mm 3 / g and 400 mm 3 / g, preferably between 250 mm 3 / g and 350 mm 3 / g, particularly preferably between 300 and 350 mm 3 / g.
- the proportion of the pore volume of the pores with a radius of 7.0 to 40.0 nm of the shaped catalyst body according to the invention is between 50 and 95%, preferably between 80 and 90% of the total pore volume.
- the invention also provides the use of the invention
- Typical reaction temperatures of the methanol synthesis are between 200 and 300 ° C, preferably between 210 to 280 ° C, the pressure is usually in a range of 40 to 150 bar, preferably from 60 to 100 bar, and the space velocity of
- Gas composition is in the range of 2000 to 22000 h ⁇ 1 .
- Room velocity is the quotient of the volume flow of the synthesis gas and the volume of the catalyst in the case of a catalyst bed, the bulk volume of this bed, to understand per hour.
- Catalyst body was a certain amount under reducing gas (2% by volume of H 2 in N 2 ) heated to 200 ° C and reduced at this temperature for 24 h. The material was cooled to room temperature under a stream of nitrogen. After that was the
- Nitrogen stream dosed synthetic air and passivated the material. Thereafter, for the thus treated samples, their lateral compressive strength was determined as described in the previous paragraph.
- the determination of the breaking strength was carried out by adding 100g of the
- Diameter of 60 mm and a length of 3 m were dropped. After passing through the steel tube, the tablets were collected in a beaker.
- the fracture fraction can be determined as the difference between the tablets used and the tablets which have withstood the dropping process without flaking, the formation of break edges or other deviations from the original cylindrical shape, divided by the weight of the tablets used.
- the BET specific surface areas were determined by means of nitrogen adsorption according to DIN 66131.
- the proportion by weight of calcium aluminate in the shaped catalyst body could by means of
- X-ray diffractometry can be determined.
- the sample was measured over a range of 5 to 90 2 ° ⁇ (step sequence 0.020 2 ° ⁇ , 1.5 sec. Measuring time per step). CuKa radiation was used.
- the obtained spectrum of the reflection intensities was quantitatively analyzed by Rietveld refinement and the proportion of calcium aluminate in the sample certainly.
- the TOPAS software from BRUKER was used.
- the Cu surface was determined by first mortaring a shaped catalyst body and introducing about 100 mg of the sieve fraction of 100-250 ⁇ m into a quartz glass reactor. Subsequently, the catalyst was reduced / activated at normal pressure as described above. After completion of the reduction of the catalyst under He was heated to 35 ° C. In the exhaust stream of the reactor was a calibrated mass spectrometer, which was aligned for the detection of N 2 0 and N 2 . Now one became
- the consumption in N 2 0 in mol could be determined. Assuming a specific copper surface area of 1 .47 10 19 atoms Cu / m 2 , a calculation of the surface was possible, the Cu surface was thus determined as the quotient of the surface and the weighed sample.
- a 14% strength by weight aqueous sodium carbonate solution was prepared and heated to 50.degree.
- 120 g of zinc oxide and 260 g of aluminum nitrate in 900 g of water and 270 g of 68 wt .-% HN0 3 was dissolved at 50 ° C.
- the nitrate solution and the soda solution were combined at a temperature of 65 ° C simultaneously while maintaining the pH of 6.5 (precipitation).
- the suspension was continuously pumped from the precipitation vessel into an aging vessel. After completion of the precipitation, the suspension was aged for at least 120 minutes at 70 ° C. The color changed from light blue (onset of aging) to green (end of aging). After aging, the suspension was filtered and the filter cake was washed until the sodium content of the filter cake, as determined by atomic absorption spectroscopy, was less than 350 ppm.
- the filter cake was made by adding water
- Catalyst precursor thermally treated at 330 ° C for 2 h.
- the chemical composition was (in% by weight): 64.0% CuO, 27.8% ZnO, 8.2% Al 2 0 3 , based on the
- the dried powder was then thermally treated at 320 ° C for 2 hours and served as the starting material for the tabletting examples.
- Comparative Catalyst A was prepared by mixing 500 g of the catalyst powder with 2 g of graphite and then forming into tablets measuring 6 mm in diameter and 4 mm in height.
- 500 g of the catalyst powder were mixed with 50 g of Caiciumaluminat (type SECAR 71, 30 wt .-% CaO, 70 wt .-% Al 2 0 3 ) and 10 g of graphite. Subsequently, the mixture was molded into tablets having dimensions of 6 mm in diameter and 4 mm in height. The thus tableted sample was not subjected to any thermal treatment.
- Caiciumaluminat type SECAR 71, 30 wt .-% CaO, 70 wt .-% Al 2 0 3
- 500 g of the catalyst powder were mixed with 50 g of Caiciumaluminat (type SECAR 71, 30 wt .-% CaO, 70 wt .-% Al 2 0 3 ) and 10 g of graphite. Subsequently, the mixture was molded into tablets having dimensions of 6 mm in diameter and 4 mm in height. The thus-tableted sample was then thermally treated at 400 ° C for 2 hours.
- Caiciumaluminat type SECAR 71, 30 wt .-% CaO, 70 wt .-% Al 2 0 3
- the catalyst powder 500 g were mixed with 62.5 g of Caiciumaluminat (type SECAR 71, 30% by weight of CaO, 70 wt .-% Al 2 0 3 ) and 10 g of graphite. Subsequently, the mixture was molded into tablets having dimensions of 6 mm in diameter and 4 mm in height. The thus-tableted sample was then thermally treated at 400 ° C for 2 hours.
- Caiciumaluminat type SECAR 71, 30% by weight of CaO, 70 wt .-% Al 2 0 3
- 500 g of the catalyst powder were mixed with 100 g of Caiciumaluminat (type SECAR 71, 30% by weight of CaO, 70 wt .-% Al 2 0 3 ) and 10 g of graphite. Subsequently, the mixture was molded into tablets having dimensions of 6 mm in diameter and 4 mm in height. The thus-tableted sample was then thermally treated at 400 ° C for 2 hours.
- Caiciumaluminat type SECAR 71, 30% by weight of CaO, 70 wt .-% Al 2 0 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102016225171.6A DE102016225171A1 (en) | 2016-12-15 | 2016-12-15 | Tableted catalyst for methanol synthesis with increased mechanical stability |
PCT/EP2017/082815 WO2018109083A1 (en) | 2016-12-15 | 2017-12-14 | Tableted catalyst for methanol synthesis having increased mechanical stability |
Publications (1)
Publication Number | Publication Date |
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EP3554690A1 true EP3554690A1 (en) | 2019-10-23 |
Family
ID=61226523
Family Applications (1)
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EP17842317.4A Withdrawn EP3554690A1 (en) | 2016-12-15 | 2017-12-14 | Tableted catalyst for methanol synthesis having increased mechanical stability |
Country Status (5)
Country | Link |
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US (1) | US11000833B2 (en) |
EP (1) | EP3554690A1 (en) |
CN (1) | CN110072614A (en) |
DE (1) | DE102016225171A1 (en) |
WO (1) | WO2018109083A1 (en) |
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CN114786809A (en) | 2019-12-11 | 2022-07-22 | 巴斯夫欧洲公司 | Method for producing a molded article comprising a zeolite catalyst and method for converting an oxygenate to an olefin using the catalytic molded article |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1296212A (en) | 1969-03-04 | 1972-11-15 | ||
FR2106636A5 (en) * | 1970-09-18 | 1972-05-05 | Azote & Prod Chim | Complex metal oxide catalysts - from decomposition of molten nitrates in hot gas |
CA1021354A (en) | 1972-04-20 | 1977-11-22 | Alvin B. Stiles | Methanol synthesis catalyst |
FR2352588A1 (en) | 1976-05-28 | 1977-12-23 | Catalyse Soc Prod Francais | CATALYST CONTAINING COPPER OXIDE AND ZINC OXIDE, ITS PREPARATION AND USE IN CARBON OXIDE CONVERSION REACTIONS |
FR2444654A1 (en) * | 1978-12-19 | 1980-07-18 | Inst Francais Du Petrole | PROCESS FOR THE MANUFACTURE OF ALCOHOLS AND MORE PARTICULARLY PRIMARY, SATURATED AND LINEAR ALCOHOLS FROM SYNTHESIS GAS |
DE3317725A1 (en) | 1983-05-16 | 1984-11-22 | Süd-Chemie AG, 8000 München | CATALYST FOR METHANOL SYNTHESIS |
GB8610196D0 (en) * | 1986-04-25 | 1986-05-29 | Ici Plc | Sulphur compounds removal |
DE4142900A1 (en) | 1991-12-23 | 1993-06-24 | Sued Chemie Ag | USE OF COPPER OXIDE ALUMINUM OXIDE MAGNESIUM OXIDE CATALYSTS FOR CONVERTING CARBON MONOXIDE |
GB9515300D0 (en) | 1995-07-26 | 1995-09-20 | Ici Plc | Catalyst |
GB9619724D0 (en) | 1996-09-20 | 1996-11-06 | Ici Plc | Catalyst |
DE19942895A1 (en) | 1999-09-08 | 2001-03-15 | Basf Ag | Catalyst and process for the hydrogenation of carbonyl compounds |
RU2172210C1 (en) * | 2000-11-29 | 2001-08-20 | Меньшов Владимир Никифорович | Method of preparing catalyst for redox processes |
DE10160487A1 (en) | 2001-12-08 | 2003-06-12 | Sued Chemie Ag | Production of copper-zinc-aluminum catalyst, e.g. for methanol synthesis, involves two-stage precipitation from metal salt solution with alkali, using a different copper to zinc atom ratio in each stage |
DE10160486A1 (en) | 2001-12-08 | 2003-06-12 | Sued Chemie Ag | Copper-zinc-aluminium catalyst for use in methanol synthesis has a relatively low copper to zinc atom ratio and contains the aluminum oxide component in the form of an aluminum hydroxide sol |
DE10313702A1 (en) | 2003-03-27 | 2004-10-07 | Basf Ag | Catalyst and process for the hydrogenation of carbonyl compounds |
DE102004011335A1 (en) | 2004-03-09 | 2005-09-22 | Süd-Chemie AG | Preparation of supported metal / metal oxide catalysts by precursor chemical nanometallurgy in defined reaction spaces of porous supports by means of organometallic and / or inorganic precursors and metal-containing reducing agents |
CN102451701B (en) * | 2010-10-22 | 2014-08-06 | 中国石油化工股份有限公司 | High-concentration CO synthesis gas sulfur tolerance conversion pre-conversion treatment method |
DE102011086451A1 (en) | 2011-11-16 | 2013-05-16 | Süd-Chemie Ip Gmbh & Co. Kg | METHANOL SYNTHESIS CATALYST BASED ON COPPER, ZINC AND ALUMINUM |
DE102014004391A1 (en) * | 2014-03-26 | 2015-10-15 | Clariant International Ltd. | Process for the preparation of catalysts with increased strength and reduced volume shrinkage |
DE102014004413A1 (en) * | 2014-03-26 | 2015-10-01 | Clariant International Ltd. | Hydrogenation catalyst and process for its preparation |
CN104475115A (en) * | 2014-11-20 | 2015-04-01 | 西南化工研究设计院有限公司 | Gaseous hydrocarbon pre-conversion catalyst and preparation method thereof |
-
2016
- 2016-12-15 DE DE102016225171.6A patent/DE102016225171A1/en active Pending
-
2017
- 2017-12-14 EP EP17842317.4A patent/EP3554690A1/en not_active Withdrawn
- 2017-12-14 CN CN201780077457.4A patent/CN110072614A/en active Pending
- 2017-12-14 US US16/463,551 patent/US11000833B2/en active Active
- 2017-12-14 WO PCT/EP2017/082815 patent/WO2018109083A1/en unknown
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WO2018109083A1 (en) | 2018-06-21 |
US20200001278A1 (en) | 2020-01-02 |
US11000833B2 (en) | 2021-05-11 |
DE102016225171A1 (en) | 2018-06-21 |
CN110072614A (en) | 2019-07-30 |
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