CN114700079B - 一种催化合成气一步法制甲酸甲酯的催化剂及其制备方法与应用 - Google Patents
一种催化合成气一步法制甲酸甲酯的催化剂及其制备方法与应用 Download PDFInfo
- Publication number
- CN114700079B CN114700079B CN202210414059.XA CN202210414059A CN114700079B CN 114700079 B CN114700079 B CN 114700079B CN 202210414059 A CN202210414059 A CN 202210414059A CN 114700079 B CN114700079 B CN 114700079B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- synthesis gas
- methyl formate
- catalytic layer
- preparing
- 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.)
- Active
Links
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 73
- 230000003197 catalytic effect Effects 0.000 claims abstract description 66
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 55
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 54
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 30
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 29
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000002955 isolation Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 238000005303 weighing Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 239000006004 Quartz sand Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 150000003841 chloride salts Chemical group 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000007790 solid phase Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- -1 alkaline earth metal alkoxide Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229960002135 sulfadimidine Drugs 0.000 description 1
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/80—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
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
-
- 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
Landscapes
- 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
本发明公开一种催化合成气一步法制甲酸甲酯的催化剂,由独立的催化层A、隔绝层和催化层B组成;所述催化层A为金属氧化物催化剂,标记为CuO‑ZnO‑Al2O3‑MOx,M为Ce、Zr、Mn、Mg中的至少一种,x为满足金属元素M氧化态所需的氧原子数;所述催化层B为Cu基催化剂,由Cu、助剂、载体组成,按照总重量100%计,各组分的含量如下:Cu 5‑12%,助剂0.5‑2%,余量为载体;所述助剂为K、Mg、La或Ce中的至少一种。同时,本发明还公开所述催化剂的制备方法和应用。本发明提供的催化剂制备方法简单、制备过程环境友好;实现了气固相条件下催化合成气一步法制甲酸甲酯,且反应条件温和。
Description
技术领域
本发明属于甲酸甲酯制备技术领域,具体涉及一种催化合成气一步法制甲酸甲酯的催化剂及其制备方法与应用。
背景技术
甲酸甲酯具有醛和酯的双重反应性,被称作C1化学的基本结构单元,工业上可由甲酸甲酯生产甲酸、乙酸、乙二醇、碳酸二甲酯、乙醇酸甲酯及有机合成中的甲酰化试剂等,这些过程的反应条件都比较温和。此外,甲酸甲酯还可用作汽油高辛烷值添加剂。在农业领域,可用作杀虫剂、杀菌剂、谷类作物熏蒸剂、烟草处理剂、果品干燥剂等。在医学领域,甲酸甲酯作为合成磺胺甲基嘧啶等药物的原料。
甲酸甲酯的合成方法主要有:(1)酯化法,由甲酸与甲醇通在浓硫酸催化下合成甲酸甲酯,该方法由于工艺落后,设备腐蚀严重,成本高,在国外已被淘汰。(2)甲醇羰基化法,甲醇在甲醇钠或甲醇钾等强碱性催化剂作用下与CO高压反应生成甲酸甲酯。该方法必须使用无水甲醇,CO浓度要求高,造成甲酸甲酯生产成本较高。(3)甲醇脱氢法,甲醇在Cu基等催化剂上脱氢生成甲酸甲酯,该方法难以突破热力学限制。(4)甲醇与CO2加氢缩合法,该方法CO2转化率低,甲酸甲酯收率低。(5)合成气直接合成法,合成气直接转化制甲酸甲酯是一个典型的原子经济反应。该方法生产步骤少,能耗低,是甲酸甲酯合成方法中最有前途的。
合成气一步法直接制备甲酸甲酯研究主要集中在低温液相合成领域。专利US5384335报道了CuCr和碱金属/碱土金属复合催化剂,100-160℃、4.0-6.5MPa液相条件下,催化合成气直接合成甲酸甲酯。专利CN 1050116报道合成气在铜铬催化剂和甲醇钠体系中低温液相条件下一步法合成甲酸甲酯。专利CN 103949268 B报道了铜锰和锆基固体碱氧化物催化剂液相条件下催化合成气一步合成甲酸甲酯。这些专利都是在液相条件下催化合成气合成气甲酸甲酯,产物分离复杂,有些需要碱金属或碱土金属的醇盐,对反应物纯度要求高,这些都成为该技术发展的瓶颈。
发明内容
针对现有技术的缺陷,本发明提供一种催化合成气一步法制甲酸甲酯的催化剂及其制备方法与应用,所述催化剂制备方法简单,能实现催化合成气一步法制备甲酸甲酯,反应条件温和。
一种催化合成气一步法制甲酸甲酯的催化剂,由独立的催化层A、隔绝层和催化层B组成;
所述催化层A为金属氧化物催化剂,标记为CuO- ZnO-Al2O3- MOx,所述金属氧化物中,所述Cu、Zn、Al、M的总重量按照100%计,各组分含量如下:Cu 40-55%,Zn 20-30%、Al 4-8%,余量为M;M为Ce、Zr、Mn、Mg中的至少一种,x为满足金属元素M氧化态所需的氧原子数;
所述隔绝层为石英砂;
所述催化层B为Cu基催化剂,由Cu、助剂、载体组成,按照总重量100%计,各组分的含量如下:Cu 5-12%,助剂0.5-2%,余量为载体;所述助剂为K、Mg、La或Ce中的至少一种,所述载体为石墨烯、碳纳米管或者活性炭,且所述载体的比表面积大于200 m2/g。
优选地,所述催化层A与催化层B的质量比为1:(1-4),所述催化层A与隔绝层的比例为(1.5-2)g:(0.5-2)mL。
所述催化合成气一步法制甲酸甲酯的催化剂的制备方法,包括以下步骤:
(1)制备金属氧化物催化剂:
(11)在60-90℃下,将金属Cu、Zn、Al、M的盐溶液和沉淀剂溶液同时滴加至水中,通过控制沉淀剂溶液的滴加速度,控制体系的pH值至7.0-9.5;
(12)继续在60-90℃下老化反应2h,然后经过洗涤、烘干、焙烧、压片成型、筛分,得到金属氧化物催化剂;
(2)制备Cu基催化剂:
(21)将铜盐和助剂前驱体溶于水或者乙醇中,形成溶液A;
(22)将载体加入溶液A中,超声0.5-2h,然后室温搅拌至容器中无液体,然后烘干、压片成型,筛分;
(3)制备催化剂:
按照比例称,取金属氧化物催化剂得到催化层A;称取石英砂,得到隔绝层;称取Cu基催化剂,得到催化层B。
优选地,步骤(11)中,金属Cu、Zn、Al、M的盐溶液为对应金属的硝酸盐或者氯化盐溶液,且金属Cu、Zn、Al、M的离子总浓度为0.1-1mol/L。
优选地,步骤(11)中,所述沉淀剂溶液为0.1-1mol/L的NaOH溶液、Na2CO3溶液或KOH溶液。
优选地,步骤(2)中,所述铜盐和助剂前驱体为对应金属的硝酸盐或者氯化盐,且载体与溶液A的比例为1g:(30-60)mL。
优选地,步骤(12)和步骤(22)中,所述烘干的条件为在90-150℃烘干6-15h,所述筛分为过20-80目筛;步骤(12)中,所述焙烧的条件为300-500℃下焙烧3-10h。
所述催化剂在催化合成气一步法制甲酸甲酯中的应用,具体如下:将所述催化剂中的催化层B、隔绝层、催化层A由下至上依次分层装填入固定床反应器中,通入含氢气体进行还原活化,调节反应温度为200-260℃,然后切换通入合成气升压至0.5-2MPa进行反应。
优选地,所述还原活化的条件为还原温度250-350℃、还原时间1-8h、还原压力为常压;所述合成气中CO:H2的体积比为(1-4):1;所述合成气相对于催化层A的空速为100-5000h-1。
优选地,所述含氢气体由体积占比5-50%的氢气和余量的平衡气组成,所述平衡气为氮气、氦气或氩气;所述含氢气体的流量为20-100 mL/min。
本发明的优点:
(1)本发明提供的催化剂制备方法简单、制备过程环境友好;
(2)实现了气固相条件下催化合成气一步法制甲酸甲酯,且反应条件温和、过程简洁,属于高效的原子经济反应。
具体实施方式
实施例1
1. 一种催化合成气一步法制甲酸甲酯的催化剂,由独立的催化层A 2.0g、隔绝层1mL和催化层B 2.0g组成;
所述催化层A为金属氧化物催化剂,标记为CuO-ZnO-Al2O3-ZrO2,所述金属氧化物中,所述Cu、Zn、Al、Zr的重量比如下:Cu:Zn:Al:Zr=50:30:4:16;
所述隔绝层为石英砂;
所述催化层B为Cu基催化剂,由Cu、助剂、载体组成,所述助剂为La,所述载体为比表面积大于200 m2/g的碳纳米管,按照总重量100%计,各组分的含量如下:Cu 10%,助剂La1%,余量为载体碳纳米管,标记为1.0La10Cu/CNTs。
2. 所述催化合成气一步法制甲酸甲酯的催化剂的制备方法,包括以下步骤:
(1)制备金属氧化物催化剂:
(11)将硝酸铜、硝酸锌、硝酸铝和硝酸锆配制成总金属离子浓度为1mol/L的盐溶液,同时配制0.1mol/L碳酸钠溶液作为沉淀剂;在75℃下,将所述盐溶液和沉淀剂同时滴加至去离子水中,通过控制沉淀剂溶液的滴加速度,控制体系的pH值至7.0-8.0;
(12)继续在75℃下老化反应2h,然后经过洗涤、110℃烘干干燥10h、马弗炉中350℃焙烧4h、压片成型、筛分过40-60目筛,得到CuO-ZnO-Al2O3-ZrO2金属氧化物催化剂;
(2)制备Cu基催化剂:
(21)将硝酸铜和硝酸镧溶于乙醇中,形成溶液A;
(22)按照1g:60mL将载体碳纳米管加入溶液A中,超声2h,然后室温搅拌至容器中无液体,然后90℃烘干干燥15h、压片成型,筛分过40-60目;
(3)制备催化剂:
按照比例称,取金属氧化物催化剂得到催化层A;称取石英砂,得到隔绝层;称取Cu基催化剂,得到催化层B。
3. 所述催化剂在催化合成气一步法制甲酸甲酯中的应用,具体如下:将所述催化剂中的催化层B、隔绝层、催化层A由下至上依次分层装填入固定床反应器中,以30mL/min的流量通入含氢气体在250℃下常压还原活化2h,所述含氢气体由体积占比10%的氢气和余量的氮气组成;然后调节反应温度为220℃,切换通入合成气升压至2MPa进行反应;所述合成气中CO:H2的体积比为2:1;所述合成气相对于催化层A的空速为1500h-1,气相色谱全组分进行在线分析,结果见表1。
实施例2
1. 一种催化合成气一步法制甲酸甲酯的催化剂,由独立的催化层A 2.0g、隔绝层2mL和催化层B 3.0g组成;
所述催化层A为金属氧化物催化剂,标记为CuO-ZnO-Al2O3-CeO2,所述金属氧化物中,所述Cu、Zn、Al、Ce的重量比如下:Cu:Zn:Al: Ce=55:26:4:15;
所述隔绝层为石英砂;
所述催化层B为Cu基催化剂,由Cu、助剂、载体组成,所述助剂为K和Mg,所述载体为比表面积大于200 m2/g的活性炭,按照总重量100%计,各组分的含量如下:Cu 5%,助剂K0.5%,助剂Mg 1.5%,余量为载体活性炭,标记为0.5K1.5Mg5Cu/AC。
2. 所述催化合成气一步法制甲酸甲酯的催化剂的制备方法,包括以下步骤:
(1)制备金属氧化物催化剂:
(11)将硝酸铜、硝酸锌、氯化铝和硝酸铈配制成总金属离子浓度为0.5mol/L的盐溶液,同时配制1mol/L氢氧化钾溶液作为沉淀剂;在90℃下,将所述盐溶液和沉淀剂同时滴加至去离子水中,通过控制沉淀剂溶液的滴加速度,控制体系的pH值至8.0-9.0;
(12)继续在90℃下老化反应2h,然后经过洗涤、90℃烘干干燥15h、马弗炉中450℃焙烧4h、压片成型、筛分过40-60目筛,得到CuO-ZnO-Al2O3-CeO2金属氧化物催化剂;
(2)制备Cu基催化剂:
(21)将硝酸铜、氯化钾和氯化镁溶于水中,形成溶液A;
(22)按照1g:50mL将载体活性炭加入溶液A中,超声0.5h,然后室温搅拌至容器中无液体,然后110℃烘干干燥10h、压片成型,筛分过20-40目;
(3)制备催化剂:
按照比例称,取金属氧化物催化剂得到催化层A;称取石英砂,得到隔绝层;称取Cu基催化剂,得到催化层B。
3. 所述催化剂在催化合成气一步法制甲酸甲酯中的应用,具体如下:将所述催化剂中的催化层B、隔绝层、催化层A由下至上依次分层装填入固定床反应器中,以50mL/min的流量通入含氢气体在300℃下常压还原活化3h,所述含氢气体由体积占比50%的氢气和余量的氦气组成;然后调节反应温度为200℃,切换通入合成气升压至0.5MPa进行反应;所述合成气中CO:H2的体积比为3:1;所述合成气相对于催化层A的空速为2000h-1,气相色谱全组分进行在线分析,结果见表1。
实施例3
1. 一种催化合成气一步法制甲酸甲酯的催化剂,由独立的催化层A 1.5g、隔绝层2mL和催化层B 6.0g组成;
所述催化层A为金属氧化物催化剂,标记为CuO-ZnO-Al2O3-ZrO2-MnO2,所述金属氧化物中,所述Cu、Zn、Al、Zr、Mn的重量比如下:Cu:Zn:Al:Zr:Mn =40:30:8:15:7;
所述隔绝层为石英砂;
所述催化层B为Cu基催化剂,由Cu、助剂、载体组成,所述助剂为Ce,所述载体为比表面积大于200 m2/g的石墨烯,按照总重量100%计,各组分的含量如下:Cu 12%,助剂Ce1.2%,余量为载体石墨烯,标记为1.2Ce12Cu/Graphene。
2. 所述催化合成气一步法制甲酸甲酯的催化剂的制备方法,包括以下步骤:
(1)制备金属氧化物催化剂:
(11)将硝酸铜、氯化锌、硝酸铝、硝酸锆和硝酸锰配制成总金属离子浓度为0.1mol/L的盐溶液,同时配制0.3mol/L氢氧化钠溶液作为沉淀剂;在60℃下,将所述盐溶液和沉淀剂同时滴加至去离子水中,通过控制沉淀剂溶液的滴加速度,控制体系的pH值至8.5-9.5;
(12)继续在60℃下老化反应2h,然后经过洗涤、150℃烘干干燥6h、马弗炉中500℃焙烧3h、压片成型、筛分过20-40目筛,得到CuO-ZnO-Al2O3-ZrO2-MnO2金属氧化物催化剂;
(2)制备Cu基催化剂:
(21)将硝酸铜和硝酸铈溶于水中,形成溶液A;
(22)按照1g:30mL将载体石墨烯加入溶液A中,超声0.5h,然后室温搅拌至容器中无液体,然后150℃烘干干燥6h、压片成型,筛分过60-80目;
(3)制备催化剂:
按照比例称,取金属氧化物催化剂得到催化层A;称取石英砂,得到隔绝层;称取Cu基催化剂,得到催化层B。
3. 所述催化剂在催化合成气一步法制甲酸甲酯中的应用,具体如下:将所述催化剂中的催化层B、隔绝层、催化层A由下至上依次分层装填入固定床反应器中,以100mL/min的流量通入含氢气体在350℃下常压还原活化1h,所述含氢气体由体积占比5%的氢气和余量的氩气组成;然后调节反应温度为260℃,切换通入合成气升压至1MPa进行反应;所述合成气中CO:H2的体积比为4:1;所述合成气相对于催化层A的空速为4000h-1,气相色谱全组分进行在线分析,结果见表1。
实施例4
1. 一种催化合成气一步法制甲酸甲酯的催化剂,由独立的催化层A 2.0g、隔绝层1mL和催化层B 4.0g组成;
所述催化层A为金属氧化物催化剂,标记为CuO-ZnO-Al2O3-MgO,所述金属氧化物中,所述Cu、Zn、Al、Mg的重量比如下:Cu:Zn:Al:Mg =50:20:7:23;
所述隔绝层为石英砂;
所述催化层B为Cu基催化剂,由Cu、助剂、载体组成,所述助剂为Mg,所述载体为比表面积大于200 m2/g的石墨烯,按照总重量100%计,各组分的含量如下:Cu 9%,助剂Mg0.5%,余量为载体石墨烯,标记为0.5Mg9Cu/Graphene。
2. 所述催化合成气一步法制甲酸甲酯的催化剂的制备方法,包括以下步骤:
(1)制备金属氧化物催化剂:
(11)将硝酸铜、硝酸锌、硝酸铝、氯化镁制成总金属离子浓度为0.8mol/L的盐溶液,同时配制0.8mol/L碳酸钠溶液作为沉淀剂;在80℃下,将所述盐溶液和沉淀剂同时滴加至去离子水中,通过控制沉淀剂溶液的滴加速度,控制体系的pH值至7.0-8.0;
(12)继续在80℃下老化反应2h,然后经过洗涤、120℃烘干干燥7h、马弗炉中300℃焙烧10h、压片成型、筛分过40-60目筛,得到CuO- ZnO-Al2O3- MgO金属氧化物催化剂;
(2)制备Cu基催化剂:
(21)将硝酸铜和氯化镁溶于乙醇中,形成溶液A;
(22)按照1g:40mL将载体石墨烯加入溶液A中,超声1.5h,然后室温搅拌至容器中无液体,然后120℃烘干干燥8h、压片成型,筛分过40-60目;
(3)制备催化剂:
按照比例称,取金属氧化物催化剂得到催化层A;称取石英砂,得到隔绝层;称取Cu基催化剂,得到催化层B。
3. 所述催化剂在催化合成气一步法制甲酸甲酯中的应用,具体如下:将所述催化剂中的催化层B、隔绝层、催化层A由下至上依次分层装填入固定床反应器中,以20mL/min的流量通入含氢气体在280℃下常压还原活化2h,所述含氢气体由体积占比30%的氢气和余量的氮气组成;然后调节反应温度为230℃,切换通入合成气升压至1.5MPa进行反应;所述合成气中CO:H2的体积比为1:1;所述合成气相对于催化层A的空速为2000h-1,气相色谱全组分进行在线分析,结果见表1。
对比例 1
催化剂只含有催化层A,所述催化层A同实施例1。
所述催化剂在合成气一步法制甲酸甲酯中的应用:将所述催化剂直接固定床反应器中,其他同实施例1,结果见表1。
对比例2
催化剂只含有催化层B,所述催化层B同实施例1。
所述催化剂在合成气一步法制甲酸甲酯中的应用:将所述催化剂直接固定床反应器中,其他同实施例1,结果见表1。
表1 反应结果
备注:甲酸甲酯等产物选择性为除CO2外产物中甲酸甲酯的摩尔选择性;其它指少量二甲醚、乙醇和烃类。
Claims (9)
1.一种催化合成气一步法制甲酸甲酯的催化剂,其特征在于:由独立的催化层A、隔绝层和催化层B组成;
所述催化层A为金属氧化物催化剂,标记为CuO-ZnO-Al2O3-MOx,所述金属氧化物中,所述Cu、Zn、Al、M的总重量按照100%计,各组分含量如下:Cu 40-55%,Zn 20-30%、Al 4-8%,余量为M;M为Ce、Zr、Mn、Mg中的至少一种,x为满足金属元素M氧化态所需的氧原子数;
所述隔绝层为石英砂;
所述催化层B为Cu基催化剂,由Cu、助剂、载体组成,按照总重量100%计,各组分的含量如下:Cu 5-12%,助剂0.5-2%,余量为载体;所述助剂为K、Mg、La或Ce中的至少一种,所述载体为石墨烯、碳纳米管或者活性炭,且所述载体的比表面积大于200 m2/g;
所述催化层A与催化层B的质量比为1:(1-4),所述催化层A与隔绝层的比例为(1.5-2)g:(0.5-2)mL。
2.权利要求1所述催化合成气一步法制甲酸甲酯的催化剂的制备方法,其特征在于:包括以下步骤:
(1)制备金属氧化物催化剂:
(11)在60-90℃下,将金属Cu、Zn、Al、M的盐溶液和沉淀剂溶液同时滴加至水中,通过控制沉淀剂溶液的滴加速度,控制体系的pH值至7.0-9.5;
(12)继续在60-90℃下老化反应2h,然后经过洗涤、烘干、焙烧、压片成型、筛分,得到金属氧化物催化剂;
(2)制备Cu基催化剂:
(21)将铜盐和助剂前驱体溶于水或者乙醇中,形成溶液A;
(22)将载体加入溶液A中,超声0.5-2h,然后室温搅拌至容器中无液体,然后烘干、压片成型,筛分;
(3)制备催化剂:
按照比例称,取金属氧化物催化剂得到催化层A;称取石英砂,得到隔绝层;称取Cu基催化剂,得到催化层B。
3.根据权利要求2所述催化合成气一步法制甲酸甲酯的催化剂的制备方法,其特征在于:步骤(11)中,金属Cu、Zn、Al、M的盐溶液为对应金属的硝酸盐或者氯化盐溶液,且金属Cu、Zn、Al、M的离子总浓度为0.1-1mol/L。
4.根据权利要求3所述催化合成气一步法制甲酸甲酯的催化剂的制备方法,其特征在于:步骤(11)中,所述沉淀剂溶液为0.1-1mol/L的NaOH溶液、Na2CO3溶液或KOH溶液。
5.根据权利要求4所述催化合成气一步法制甲酸甲酯的催化剂的制备方法,其特征在于:步骤(2)中,所述铜盐和助剂前驱体为对应金属的硝酸盐或者氯化盐,且载体与溶液A的比例为1g:(30-60)mL。
6.根据权利要求5所述催化合成气一步法制甲酸甲酯的催化剂的制备方法,其特征在于:步骤(12)和步骤(22)中,所述烘干的条件为在90-150℃烘干6-15h,所述筛分为过20-80目筛;步骤(12)中,所述焙烧的条件为300-500℃下焙烧3-10h。
7.权利要求1所述催化剂在催化合成气一步法制甲酸甲酯中的应用,其特征在于:所述应用具体如下:将所述催化剂中的催化层B、隔绝层、催化层A由下至上依次分层装填入固定床反应器中,通入含氢气体进行还原活化,调节反应温度为200-260℃,然后切换通入合成气升压至0.5-2MPa进行反应。
8.根据权利要求7所述催化剂在催化合成气一步法制甲酸甲酯中的应用,其特征在于:所述还原活化的条件为还原温度250-350℃、还原时间1-8h、还原压力为常压;所述合成气中CO:H2的体积比为(1-4):1;所述合成气相对于催化层A的空速为100-5000h-1。
9.根据权利要求8所述催化剂在催化合成气一步法制甲酸甲酯中的应用,其特征在于:所述含氢气体由体积占比5-50%的氢气和余量的平衡气组成,所述平衡气为氮气、氦气或氩气;所述含氢气体的流量为20-100 mL/min。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210414059.XA CN114700079B (zh) | 2022-04-20 | 2022-04-20 | 一种催化合成气一步法制甲酸甲酯的催化剂及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210414059.XA CN114700079B (zh) | 2022-04-20 | 2022-04-20 | 一种催化合成气一步法制甲酸甲酯的催化剂及其制备方法与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114700079A CN114700079A (zh) | 2022-07-05 |
CN114700079B true CN114700079B (zh) | 2023-07-21 |
Family
ID=82174002
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210414059.XA Active CN114700079B (zh) | 2022-04-20 | 2022-04-20 | 一种催化合成气一步法制甲酸甲酯的催化剂及其制备方法与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114700079B (zh) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102600847B (zh) * | 2012-01-19 | 2013-09-25 | 中国科学院山西煤炭化学研究所 | 一种合成甲酸甲酯的催化剂及制备方法和应用 |
CN103691449B (zh) * | 2013-12-09 | 2016-01-20 | 中国科学院山西煤炭化学研究所 | 一种合成甲酸甲酯的催化剂及制备方法和应用 |
CN103949268B (zh) * | 2014-04-17 | 2016-01-20 | 中国科学院山西煤炭化学研究所 | 合成甲酸甲酯的铜锰催化剂及制法和应用 |
CN111774070B9 (zh) * | 2020-07-13 | 2023-09-29 | 陕西延长石油(集团)有限责任公司 | 一种催化甲醇脱氢制备甲酸甲酯的催化剂及其制备方法与应用 |
CN113996337B (zh) * | 2021-12-06 | 2023-08-22 | 陕西延长石油(集团)有限责任公司 | 一种催化高碳氢比合成气制乙酸的催化剂及其制备方法与应用 |
-
2022
- 2022-04-20 CN CN202210414059.XA patent/CN114700079B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN114700079A (zh) | 2022-07-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108236955B (zh) | 一种草酸二甲酯加氢合成乙醇用催化剂的制备方法以及由此得到的催化剂和其应用 | |
CN111774070B9 (zh) | 一种催化甲醇脱氢制备甲酸甲酯的催化剂及其制备方法与应用 | |
CN111889132B (zh) | 一种金属氧化物-分子筛催化剂及其制备方法和应用 | |
CN113996337B (zh) | 一种催化高碳氢比合成气制乙酸的催化剂及其制备方法与应用 | |
CN111233626A (zh) | 一种二苯甲酮加氢制备二苯甲醇的方法 | |
CN112755996A (zh) | 用于二氧化碳加氢合成甲醇的催化剂、制备方法及应用 | |
EP2539309A2 (en) | A process for preparation of hydroxyacetone or propylene glycol | |
CN113385171A (zh) | 一种寡层碳保护的金属基催化剂及其在环氧乙烷羰基化中的应用 | |
CN108484383B (zh) | 一种制备羟基乙酸化合物的方法 | |
CN114700079B (zh) | 一种催化合成气一步法制甲酸甲酯的催化剂及其制备方法与应用 | |
CN109608304A (zh) | 一种糠醛加氢直接生产1,2-戊二醇的方法 | |
CN110872208B (zh) | 一种耦合环己烷混合物脱氢技术的环己醇制备方法 | |
CN114570419B (zh) | 一种催化高碳氢比合成气制乙酸甲酯的催化剂及其制备方法与应用 | |
CN113856688B (zh) | 一种用于CO2加氢制甲醇的Cu基催化剂的制备方法 | |
JP3506602B2 (ja) | メタノールの製造方法 | |
CN113908841A (zh) | 一种Cu基催化剂在糠醇氢解制备戊二醇中的应用 | |
CN114682261A (zh) | 一种用于co2加氢制备低碳烯烃的串联催化体系及其应用 | |
CN114433059A (zh) | Co2加氢合成低碳烯烃化合物的催化剂及制备和应用 | |
CN116328779A (zh) | 一种液态阳光零碳排放甲醇合成催化剂及其制备方法和应用 | |
CN111389455A (zh) | 一种液固相催化合成1-丁烯-3,4-二醇的方法 | |
CN104525193A (zh) | 一种苯选择加氢制环己烯负载型催化剂的制备方法 | |
CN113019444B (zh) | 羰基化-除水双功能催化剂前驱体及其制备方法、羰基化-除水双功能催化剂及其应用 | |
CN115672341B (zh) | 一种双功能复合金属氧化物催化剂及其制备方法和应用 | |
CN112661618B (zh) | 一种环戊酮的铜催化制备方法 | |
CN112661619B (zh) | 一种制备环戊酮的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |