WO2012040977A1 - 一种二氧化碳催化加氢制甲醇的催化剂及制备方法 - Google Patents
一种二氧化碳催化加氢制甲醇的催化剂及制备方法 Download PDFInfo
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- WO2012040977A1 WO2012040977A1 PCT/CN2010/079556 CN2010079556W WO2012040977A1 WO 2012040977 A1 WO2012040977 A1 WO 2012040977A1 CN 2010079556 W CN2010079556 W CN 2010079556W WO 2012040977 A1 WO2012040977 A1 WO 2012040977A1
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- methanol
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 claims abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 36
- 239000001569 carbon dioxide Substances 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 18
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 2
- 229910052749 magnesium Inorganic materials 0.000 claims 2
- 235000013877 carbamide Nutrition 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 235000011181 potassium carbonates Nutrition 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 2
- XQMVBICWFFHDNN-UHFFFAOYSA-N 5-amino-4-chloro-2-phenylpyridazin-3-one;(2-ethoxy-3,3-dimethyl-2h-1-benzofuran-5-yl) methanesulfonate Chemical compound O=C1C(Cl)=C(N)C=NN1C1=CC=CC=C1.C1=C(OS(C)(=O)=O)C=C2C(C)(C)C(OCC)OC2=C1 XQMVBICWFFHDNN-UHFFFAOYSA-N 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000000975 co-precipitation Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000969 carrier Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- ANBZWDBEKOZNHY-UHFFFAOYSA-N ethanol;oxalic acid Chemical compound CCO.OC(=O)C(O)=O ANBZWDBEKOZNHY-UHFFFAOYSA-N 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000002699 waste material Substances 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
-
- 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
Definitions
- the invention belongs to the technical field of catalysts, and relates to a catalyst for preparing hydrogenation of carbon dioxide to methanol and a preparation method thereof. Background technique
- the carrier selection is more novel.
- Common carriers include Zr0 2 , A1 2 0 3 , Ti0 2 , activated carbon (AC), etc.
- CNTs carbon nanotubes
- the research on the catalytic hydrogenation of carbon dioxide to copper catalysts mainly focuses on the further optimization and improvement of the preparation method. The purpose is to improve the activity of the catalyst, the selectivity and stability of methanol, and improve the performance of the catalyst by adding additives.
- the methanol synthesis catalyst involved in Chinese patent application CN1660490 is composed of CuO/ZnO/Al 2 O 3 with a molar ratio of 6:3:1 and a certain amount of surfactant. It is prepared by coprecipitation or step precipitation. .
- the methanol synthesis catalyst involved in Chinese patent application CN1329938, CuO/ZnO/A1203 is composed according to a certain ratio.
- the preparation of the catalyst masterbatch is divided into two parts, one is to form copper containing by coprecipitation method.
- the coprecipitation precursor of zinc and aluminum, and the second is a coprecipitation method for preparing copper-free and zinc coprecipitated precursors without aluminum. Summary of the invention
- the invention provides a catalyst for preparing hydrogenation of carbon dioxide to methanol and a preparation method thereof.
- the catalyst is improved by adding a promoter MgO, and the technical problem is to improve the activity of the catalyst, the selectivity of the methanol and the stability of the catalyst.
- the preparation of the catalyst of the invention adopts a coprecipitation method and includes the following steps:
- Step (1) dissolving copper, zinc, aluminum, magnesium nitrate in anhydrous ethanol or water to obtain a mixed solution having a total metal ion concentration of 0.1 to 5 mol/L, wherein the magnesium oxide is added according to the desired catalyst.
- the mass percentage of the obtained MgO is converted and controlled between 0.1 and 20%;
- Step (2) Configuring an oxalic acid ethanol solution or an aqueous oxalic acid solution of 0.1 to 3 mol/L, wherein the oxalic acid may be replaced by one of sodium carbonate, urea, potassium carbonate or ammonium carbonate;
- Step (3) adding the oxalic acid ethanol solution or the aqueous oxalic acid solution of the step (2) to the mixed solution of the step (1) under heating and stirring, the temperature is controlled at 50 to 80 ° C, heating, stirring, and reacting. Until the ethanol is completely evaporated, if the solvent is water, react for 4 hours, aging for 1 hour, then the precipitate precursor is filtered, washed, and the pH of the filtrate is controlled between 7 and 8; the catalyst precursor is dried at 11 CTC overnight, then The catalyst was heated to 350 ° C for 4 hours at a temperature of 3.0 ° C / min, and was cooled to room temperature.
- the catalyst for hydrogenation of carbon dioxide to methanol was obtained by grinding, tableting, crushing and sieving.
- the invention has the advantages and benefits that the catalyst for hydrogenation of carbon dioxide prepared by the method has the advantages of activity, methanol selectivity and stability, and is superior to the same proportion of CuO-ZnO-A1203 catalyst without adding MgO auxiliary agent, which is in line with energy saving. Consumable and environmentally friendly, suitable for carbon dioxide and hydrogen to react at lower temperatures and pressures.
- the surfactant added to the patent application CN1660490 does not increase the adsorption of carbon dioxide, and the selectivity of methanol is not greatly improved.
- the patent application CN1329938 is complicated in preparation method. Compared with the above two patents, the invention has neither surfactant added nor It is not necessary to prepare the catalyst precursor for the two parts, and only the promoter MgO can be added, the preparation process is simple, the environmental pollution is small, and the cost is low. detailed description
- Example 1 Specific embodiments of the present invention are described in detail below in conjunction with the technical solutions.
- Example 2 B is dropped into the solution A to coprecipitate to obtain a precipitate (1), and the mixture is stirred at 70 ° C until the ethanol is completely evaporated, and then the obtained catalyst precursor is dried at 11 CTC for 12 hours to 3.0 °.
- the temperature of C/min is calcined to 350 ° C for 4 hours, and is reduced to room temperature. The particles are crushed, crushed, crushed and sieved to obtain particles of a certain size, that is, a catalyst for hydrogenation of carbon dioxide to methanol is obtained.
- Example 2
- the value is between 7 and 8.
- the filter cake is dried at 11 CTC for 12 hours, heated to 350 ° C for 4 hours at a temperature of 3.0 ° C / min, and cooled to room temperature. Grinding, tableting, crushing and sieving A certain particle size particle is obtained by catalytic hydrogenation of carbon dioxide to a methanol catalyst.
- the obtained catalyst precursor was precipitated and washed, and the pH of the filtrate was controlled to be 7-8.
- the filter cake was dried at 11 CTC for 12 hours, and then calcined at 350 ° C for 4 hours at a temperature of 3.0 ° C / min, and then cooled to room temperature, ground, tableted, crushed, sieved to obtain particles of a certain size, that is, A catalyst for catalytic hydrogenation of carbon dioxide to methanol is obtained.
- the pH value is between 7 and 8.
- the filter cake is dried at 110 ° C for 12 hours, heated to 350 ° C for 4 hours at a temperature of 3.0 ° C / min, cooled to room temperature, ground, pressed, broken, A certain particle size particle is obtained by sieving, that is, a catalyst for hydrogenation of carbon dioxide to obtain methanol is obtained.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
一种二氧化碳催化加氢制甲醇的催化剂及制备方法 技术领域
本发明属于催化剂技术领域, 涉及一种二氧化碳催化加氢制甲醇催化剂及制备方法。 背景技术
随着工业化发展速度的加快说, 特别是石油化工行业的迅猛发展, 二氧化碳温室气体超标 准排放, 所引起的 "温室效应"和 "臭氧空洞" 日益影响人类与大自然的和谐相处, 已经引 起全世界范围的广泛关注, 2009年哥本哈根会议, 再一次把世人的目光会聚到温室气体的排 放上。 二氧化碳气体的随意排放不仅造成严重的环境问题, 而且造成碳资源的严重浪费。 二 氧化碳催化加氢, 则可生成高附加值的化工产品如甲醇、 甲烷、 甲酸、 二甲醚、 乙醇等, 这 些产物进一步转化, 可生产汽油和其它有机聚合物等, 可以缓解目前资源紧缺的局面, 具有 化工、 环保、 经济等多重意义。 书 二氧化碳催化加氢制甲醇是目前研究的热点, 1923年世界上第一个甲醇工厂在 BASF公 司建立, 所用催化剂是 ZnO/Cr203, 反应条件为 300 。C、 20 MPa。 目前采用最多的是高活性、 高选择性的 ΟιΟ-ΖηΟ-Α1203催化剂, 该催化剂在 200 °C就具有较好的活性和甲醇选择性。 但 是随着研究的进一步深入,新的高效催化剂和更缓和的反应条件不断呈现。 ΟιΟ-ΖηΟ-Α1203催 化剂的制备技术不断推陈出新, 超细颗粒催化剂具有较高的比表面积、 高分散度、 热稳定性 好、 高表面能和表面活性点多等特点, 表现出不同于常规材料的独特催化性能, 同时超细催 化剂具有副产物少和甲醇选择性高等特点。载体选择更加新颖化,常见的载体有 Zr02、 A1203、 Ti02、 活性炭 (AC) 等, 目前已出现用碳纳米管 (CNTs) 作为载体和用复合载体的催化剂, 表现出更高的活性、 甲醇选择性和热稳定性。 目前对二氧化碳催化加氢制甲醇铜基催化剂的 研究主要集中在制备方法的进一步优化和改进上, 目的是提高催化剂的活性、 甲醇选择性和 稳定性, 通过添加助剂来改善催化剂的性能是研究者追求的目标之一。
中国专利申请 CN1660490所涉及的甲醇合成催化剂,由 CuO/ZnO/Al203,摩尔比为 6:3:1, 并加入一定量的表面活性剂组成, 采用共沉淀法或分步沉淀法制得。
中国专利申请 CN1329938所涉及的甲醇合成催化剂, CuO/ZnO/A1203按一定配比组成, 在制备方法上与其它方法不同, 将催化剂母料制备分为两部分, 一是用共沉淀法制成含铜、 锌、 铝的共沉淀前驱体, 二是采用共沉淀法制备不含铝的铜、 锌共沉淀前驱体。
发明内容
本发明提供一种二氧化碳催化加氢制甲醇催化剂及制备方法, 通过添加一种助催化剂 MgO来改善催化剂的性能, 解决的技术问题是提高催化剂的活性、 甲醇选择性和催化剂的稳 定性。
本发明的技术方案是:
本发明所述的二氧化碳催化加氢制甲醇催化剂包括下述质量分数的组分: CuO: ZnO: AI2O3: MgO=A: B: C: D, 其 A: B的范围在 l/5~5/l之间, C的范围在 1~10%之间, D的 范围在 0·1~20%之间, CuO: 20-70% (WAV ) , ZnO: 20-70% (WAV ) , A1203: 5-10% (WAV ) , MgO: 0.1-20% (WAV ) 。
本发明催化剂的制备采用共沉淀法, 包括以下步骤:
步骤 (1 ) : 将铜、 锌、 铝、 镁的硝酸盐溶解在无水乙醇或水中, 得到金属离子总浓度 为 0.1~5mol/L的混合溶液, 其中氧化镁加入量根据所得催化剂中所欲得到的 MgO的质量百 分含量进行换算, 控制在 0.1~20%之间;
步骤 (2) : 配置草酸乙醇溶液或草酸水溶液 0.1~3mol/L, 其中草酸可用碳酸钠、 尿素、 碳酸钾、 碳酸氨其中一种代替;
步骤 (3 ) : 将步骤 (2) 的草酸乙醇溶液或草酸水溶液在加热和搅拌的条件下, 滴入步 骤 (1 ) 的混合溶液中, 温度控制在 50~80°C, 加热、 搅拌、 反应直至乙醇完全蒸发, 如果溶 剂为水, 反应 4小时, 老化 1小时, 然后将沉淀物前驱体过滤、 洗涤、 控制滤液 PH值在 7~8 之间; 将催化剂前驱体在 11CTC下干燥过夜, 然后以 3.0°C/min的程序升温至 350°C焙烧 4小 时, 降至室温, 研磨、 压片、 破碎、 筛分即得到二氧化碳催化加氢制甲醇的催化剂。
本发明的效果和益处是所述方法制备的二氧化碳催化加氢制甲醇催化剂, 活性、 甲醇选 择性和稳定性, 均优于不添加 MgO助剂的同比例 CuO-ZnO-A1203催化剂, 符合节能降耗和 环保要求, 适用于二氧化碳和氢气在较低温度和压力下反应。
专利申请 CN1660490所加入表面活性剂不能提高对二氧化碳的吸附, 甲醇选择性提高 不大, 专利申请 CN1329938在制备方法上较为复杂, 本发明与以上两种专利相比, 既没有加 入表面活性剂, 又不必为两部分制备催化剂前驱体, 只需加入助催化剂 MgO即可, 制备工艺 简单, 环境污染小, 成本低。 具体实施方式
以下结合技术方案详细叙述本发明的具体实施方式。
实施例 1
称取 4.55g Cu(N03)2-3H20, 10.95g Ζη(Ν03)2·6Η20, 3.68g Α1(Ν03)3·9Η20禾卩 0.64g Mg(N03)2.6H20溶于 100 ml乙醇中, 溶液记为 A液, 称取 8.91g H2C204.H20溶于 50 ml乙醇 中, 溶液记为 B液, 在 70°C和搅拌条件下, 把 B液滴入 A液中共沉淀反应, 得到沉淀液(1 ), 在 70°C和搅拌条件下直至乙醇完全蒸发, 然后把得到的催化剂前驱体在 11CTC下烘干 12小 时, 以 3.0°C/min的程序升温至 350°C焙烧 4小时, 降至室温, 研磨、 压片、 破碎、 筛分得 一定粒径颗粒, 即得到二氧化碳催化加氢制甲醇催化剂。 实施例 2
称取 4.55g Cu(N03)2-3H20, 10.95g Ζη(Ν03)2·6Η20, 3.68g Α1(Ν03)3·9Η20禾卩 0.64g ^¾(1^03)2.6¾0溶于100 1111水中, 溶液记为 A液, 称取 8.91gH2C204.H20溶于 50 ml水中, 溶 液记为 B液, 在 70°C和搅拌条件下, 把 B液滴入 A液中共沉淀反应, 得到沉淀液 (1 ), 在 70 °C和搅拌条件下反应 4小时, 老化 1小时, 然后把得到的催化剂前驱体沉淀过滤、 洗涤, 控制滤液 PH值在 7~8之间, 把滤饼在 11CTC下烘干 12小时, 以 3.0°C/min的程序升温至 350 °C焙烧 4小时, 降至室温, 研磨、 压片、 破碎、 筛分得一定粒径颗粒, 即得到二氧化碳催 化加氢制甲醇催化剂。 实施例 3
称取 4.55g Cu(N03)2-3H20, 10.95g Ζη(Ν03)2·6Η20, 3.68g Α1(Ν03)3·9Η20禾卩 0.64g ^¾(1^03)2.61¾0溶于100 1111水中, 溶液记为 A液, 称取 8.22gNa2C03溶于 50 ml水中, 溶液记 为 B液, 在 70°C和搅拌条件下, 把 B液滴入 A液中共沉淀反应, 得到沉淀液 (1 ), 在 70°C和 搅拌条件下反应 4小时, 老化 1小时, 然后把得到的催化剂前驱体沉淀过滤、 洗涤, 控制 滤液 PH值在 7~8之间, 把滤饼在 11CTC下烘干 12小时, 以 3.0°C/min的程序升温至 350°C焙 烧 4小时, 降至室温, 研磨、 压片、 破碎、 筛分得一定粒径颗粒, 即得到二氧化碳催化加 氢制甲醇催化剂。 实施例 4
称取 4.55g Cu(N03)2-3H20 , 10.95g Ζη(Ν03)2·6Η20, 3.68g Α1(Ν03)3·9Η20禾卩 0.64g ^¾(1^03)2.6¾0溶于100 1111水中, 溶液记为 A液, 称取 11.12g K2C03溶于 50 ml水中, 溶液记 为 B液, 在 70°C和搅拌条件下, 把 B液滴入 A液中共沉淀反应, 得到沉淀液(1 ), 在 70°C和搅 拌条件下反应 4小时, 老化 1小时, 然后把得到的催化剂前驱体沉淀过滤、 洗涤, 控制滤液
PH值在 7~8之间, 把滤饼在 110°C下烘干 12小时, 以 3.0°C/min的程序升温至 350°C焙烧 4 小时, 降至室温, 研磨、 压片、 破碎、 筛分得一定粒径颗粒, 即得到二氧化碳催化加氢制甲 醇催化剂。
实施例 5
催化剂催化性能测试 (g cat)
催化剂: CuO-ZnO-Al203/MgO, CuO/ZnO/Al203/MgO =3/6/1/Χ (质量比, 其中 X=0.001~0.2);
反应条件: T=195°C, P=3.2Mpa, SV=3600 h"1 , H2/C02=3/l (体积比), 反应前用 10% H2/N2 (体积比) 程序升温至 250°C还原 2小时。
实验结果如下表:
MgO质量百分含量 (wt.% ) C02转化率 (%) 甲醇选择性 (%) 甲醇收率 (%)
0 wt. 1.93 49.20 0.95
2 wt.% 4.18 59.85 2.50
4 wt.% 2.94 68.70 2.02
6 wt.% 2.26 70.54 1.59
8 wt.% 1.83 70.91 1.30
Claims
( 1 ) 配制溶液 A: 溶质为铜、 锌、 铝、 镁的硝酸盐, 溶剂为无水乙醇或水, 所得混 合溶液中金属离子总浓度为 0.1~5mol/L, 硝酸镁的加入量根据所得催化剂中 MgO的质量 百分含量为 0.1~20%进行换算;
(2) 配制溶液 B: 溶质为草酸、 碳酸钠、 尿素、 碳酸钾或碳酸氨, 溶剂为乙醇或水, 溶液 B浓度 0.1~3mol/L;
( 3 ) 将溶液 B在加热和搅拌的条件下, 滴入溶液 A中, 温度控制在 50~80°C ; 充分 反应后得催化剂前驱体; 经后续处理后得到所述的催化剂。 、 权利要求 4所述的催化剂的制备方法, 其特征在于所述步骤 (1 ) 的溶液 A中铝和镁的摩 尔浓度和为 0.1~0.2 mol/L。 、 权利要求 4所述的催化剂的制备方法, 其特征在于步骤 (3 ) 中当溶剂为乙醇时, 乙醇完 全蒸发为充分反应, 残留物即催化剂前驱体; 当溶剂为水时, 反应 4小时, 老化 1小时后 过滤, 洗涤, 所得沉淀即为催化剂前驱体, 洗涤过程控制滤液 PH值在 7~8之间。 、权利要求 4所述的催化剂的制备方法, 其特征在于所述的后续处理包括对催化剂前驱体的 干燥、 焙烧、 降温、 研磨、 压片、 破碎及筛分。 、 权利要求 7所述的催化剂的制备方法, 其特征在于所述的焙烧是以 3.0°C/min的程序升温 至 350 °C焙烧 4小时。 、 权利要求 7所述的催化剂的制备方法, 其特征在于所述的干燥是将催化剂前驱体在 11CTC 下干燥 12小时。
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