CN117258794A - 一种用于丙酮气相加氢制异丙醇的催化剂及其制备方法 - Google Patents
一种用于丙酮气相加氢制异丙醇的催化剂及其制备方法 Download PDFInfo
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 150000003751 zinc Chemical class 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 239000012670 alkaline solution Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000012808 vapor phase Substances 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 238000009530 blood pressure measurement Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000010949 copper Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910017813 Cu—Cr Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali 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
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- -1 ketone nitrate Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种用于丙酮气相加氢制异丙醇的催化剂的制备方法,包括以下步骤:(1)将锌盐溶液和铜盐溶液同时加入到弱碱性溶液中,搅拌,中和、老化;(2)将锌盐溶液、铝盐溶液及弱碱性溶液同时加入到步骤(1)所得浆液中,搅拌,中和、老化,形成共沉淀;(3)共沉淀水洗、过滤、干燥、焙烧,压片成型。本发明选取Al2O3为助剂成分,并合理控制各组分比例及通过将Zn元素分步成型于催化剂中,使得催化剂的酸性位与加氢活性位可以合理匹配,从而减少醚化等副反应的发生,实现高丙酮转化率和异丙醇选择性。
Description
技术领域
本发明属于催化剂领域,具体涉及一种用于丙酮气相加氢制异丙醇的催化剂及其制备方法。
背景技术
目前,工业上丙酮主要由异丙苯过氧化法获得,并与苯酚联产。由于苯酚的需求量增加,联产出大量的丙酮,因需求的不平衡,经常导致丙酮过剩,由此引发出丙酮利用的问题。
工业上丙酮加氢制异丙醇路线是丙酮利用的有效经济途径之一。目前,用于丙酮加氢的催化剂主要有负载型金属催化剂、合金催化剂以及金属氧化物催化剂。负载型催化剂一般是将Ni、Pt等金属负载于TiO2、Al2O3等载体上,其丙酮转化率和异丙醇选择性不超过97%。合金催化剂主要是将Ni、Cu、Ru等金属与其他催化剂复合,催化剂稳定性好,寿命长,但存在转化率低、催化剂工业放大难度高等缺点。金属氧化物催化剂主要是氧化铜和氧化铬催化剂,90年代中期起,以Cu-Zn为活性组分的催化剂开始逐步替代Cu-Cr催化剂,相对Cu-Cr催化剂而言,Cu-Zn催化剂具有污染小、寿命长、机械强度高的特点。
日本专利平3-141235采用Raney Ni催化剂进行丙酮加氢,其转化率和生成异丙醇的选择性均达到99.9%;平2-278643采用Ru/Al2O3催化剂进行丙酮加氢,以异丙醇为溶剂,在9.0Mpa氢气压力下,最高转化率和选择性均达到99.9%。这两种催化剂存在价格高,反应条件苛刻等特点。
苏联专利SU1051055A、SU1118632A采用Cu-Cr催化剂进行丙酮加氢,采用该类型催化剂丙酮转化率和异丙醇选择性均低于99.5%。该催化剂所采用的Cr化合物对环境污染严重。
中国专利CN1255482A介绍一种丙酮加氢制异丙醇的方法,采用压片成型的CuO-ZnO氧化物混合物催化剂,在装在该催化剂的固定床反应器内,丙酮加氢制备异丙醇。在一定温度和压力下,丙酮的转化率和异丙醇的选择性可达99%。该方法制备催化剂时加入了聚乙烯醇等有机助剂,且氧化铜含量较高,导致成本增加,丙酮加氢制异丙醇过程中需要的压力较大。
中国专利CN103030526A公布了一种丙酮气相加氢制备异丙醇的方法,该方法以丙酮和氢气为原料,氢气/丙酮的摩尔比为1~20:1,在反应温度100~200℃,反应压力0.1~5Mpa,液体总空速0.5~6.0h-1条件下,反应生成异丙醇,丙酮的转化率和异丙醇的选择性可达99%。该方法原料中掺入75%异丙醇作为溶剂,所需反应温度、压力相对较高。
发明内容
本发明的目的在于提供一种丙酮气相加氢制异丙醇的催化剂的制备方法,以解决使用现有催化剂进行异丙醇气相加氢时工艺条件相对较为苛刻,催化剂价格昂贵、环境不友好的缺陷。
本发明的目的还在于还提供一种丙酮气相加氢制异丙醇的催化剂。
为实现上述目的,本发明提供一种用于丙酮气相加氢制异丙醇的催化剂的制备方法,包括以下步骤:
(1)将锌盐溶液和铜盐溶液同时加入到弱碱性溶液中,搅拌,中和、老化;
(2)将锌盐溶液、铝盐溶液及弱碱性溶液同时加入到步骤(1)所得浆液中,搅拌,中和、老化,形成共沉淀;
(3)共沉淀水洗、过滤、干燥、焙烧,压片成型。
本发明所述的用于丙酮气相加氢制异丙醇的催化剂的制备方法,步骤(1)中锌盐和步骤(2)中锌盐的质量比为1.5~3.3:1。
本发明所述的用于丙酮气相加氢制异丙醇的催化剂的制备方法,步骤(1)中锌盐和铜盐的总量与弱碱性物质的摩尔比为1~1.5:1,步骤(2)中锌盐和铝盐的总量与弱碱性物质的摩尔比为1~1.5:1。
本发明所述的用于丙酮气相加氢制异丙醇的催化剂的制备方法,弱碱性溶液为碳酸钠或碳酸氢钠溶液。
本发明所述的用于丙酮气相加氢制异丙醇的催化剂的制备方法,步骤(1)和步骤(2)的反应过程中pH值控制在6~8之间,温度控制在35~65℃,中和反应时间为20~50min,老化时间为20~40分钟。
本发明所述的用于丙酮气相加氢制异丙醇的催化剂的制备方法,压片过程中加入石墨。
为实现上述目的,本发明还提供一种上述的方法制备的催化剂,以质量百分比计,包含氧化铜28%~40%,氧化锌50%~70%,氧化铝0.1%~10%,石墨1~3%。
本发明的催化剂,BET比表面积为30~80m2/g,孔容为0.1~0.35cm3/g,平均孔径为6~25nm,测压强度大于200N/cm。
本发明有益效果是:
本发明选取Al2O3为助剂成分,并合理控制各组分比例及通过将Zn元素分步成型于催化剂中,使得催化剂的酸性位与加氢活性位可以合理匹配,从而减少醚化等副反应的发生,实现高丙酮转化率和异丙醇选择性。同时,助催化剂成分起到担载主活性组分铜单质的作用,通过本发明所述方法,铜晶粒均匀分散在载体上,避免了聚集现象出现,保证了催化剂的活性稳定性。
使用本发明提供的催化剂,催化剂经H2还原活化后,在反应温度100~180℃,反应压力0.4~0.8Mpa,体积空速≯1.0h-1,氢气与丙酮体积比1~5:1,循环氢氢气体积浓度≮70%的工况下,丙酮原料无需溶剂异丙醇稀释,其转化率和异丙醇选择性均高于99.0%,1000h长周期运转结果显示,催化剂活性稳定性好。另,催化剂中Cu含量较低,成本减少,且不含Ru等贵金属以及Cr等对环境有害物种。
具体实施方式
下面通过实施例对本发明进行具体描述。有必要在此指出的是以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,该领域的技术熟练人员可以根据上述本发明内容对本发明作出一些非本质的改进和调整。
实施例1
(1)将硝酸锌溶液和硝酸铜溶液同时加入到碳酸钠溶液中,硝酸锌和硝酸铜的总量与碳酸钠摩尔比为1,在35~40℃下反应20min,老化30min,期间通过碳酸钠控制体系pH为6~6.5,得到浆液;
(2)将硝酸锌溶液、硝酸铝溶液和碳酸钠溶液同时加入到步骤(1)所得浆液中,硝酸锌和硝酸铝的总量与碳酸钠摩尔比为1.2,在35~40℃下反应20min,老化30min,形成共沉淀,期间通过碳酸钠控制体系pH为6~6.5;
(3)将所得共沉淀水洗、过滤、干燥、焙烧后加入石墨压片成型,所得催化剂成分及物理性质如表1和表2所示。
实施例2
按照实施例1中的各步骤制备,区别在于步骤(1)中硝酸锌与硝酸铜的总量与碳酸钠摩尔比为1.5,及催化剂组分含量不同,所得催化剂成分及物理性质如表1和表2所示。
实施例3
按照实施例1中的各步骤制备,区别在于步骤(1)和(2)中体系的pH为6.5~7.5,及催化剂组分含量不同,所得催化剂成分及物理性质如表1和表2所示。
实施例4
按照实施例1中的各步骤制备,区别在于步骤(1)和(2)中体系的pH为7~8,及催化剂组分含量不同,所得催化剂成分及物理性质如表1和表2所示。
实施例5
按照实施例1中的各步骤制备,区别在于步骤(1)和(2)中控制反应温度为55~60℃,及催化剂组分含量不同,所得催化剂成分及物理性质如表1和表2所示。
对比例1
以中国专利CN1255482A的方法制备出对比催化剂。
催化剂由可溶性铜盐和锌盐的水溶液,加入碱液共沉淀,沉淀物经干燥、焙烧后获得氧化物混合物,再加入无机或有机粘结剂压片成型制得。催化剂组成按重量计:含CuO50%,ZnO 45%,5%聚乙烯醇和石墨碳。
对比例2
本实例以中国专利CN103030526A的方法制备出对比催化剂。
将所需量的氧化铝粉末与水混合搅拌得到浆液I,将所需的硝酸酮、硝酸镍及硝酸镁的混合溶液与碳酸钠水溶液同时滴入浆液I中进行反应,反应温度为70℃,控制溶液PH值为7.5,沉淀完毕后在70℃下陈化2小时后洗涤过滤,于120℃下干燥12小时,经400℃焙烧后压片成型制得对比催化剂。
上述各例所制得催化剂组成分析列于表1。
表1各例催化剂组成
表2各例催化剂物理性质
在200毫升固定床加氢评价装置上评价,实施例1~5和对比例1~3的还原条件为:氮气为载气配氢气为还原气,氢气体积浓度2%,还原温度190℃,还原压力0.45MPa,还原时间10小时。评价以工业丙酮为原料,反应器热点温度140℃,体积空速06h-1,氢气与丙酮体积比3:1,循环氢氢气纯度70%,反应压力为0.4Mpa。
表3各例丙酮加氢性能
选用实施例2中的催化剂2,考察不同工艺条件下加氢性能,结果见表4。
表4实施例2不同工艺条件催化剂性能
由表2、3可以看出,该技术用于制备异丙醇,在更为缓和的工况下,催化剂表现出良好的加氢活性。催化剂铜含量较低,不含Ni\Cr,环境友好。
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (8)
1.一种用于丙酮气相加氢制异丙醇的催化剂的制备方法,其特征在于,包括以下步骤:
(1)将锌盐溶液和铜盐溶液同时加入到弱碱性溶液中,搅拌,中和、老化;
(2)将锌盐溶液、铝盐溶液及弱碱性溶液同时加入到步骤(1)所得浆液中,搅拌,中和、老化,形成共沉淀;
(3)共沉淀水洗、过滤、干燥、焙烧,压片成型。
2.根据权利要求1所述的用于丙酮气相加氢制异丙醇的催化剂的制备方法,其特征在于,步骤(1)中锌盐和步骤(2)中锌盐的质量比为1.5~3.3:1。
3.根据权利要求1所述的用于丙酮气相加氢制异丙醇的催化剂的制备方法,其特征在于,步骤(1)中锌盐和铜盐的总量与弱碱性物质的摩尔比为1~1.5:1,步骤(2)中锌盐和铝盐的总量与弱碱性物质的摩尔比为1~1.5:1。
4.根据权利要求1所述的用于丙酮气相加氢制异丙醇的催化剂的制备方法,其特征在于,弱碱性溶液为碳酸钠或碳酸氢钠溶液。
5.根据权利要求1所述的用于丙酮气相加氢制异丙醇的催化剂的制备方法,其特征在于,步骤(1)和步骤(2)的反应过程中pH值控制在6~8之间,温度控制在35~65℃,中和反应时间为20~50min,老化时间为20~40分钟。
6.根据权利要求1所述的用于丙酮气相加氢制异丙醇的催化剂的制备方法,其特征在于,压片过程中加入石墨。
7.权利要求1~6中任一项所述的方法制备的催化剂,其特征在于,以质量百分比计,包含氧化铜28%~40%,氧化锌50%~70%,氧化铝0.1%~10%,石墨1~3%。
8.根据权利要求7所述的催化剂,其特征在于,BET比表面积为30~80m2/g,孔容为0.1~0.35cm3/g,平均孔径为6~25nm,测压强度大于200N/cm。
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