CN105777488A - 一种催化制备脂肪醇的方法 - Google Patents
一种催化制备脂肪醇的方法 Download PDFInfo
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- CN105777488A CN105777488A CN201610186309.3A CN201610186309A CN105777488A CN 105777488 A CN105777488 A CN 105777488A CN 201610186309 A CN201610186309 A CN 201610186309A CN 105777488 A CN105777488 A CN 105777488A
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- 150000002191 fatty alcohols Chemical class 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims abstract description 4
- HOLQXBRPSSZJMZ-FGRXCANLSA-N (2s)-n-[(2s)-1-[[(2s)-6-amino-1-[[(2s)-1-[[(2s)-1-[[(2s)-1-[[(2s)-1-[[(2s)-1-[[(2s)-1-[[(2s)-6-amino-1-[[(2s)-1-[[(2s)-1-[[(2s)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-1-oxopropan-2-yl]amino]-1-oxohexan-2-yl]amino]-1-oxop Chemical compound CC[C@H](C)[C@H](N)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O HOLQXBRPSSZJMZ-FGRXCANLSA-N 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 3
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000000969 carrier Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 114
- 239000000047 product Substances 0.000 description 43
- 239000002253 acid Substances 0.000 description 22
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 20
- 229910052740 iodine Inorganic materials 0.000 description 20
- 239000011630 iodine Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 230000006837 decompression Effects 0.000 description 19
- 238000004821 distillation Methods 0.000 description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 19
- 238000009413 insulation Methods 0.000 description 19
- 239000011541 reaction mixture Substances 0.000 description 19
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- 239000006228 supernatant Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 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 3
- 239000010949 copper Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 fatty acid ester Chemical class 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- CTHCNINEXYPGQP-UHFFFAOYSA-N [Zn].[Cu].[Zr] Chemical compound [Zn].[Cu].[Zr] CTHCNINEXYPGQP-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 108010067495 formaldehyde reductase Proteins 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
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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
- C07C29/132—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
- C07C29/147—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 carboxylic acids or derivatives thereof
- C07C29/149—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 carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
一种催化制备脂肪醇的方法，即一种负载金属加氢催化剂催化脂肪酸甲酯加氢制备脂肪醇的方法，其特征在于所述金属加氢催化剂的负载载体为MCM‑41、MAS‑7、ZSM‑5、SBA‑15、β分子筛、ZrO2、CeO2、Al2O3、SiO2中的一种，负载金属加氢催化剂为Pd、Cu、Ni、Ru中的一种，在金属加氢催化剂和负载载体的质量比为1:500～1:10、金属加氢催化剂和脂肪酸甲酯质量比为1:200～1:10、反应温度100～250℃、氢气压力0.5～12MPa下反应0.5～10h制备脂肪醇，并回收重复利用催化剂。与现有技术相比：1.负载金属催化剂活性高，反应条件温和。2.操作简单，产物选择性高，符合绿色环保的生产工艺。3.所用催化剂回收方便，可重复使用，对产率基本没有影响。
Description
技术领域
本发明涉及一种催化制备脂肪醇的方法，即涉及一种负载金属催化剂催化脂肪酸甲酯加氢制备脂肪醇的新方法。
背景技术
天然高级脂肪醇，是洗涤剂、表面活性剂、塑料增塑剂等精细化工品的基础原料，在工业生产中发挥着巨大作用。脂肪醇可由油脂钠还原法、脂肪酸加氢法、脂肪酸甲酯加氢法等方法合成。钠还原法可得到不饱和脂肪醇，但是存在还原剂金属钠价格昂贵、能耗高、收率低等缺点，且过程中会产生剧毒物质氰化钠。脂肪酸加氢法需要高温、高压等苛刻的反应条件，且产物醇产率低、烃含量较高。与之相比，脂肪酸酯加氢所需反应条件温和、所得产品品质高，尤其是得益于生物柴油产业的发展，使得脂肪酸甲酯加氢更具工业化前景。但是，由于羧酸酯催化加氢反应易发生水解等副反应，所以高效催化剂研制和选择显得尤为关键。由此，本发明采用一种可循环使用的负载型催化剂催化脂肪酸甲酯加氢制备脂肪醇。
发明内容
本发明的目的提供一种催化性能优良的负载型催化剂催化脂肪酸甲酯加氢制备脂肪醇，并回收重复使用催化剂。基于如上所述，本发明提供一种催化制备脂肪醇的方法，即一种负载金属加氢催化剂催化脂肪酸甲酯加氢制备脂肪醇的方法，其特征在于所述金属加氢催化剂的负载载体为MCM-41、MAS-7、ZSM-5、SBA-15、β分子筛、ZrO2、CeO2、Al2O3、SiO2中的一种，负载金属加氢催化剂为Pd、Cu、Ni、Ru中的一种，在金属加氢催化剂和负载载体的质量比为1:500～1:10、金属加氢催化剂和脂肪酸甲酯质量比为1:200～1:10、反应温度100～250℃、氢气压力0.5～12MPa下反应0.5～10h制备脂肪醇，并回收重复利用催化剂。
本发明所述的反应条件以金属加氢催化剂Pd和负载载体MCM-41的质量比为3:500～3:100、金属加氢催化剂和脂肪酸甲酯质量比为3:200～3:100、反应温度180～230℃、氢气压力4～6MPa、反应时间5～7h为最佳。
本发明通过以下技术方案解决这一技术问题：
以Pd-ZSM-5作为催化剂为例说明具体的技术方案。
Pd-ZSM-5的制备方法：首先，称取0.067gPdCl2于250mL的烧杯中，加10mL去离子水搅拌溶解10min。用氨水调节PdCl2水溶液的pH到10后，搅拌下一次加入2g载体ZSM-5，并于室温下搅拌24h。所得混合物经过滤并洗涤至中性，滤饼在60℃下过夜干燥后，于在550℃下煅烧5h。将煅烧后的样品在70℃的水浴中用30mL甲醛还原2h后，过滤、去离子水洗涤滤饼4次，并于3kPa真空下于60℃干燥至恒重，得到负载Pd的分子筛材料，命名为Pd-ZSM-5。采用类似的方法可制备其他负载型金属加氢催化剂，但所使用的金属盐分别为Cu(NO3)2、Ni(NO3)2和RuCl2。
以Pd-ZSM5为催化剂催化脂肪酸甲酯制备脂肪醇，将金属Pd和负载载体ZSM-5的质量比为3:500～3:100、催化剂和脂肪酸甲酯的质量比按3:200～3:100投入带有磁力搅拌的高压反应釜中，将釜装好密封，用1-2MPa的氢气置换5次后，向釜内充入4～6MPa氢气，加热至180～230℃保温反应5～7h，反应结束后，降温、卸压、开釜，加入甲醇溶液使反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，并测其羟值、碘值和酸值。下层催化相直接用于下次反应。
本发明与传统反应相比，其特点是：
1.负载金属催化剂活性高，反应条件温和。
2.操作简单，产物选择性高，符合绿色环保的生产工艺。
3.所用催化剂回收方便，可重复使用，对产率基本没有影响。
具体实施方法
下面结合实施例对本发明的方法做进一步说明，并不是对本发明的限定。
实施例1：在高压反应釜中加入脂肪酸甲酯10g和金属与载体质量比为1:50的Pd-ZSM-5催化剂0.2g。将釜装好密封，用1-2MPa的氢气置换5次后，向釜内充入6MPa氢气，加热至210℃保温反应4h，反应结束后，降温、卸压、开釜，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为198mgKOH/g，碘值为2I2g/100g，酸值为1mgKOH/g。
对比实施例1：在高压反应釜中加入10g脂肪酸甲酯和铜铬质量比为1:1的CuO-CrO2催化剂0.2g。将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入6MPa氢气，加热至210℃保温反应4h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为158mgKOH/g，碘值为37I2g/100g，酸值为3mgKOH/g。
对比实施例2：在高压反应釜中加入10g脂肪酸甲酯和0.2gTMPGP(三甲氧基聚乙二醇单甲醚亚磷酸酯)与氯化钯摩尔比为10:1原位合成的温控相转移催化剂PdCl2/TMPGP。将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入6MPa氢气，加热至210℃保温反应4h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为174mgKOH/g，碘值为45I2g/100g，酸值为49mgKOH/g。
对比实施例3：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:50的CuO-SiO2催化剂0.2g。将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入6MPa氢气，加热至210℃保温反应4h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为94mgKOH/g，碘值为55I2g/100g，酸值为9mgKOH/g。
对比实施例4：在高压反应釜中加入10.008g脂肪酸甲酯和铜锆锌质量比为1:1:1的Cu2O-ZrO-ZnO催化剂。将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入6MPa氢气，加热至210℃保温反应4h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为122mgKOH/g，碘值为21I2g/100g，酸值为4mgKOH/g。
对比实施例5：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:50的Ru/TiO2催化剂0.2g。将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入6MPa氢气，加热至210℃保温反应4h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为132mgKOH/g，碘值为15I2g/100g，酸值为2mgKOH/g。
对比实施例6：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:500的Pd/C催化剂1.0g。将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入12MPa氢气，加热至210℃保温反应4h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为82mgKOH/g，碘值为52I2g/100g，酸值为8mgKOH/g。
实施例2：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:10的Pd-MCM-41催化剂0.05g。将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入6MPa氢气，加热至230℃保温反应10h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为186mgKOH/g，碘值为9I2g/100g，酸值为6mgKOH/g。
实施例3：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:200的Cu-ZSM-5催化剂0.06g,将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入10MPa氢气，加热至180℃保温反应2h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为181mgKOH/g，碘值为9I2g/100g，酸值为8mgKOH/g。
实施例4：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为3:500的Ni-SBA-15催化剂0.11g，将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入7MPa氢气，加热至250℃保温反应1h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为174mgKOH/g，碘值为9I2g/100g，酸值为8mgKOH/g。
实施例5：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:300的Rh-SiO2催化剂0.15g。将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入5MPa氢气，加热至200℃保温反应5h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为191mgKOH/g，碘值为6I2g/100g，酸值为4mgKOH/g。
实施例6：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:200的Pd-Al2O3催化剂0.19g，将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入0.5MPa氢气，加热至250℃保温反应10h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为185mgKOH/g，碘值为5I2g/100g，酸值为3mgKOH/g。
实施例7：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为3:200的Ni-MCM-41催化剂0.3g。将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入6MPa氢气，加热至230℃保温反应7h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为188mgKOH/g，碘值为4I2g/100g，酸值为4mgKOH/g。
实施例8：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:100的Pd-CeO2催化剂0.08g，将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入10MPa氢气，加热至130℃保温反应9h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为176mgKOH/g，碘值为6I2g/100g，酸值为6mgKOH/g。
实施例9：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:40的Cu-ZrO2催化剂0.2g，将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入7MPa氢气，加热至230℃保温反应7h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为189mgKOH/g，碘值为3I2g/100g，酸值为3mgKOH/g。
实施例10：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:50的Ni-MAS-7催化剂0.2g，将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入6MPa氢气，加热至220℃保温反应7h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为191mgKOH/g，碘值为2I2g/100g，酸值为2mgKOH/g。
实施例11：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为3:200的Rh-β分子筛催化剂0.19g，将釜装好密封，用1-2MPa的氢气置换3次后，向釜内充入8MPa氢气，加热至200℃保温反应8h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为188mgKOH/g，碘值为5I2g/100g，酸值为3mgKOH/g。
实施例12：在高压反应釜中加入10g脂肪酸甲酯和金属与载体质量比为1:500的Ni-SBA-15催化剂0.07g，将釜装好密封，用1-3MPa的氢气置换3次后，向釜内充入4MPa氢气，加热至240℃保温反应9h，反应结束后，向釜中加入10ml甲醇，反应混和物为两层，其中上层为产物相，下层为催化剂相。将混合物离心取上层清液，减压蒸馏除净甲醇，即得产物脂肪醇，脂肪醇的羟值为191mgKOH/g，碘值为7I2g/100g，酸值为7mgKOH/g。
实施例13：采用实施例1分离所得的催化剂，在相同的实验条件下进行催化剂的重复使用性考察。实验结果表明：Pd-ZSM-5不经过处理直接循环使用10次后，所得产物的羟值、碘值分别为189mgKOH/g和6I2g/100g，酸值为4mgKOH/g。
Claims (2)
1.一种催化制备脂肪醇的方法，即一种负载金属加氢催化剂催化脂肪酸甲酯加氢制备脂肪醇的方法，其特征在于所述金属加氢催化剂的负载载体为MCM-41、MAS-7、ZSM-5、SBA-15、β分子筛、ZrO2、CeO2、Al2O3、SiO2中的一种，负载金属加氢催化剂为Pd、Cu、Ni、Ru中的一种，在金属加氢催化剂和负载载体的质量比为1:500～1:10、金属加氢催化剂和脂肪酸甲酯质量比为1:200～1:10、反应温度100～250℃、氢气压力0.5～12MPa下反应0.5～10h制备脂肪醇，并回收重复利用催化剂。
2.如权利要求1所述的制备方法，其特征在于所述的反应条件以金属加氢催化剂Pd和负载载体MCM-41的质量比为3:500～3:100、金属加氢催化剂和脂肪酸甲酯质量比为3:200～3:100、反应温度180～230℃、氢气压力4～6MPa、反应时间5～7h为最佳。
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| CN107987868A (zh) * | 2016-10-26 | 2018-05-04 | 中国石油天然气股份有限公司 | 油脂分步脱氧制备液体燃料的方法 |
| CN107987868B (zh) * | 2016-10-26 | 2020-02-14 | 中国石油天然气股份有限公司 | 油脂分步脱氧制备液体燃料的方法 |
| CN107353950A (zh) * | 2017-06-28 | 2017-11-17 | 常州市瑞泰物资有限公司 | 一种柴油抗磨剂的制备方法 |
| CN110075764A (zh) * | 2019-05-05 | 2019-08-02 | 江苏东普新材料科技有限公司 | 一种异体式喷射膜反应器及采用该反应器制备脂肪醇的方法 |
| CN110252383A (zh) * | 2019-05-17 | 2019-09-20 | 江苏大学 | 一种Cu@Ru/MCM-41纳米催化剂及其制备方法和应用 |
| CN111437877A (zh) * | 2020-04-22 | 2020-07-24 | 陕西延长石油（集团）有限责任公司 | 一种Cu/Zr双金属骨架型高硅β分子筛催化剂及其制备方法与应用 |
| CN111437877B (zh) * | 2020-04-22 | 2023-03-10 | 陕西延长石油（集团）有限责任公司 | 一种Cu/Zr双金属骨架型高硅β分子筛催化剂及其制备方法与应用 |
| CN112973697A (zh) * | 2021-03-01 | 2021-06-18 | 广东工业大学 | 一种加氢反应用催化剂及其催化脂肪酸甲酯的合成方法 |
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