CN110152642B - 一种用于制备间苯二甲胺的催化剂及应用 - Google Patents
一种用于制备间苯二甲胺的催化剂及应用 Download PDFInfo
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- CN110152642B CN110152642B CN201910439999.2A CN201910439999A CN110152642B CN 110152642 B CN110152642 B CN 110152642B CN 201910439999 A CN201910439999 A CN 201910439999A CN 110152642 B CN110152642 B CN 110152642B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 229920006391 phthalonitrile polymer Polymers 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 45
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 claims description 44
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 39
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 238000007598 dipping method Methods 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 238000005470 impregnation Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 18
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 17
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 14
- 238000006386 neutralization reaction Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims description 8
- 235000019359 magnesium stearate Nutrition 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 159000000003 magnesium salts Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 22
- 238000005507 spraying Methods 0.000 description 17
- 238000013019 agitation Methods 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 15
- 239000011265 semifinished product Substances 0.000 description 14
- 239000011572 manganese Substances 0.000 description 10
- 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 9
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 241000219782 Sesbania Species 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- SEGOJYCSWLUCKJ-UHFFFAOYSA-N magnesium dinitrate tetrahydrate Chemical compound O.O.O.O.[Mg++].[O-][N+]([O-])=O.[O-][N+]([O-])=O SEGOJYCSWLUCKJ-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
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- -1 m-xylylene nitrile Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—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
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- 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
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- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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Abstract
本发明公开了一种用于制备间苯二甲胺的催化剂及应用,属于加氢催化剂领域,载体为氧化铝或镁铝混合物,活性元素为Ni,助剂1为Co、Mn中的一种,助剂2为Na、K中的一种,通过催化剂载体的制备、活性组分的浸渍以及助剂浸渍,催化剂活化,最终制得催化剂。并且制备方法工艺简单、成本低,适合工业生产。催化剂具有合适的孔道,添加了合适助剂,优化了反应工艺条件,使得催化剂具有活性高、孔道不易堵塞、使用寿命长等特点。应用于间苯二甲腈加氢制备间苯二甲胺,间苯二甲腈转化率达100%,间苯二甲胺选择性达到99%以上。
Description
技术领域
本发明属于有机合成领域,具体涉及一种间苯二甲胺的合成方法以及所使用的加氢催化剂。
背景技术
间苯二甲胺,常温下为无色液体,是一种重要的化工原料,用作环氧树脂常温、低毒的固化剂,还用作光敏塑料、橡胶助剂、聚氨酯树脂及涂料生产原料和有机合成的中间体。
现有技术中主要采用间苯二甲腈(IPN)催化加氢的生产工艺来制备间苯二甲胺,所用催化剂一般为雷尼镍或雷尼钴催化剂。常采用搅拌釜间歇生产,如JP54-41804公开了一种间苯二甲胺的制备方法,该方法使用雷尼镍或雷尼钴催化剂,采用低碳醇与芳烃的混合溶剂,在间歇搅拌釜中,由间苯二甲腈加氢制备间苯二甲胺,实施例中氢压高达11MPa。由间苯二甲腈催化加氢制备间苯二甲胺,也可采用固定床反应器。JP2003-327563公开了一种如间苯二甲腈连续加氢制备芳香族二甲胺的方法,使用含镍或钴的催化剂,反应物间苯二甲腈的浓度为1-10%(重量),在固定床(滴流床)反应器中,连续加氢制备间苯二甲胺。
USP6881864公开了一种间苯二甲胺二级加氢的制备方法,该方法采用含镍和/或钴的非均相催化剂,在两个串联的固定床反应器中,由间苯二甲腈加氢制备间苯二甲胺。该方法的特征在于间苯二甲腈在第一反应器中,转化率达90%以上;然后再进入第二反应器,第二反应器的反应温度比第一反应器高10℃以上,进一步加氢反应至间苯二甲腈转化率达99.5%以上。。此方法需要二段加氢工艺,工艺复杂。
专利CN101955433A公开了一种制备间苯二甲胺的方法,在高压反应釜中,以雷尼镍为催化剂,以芳烃和醇组成的混合物为溶剂,在反应温度为40-120℃,反应压力为2-10MPa条件下,使间苯二甲腈加氢反应20-90min生成间苯二甲胺,采用间歇反应釜的生产工艺,不利于工业化的实施。
CN104148080A公开了以间苯二甲腈溶液和氢气为原料,采用镍/SiO2催化剂,在反应温度为60~160℃,反应压力为6.0~12.0MPa,原料质量空速为0.6~2.0h-1的条件下,间苯二甲腈转化率达98%,间苯二甲胺收率达96%,但是反应压力较高,对反应设备要求较高。
发明内容
本发明所要解决的技术问题是解决现有技术存在的催化剂在固定床连续加氢条件下因聚合、脱胺基等问题,导致活性和选择性不高,并且目前催化反应中使用的溶剂多为多种混合溶剂,不仅成分高,而且后续分离复杂,另外本发明所解决的技术问题是本发明相对应的催化剂的用途。
为解决上述技术问题,本发明采用的催化剂制备技术方案步骤如下:
(1)载体制备过程:配制硝酸铝(或硝酸铝和硝酸镁或乙酸镁混合)溶液加入到带搅拌的反应釜中加热至50℃~80℃,滴加氨水溶液,进行中和沉淀,中和时间为15分钟~30分钟,调节终点pH值7.0~8.0,陈化20分钟~40分钟,固定晶型,过滤后得到滤饼;滤饼烘干,粉碎添加成型助剂和造孔助剂,挤条或压片成型,然后在温度为700℃~900℃下再进行焙烧,得到催化剂载体A;
(2)活性组分的浸渍过程:用硝酸镍和氨水配置镍氨溶液B,将载体A加入到溶液B中,在温度60~80℃,压力-80~-40kPa的条件下,浸渍2~4小时,滤出催化剂,烘干,350~400℃焙烧2~4小时得到半成品催化剂C;
(3)助剂1的浸渍过程:将助剂1的可溶性硝酸盐溶液采用等量浸渍法浸渍到催化剂C上,在350~400℃焙烧2~4小时,得到半成品催化剂D;
(4)助剂2的浸渍过程:将助剂2的碱溶液或者碳酸盐溶液采用等量浸渍法浸渍到催化剂D上,烘干得到催化剂E;
(5)催化剂的活化:将催化剂E在400~500℃下用20%氢气/氮气还原2~4小时,得到催化剂产品。
本发明载体制备的成型助剂为硬脂酸或硬脂酸镁;造孔助剂为田菁粉或羧甲基纤维素。
镁铝催化剂载体的质量组成为MgO为0.3%~48%,其余为Al2O3。
本发明制备的催化剂载体为氧化铝或镁铝混合物,活性元素为Ni,质量含量为18%~40%,助剂1为Co、Mn中的一种,质量含量为0.2%~5%。助剂2为Na、K中的一种,质量含量为0.02%~0.5%。制备的催化剂的比表面80~160m2/g,平均孔径4~8nm,平均孔容0.2~0.6ml/g,其余为载体质量。
本发明所采用的催化剂载体制备方法得到的载体,具有合适的孔结构,适合间苯二甲腈加氢,同时通过添加的助剂1与镍的协同作用,优化了反应工艺条件,降低了反应温度和压力,同时也降低了副反应的发生,助剂2的添加有效控制了催化剂表面的酸碱中心,提高了目标产物的选择性。
本发明的催化剂应用于固定床上间苯二甲腈加氢制备间苯二甲胺,加氢工艺条件为:反应温度70~120℃,压力3~5MPa,液空速0.2~0.6h-1。溶剂为N,N-二甲基环己胺(DMCHA)、N,N-二甲基乙醇胺(DMEA)、甲基乙醇胺(MMEA)中的一种。
通过添加碱性助剂,能够有效抑制反应物及生产物的聚合,提高了反应过程的目标产物的收率。
具体实施方式
下面结合实施例对本发明方法加以详细描述,但本发明不局限于实施例。其中实施例1~7为载体制备,实施例8~17为催化剂制备。
实施例1
称取1000g九水硝酸铝加去离子水配置成1L溶液,倒入带搅拌和加热的3L玻璃反应釜中升温至60℃,滴加18%氨水溶液,进行中和沉淀,中和时间为15分钟,调节终点pH值7.6,陈化40分钟,固定晶型,过滤后得到滤饼;滤饼烘干,粉碎添加成型助剂硬脂酸镁5.2g,造孔助剂羧甲基纤维素1.4g,压成片剂,然后在温度为800℃下再进行焙烧2小时,得到载体Z1。具体载体物化数据见表1。
实施例2
称取800g硝酸铝和200g六水硝酸镁加去离子水配置成1L溶液,倒入带搅拌和加热的3L玻璃反应釜中升温至80℃,滴加15%氨水溶液,进行中和沉淀,中和时间为25分钟,调节终点pH值7.2,陈化20分钟,固定晶型,过滤后得到滤饼;滤饼烘干,粉碎添加成型助剂硬脂酸镁1.9g,造孔助剂田菁粉3.0g,压成片剂,然后在温度为700℃下再进行焙烧4小时,得到载体Z2。具体载体物化数据见表1。
实施例3
称取700g硝酸铝和350g四水乙酸镁加去离子水配置成1L溶液,倒入带搅拌和加热的3L玻璃反应釜中升温至70℃,滴加10%氨水溶液,进行中和沉淀,中和时间为35分钟,调节终点pH值7.8,陈化30分钟,固定晶型,过滤后得到滤饼;滤饼烘干,粉碎添加成型助剂硬脂酸2.0g,造孔助剂羧甲基纤维素3.0g,压成片剂,然后在温度为900℃下再进行焙烧2小时,得到载体Z3。具体载体物化数据见表1。
实施例4
称取900g硝酸铝和100g六水硝酸镁加去离子水配置成1L溶液,倒入带搅拌和加热的3L玻璃反应釜中升温至70℃,滴加15%氨水溶液,进行中和沉淀,中和时间为40分钟,调节终点pH值7.0,陈化30分钟,固定晶型,过滤后得到滤饼;滤饼烘干,粉碎添加成型助剂硬脂酸2.0g,造孔助剂田菁粉4.0g,压成片剂,然后在温度为850℃下再进行焙烧3小时,得到载体Z4。具体载体物化数据见表1。
实施例5
称取900g硝酸铝和100g四水硝酸镁加去离子水配置成1L溶液,倒入带搅拌和加热的3L玻璃反应釜中升温至70℃,滴加14%氨水溶液,进行中和沉淀,中和时间为15分钟,调节终点pH值8.0,陈化30分钟,固定晶型,过滤后得到滤饼;滤饼烘干,粉碎添加成型助剂硬脂酸镁2.0g,造孔助剂田菁粉3.0g,压成片剂,然后在温度为750℃下再进行焙烧3.5小时,得到载体Z5。具体载体物化数据见表1。
实施例6
称取600g硝酸铝和400g四水硝酸镁加去离子水配置成1L溶液,倒入带搅拌和加热的3L玻璃反应釜中升温至65℃,滴加12%氨水溶液,进行中和沉淀,中和时间为25分钟,调节终点pH值7.5,陈化30分钟,固定晶型,过滤后得到滤饼;滤饼烘干,粉碎添加成型助剂硬脂酸镁4.0g,造孔助剂田菁粉3.8g,压成片剂,然后在温度为820℃下再进行焙烧4小时,得到载体Z6。具体载体物化数据见表1。
实施例7
称取600g硝酸铝和400g六水硝酸镁加去离子水配置成1L溶液,倒入带搅拌和加热的3L玻璃反应釜中升温至75℃,滴加15%氨水溶液,进行中和沉淀,中和时间为20分钟,调节终点pH值7.5,陈化30分钟,固定晶型,过滤后得到滤饼;滤饼烘干,粉碎添加成型助剂硬脂酸镁1.6g,造孔助剂田菁粉6.3g,压成片剂,然后在温度为900℃下再进行焙烧4小时,得到载体Z7。具体载体物化数据见表1。
表1不同条件制备载体的物化性能
样品 | 比表面m<sup>2</sup>/g | 孔容ml/g | 平均孔径nm | 氧化铝% | 氧化镁% |
Z1 | 115.7 | 0.44 | 5.5 | 99.74 | 0.26 |
Z2 | 158.9 | 0.23 | 4.2 | 83.10 | 16.90 |
Z3 | 88.8 | 0.56 | 7.3 | 59.39 | 40.61 |
Z4 | 109.6 | 0.38 | 6.5 | 91.75 | 8.25 |
Z5 | 141.3 | 0.29 | 4.5 | 86.73 | 13.27 |
Z6 | 96.8 | 0.51 | 7.0 | 52.22 | 47.78 |
Z7 | 81.4 | 0.58 | 7.7 | 64.91 | 35.09 |
实施例8
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1M的硝酸镍溶液中,使得pH值为9.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z1加入到①的镍氨络合物溶液中,将温度控制在65℃,在有搅动压力为-60kPa下保持4小时,浸渍完成。③分离、干燥,350℃焙烧3小时。(4)将Mn含量为4.2g/L的50mL硝酸锰溶液,均匀喷洒在上述催化剂半成品上,烘干,350℃焙烧4小时。(5)将K含量1.0g/L的碳酸钾溶液50mL均匀喷洒在上述催化剂半成品上,烘干。(6)将催化剂在20vol%氢气/氮气气氛中,450℃保持3小时活化后,得到催化剂成品C1。具体催化剂物化数据见表2。
实施例9
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL0.5M的硝酸镍溶液中,使得pH值为8.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z2加入到①的镍氨络合物溶液中,将温度控制在75℃,在有搅动压力为-80kPa下保持2小时,浸渍完成。③分离、干燥,380℃焙烧2小时。(4)将Mn含量为19.6g/L的50mL硝酸锰溶液,均匀喷洒在上述催化剂半成品上,烘干,400℃焙烧2小时。5○将Na含量为0.4g/L碳酸钠溶液50mL均匀喷洒在催化剂上,烘干。○6将催化剂在20vol%氢气/氮气气氛中,440℃保持4小时活化后,得到催化剂成品C2。具体催化剂物化数据见表2。
实施例10
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1.2M的硝酸镍溶液中,使得pH值为8.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z3加入到①的镍氨络合物溶液中,将温度控制在60℃,在有搅动压力为-40kPa下保持4小时,浸渍完成。③分离、干燥,360℃焙烧2.5小时。④将Co含量为74.4g/L50mL硝酸钴溶液,均匀喷洒在上述催化剂半成品上,烘干,380℃焙烧3小时。(5)将K含量为7.5g/L氢氧化钾溶液50mL均匀喷洒在催化剂上,烘干。(6)将催化剂在20vol%氢气/氮气气氛中,450℃保持2小时活化后,得到催化剂成品C3。具体催化剂物化数据见表2。
实施例11
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1M的硝酸镍溶液中,使得pH值为9.0,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z4加入到①的镍氨络合物溶液中,将温度控制在80℃,在有搅动压力为-50kPa下保持4小时,浸渍完成。③分离、干燥,400℃焙烧2小时。④将Mn含量为94.5g/L硝酸锰溶液50mL,均匀喷洒在上述催化剂半成品上,烘干,350℃焙烧4小时。(5)将Na含量为11.8g/L的氢氧化钠溶液50mL均匀喷洒在催化剂上,烘干。(6)将催化剂在20vol%氢气/氮气气氛中,500℃保持2小时活化后,得到催化剂成品C4。具体催化剂物化数据见表2。
实施例12
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1M的硝酸镍溶液中,使得pH值为9.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z5加入到①的镍氨络合物溶液中,将温度控制在65℃,在有搅动压力为-60kPa下保持4小时,浸渍完成。③分离、干燥,350℃焙烧3小时。④将Mn含量为112.4g/L硝酸锰溶液50mL,均匀喷洒在上述催化剂半成品上,烘干,350℃焙烧4小时。(5)将K含量为9g/L氢氧化钾溶液50mL均匀喷洒在催化剂上,烘干。(6)将催化剂在20vol%氢气/氮气气氛中,450℃保持3小时活化后,得到催化剂成品C5。具体催化剂物化数据见表2。
实施例13
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1.3M的硝酸镍溶液中,使得pH值为8.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z6加入到①的镍氨络合物溶液中,将温度控制在80℃,在有搅动压力为-80kPa下保持4小时,浸渍完成。③分离、干燥,380℃焙烧2小时。④将Mn含量为13.2g/L的50mL硝酸锰溶液,均匀喷洒在上述催化剂半成品上,烘干,400℃焙烧2小时。(5)将K含量为5.3g/L的碳酸钾溶液50mL均匀喷洒在催化剂上,烘干。(6)将催化剂在20vol%氢气/氮气气氛中,440℃保持4小时活化后,得到催化剂成品C6。具体催化剂物化数据见表2。
实施例14
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1M的硝酸镍溶液中,使得pH值为9.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z7加入到①的镍氨络合物溶液中,将温度控制在60℃,在有搅动压力为-40kPa下保持3小时,浸渍完成。③分离、干燥,360℃焙烧2.5小时。④将Mn含量为41.2g/L的50mL硝酸锰溶液,均匀喷洒在上述催化剂半成品上,烘干,380℃焙烧3小时。(5)将K含量为4.2g/L的氢氧化钾溶液50mL均匀喷洒在催化剂上,烘干。(6)将催化剂在20vol%氢气/氮气气氛中,450℃保持2小时活化后,得到催化剂成品C7。具体催化剂物化数据见表2。
实施例15
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1M的硝酸镍溶液中,使得pH值为9.0,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z4加入到①的镍氨络合物溶液中,将温度控制在80℃,在有搅动压力为-70kPa下保持3小时,浸渍完成。③分离、干燥,480℃焙烧2小时。(4)将Co含量为79g/L的50mL硝酸钴溶液,均匀喷洒在上述催化剂半成品上,烘干,400℃焙烧4小时。(5)将K含量为6.8g/L的氢氧化钾溶液50mL均匀喷洒在催化剂上,烘干。(6)将催化剂在20vol%氢气/氮气气氛中,450℃保持2小时活化后,得到催化剂成品C8。具体催化剂物化数据见表2。
实施例16
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1M的硝酸镍溶液中,使得pH值为9.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z5加入到①的镍氨络合物溶液中,将温度控制在80℃,在有搅动压力为-50kPa下保持3小时,浸渍完成。③分离、干燥,400℃焙烧2.5小时。(4)将Co含量为72.6g/L的50mL硝酸钴溶液,均匀喷洒在上述催化剂半成品上,烘干,350℃焙烧4小时。(5)将Na含量为8.8g/L的碳酸钠溶液50mL均匀喷洒在催化剂上,烘干。(6)将催化剂在20vol%氢气/氮气气氛中,480℃保持4小时活化后,得到催化剂成品C9。具体催化剂物化数据见表2。
对比实施例1
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1.3M的硝酸镍溶液中,使得pH值为8.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z6加入到①的镍氨络合物溶液中,将温度控制在80℃,在有搅动压力为-80kPa下保持4小时,浸渍完成。③分离、干燥,380℃焙烧2小时。(4)将催化剂在20vol%氢气/氮气气氛中,440℃保持4小时活化后,得到催化剂成品D1。具体催化剂物化数据见表2。
对比实施例2
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1.3M的硝酸镍溶液中,使得pH值为8.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z6加入到①的镍氨络合物溶液中,将温度控制在80℃,在有搅动压力为-80kPa下保持4小时,浸渍完成。③分离、干燥,380℃焙烧2小时。(4)将Mn含量为13.2g/L的50mL硝酸锰溶液,均匀喷洒在上述催化剂半成品上,烘干,400℃焙烧2小时。(5)将催化剂在20vol%氢气/氮气气氛中,440℃保持4小时活化后,得到催化剂成品D2。具体催化剂物化数据见表2。
对比实施例3
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1.3M的硝酸镍溶液中,使得pH值为8.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z6加入到①的镍氨络合物溶液中,将温度控制在80℃,在有搅动压力为-80kPa下保持4小时,浸渍完成。③分离、干燥,380℃焙烧2小时。(4)将K含量为5.3g/L的碳酸钾溶液50mL均匀喷洒在催化剂上,烘干。(5)将催化剂在20vol%氢气/氮气气氛中,440℃保持4小时活化后,得到催化剂成品D3。具体催化剂物化数据见表2。
对比实施例4
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①硝酸镍配置成1000mL1.3M的硝酸镍溶液。②浸渍:将100g载体Z6加入到①的镍溶液中,将温度控制在80℃,在有搅动压力为-80kPa下保持4小时,浸渍完成。③分离、干燥,380℃焙烧2小时。(4)将Mn含量为13.2g/L的50mL硝酸锰溶液,均匀喷洒在上述催化剂半成品上,烘干,400℃焙烧2小时。(5)将K含量为5.3g/L的碳酸钾溶液50mL均匀喷洒在催化剂上,烘干。(6)将催化剂在20vol%氢气/氮气气氛中,440℃保持4小时活化后,得到催化剂成品D4。具体催化剂物化数据见表2。
对比实施例5
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1.3M的硝酸镍溶液中,使得pH值为8.5,配制成澄清的镍氨络合物溶液。②浸渍:将100g市售球形氧化铝载体(江苏三剂提供)加入到①的镍氨络合物溶液中,将温度控制在80℃,在有搅动压力为-80kPa下保持4小时,浸渍完成。③分离、干燥,380℃焙烧2小时。(4)将Mn含量为13.2g/L的50mL硝酸锰溶液,均匀喷洒在上述催化剂半成品上,烘干,400℃焙烧2小时。(5)将K含量为5.3g/L的碳酸钾溶液50mL均匀喷洒在催化剂上,烘干。(6)将催化剂在20vol%氢气/氮气气氛中,440℃保持4小时活化后,得到催化剂成品C6。具体催化剂物化数据见表2。
对比实施例6
催化剂制备是在密闭2L玻璃反应釜中,按以下几步进行实施。①配制镍氨液:将氨水溶液缓慢滴加到1000mL1M的硝酸镍溶液中,使得pH值为9.0,配制成澄清的镍氨络合物溶液。②浸渍:将100g载体Z4加入到①的镍氨络合物溶液中,将温度控制在80℃,在有搅动压力为-70kPa下保持3小时,浸渍完成。③分离、干燥,480℃焙烧2小时。(4)将Co含量为85.8g/L的50mL硝酸钴溶液,均匀喷洒在上述催化剂半成品上,烘干,400℃焙烧4小时。(5)将催化剂在20vol%氢气/氮气气氛中,450℃保持2小时活化后,得到催化剂成品D6。具体催化剂物化数据见表2。
表2催化剂的物化性能
应用实施例
将实施例8~16得到催化剂产品,在规格¢30×3mm固定床反应器中进行催化加氢反应,催化剂装量为40ml,氢气通过质量流量计,间苯二甲腈溶液(该溶液的质量分数为30%)通过计量泵与氢气混合后预热进入加氢反应器进行催化加氢(氢气与间苯二甲腈的摩尔比为8),产物经冷凝分离后,氢气放空,液体产品收集进行分析,加氢前后产品采用气相色谱进行分析,计算出转化率和选择性。具体催化剂及工艺条件及测试结果见表3。
表3催化剂评价结果
从表中数据可看出,制备的一系列催化剂具有较高的转化率,同时具有较高的产品选择性,工业应用前景很好。
Claims (5)
1.一种用于制备间苯二甲胺的催化剂的应用,其特征在于,将催化剂应用于固定床上,将间苯二甲腈加氢制备间苯二甲胺,加氢工艺条件为:反应温度70~120℃,压力3~5MPa,液空速0.2~0.6h-1;
催化剂包括载体为氧化铝或镁铝混合物,活性元素为Ni,质量含量为18%~40%,助剂1为Co、Mn中的一种,质量含量为0.2%~5%,助剂2为Na、K中的一种,质量含量为0.02%~0.5%;其中质量含量是相应组分占催化剂总质量的百分数;
所述催化剂的制备包括以下步骤:
(1)载体制备过程:配制可溶性铝盐或可溶性铝盐和可溶性镁盐溶液加入反应釜中,升温至50℃~80℃,滴加氨水溶液,进行中和沉淀,中和时间为15分钟~30分钟,调节终点pH值7.0~8.0,陈化20分钟~40分钟,固定晶型,过滤后得到滤饼;滤饼烘干,粉碎后添加成型助剂和造孔助剂,挤条或压片成型,然后在温度为700℃~900℃下再进行焙烧,得到催化剂载体A;
(2)活性组分的浸渍过程:用硝酸镍和氨水配置镍氨溶液B,将载体A加入到溶液B中,在温度60~80℃,压力-80~-40kPa的条件下,浸渍2~4小时,滤出催化剂,烘干,在350~400℃焙烧2~4小时得到半成品催化剂C;
(3)助剂1的浸渍过程:将助剂1的可溶性硝酸盐溶液采用等量浸渍法浸渍到催化剂C上,在350~400℃焙烧2~4小时,得到半成品催化剂D;
(4)助剂2的浸渍过程:将助剂2的碱溶液或者碳酸盐溶液采用等量浸渍法浸渍到催化剂D上,烘干得到催化剂E;
(5)催化剂的活化:将催化剂E在400~500℃下用体积分数20%氢气/氮气还原2~4小时,得到催化剂产品。
2.根据权利要求1所述的用于制备间苯二甲胺的催化剂的应用,其特征在于,所述制备的催化剂的比表面80~160m2/g,平均孔径4~8nm,平均孔容0.2~0.6ml/g。
3.根据权利要求1所述的用于制备间苯二甲胺的催化剂的应用,其特征在于所述载体制备的成型助剂为硬脂酸或硬脂酸镁;造孔助剂为田菁粉或羧甲基纤维素。
4.根据权利要求1所述的用于制备间苯二甲胺的催化剂的应用,其特征在于,所述制备的镁铝载体的质量组成为MgO为0.3%~48%,其余为Al2O3。
5.根据权利要求1所述的用于制备间苯二甲胺的催化剂的应用,其特征在于:间苯二甲腈加氢所用的溶剂为N,N-二甲基环己胺、N,N-二甲基乙醇胺、甲基乙醇胺中的一种。
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