CN114534733A - 一种硝基化合物加氢制芳胺催化剂的制备方法 - Google Patents
一种硝基化合物加氢制芳胺催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 47
- 150000002828 nitro derivatives Chemical class 0.000 title claims abstract description 16
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000011273 tar residue Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 3
- 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 3
- 150000003057 platinum Chemical class 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- CWDUIOHBERXKIX-UHFFFAOYSA-K lanthanum(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] CWDUIOHBERXKIX-UHFFFAOYSA-K 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 15
- 239000011269 tar Substances 0.000 abstract description 11
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 3
- 150000001718 carbodiimides Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
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- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- -1 and preferably Chemical compound 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000002641 tar oil Substances 0.000 description 1
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Classifications
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- 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
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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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- 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
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- Y02P20/584—Recycling of catalysts
Abstract
本发明提供了一种硝基化合物液相加氢制芳胺催化剂的制备方法。所述催化剂采用浸渍法制备,包括制备载体、负载、还原和焙烧活化步骤。该方法利用TDI焦油残渣制备催化剂载体,实现了TDI焦油的资源化利用,在回收TDI焦油残渣中加氢活性金属的同时,利用TDI焦油残渣中N元素与加氢活性金属的协同作用增强了催化剂的加氢活性,提升了加氢催化剂的活性。本发明还提供了采用该催化剂加氢制备苯胺的用途,催化剂的反应性能优良且具有良好的稳定性。
Description
技术领域
本发明属于催化剂领域,具体涉及一种硝基化合物加氢制芳胺催化剂的制备方法。
背景技术
芳胺是合成众多精细化学品的重要中间体,用途广泛,主要用于制造染料、药物、树脂等,例如苯胺(AN)、甲苯二胺(TDA)等,随着二苯基甲基二异氰酸酯(MDI)、甲基二异氰酸酯等的快速发展,芳胺需求量日益增长。
硝基化合物催化加氢法是目前工业生产芳胺的主要方法,主要包括气相加氢技术和液相加氢技术两种。气相加氢技术需要大量的循环氢气,对循环氢气压缩机的能力要求较高,反应温度不容易控制,设备较为复杂,占地较大。液相加氢技术能够克服上述缺点,生产技术成熟,另外具有能耗低、装置生产能力大和成本低等优点。硝基化合物液相加氢催化剂主要有贵金属催化剂和镍系催化剂两种,贵金属催化剂主要活性组分为铂系金属,该类催化剂催化活性高,选择型好,例如专利CN103551142A公开的Pt-C催化剂等;镍系催化剂主要为负载型镍催化剂及骨架镍催化剂,上述催化剂在芳胺工业化生产中均有应用,体系较为成熟。
TDI在生产过程中会产生焦油残渣,主要成分为大分子CDI(碳化二亚胺)、脲类物质;另外由于甲苯硝化和二硝基甲苯催化加氢过程中会有部分金属引入至TDI焦油中(Pt、Pd、Ni、Fe,主要来自催化剂夹带和腐蚀等金属流失,其中Pt、Pd、Ni为加氢活性金属),这部分活性金属最终随TDI焦油残渣排出。TDI焦油残渣为致密固体,目前多破碎后,采用焚烧的方式处理,造成资源浪费,且产生大量氮氧化物;专利CN201520845024.7提供了一种TDI焦油残渣资源化利用回收TDA的方法,利用高温高压水解的方法使焦油残渣中的脲及CDI向TDA转化,从而回收TDA,但该方法在生产过程中产生了大量难处理的废水。专利CN201910304883.8提供了一种利用TDI焦油残渣制备液体燃料的方法,但其制备过程较为复杂,焦油中大量的N元素作为液体燃料焚烧也会产生大量NOx。专利CN201910304878.7提供了一种TDI焦油残渣中贵金属Pt元素的一种回收方法,其工艺流程较长,回收经济性不高。
发明内容
本发明的目的在于针对现有技术中的不足,提供一种硝基化合物液相加氢制芳胺催化剂的制备方法,该方法可以制备出高活性、高选择性的加氢催化剂。该催化剂能够实现TDI生产工艺中TDI焦油残渣的资源化利用,回收TDI焦油残渣中的加氢活性金属,同时利用焦油残渣中的N元素与加氢活性金属的协同作用强化催化剂活性。
为实现上述发明目的和达到上述技术效果,本发明技术方案如下:
一种硝基苯加氢制苯胺的加氢催化剂制备方法,该方法包含如下步骤:
S1:制备载体,用TDI焦油残渣制备多孔碳载体;
S2:负载,用络合剂、可溶性金属盐和可溶性金属盐助剂浸渍多孔碳载体;
S3:还原,还原S2制备的催化剂中间体;
S4:活化,焙烧活化S3制备的催化剂中间体,得到目标催化剂。
本发明中TDI焦油残渣中含有Ni、Pd、Pt、Fe元素,其来自于制备TDI的甲苯硝化过程和二硝基甲苯加氢过程,TDI焦油中所含的金属元素可继续用于催化加氢反应,且可以同时利用焦油残渣中的N元素与加氢活性金属的协同作用强化催化剂活性。S2中通过使用金属可溶性盐与络合剂形成金属的络合物前驱体进行活性组分负载,同时增加负载La2O3和Fe助剂,避免了载体表面金属晶粒在干燥、焙烧过程中的迁移、凝聚,同时提高催化剂的寿命和活性。S4中控制制备的催化剂粒径,不但能够有效消除内扩散的影响,还能保证催化剂的过滤性能,同时控制负载在载体上金属晶粒的粒径,还可以有效地提高催化剂的活性。
本发明中,所述S1中将TDI焦油残渣进行研磨、焙烧处理;优选地,研磨后TDI焦油残渣平均粒径5-15μm;优选地,焙烧温度350-600℃,焙烧时间0.5-8h,焙烧环境为氮气环境。在焙烧过程中,TDI焦油残渣不断生成NH3和CO2气体,气体的生成在焦油颗粒内部形成多孔结构,焙烧后TDI焦油残渣中N元素含量控制0.1wt%-1wt%,优选0.2wt%-0.5wt%。
本发明中,所述S2中将络合剂、可溶性金属盐和可溶性金属盐助剂先加入水中,调节pH值,溶解后,加入S1制备的多孔碳载体,超声处理浸渍,干燥;优选地,滴加氨水调节溶液pH值为8-12,优选氨水浓度为10wt%-50wt%;优选地,浸渍温度为25-35℃,超声频率为28-40KHz,浸渍时间为8-12h;优选地,干燥温度100-150℃,干燥时间12-24h。
本发明中,所述S2中络合剂为乙二胺四乙酸(EDTA)、亚氨基二乙酸(IDA)、反式1,2环己二胺四乙酸(CrDTA)和醋酸(AC)中的一种或多种,优选乙二胺四乙酸。
本发明中,所述可溶性金属盐为可溶性镍盐、可溶性钯盐、可溶性铂盐、可溶性铂酸、可溶性铂盐和可溶性铂酸及其水合物中的一种或多种,优选自硝酸镍、六水合硝酸镍、氯化钯和氯铂酸中的一种或多种。
本发明中,所述可溶性金属盐助剂同时包含可溶性镧盐或其水合物,以及可溶性铁盐或其水合物;优选地,所述可溶性镧盐或其水合物选自六水合硝酸镧、氯化镧和六水合氯化镧中的一种或多种,优选六水合硝酸镧;优选地,所述可溶性铁盐或其水合物选自氯化铁、硝酸铁和九水合硝酸铁中的一种或多种,优选九水合硝酸铁;优选地,所述可溶性金属盐,按纯金属计,载体与加氢活性金属加入量比例为1:(0-2),载体与镧加入量比例为1:(0.01-0.14),载体与铁加入量比例为1:(0.03-0.26)。
本发明中,所述S3中优选用水合肼还原;优选地,所述水合肼配置为溶液,溶液浓度为50wt%-60wt%;优选地,所述还原的时间为2-5h。
本发明中,所述S3中还原后进行过滤、洗涤。
本发明中,所述S4中需先进行干燥,优选真空环境,干燥温度60-80℃,干燥时间10-12h。
本发明中,S4中所述焙烧环境为氮气环境,焙烧温度300-350℃,焙烧时间3-4h。
本发明的另一目的在于提供一种负载催化剂。
一种负载催化剂,采用上述方法制备,所述负载催化剂中加氢活性金属含量为加氢活性金属含量为2wt%-60wt%,优选5wt%-32wt%;La2O3为1wt%-5wt%,优选3wt%-4wt%;Fe为1wt%-8wt%,优选3wt%-5wt%;载体为30wt%-87wt%,优选60wt%-86wt%;以负载催化剂总质量计;优选地,所述加氢活性金属为镍,或钯、铂中的一种或多种。
本发明中,所述催化剂平均粒径为5-15μm,优选10-12μm。
本发明中,所述催化剂中加氢活性组分晶粒的粒径为4-10nm。
本发明中,所述催化剂中多孔碳载体的比表面积为300-600m2/g。
本发明的又一目的在于提供一种负载催化剂的用途。
一种负载催化剂的用途,所述催化剂用于硝基化合物加氢制芳胺,优选用于硝基化合物液相加氢制芳胺,更优选用于硝基化合物液相加氢制苯胺或甲苯二胺。
与现有技术相比,本发明具有以下积极效果:
1、载体采用TDI焦油作为催化剂原料,利用TDI焦油残渣中的加氢活性金属,同时利用焦油残渣中的N元素与加氢活性金属的协同作用强化催化剂活性,实现了TDI生产工艺中TDI焦油残渣的资源化利用。
2、通过使用金属可溶性盐与络合剂形成金属的络合物前驱体进行活性组分负载,同时增加负载La2O3和Fe助剂,避免了载体表面金属晶粒在干燥、焙烧过程中的迁移、凝聚,同时提高催化剂的活性。
3、制备的催化剂粒径为8-15μm,不但能够有效消除内扩散的影响,还能保证催化剂的过滤性能;负载在载体上金属晶粒的粒径控制在4-10nm,有效地提高了催化剂的活性。
具体实施方式
下面的实施例是对本发明所提供的技术方案予以进一步地说明,但本发明不限于所列出的实施例,还包括在本发明权利范围内其它任何公知的改变。
实例中制备催化剂所用化学药品均来自国药化学试剂有限公司,分析纯;加氢实验所用化学药品来自万华化学生产装置,TDI焦油来自万华化学原料生产生产装置,由于上游生产工艺不同,TDI焦油中金属种类及含量不同:
焦油残渣A组成为N19.47%,C 69.56%,H 4.13%,Ni 0.07%,O 6.77%;
焦油残渣B组成为N19.37%,C 69.87%,H 4.19%,Ni 0.14%,O 5.87%;
焦油残渣C组成为N18.35%,C 68.47%,H 5.19%,Pt 0.037%,O 7.95%;
焦油残渣D组成为N19.35%,C 71.47%,H 4.19%,Pd 0.036%,O 4.95%;
焦油残渣E组成为N18.35%,C 65.47%,H 4.19%,Pd 3.14%,Pt 0.36%,O8.85%。
催化剂制备过程中干燥过程在上海精奇DZF-6020真空干燥箱内部进行,焙烧过程在上海精钊1800型真空烧结炉内进行。
产品中的有机物含量由安捷伦公司7890A气相色谱测定,采用FID检测器和DB-5色谱柱(30m×0.53mm×1.5μm),进样口温度280℃,检测器温度280℃,载气(氮气)流速3ml/min,空气流速400ml/min,氢气流速40ml/min。
转化率的计算方法如下:
转化率=(硝基化合物进料质量-产物中硝基化合物残余质量)/硝基化学物进料质量
催化剂表征:比表面积测试,用日本BEL公司的BELSORP-Ⅱ型吸附仪对催化剂进行N2吸附-脱附测试,样品首先在200℃下真空脱水3h,然后再开展相关测试,运用BET方程计算比表面积,并使用BJH模型计算催化剂的孔容;镍晶粒的粒径,通过XRD测得,XRD使用日本Rigaku公司的SarmtLab衍射仪进行检测,CuKα靶(λ=0.154nm),管电压40kV,管电流100mA,扫描步长0.02°,扫描速率0.05s/step,10°-80°扫描;催化剂粒径分析,在德国新帕泰克公司的HELOS 1BF型粒度仪上进行,采用荷兰Philips公司的PW2424型X射线荧光光谱仪(XRF)对催化剂进行表征,将催化剂置于样品室,启动扫描开关,绘制记录X射线荧光光谱图,系统软件根据衍射角2θ和衍射峰强度Ι,对样品进行定性和定量分析。
实施例1
称取300g TDI焦油残渣A,研磨处理,研磨后焦油残渣平均粒径11μm,将研磨后焦油残渣氮气环境下380℃焙烧热解处理2h(焙烧过程产生NH3及CO2),降温得到多孔碳载体,载体N元素含量0.3%,Ni元素含量0.3%。
称取0.80g La(NO3)3·6H2O,1.43g Fe(NO3)3·9H2O,19.82g Ni(NO3)2·6H2O,19.91g EDTA于300ml去离子水中,剧烈搅拌下将30wt%的氨水缓慢滴加至上述溶液中,调节pH值为8,加入5.5g载体粉末,在25℃下以28KHz超声处理12h,然后在120℃条件下干燥12h。得到固体粉末,在50wt%水合肼水溶液中回流还原2小时,将还原后的催化剂过滤,用去离子水洗至中性,300℃氮气环境下焙烧4h,得到催化剂A。催化剂A的Ni含量为40wt%,La2O3含量为3wt%,Fe含量为2wt%,载体含量55%。所制得催化剂活性组分镍晶粒的粒径为5nm;催化剂平均粒径为11μm;载体的比表面积为300m2/g。
实施例2
称取300g TDI焦油残渣B,将研磨后焦油残渣氮气环境下450℃焙烧热解处理4h(焙烧过程产生NH3及CO2),降温得到多孔碳载体,载体N元素含量0.1%,Ni元素含量0.1%。
称取0.21g LaCl3·6H2O,0.29g FeCl3,2.21g NiCl2,4.98g EDTA于200ml去离子水中,剧烈搅拌下将50wt%的氨水缓慢滴加至上述溶液中,调节pH值为8.5,加入8.8g载体粉末,在35℃下以40KHz超声处理10h,在150℃条件下干燥24h。得到固体粉末,并在60wt%水合肼水溶液中回流还原3小时,将还原后的催化剂过滤,用去离子水洗至中性,300℃氮气环境下焙烧4h,得到催化剂B。催化剂B的Ni含量为10wt%,La2O3含量为1wt%,Fe含量为1wt%,载体含量为88wt%。所制得催化剂活性组分镍晶粒的粒径为4nm;催化剂平均粒径为8μm;载体比表面积为450m2/g。
实施例3
称取300g TDI焦油残渣C,研磨处理,研磨后焦油残渣平均粒径15μm,将研磨后焦油残渣氮气环境下600℃焙烧热解处理0.5h(焙烧过程产生NH3及CO2),降温得到多孔碳载体,载体N元素含量1%,Pt元素含量0.05%。
称取0.133g La(NO3)3·6H2O,3.61g Fe(NO3)3·9H2O,0.33g PdCl2,0.80gH2PtCl6·6H2O,1.55g CrDTA于300ml去离子水中,剧烈搅拌下将30wt%的氨水缓慢滴加至上述溶液中,调节pH值为8,加入8.9g载体粉末,在30℃下以34KHz超声处理12h,在120℃条件下干燥12h。得到固体粉末,并在55wt%水合肼水溶液中回流还原2小时,将还原后的催化剂过滤,用去离子水洗至中性,350℃氮气环境下焙烧3h,得到催化剂C。催化剂C的Pd含量为2.0wt%,Pt含量为3.0wt%,La2O3含量为1.0wt%,Fe含量为5.0wt%,C含量为89wt%。所制得催化剂活性组分镍晶粒的粒径为10nm;催化剂平均粒径为15μm;载体的比表面积为300m2/g。
实施例4
称取300g TDI焦油残渣D,研磨处理,研磨后焦油残渣平均粒径5μm,将研磨后焦油残渣置于固定床反应器或马弗炉内350℃焙烧热解处理8h(焙烧过程产生NH3及CO2),降温得到多孔碳载体,载体N元素含量0.6%,Pd元素含量0.05%。
称取0.21g LaCl3·6H2O,2.89g Fe(NO3)3·9H2O,0.75g PdCl2,0.133g H2PtCl6·6H2O,0.59g IDA于200ml去离子水中,剧烈搅拌下将10wt%的氨水缓慢滴加至上述溶液中,调节pH值为12,加入8.9g载体粉末,在25℃下以30KHz超声处理8h,在100℃条件下干燥18h。得到固体粉末,并在55wt%水合肼水溶液中回流还原5小时,将还原后的催化剂过滤,用去离子水洗至中性,在80℃条件下真空干燥10h,330℃氮气环境下焙烧3h,得到催化剂D。催化剂D的Pd含量为4.5wt%,Pt含量为0.5wt%,La2O3含量为2.0wt%,Fe含量为4.0wt%,C含量为89wt%。所制得催化剂活性组分镍晶粒的粒径为10nm;催化剂平均粒径为5μm;载体的比表面积为320m2/g。
实施例5
称取300g TDI焦油残渣E,研磨处理,研磨后焦油残渣平均粒径5μm,将研磨后焦油残渣置于固定床反应器或马弗炉内350℃焙烧热解处理8h(焙烧过程产生NH3及CO2),降温得到多孔碳载体,载体N元素含量0.6%,Pd元素含量4.8%,Pt元素含量0.54%。
称取0.21g LaCl3·6H2O,2.89g Fe(NO3)3·9H2O,0.59g IDA于200ml去离子水中,剧烈搅拌下将10wt%的氨水缓慢滴加至上述溶液中,调节pH值为12,加入9.4g载体粉末,在25℃下以30KHz超声处理8h,在100℃条件下干燥18h。得到固体粉末,并在55wt%水合肼水溶液中回流还原5小时,将还原后的催化剂过滤,用去离子水洗至中性,在80℃条件下真空干燥10h,330℃氮气环境下焙烧3h,得到催化剂E。催化剂E的Pd含量为4.5wt%,Pt含量为0.5wt%,La2O3含量为2.0wt%,Fe含量为4.0wt%,C含量为89wt%。所制得催化剂活性组分镍晶粒的粒径为6nm;催化剂平均粒径为7μm;载体的比表面积为380m2/g。
实施例6
称取120g甲苯二胺、80g去离子水、1.6g催化剂混合于烧杯中,搅拌均匀后加入体积为1L的连续加氢反应釜中,设置反应压力0.85MPa,反应温度135℃,搅拌转速1000r/min,二硝基甲苯进料量为0.83ml/min(停留时间4h),氢气进料量为0.33NL/min,反应8h后,反应产物分析结果见表1。
表1加氢反应主要产物和副产物
从表中可以看出所制备的催化剂转化率均达到了100%,产物中焦油含量均维持较低水平,催化剂具有良好的活性。
实施例7
称取350g苯胺、150g去离子水、8.5g催化剂A-C混合于烧杯中,搅拌均匀后加入体积为1L的连续加氢反应釜中,设置反应压力常压,反应温度100℃,,硝基苯进料量为8.4ml/min(停留时间1h),氢气进料量为5.8NL/min,连续反应8h后,反应产物分析结果见表2。
表2加氢反应主要产物和主要副产物
项目 | 转化率,% | 苯胺,% | 环己胺 | 焦油 |
催化剂A | 99.8 | 99.5 | 1523ppm | 0.14% |
催化剂B | 99.9 | 99.7 | 1350ppm | 0.10% |
催化剂C | 99.9 | 99.4 | 2005ppm | 0.26% |
从表中可以看出所制备的催化剂转化率近100%,产物中焦油含量均维持较低水平,催化剂具有良好的活性。
对比例1
参照专利CN108620084A中的实施例1,其制备的催化剂比表面积在63.4m2/g,比表面积较小,利用该催化剂进行硝基苯加氢,硝基苯质量空速1h-1,反应温度100℃,常压下,氢气流量250ml/min下,硝基苯转化率为83.4%,催化剂活性较差。
通过上述实施例和对比例的比较可以发现,本专利制备的催化剂表面积大,活性高,并且实现了TDI焦油的资源化利用,优势显著。
Claims (9)
1.一种硝基化合物加氢制苯胺的加氢催化剂制备方法,其特征在于,该方法包含如下步骤:
S1:制备载体,用TDI焦油残渣制备多孔碳载体;
S2:负载,用络合剂、可溶性金属盐和可溶性金属盐助剂浸渍多孔碳载体;
S3:还原,还原S2制备的催化剂中间体;
S4:活化,焙烧活化S3制备的催化剂中间体,得到目标催化剂。
2.根据权利要求1所述的制备方法,其特征在于,所述S1中将TDI焦油残渣进行研磨、焙烧处理;
优选地,研磨后TDI焦油残渣平均粒径5-15μm;
优选地,焙烧温度350-600℃,焙烧时间0.5-8h,焙烧环境为氮气环境。
3.根据权利要求1所述的制备方法,其特征在于,所述S2中将络合剂、可溶性金属盐和可溶性金属盐助剂先加入水中,调节pH值,溶解后,加入S1制备的多孔碳载体,超声处理浸渍,干燥;
优选地,滴加氨水调节溶液pH值为8-12,优选氨水浓度为10wt%-50wt%;
优选地,浸渍温度为25-35℃,超声频率为28-40KHz,浸渍时间为8-12h;
优选地,干燥温度100-150℃,干燥时间12-24h。
4.根据权利要求1或3所述的制备方法,其特征在于,所述S2中络合剂为乙二胺四乙酸、亚氨基二乙酸、反式1,2环己二胺四乙酸和醋酸中的一种或多种,优选乙二胺四乙酸;
和/或,所述可溶性金属盐为可溶性镍盐、可溶性钯盐、可溶性铂盐、可溶性铂酸及其水合物中的一种或多种,优选自硝酸镍、六水合硝酸镍、氯化钯和氯铂酸及其水合物中的一种或多种;
和/或,所述可溶性金属盐助剂同时包含可溶性镧盐或其水合物,以及可溶性铁盐或其水合物;
优选地,所述可溶性镧盐或其水合物选自六水合硝酸镧、氯化镧和六水合氯化镧中的一种或多种,优选六水合硝酸镧;
优选地,所述可溶性铁盐或其水合物选自氯化铁、硝酸铁和九水合硝酸铁中的一种或多种,优选九水合硝酸铁;
优选地,所述可溶性金属盐,按纯金属计,载体与加氢活性金属加入量比例为1:(0-2),载体与镧加入量比例为1:(0.01-0.14),载体与铁加入量比例为1:(0.03-0.26)。
5.根据权利要求1所述的制备方法,其特征在于,所述S3中还原剂为水合肼和/或氢气,优选水合肼;
优选地,所述水合肼配置为溶液,溶液浓度为50wt%-60wt%;
优选地,所述还原的时间为2-5h;
和/或,还原后进行过滤、洗涤。
6.根据权利要求1所述的制备方法,其特征在于,所述焙烧环境为氮气环境,焙烧温度300-350℃,焙烧时间3-4h。
7.一种负载催化剂,采用权利要求1-6中任一项所述方法制备,其特征在于,所述负载催化剂中加氢活性金属含量为2wt%-60wt%,优选5wt%-32wt%;La2O3为1wt%-5wt%,优选3wt%-4wt%;Fe为1wt%-8wt%,优选3wt%-5wt%;载体为30wt%-87wt%,优选60wt%-86wt%;以负载催化剂总质量计;
优选地,所述加氢活性金属为镍、铂和钯中的一种或多种。
8.根据权利要求7所述的催化剂,其特征在于,所述催化剂平均粒径为5-15μm,优选10-12μm;
和/或,所述催化剂中加氢活性组分晶粒的粒径为4-10nm;
和/或,所述催化剂中多孔碳载体的比表面积为300-600m2/g。
9.一种负载催化剂的用途,权利要求1-6中任一项所述方法制备的催化剂、或权利要求7或8所述催化剂的用途,该催化剂用于硝基化合物加氢制芳胺,优选用于硝基化合物液相加氢制芳胺,更优选用于硝基化合物液相加氢制苯胺或甲苯二胺。
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