CN106238099B - 1,5-二硝基萘加氢催化剂的制备方法及应用 - Google Patents
1,5-二硝基萘加氢催化剂的制备方法及应用 Download PDFInfo
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- CN106238099B CN106238099B CN201610704781.1A CN201610704781A CN106238099B CN 106238099 B CN106238099 B CN 106238099B CN 201610704781 A CN201610704781 A CN 201610704781A CN 106238099 B CN106238099 B CN 106238099B
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- catalyst
- phenolic resin
- diaminonaphthalene
- dinitronaphthalene
- reaction
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- ZUTCJXFCHHDFJS-UHFFFAOYSA-N 1,5-dinitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=CC=CC2=C1[N+]([O-])=O ZUTCJXFCHHDFJS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 6
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000005011 phenolic resin Substances 0.000 claims abstract description 42
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical group O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- XNKFCDGEFCOQOM-UHFFFAOYSA-N 1,2-dinitronaphthalene Chemical compound C1=CC=CC2=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C21 XNKFCDGEFCOQOM-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- -1 diformazan fluosite Chemical compound 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
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- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
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- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 claims 1
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- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 11
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 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 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
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- WRTGYBLJWHMHEP-UHFFFAOYSA-N CO.[N+](=O)([O-])C1=CC=CC2=C(C=CC=C12)[N+](=O)[O-] Chemical compound CO.[N+](=O)([O-])C1=CC=CC2=C(C=CC=C12)[N+](=O)[O-] WRTGYBLJWHMHEP-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- 159000000021 acetate salts Chemical class 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940035422 diphenylamine Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- NFMHSPWHNQRFNR-UHFFFAOYSA-N hyponitrous acid Chemical class ON=NO NFMHSPWHNQRFNR-UHFFFAOYSA-N 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
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- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了1,5‑二硝基萘加氢催化剂的制备方法及应用,涉及1,5‑二氨基萘的合成技术领域。催化剂制备方法以酚醛树脂为前体,添加固化剂,负载第Ⅷ族金属元素的一种或多种,一步法制得具有纳米孔径的酚醛树脂基催化剂。涉及的连续合成工艺为:在填有上述催化剂的固定床床层上,以1,5‑二硝基萘为反应原料,以单质氢为还原剂,在温度为40~110℃,氢气压力为0.3~3 MPa,停留时间为0.1~5 min的条件下进行催化还原反应,高效转化合成1,5‑二氨基萘产品。依本发明方法制备的催化剂具有制备过程简单、催化活性高、抗失活能力强、使用安全性高、经济合理的特点。
Description
技术领域
本发明涉及1,5-二氨基萘的合成技术领域,具体的说是一种1,5-二硝基萘加氢催化剂的制备方法及将该催化剂应用于连续固定床催化加氢合成1,5-二氨基萘的工艺。
背景技术
二氨基萘有多种同分异构体结构,不同的二氨基萘在有机合成、颜料、染料、高级聚氨酯材料等传统化工及化工新技术领域都有着不可替代的作用。另外1,5-二氨基萘还可作为被禁用的联苯胺类染料的优良替代品及1,5-萘二异氰酸酯的主要原料,具有广阔的应用前景。
目前,1,5-二氨基萘的合成工艺路线主要有以下几种:
①以铁粉作为还原介质的铁粉还原法
铁粉还原法的反应方程式为:
CN1100403A提出将二硝基萘、铁粉、酒精、水、冰醋酸、火碱、亚硫酸氢钠等按一定比例混合,经搅拌、反应、后处理等一系列单元操作生产1,5-二氨基萘的方法。该方法是目前工业界生产1,5-二氨基萘的最主要方法,具有成本低、产品质量高的优点。此方法的不足之处是:间歇操作,人工劳动强度大,对设备腐烛、磨损严重,操作维护费用高,生成的铁泥对环境造成很大污染、铁泥的沉降后处理较麻烦。
② 电化学还原制备1,5-二氨基萘
电化学还原法的反应方程式为:
该方法通过恒电位电解发生还原反应,使1,5-二硝基萘经亚硝基、羟胺类中间体,最终还原为1,5-二氨基萘。该工艺避免了有机废酸和其它废料的处理,但该方法设备较复杂,溶液中底物浓度很低,废水产生量大,产品质量不稳定,成本高,不易放大生产。
③ 水合肼还原法:
CN102070467A提出在常压下以六水氯化铁和活性炭作催化剂,N,N-二甲基甲酰胺、N-甲基吡咯烷酮、邻二氯苯、氯苯等为溶剂,滴加40%~80%的水合肼还原二硝基萘,产品收率最高可达95.0%。但该方法操作较繁琐,工艺稳定性差,后处理麻烦。
④ 催化加氢法:
催化加氢法是目前最具工业化前景的1,5-二氨基萘新型绿色合成方法。反应方程式为:
该方法是一种较为先进的生产工艺,产物易分离,且无三废排放,是一种绿色、有发展前景的工艺。专利CN101575295、CN102172528A、CN101544569A等均提出采用该方法,于带搅拌的不锈钢高压反应釜中完成1,5-二氨基萘的合成,可获得令人满意的原料转化率和产物选择性。但该方法使用了高活性的贵重催化剂,反应时间较长,催化剂利用率低,设备要求性高。
具体工艺中,CN101544569A、CN101575295A提出以5%的Pd/C为催化剂,在反应体系中加入金属离子为助剂,用于合成二氨基萘类化合物,可取得较高的反应收率。Pd/C催化剂作为目前该方法使用最广泛的催化剂,能取得较高的收率,但Pd/C催化剂本身存在易失活、使用或重生过程的安全性差、重生效率低等缺陷。
CN102174528A提出采用液相催化加氢法,以碳纳米管为载体,由第Ⅷ族金属元素和第1VB族金属元素制备用于催化加氢合成1,5-二氨基萘的催化剂。该专利提出的方法中,催化剂和溶剂可重复使用,工艺清洁无污染。但该方法制备催化剂的原料成本较高,制备过程较为复杂。
RU2307120(C2)则提出以氧化铝、硫酸化氧化锆为载体,负载活性组分钯,并通过对加氢反应装置进行创新设计,简化反应操作,最终合成高品质的1,5-二氨基萘产品。但该专利提出的方法存在反应装置复杂、反应时间长、催化剂制作与更换步骤繁琐等问题。
CN103420851A提出,通过将Ni、Mn、Mo中的一种或几种负载在γ-Al2O3和钛硅分子筛上,可制备用于催化合成1,5-二氨基萘的催化剂。在该催化剂催化下,原料萘、氨水、双氧水可一步合成1,5-二氨基萘。但该方案的收率低,催化剂制备复杂,生产安全性差。
酚醛树脂是由苯酚和甲醛或其衍生物经缩聚反应制得的不熔树脂聚合物。酚醛树脂自投入生产以来,在化工产业中得到广泛的应用,其中,纳米孔径酚醛树脂是制备树脂基泡沫碳的前驱体材料。纳米孔径酚醛树脂具有结构致密、比表面积大、线胀系数低、抗压性良好等特点,在热控材料、催化剂载体、高温隔热等领域中均有广泛的应用前景。而以纳米孔径酚醛树脂负载Pd制备加氢还原催化剂,可以显著改善非均相催化剂的使用性能。目前有关纳米孔径酚醛树脂负载Pd的催化剂制备方法鲜有报道,将该方法制备的催化剂用于加氢催化合成1,5-二氨基萘更是未见报道。开发相应的简便、高效的催化剂类型、制备方法及催化剂应用工艺具有显著的使用价值。
发明内容
本发明公开了一种用于催化1,5-二硝基萘加氢还原合成1,5-二氨基萘的催化剂制备方法,该催化剂制备方法具有制备过程简单、催化剂活性高、催化剂抗失活能力强、使用安全性高、经济合理的特点。本发明还涉及一种固定床连续催化加氢合成1,5-二氨基萘的工艺,以固定床反应器取代传统高压釜式反应装置,可精简反应操作、缩短反应时间、提升催化效率,使工艺简单洁净,产品品质高,后处理简单。
本发明采取的技术路线是:以酚醛树脂为前体,添加固化剂,负载第Ⅷ族金属元素钴、镍、钯、铂中的一种或几种,一步法制得具有纳米孔径的酚醛树脂基催化剂;然后将所制备的催化剂用于固定床连续催化加氢合成1,5-二氨基萘的工艺。
1,5-二硝基萘加氢催化剂的制备方法,按照下述步骤进行:
(1)将酚醛树脂溶于1~15倍质量的甲醇中,静止后过滤除杂;
(2)按比例称取一定质量的第Ⅷ族金属化合物,满足活性组分质量为催化剂质量的0.1%~30%,再加入酚醛树脂质量1~15%的固化剂,混合均匀;
(3)将原料(1)、(2)混合,氮气置换体系中空气,充压0.1~1.0 MPa;
(4)程序升温,在90~190 ℃下固化4~12小时;
(5)反应结束后经过滤、洗涤、干燥得到催化剂。
以上催化剂制备技术方案中,所述的制备的酚醛树脂基催化剂的孔径范围为200~600 nm,密度为0.10~0.30 g/cm3。
以上催化剂制备技术方案中,所述的酚醛树脂为苯酚甲醛酚醛树脂、二甲酚甲醛树脂、间苯二酚甲醛树脂中的一种或几种。
以上催化剂制备技术方案中,所述的酚醛树脂固化剂为六亚甲基四胺、多聚甲醛、苯胺中的一种或几种。
以上催化剂制备技术方案中,所述的第Ⅷ族金属元素为钴、镍、钯、铂中的一种或几种。
以上催化剂制备技术方案中,所述的负载第Ⅷ族金属用量为催化剂质量的0.1~30%。固化剂用量为催化剂质量的1~15%。
以上催化剂制备技术方案中,所述的第Ⅷ族金属化合物为金属醋酸盐、硝酸盐、盐酸盐化合物中的一种或几种。
本发明的催化剂应用工艺为:将所制备的催化剂应用于固定床催化连续加氢合成1,5-二氨基萘的工艺,按照下述步骤进行:
固定床反应器的控压范围为:常压~10 MPa,控温范围为:20℃(室温)~550 ℃。
所述的一种固定床催化连续加氢合成1,5-二氨基萘的工艺,1,5-二硝基萘的反应溶剂选自苯胺、甲醇、异丙醇、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或几种的混合物。1,5-二氨基萘的质量浓度为5~20%。
所述的一种固定床连续催化加氢合成1,5-二氨基萘的工艺,反应温度为40~110℃,反应氢气压力0.3~3 MPa,反应停留时间0.1~5 min。
本发明的催化剂制备方法与现有的催化剂制备方法相比的优势为:一步法同时完成纳米孔径酚醛树脂的制备及催化剂的负载,制作过程简易、安全;纳米孔径酚醛树脂优异的结构特性,赋予制备的催化剂活性高、不易失活;催化剂储存、使用安全高,制作成本经济;另外,其独特的结构特性使之十分合适作为固定床催化加氢的催化剂。与现有工艺相比,该催化工艺采用固定床反应器代替传统高压釜式反应器,缩短反应时间,精简反应步骤,简化反应后处理,降低催化剂的机械损伤,工艺清洁,产品质量高。
附图说明
图1为本发明工艺流程图。
图2为本发明工艺主要装置示意图。1.反应管柱;2.惰性填充物;3.催化剂;4.温度计探头;5.控温装置;6.冷凝装置;7.安全阀;8.储液装置。
具体实施方式
实例借助固定床反应设备进行实施。固定床反应器又称为填充床反应器,如图2所示,在元件1反应管柱中装填固体催化剂3,反应原料(包括气、液两相)按比例泵入管柱,经元件5控温作用下,反应原料通过催化剂床层,在床层上进行反应,得到产物在元件6处冷凝,于元件8处得到粗产品,粗品可在产物出口处收集或直接进行下一工序操作。
实施例1
取苯酚甲醛酚醛树脂5.0 g,醋酸钴2.4 g,六亚甲基四胺0.56 g,加入5.0 g甲醇充分溶解,置于高压反应釜中。充入1.0 MPa的氮气,于90 ℃下固化4 h,经过滤、洗涤、干燥得到灰黑色的含量10%的钴/酚醛树脂催化剂。催化剂孔径560±35nm,密度0.10g/cm3。
配制质量分数10%的1,5-二硝基萘的苯胺溶液,在固定床反应器中,填入10%的钴/酚醛树脂催化剂5.0 g,反应管中催化剂上下层以石英砂填充,用氮气置换固定床内空气5次。控制固定床反应区压力1.0 MPa,温度70 ℃,泵入1,5-二硝基萘反应液,通过调节流速,控制停留时间为3.0 min。反应得到无色液体,空气中迅速变红。产物经色谱分析,1,5-二硝基萘的转化率为99.6%,1,5-二氨基萘的选择性为91.2%。
实施例2
取苯酚甲醛酚醛树脂5.0 g,硝酸铂0.043 g,多聚甲醛0.36 g,加入75.0 g甲醇充分溶解,置于高压反应釜中。充入0.5 MPa的氮气,于140 ℃下固化8 h,经过滤、洗涤、干燥得到灰白色含量约0.5%的铂/酚醛树脂催化剂。催化剂孔径420±30nm,密度0.18g/cm3。
配制质量分数5%的1,5-二硝基萘的甲醇溶液,在固定床反应器中,填入约5%的铂/酚醛树脂催化剂5.0 g,反应管中催化剂上下层以石英砂填充,用氮气置换固定床内空气5次。控制固定床反应区压力3.0 MPa,温度90 ℃,泵入1,5-二硝基萘反应液,通过调节流速,控制停留时间为0.8 min,得到***液体,空气中红色加深。产物经色谱分析,1,5-二硝基萘的转化率为92.4%,1,5-二氨基萘的选择性为61.7%。
实施例3
取苯酚甲醛酚醛树脂10.0 g,硝酸镍16.5 g,六亚甲基四胺1.65 g,加入120.0 g甲醇充分溶解,置于高压反应釜中。充入0.1 MPa的氮气,于170 ℃下固化12 h,经过滤、洗涤、干燥得到灰白色含量约30%的镍/酚醛树脂催化剂。催化剂孔径230±25nm,密度0.24g/cm3。
配制质量分数20%的1,5-二硝基萘的N,N-二甲基乙酰胺溶液,在固定床反应器中,填入约30%的镍/酚醛树脂催化剂10.0 g,反应管中催化剂上下层以石英砂填充。用氮气置换固定床内空气5次。控制固定床反应区压力1.5 MPa,温度110 ℃,泵入1,5-二硝基萘反应液,通过调节流速,控制停留时间为2.0 min。得到无色液体,空气中迅速变红。产物经色谱分析,1,5-二硝基萘的转化率为100%,1,5-二氨基萘的选择性为98.3%。
实施例4
取间苯二酚甲醛树脂10.0 g,醋酸钯0.43 g,苯胺1.1 g,加入45.0 g甲醇充分溶解,置于高压反应釜中。充入0.4 MPa的氮气,于190 ℃下固化10 h,经过滤、洗涤、干燥得到灰白色含量约2%的钯/酚醛树脂催化剂。催化剂孔径210±15nm,密度0.30g/cm3。
配制质量分数20%的1,5-二硝基萘的四氢呋喃溶液,在固定床反应器中,填入约2%的钯/酚醛树脂催化剂10.0 g,反应管中催化剂上下层以石英砂填充。用氮气置换固定床内空气5次。控制固定床反应区压力0.3MPa,温度40 ℃,泵入1,5-二硝基萘反应液,通过调节流速,控制停留时间为0.1 min。得到***液体,空气中红色加深。产物经色谱分析,1,5-二硝基萘的转化率为98.1%,1,5-二氨基萘的选择性为58.8%。
实施例5
取间苯二酚甲醛树脂10.0 g,醋酸钯1.08 g,苯胺1.1 g,加入70.0 g甲醇充分溶解,置于高压反应釜中。充入0.5 MPa的氮气,在170 ℃下固化4 h,经过滤、洗涤、干燥得到灰白色含量约5%的钯/酚醛树脂催化剂。催化剂孔径230±15nm,密度0.26g/cm3。
配制质量分数20%的1,5-二硝基萘的N,N-二甲基甲酰胺溶液,在固定床反应器中,填入约5%的钯/酚醛树脂催化剂10.0 g,反应管中催化剂上下层以石英砂填充。用氮气置换固定床内空气5次。控制固定床反应区压力0.8 MPa,温度75 ℃,泵入1,5-二硝基萘反应液,通过调节流速,控制停留时间为0.5min。得到***液体,空气中红色加深。产物经色谱分析,1,5-二硝基萘的转化率为93.3%,1,5-二氨基萘的选择性为75.8%。
实施例6
取苯酚甲醛酚醛树脂10.0 g,硝酸镍0.91 g,多聚甲醛0.72 g,加入40.0 g甲醇充分溶解,置于高压反应釜中。充入0.1 MPa的氮气,于90 ℃下固化12 h,经过滤、洗涤、干燥得到灰白色含量约2.5%的镍/酚醛树脂催化剂。催化剂孔径540±30nm,密度0.11g/cm3。
配制质量分数10%的1,5-二硝基萘的甲醇溶液,在固定床反应器中,填入约2.5%的镍/酚醛树脂催化剂5.0 g,反应管中催化剂上下层以石英砂填充。用氮气气置换固定床内空气5次。控制固定床反应区压力2.5 MPa,温度110 ℃,泵入1,5-二硝基萘反应液,通过调节流速,控制停留时间为5.0 min。得到无色液体,空气中逐渐变红。产物经色谱分析,1,5-二硝基萘的转化率为99.8%,1,5-二氨基萘的选择性为98.0%。
实施例7
取二甲酚甲醛树脂10.0 g,氯化钯0.017 g,六亚甲基四胺0.55 g,加入100.0g甲醇充分溶解,置于高压反应釜中。充入0.2 MPa的氮气,于110 ℃下固化7 h,经过滤、洗涤、干燥得到灰白色含量约0.1%的钯/酚醛树脂催化剂。催化剂孔径460±30nm,密度0.14g/cm3
配制质量分数20%的1,5-二硝基萘的异丙醇溶液,在固定床反应器中,填入约0.1%的镍/酚醛树脂催化剂10.0 g,反应管中催化剂上下层以石英砂填充。用氮气置换固定床内空气5次。控制固定床反应区压力1.0 MPa,温度80 ℃,泵入1,5-二硝基萘反应液,通过调节流速,控制停留时间为3.5 min。得到***液体,空气中变红加深。产物经色谱分析,1,5-二硝基萘的转化率为98.3%,1,5-二氨基萘的选择性为66.4%。
Claims (2)
1.一种1,5-二硝基萘催化加氢合成1,5-二氨基萘的催化剂制备方法,其特征在于:按照下述步骤进行:
(1)将酚醛树脂溶于1~15倍质量的甲醇中,静止后过滤除杂;
(2)按比例称取一定质量的第Ⅷ族金属化合物,满足活性组分质量为催化剂质量的0.1%~30%,再加入酚醛树脂质量1~15%的固化剂,混合均匀;
(3)将原料(1)、(2)混合,氮气置换体系中空气,充压0.1~1.0 MPa;
(4)程序升温,在90~190 ℃下固化4~12小时;
(5)反应结束后经过滤、洗涤、干燥得到催化剂;
其中制备的酚醛树脂基催化剂的孔径范围为200~600 nm,密度为0.10~0.30 g/cm3;
其中所述的酚醛树脂载体为苯酚甲醛酚醛树脂、二甲酚甲醛树脂、间苯二酚甲醛树脂中的一种或几种;
其中所述的酚醛树脂的固化剂为六亚甲基四胺、多聚甲醛、苯胺中的一种或几种;
其中所述的第Ⅷ族金属元素为钴、镍、钯、铂中的一种或几种;
其中所述的第Ⅷ族金属化合物为相应金属的醋酸盐、硝酸盐、盐酸盐化合物中的一种或几种。
2.权利要求1所述的一种1,5-二硝基萘催化加氢合成1,5-二氨基萘的催化剂制备方法制备的催化剂的应用,其特征在于:将所制备的酚醛树脂基催化剂应用于固定床连续催化加氢合成1,5-二氨基萘的工艺;所述固定床反应器控压范围为:常压~10 MPa,控温范围为:20℃~550 ℃;1,5-二硝基萘的反应溶剂选自苯胺、甲醇、异丙醇、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或几种的混合物;1,5-二氨基萘的质量浓度为5%~20%;
反应氢气压力0.3~3 MPa,反应停留时间0.1~5 min;其中反应温度为40℃~110 ℃。
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