CN112642425A - 一种用于卤代芳香硝基化合物硝基还原防脱卤催化剂及其制备方法与应用 - Google Patents
一种用于卤代芳香硝基化合物硝基还原防脱卤催化剂及其制备方法与应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- -1 halogenated aromatic nitro compound Chemical class 0.000 title claims abstract description 47
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000005695 dehalogenation reaction Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052792 caesium Inorganic materials 0.000 claims abstract 2
- 229910052730 francium Inorganic materials 0.000 claims abstract 2
- 229910052744 lithium Inorganic materials 0.000 claims abstract 2
- 229910052700 potassium Inorganic materials 0.000 claims abstract 2
- 229910052701 rubidium Inorganic materials 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 57
- 238000010438 heat treatment Methods 0.000 claims description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 24
- 239000012018 catalyst precursor Substances 0.000 claims description 23
- 239000012046 mixed solvent Substances 0.000 claims description 22
- 238000006722 reduction reaction Methods 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
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- 229910052736 halogen Inorganic materials 0.000 claims description 9
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000011257 shell material Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical group [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical group [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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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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- C07C209/365—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 by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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Abstract
本发明公开一种用于卤代芳香硝基化合物硝基还原防脱卤催化剂,包括载体,所述载体为活性炭载体,还包括负载在所述载体上的活性组分A和助剂组分B,所述活性组分A为Pd、Pt或Ru;所述助剂组分B为金属元素X的氧化物,所述金属元素X为碱金属或Ba、Sr、Ga、Mg、La、Ce、Zn、Sn中的任意一种;所述碱金属为Cs、Rb、K、Li、Fr中的任意一种;按照质量百分比100%计,活性组分A的含量为0.2‑1.0%,助剂组分B的含量为0.1‑0.5%,其余为载体。同时,本发明还公开所述催化剂的制备方法及其应用。所述催化剂活性高,原料转化率大于99%,产物选择性大于99%,脱卤小于0.1%。
Description
技术领域
本发明属于化学化工合成技术领域,具体涉及一种用于卤代芳香硝基化合物硝基还原防脱卤催化剂及其制备方法与应用。
背景技术
芳胺及卤代芳胺是基础性化工原料与有机中间体,在医药、农药、染料和日用化工等领域有着广泛的用途,市场需求量很大。其生产方法主要由相应的芳香族硝基化合物通过还原而得到,还原方法有铁粉还原法、硫化碱还原法、电解还原法和催化加氢还原法等。含卤芳香族硝基化合物还原制备含卤芳胺是一类重要的有机合成单元反应。
目前应用较多的为催化加氢还原法,催化剂一般采用骨架Ni、Pd/C和Ru/C等加氢催化剂,但容易脱卤,导致催化剂中毒,催化剂寿命短。为抑制脱卤发生,一般在反应中添加脱卤抑制剂,但会使后续分离操作复杂化,且会影响产品质量。且催化加氢工艺主要采用釜式工艺,存在反应时间长、间歇操作、生成成本高等问题。
发明内容
本发明旨在克服现有技术中卤代芳香硝基化合物加氢脱卤率不好控制,选择性低,及釜式工艺操作繁琐、三废多、产量小、动力消耗大、难分离等问题。本发明提供一种活性好、选择性高、寿命长的用于卤代芳香硝基化合物硝基还原防脱卤催化剂及其制备方法,以及采用所属催化剂在连续生产卤代芳香氨基化合物的固定床连续加氢方法中的应用。
为实现上述目的,本发明采用以下技术方案:
一种用于卤代芳香硝基化合物硝基还原防脱卤催化剂,包括载体,所述载体为活性炭载体,其特征在于:还包括负载在所述载体上的活性组分A和助剂组分B,
所述活性组分A为Pd、Pt或Ru;
所述助剂组分B为金属元素X的氧化物,所述金属元素为碱金属或Ba、Sr、Ga、Mg、La、Ce、Zn、Sn中的任意一种;
按照质量百分比100%计,活性组分A的含量为0.2-1.0%,助剂组分B的含量为0.1-0.5%,其余为载体。
优选地,所述活性炭载体为煤质、果壳、木质或椰壳活性炭,所述活性炭载体的比表面积为800-1500m2/g、粒径为0.5-4mm、孔容为0.2-1.2cm3/g、孔径为2.0-4.0nm。
所述用于卤代芳香硝基化合物硝基还原防脱卤催化剂的制备方法,包括以下步骤:
(1)载体预处理:
(11)将载体加入到1-5wt%的稀硝酸溶液中,加热煮沸处理0.5-2h,过滤,洗涤至滤液pH值为3-7,干燥;
(12)将(11)中所得产物在氮气保护下微波加热至600-800℃,活化3-5h;
(2)组分负载:
(21)将溶剂a和溶剂b混合得到混合溶剂,将助剂组分B的前驱体盐用水溶解,然后向其中加入所述混合溶剂,搅拌0.5-2h,得到溶液c,然后将步骤(1)得到的载体浸没于溶液c中,搅拌10-30min,静置4-6h,过滤,干燥,焙烧,自然冷却后得负载有助剂组分B的催化剂前驱体;
所述溶剂a为甲醇、乙醇、正丙醇、乙二醇、丙酮、2-丙醇、2-丙酮、1-丁醇、乙醚、乙酸乙酯中的一种或几种;
所述溶剂b为醇胺类或酰胺类化合物;
(22)将软模板剂用溶剂d溶解,向其中加入活性组分A的前驱体盐的水溶液,得到溶液e,用碱溶液调节溶液e的pH为9-12,在30-65℃下搅拌0.5-2h,将步骤(21)得到的催化剂前驱体浸没在其中,在100-150℃下回流加热3-6h,静置4-6h,过滤,干燥,焙烧,自然冷却后得到负载有活性组分A和助剂组分B的催化剂前驱体;
所述溶剂d为甲醇、乙醇、异丙醇、正丙醇、乙二醇、三甘醇、1-丁醇、2-丁醇、2-甲基丙醇中任意一种或几种的水溶液;
(3)还原处理。
优选地,步骤(3)所述还原处理为:在氮气气氛下以0.5-2℃/min升温速率升温至200-300℃,氮气吹扫0.2-1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理2-5h,然后在氮气气氛下冷却至室温,即可。
优选地,步骤(11)、(21)和步骤(22)中所述干燥均为在100-120℃干燥4-8h;步骤(21)和(22)中所述焙烧均为在氮气气氛中以2-3℃/min速率加热至450-600℃并保持2-5h。
优选地,所述活性组分A的前驱体盐为硝酸盐、氯化盐或醋酸盐;所述助剂组分B的前驱体盐为金属元素X的水溶性盐,所述水溶性盐为碳酸盐、氯化盐、硝酸盐或醋酸盐。
优选地,所述溶剂b在混合溶剂中的质量浓度为0.5-10%;且所述混合溶剂与载体的质量比为(3-7):1。
优选地,所述碱溶液为5-10wt%的NaOH或Na2CO3溶液;所述软模板剂为聚乙烯吡咯烷酮,P123、P127、聚氧乙烯苯乙烯米酚、聚乙烯醇、聚乙烯丙烯酰胺、聚丙烯酰胺中的一种,且所述软模板剂占活性组分A的质量分数为0.1-10%;且步骤(22)中催化剂前驱体与溶剂d的质量比为1:(3-7)。
本发明所述催化剂在催化还原卤代芳香硝基化合物中的应用,所述应用采用固定床连续化方法催化还原卤代芳香硝基化合物,具体包括以下步骤:
(一)将所述催化剂与惰性瓷球逐层交替装填于固定床反应器中,通入氮气排净空气;
(二)向固定床反应器中通入氢气,在气体压力0.1-2MPa、氢气流量Q满足20m≤Q≤30m的条件下,将催化剂先以2-3℃/min的升温速率升温至50-100℃后保温1.5-2.5h,然后以1-2℃/min的升温速率升温至120-300℃后保温1.5-2.5h,之后自然降温或升温至设定反应温度后保持恒定;所述m为催化剂的质量,m的单位为g,Q的单位为mL/min;
(三)将原料液和氢气分别预热至反应温度,通入固定床反应器中,进行含卤硝基化合物的催化加氢反应,氢气与原料液中硝基摩尔比为(10-50)∶1,反应空速为0.2-1.5g/gcat/hr;
(四)将步骤(三)得到的产物送入气液分离器,分离纯化后得到含卤芳香氨基化合物;
其中,所述反应温度为30-150℃,所述原料液为卤代芳香硝基化合物。
优选地,步骤(一)中所述惰性瓷球的粒径为1.0-1.5mm,所述催化剂与惰性瓷球的体积比为2:1;所述固定床反应器的反应管内径为10-40mm、反应管的装填高度为1.0-4.0m。
本发明的有益效果在于:
(1)催化剂制备过程加入助剂组分B,能起到防脱卤的作用,同时负载过程中采用有机胺化合物为溶剂共同调控催化剂酸中心,抑制卤素离子在催化剂酸中心上的吸附,有效抑制脱卤发生。
(2)通过载体预处理,活性金属负载采用模板法结合含醇溶剂回流加热浸渍,制备的催化剂活性金属纳米粒子高度分散,粒径较小。催化剂活性高,选择性好,脱卤率低,原料转化率大于99%,产物选择性大于99%,脱卤小于0.1%。
(3)本发明采用固定床反应工艺与自制催化剂技术相配套,能够高效、连续地催化还原卤代芳香硝基化合物来制备卤代芳香氨基化合物,通过控制催化剂活性和反应液经过催化剂床层的时间,成功提高反应选择性,反应条件温和,操作简单,容易控制,生产效率高,选择性好,副产物少,三废少,产物易分离,安全环保,能有效降低生产成本。
具体实施方式
实施例1
1. 一种用于卤代芳香硝基化合物硝基还原防脱卤催化剂,包括载体,以及负载在所述载体上的活性组分Pt和助剂组分K的氧化物,按照质量百分比100%计,活性组分Pt的含量为1.0%,助剂组分K的氧化物的含量为0.1%,其余为载体;所述载体为木质活性炭,其比表面积为1200m2/g、粒径为1.5mm、孔容为0.35cm3/g、孔径为2.23nm。
2. 所述用于卤代芳香硝基化合物硝基还原防脱卤催化剂的制备方法,包括以下步骤:
(1)载体预处理:
(11)将载体加入到5wt%的稀硝酸溶液中,加热煮沸处理0.5h,过滤,洗涤至滤液pH值为5,在120℃干燥8h;
(12)将(11)中所得产物在氮气保护下微波加热至800℃,活化3h;
(2)组分负载:
(21)将溶剂a乙二醇和溶剂b DMF混合得到混合溶剂,DMF在混合溶剂中质量浓度为5%;将助剂组分的前驱体盐K2CO3用水溶解,然后按照载体与所述混合溶剂的固液质量比为1:5向其中加入所述混合溶剂,搅拌1h,得到溶液c,然后将步骤(1)得到的载体浸没于溶液c中,搅拌20min,静置6h,过滤,在120℃干燥8h,在氮气气氛中以2℃/min速率加热至500℃后焙烧3h,自然冷却后得负载有助剂组分的催化剂前驱体;
(22)将占Pt单质质量分数为5%的聚乙烯吡咯烷酮(PVP)用异丙醇的水溶液溶解,按照步骤(21)得到的催化剂前驱体与异丙醇的质量比为1:5,向其中加入氯化铂前驱体水溶液,得到溶液e,用5wt%的NaOH溶液调节溶液e的pH为10,在30℃下搅拌1h,将步骤(21)得到的催化剂前驱体浸没在其中,在120℃下回流加热6h,静置6h,过滤,在120℃干燥8h,在氮气气氛中以2℃/min速率加热至500℃后焙烧3h,自然冷却后得到负载有活性组分Pt和助剂组分K的氧化物的催化剂前驱体;
(3)还原处理:将步骤(2)得到的催化剂前驱体在氮气气氛下以1℃/min升温速率升温至300℃,氮气吹扫0.5h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理3h,然后在氮气气氛下冷却至室温,即可。
所得催化剂记为S1。
实施例2
助剂组分B为Li的氧化物,其前驱体盐采用醋酸锂,其他同实施例1,制备方法同实施例1,得到的催化剂记为S2。
实施例3
助剂组分B为Cs的氧化物,其前驱体盐采用硝酸铯,其他同实施例1,制备方法同实施例1,得到的催化剂记为S3。
实施例4
活性组分A为Pd,采用的前驱体盐为氯化钯,其他同实施例1,制备方法同实施例1,得到的催化剂记为S4。
实施例5
活性组分A为Ru,采用的前驱体盐为三氯化钌,其他同实施例1,制备方法同实施例1,得到的催化剂记为S5。
实施例6
1. 一种用于卤代芳香硝基化合物硝基还原防脱卤催化剂,包括载体,以及负载在所述载体上的活性组分Pd和助剂组分Sr的氧化物,按照质量百分比100%计,活性组分Pd的含量为0.2%,助剂组分Sr的氧化物的含量为0.5%,其余为载体;所述载体为木质活性炭,其比表面积为1200m2/g、粒径为1.5mm、孔容为0.35cm3/g、孔径为2.23nm。
2. 所述用于卤代芳香硝基化合物硝基还原防脱卤催化剂的制备方法,包括以下步骤:
(1)载体预处理:
(11)将载体加入到1wt%的稀硝酸溶液中,加热煮沸处理2h,过滤,洗涤至滤液pH值为3,在100℃干燥4h;
(12)将(11)中所得产物在氮气保护下微波加热至600℃,活化5h;
(2)组分负载:
(21)将溶剂a乙酸乙酯和溶剂b DMF混合得到混合溶剂,DMF在混合溶剂中质量浓度为10%;将助剂组分的前驱体盐氯化锶用水溶解,然后按照载体与所述混合溶剂的固液质量比为1:3向其中加入所述混合溶剂,搅拌0.5h,得到溶液c,然后将步骤(1)得到的载体浸没于溶液c中,搅拌30min,静置4h,过滤,在100℃干燥4h,在氮气气氛中以3℃/min速率加热至450℃后焙烧5h,自然冷却后得负载有助剂组分的催化剂前驱体;
(22)将占Pd单质质量分数为10%的聚乙烯吡咯烷酮(PVP)用乙二醇的水溶液溶解,按照步骤(21)得到的催化剂前驱体与乙二醇的质量比为1:3,向其中加入氯化钯前驱体水溶液,得到溶液e,用10wt%的Na2CO3溶液调节溶液e的pH为12,在65℃下搅拌2h,将步骤(21)得到的催化剂前驱体浸没在其中,在150℃下回流加热3h,静置4h,过滤,在100℃干燥4h,在氮气气氛中以3℃/min速率加热至450℃后焙烧5h,自然冷却后得到负载有活性组分Pd和助剂组分的催化剂前驱体;
(3)还原处理:将步骤(2)得到的催化剂前驱体在氮气气氛下以2℃/min升温速率升温至200℃,氮气吹扫1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理5h,然后在氮气气氛下冷却至室温,即可。
所得催化剂记为S6。
实施例7
1. 一种用于卤代芳香硝基化合物硝基还原防脱卤催化剂,包括载体,以及负载在所述载体上的活性组分Pd和助剂组分Ba的氧化物,按照质量百分比100%计,活性组分A的含量为0.5%,助剂组分Ba的氧化物的含量为0.2%,其余为载体;所述载体为木质活性炭,其比表面积为1200m2/g、粒径为1.5mm、孔容为0.35cm3/g、孔径为2.23nm。
2. 所述用于卤代芳香硝基化合物硝基还原防脱卤催化剂的制备方法,包括以下步骤:
(1)载体预处理:
(11)将载体加入到2wt%的稀硝酸溶液中,加热煮沸处理1h,过滤,洗涤至滤液pH值为7,在110℃干燥6h;
(12)将(11)中所得产物在氮气保护下微波加热至700℃,活化4h;
(2)组分负载:
(21)将溶剂a乙醚和溶剂b DMF混合得到混合溶剂,DMF在混合溶剂中质量浓度为0.5%;将助剂组分的前驱体盐氯化钡用水溶解,然后按照载体与所述混合溶剂的固液质量比为1:7向其中加入所述混合溶剂,搅拌2h,得到溶液c,然后将步骤(1)得到的载体浸没于溶液c中,搅拌10min,静置5h,过滤,在110℃干燥6h,在氮气气氛中以3℃/min速率加热至600℃后焙烧2h,自然冷却后得负载有助剂组分的催化剂前驱体;
(22)将占Pd单质质量分数为0.1%的聚乙烯醇用乙二醇的水溶液溶解,按照步骤(21)得到的催化剂前驱体与乙二醇的质量比为1:7,向其中加入氯化钯前驱体水溶液,得到溶液e,用5wt%的NaOH溶液调节溶液e的pH为9,在50℃下搅拌0.5h,将步骤(21)得到的催化剂前驱体浸没在其中,在100℃下回流加热5h,静置5h,过滤,在110℃干燥6h,在氮气气氛中以3℃/min速率加热至600℃后焙烧2h,自然冷却后得到负载有活性组分Pd和助剂组分的催化剂前驱体;
(3)还原处理:将步骤(2)得到的催化剂前驱体在氮气气氛下以0.5℃/min升温速率升温至300℃,氮气吹扫0.2h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理3h,然后在氮气气氛下冷却至室温,即可。
所得催化剂记为S7。
实施例8
活性组分为Pd,其前驱体盐采用氯化钯;助剂组分为La的氧化物,其前驱体盐采用硝酸镧,其他同实施例1,制备方法同实施例1,得到的催化剂记为S8。
实施例9
活性组分为Pd,其前驱体盐采用氯化钯;助剂组分为Sn的氧化物,其前驱体盐采用四氯化锡,其他同实施例1,制备方法同实施例1,得到的催化剂记为S9。
实施例10
活性组分为Pt,其前驱体盐采用硝酸铂;助剂组分为Zn的氧化物,其前驱体盐采用六水合硝酸锌,其他同实施例1,制备方法同实施例1,得到的催化剂记为S10。
实施例11
活性组分为Ru,其前驱体盐采用三氯化钌;助剂组分为Zn的氧化物,其前驱体盐采用六水合硝酸锌,其他同实施例1,制备方法同实施例1,得到的催化剂记为S11。
应用
本发明提供的催化剂在催化还原卤代芳香硝基化合物中的应用,所述应用采用固定床连续化方法催化还原卤代芳香硝基化合物,具体包括以下步骤:
(一)将所述催化剂与惰性瓷球逐层交替装填于固定床反应器中,通入氮气排净空气;
(二)向固定床反应器中通入氢气,在气体压力0.1-2MPa、氢气流量Q满足20m≤Q≤30m的条件下,将催化剂先以2-3℃/min的升温速率升温至50-100℃后保温1.5-2.5h,然后以1-2℃/min的升温速率升温至120-300℃后保温1.5-2.5h,之后自然降温或升温至设定反应温度后保持恒定;所述m为催化剂的质量,m的单位为g,Q的单位为mL/min;
(三)将原料液和氢气分别预热至反应温度,通入固定床反应器中,进行含卤硝基化合物的催化加氢反应,氢气与原料液中硝基摩尔比为(10-50)∶1,反应空速为0.2-1.5g/gcat/hr;
(四)将步骤(三)得到的产物送入气液分离器,分离纯化后得到含卤芳香氨基化合物;
其中,所述反应温度为30-150℃,所述原料液为卤代芳香硝基化合物。
步骤(一)中所述惰性瓷球的粒径为1.0-1.5mm,所述催化剂与惰性瓷球的体积比为2:1;所述固定床反应器的反应管内径为10-40mm、反应管的装填高度为1.0-4.0m。
将实施例1-11提供的催化剂按照上述应用中所述方法用于催化还原卤代芳香硝基化合物连续生产卤代芳香氨基化合物,具体反应参数和反应结果见表1;其他反应条件相同。
表1 反应参数和反应结果
由表1可知,本发明催化剂具有非常高的催化活性和选择性,原料卤代芳香硝基化合物转化率大于99%,产物卤代芳香氨基化合物选择性大于99%,脱卤率小于0.1%。
Claims (10)
1.一种用于卤代芳香硝基化合物硝基还原防脱卤催化剂,包括载体,所述载体为活性炭载体,其特征在于:还包括负载在所述载体上的活性组分A和助剂组分B,
所述活性组分A为Pd、Pt或Ru;
所述助剂组分B为金属元素X的氧化物,所述金属元素X为碱金属或Ba、Sr、Ga、Mg、La、Ce、Zn、Sn中的任意一种;
所述碱金属为Cs、Rb、K、Li、Fr中的任意一种;
按照质量百分比100%计,活性组分A的含量为0.2-1.0%,助剂组分B的含量为0.1-0.5%,其余为载体。
2.根据权利要求1所述用于卤代芳香硝基化合物硝基还原防脱卤催化剂,其特征在于:所述活性炭载体为煤质、果壳、木质或椰壳活性炭,所述活性炭载体的比表面积为800-1500m2/g、粒径为0.5-4mm、孔容为0.2-1.2cm3/g、孔径为2.0-4.0nm。
3.权利要求1所述催化剂的制备方法,其特征在于:包括以下步骤:
(1)载体预处理:
(11)将载体加入到1-5wt%的稀硝酸溶液中,加热煮沸处理0.5-2h,过滤,洗涤至滤液pH值为3-7,干燥;
(12)将(11)中所得产物在氮气保护下微波加热至600-800℃,活化3-5h;
(2)组分负载:
(21)将溶剂a和溶剂b混合得到混合溶剂,将助剂组分B的前驱体盐用水溶解,然后向其中加入所述混合溶剂,搅拌0.5-2h,得到溶液c,然后将步骤(1)得到的载体浸没于溶液c中,搅拌10-30min,静置4-6h,过滤,干燥,焙烧,自然冷却后得负载有助剂组分B的催化剂前驱体;
所述溶剂a为甲醇、乙醇、正丙醇、乙二醇、丙酮、2-丙醇、2-丙酮、1-丁醇、乙醚、乙酸乙酯中的一种或几种;
所述溶剂b为醇胺类或酰胺类化合物;
(22)将软模板剂用溶剂d溶解,向其中加入活性组分A的前驱体盐的水溶液,得到溶液e,用碱溶液调节溶液e的pH为9-12,在30-65℃下搅拌0.5-2h,将步骤(21)得到的催化剂前驱体浸没在其中,在100-150℃下回流加热3-6h,静置4-6h,过滤,干燥,焙烧,自然冷却后得到负载有活性组分A和助剂组分B的催化剂前驱体;
所述溶剂d为甲醇、乙醇、异丙醇、正丙醇、乙二醇、三甘醇、1-丁醇、2-丁醇、2-甲基丙醇中任意一种或几种的水溶液;
(3)还原处理。
4.根据权利要求3所述催化剂的制备方法,其特征在于:步骤(3)所述还原处理为:在氮气气氛下以0.5-2℃/min升温速率升温至200-300℃,氮气吹扫0.2-1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理2-5h,然后在氮气气氛下冷却至室温,即可。
5.根据权利要求4所述催化剂的制备方法,其特征在于:步骤(11)、(21)和步骤(22)中所述干燥均为在100-120℃干燥4-8h;步骤(21)和(22)中所述焙烧均为在氮气气氛中以2-3℃/min速率加热至450-600℃并保持2-5h。
6.根据权利要求5所述催化剂的制备方法,其特征在于:所述活性组分A的前驱体盐为硝酸盐、氯化盐或醋酸盐;所述助剂组分B的前驱体盐为金属元素X的水溶性盐,所述水溶性盐为碳酸盐、氯化盐、硝酸盐或醋酸盐。
7.根据权利要求6所述催化剂的制备方法,其特征在于:所述溶剂b在混合溶剂中的质量浓度为0.5-10%;且所述混合溶剂与载体的质量比为(3-7):1。
8.根据权利要求7所述催化剂的制备方法,其特征在于:所述碱溶液为5-10wt%的NaOH或Na2CO3溶液;
所述软模板剂为聚乙烯吡咯烷酮,P123、P127、聚氧乙烯苯乙烯米酚、聚乙烯醇、聚乙烯丙烯酰胺、聚丙烯酰胺中的一种,且所述软模板剂占活性组分A的质量分数为0.1-10%;且步骤(22)中催化剂前驱体与溶剂d的质量比为1:(3-7)。
9.权利要求1或2所述催化剂在催化还原卤代芳香硝基化合物中的应用,其特征在于:所述应用采用固定床连续化方法催化还原卤代芳香硝基化合物,具体包括以下步骤:
(一)将所述催化剂与惰性瓷球逐层交替装填于固定床反应器中,通入氮气排净空气;
(二)向固定床反应器中通入氢气,在气体压力0.1-2MPa、氢气流量Q满足20m≤Q≤30m的条件下,将催化剂先以2-3℃/min的升温速率升温至50-100℃后保温1.5-2.5h,然后以1-2℃/min的升温速率升温至120-300℃后保温1.5-2.5h,之后自然降温或升温至设定反应温度后保持恒定;所述m为催化剂的质量,m的单位为g,Q的单位为mL/min;
(三)将原料液和氢气分别预热至反应温度,通入固定床反应器中,进行含卤硝基化合物的催化加氢反应,氢气与原料液中硝基摩尔比为(10-50)∶1,反应空速为0.2-1.5g/gcat/hr;
(四)将步骤(三)得到的产物送入气液分离器,分离纯化后得到含卤芳香氨基化合物;
其中,所述反应温度为30-150℃,所述原料液为卤代芳香硝基化合物。
10.根据权利要求9所述应用,其特征在于:步骤(一)中所述惰性瓷球的粒径为1.0-1.5mm,所述催化剂与惰性瓷球的体积比为2:1;所述固定床反应器的反应管内径为10-40mm、反应管的装填高度为1.0-4.0m。
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