CN100342967C - Catalyst for preparing sec-butylamine through catalyzing, aminating and hydrogenizing butanone, and preparaation method - Google Patents
Catalyst for preparing sec-butylamine through catalyzing, aminating and hydrogenizing butanone, and preparaation method Download PDFInfo
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- CN100342967C CN100342967C CNB2004100116108A CN200410011610A CN100342967C CN 100342967 C CN100342967 C CN 100342967C CN B2004100116108 A CNB2004100116108 A CN B2004100116108A CN 200410011610 A CN200410011610 A CN 200410011610A CN 100342967 C CN100342967 C CN 100342967C
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 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
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004176 ammonification Methods 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005470 impregnation Methods 0.000 abstract description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical class [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- -1 p-toluene amide Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种甲乙酮催化氨化加氢制备仲丁胺用催化剂及其制备方法。催化剂载体为Al2O3-TiO2复合氧化物，活性组分由10-25%重量NiO，以及1-10%重量的CuO、Cr2O3、MgO、BaO中的两种组成。催化剂采用浸渍法制备，具有反应条件温和、高选择性等特点。催化剂在用工业甲乙酮、液氨、氢气为原料，在常压，反应温度170-200℃，甲乙酮与氨、氢气的摩尔比为1∶1.2∶1.2，甲乙酮转化率可达30-42%，选择性达70-97%。The invention relates to a catalyst for preparing sec-butylamine by catalytic hydrogenation and hydrogenation of methyl ethyl ketone and a preparation method thereof. The catalyst carrier is Al 2 O 3 -TiO 2 composite oxide, and the active component is composed of 10-25% by weight of NiO and 1-10% by weight of two kinds of CuO, Cr 2 O 3 , MgO and BaO. The catalyst is prepared by the impregnation method, and has the characteristics of mild reaction conditions and high selectivity. The catalyst uses industrial methyl ethyl ketone, liquid ammonia, and hydrogen as raw materials. At normal pressure, the reaction temperature is 170-200 ° C, the molar ratio of methyl ethyl ketone to ammonia and hydrogen is 1:1.2:1.2, and the conversion rate of methyl ethyl ketone can reach 30-42%. Sexuality reaches 70-97%.
Description
技术领域technical field
本发明涉及一种甲乙酮催化氨化加氢制备仲丁胺用催化剂及其制备方法。The invention relates to a catalyst for preparing sec-butylamine by catalytic hydrogenation and hydrogenation of methyl ethyl ketone and a preparation method thereof.
背景技术Background technique
仲丁胺作为优良保鲜剂，早在八十年代初，就被联合国卫生组织和粮食组织推荐随着仲丁胺需求的日趋扩大，不同的仲丁胺生产制备工艺路线相继问世，如仲丁醇的氨化加氢、甲乙酮的氨化加氢及相应的卤代烷氨解等方法。日本日东化学公司、美国空气产品和化学品公司等采用仲丁醇的氨化加氢工艺生产仲丁胺，采用的催化剂有氧化铝、氧化硅、二氧化钛、三氧化钨、白土、氧化钍、氧化铬、各种金属氧化物的混合物及磷酸盐。一般反应温度为250-500℃，压力为5.0Mpa。由于该法反应温度较高，涉及高温下原料醇的热稳定性及过程的选择性，反应一般生成伯、仲、叔三种胺的混合物。溴代仲丁烷与对甲苯黄酰胺缩合、水解制仲丁胺法由于其生产成本过高，反应工艺复杂，并伴有废酸、废碱产生，故此法在工业上已不采用。甲已酮催化氢氨化合成仲丁胺法是目前研究较为多仲丁胺生产方法。As an excellent antistaling agent, sec-butylamine was recommended by the United Nations Health Organization and the Food Organization as early as the early 1980s. With the increasing demand for sec-butylamine, different production and preparation routes for sec-butylamine have come out one after another, such as sec-butanol Ammonification and hydrogenation of methyl ethyl ketone and the corresponding haloalkane ammonolysis. Nitto Chemical Company of Japan, Air Products and Chemicals Company of the United States, etc. use the ammoniation hydrogenation process of sec-butanol to produce sec-butylamine. The catalysts used are alumina, silica, titanium dioxide, tungsten trioxide, clay, thorium oxide, Chromium oxide, mixtures of various metal oxides and phosphates. The general reaction temperature is 250-500°C and the pressure is 5.0Mpa. Due to the high reaction temperature of this method, which involves the thermal stability of the raw material alcohol at high temperature and the selectivity of the process, the reaction generally produces a mixture of primary, secondary and tertiary amines. Brominated sec-butane and p-toluene amide are condensed and hydrolyzed to produce sec-butylamine because of its high production cost, complex reaction process, and the generation of waste acid and waste alkali, so this method has not been used in industry. The method of synthesizing sec-butylamine by catalytic hydrogenation of methylhexanone is a comparatively researched production method of poly-sec-butylamine at present.
目前关于甲已酮催化氢氨化合成仲丁胺法的国内报道极少。王晓立、丁宝宏、张建中等(抚顺石油学院学报，2003，Vol.23，No.1，)报道了一种以甲乙酮为原料，改性兰尼镍为催化剂的液固相催化氨化加氢生产仲丁胺的新工艺方法。其催化剂采用改性兰尼镍，反应温度为140℃，反应时间70min，催化剂用量为每摩尔甲乙酮3g，反应总压力6MPa。在该条件下运转所得成液甲乙酮转化率近100％，仲丁胺收率91.5％。该过程为釜式反应，不适用与大规模的工业生产。At present, there are very few domestic reports on the synthesis of sec-butylamine by catalytic hydrogenation of methylhexanone. Wang Xiaoli, Ding Baohong, Zhang Jianzhong, etc. (Journal of Fushun Petroleum Institute, 2003, Vol.23, No.1,) reported a liquid-solid phase catalytic ammoniation hydrogenation production using methyl ethyl ketone as raw material and modified Raney nickel as catalyst. A new process for sec-butylamine. The catalyst is modified Raney nickel, the reaction temperature is 140° C., the reaction time is 70 minutes, the catalyst consumption is 3 g per mole of methyl ethyl ketone, and the total reaction pressure is 6 MPa. The conversion rate of liquid methyl ethyl ketone obtained by operating under this condition is nearly 100%, and the yield of sec-butylamine is 91.5%. The process is a tank reaction and is not suitable for large-scale industrial production.
发明内容Contents of the invention
本发明的目的是提供一种高活性、高选择性甲乙酮催化氨化加氢制备仲丁胺用负载型复合催化剂及其制备方法。The purpose of the present invention is to provide a high activity, high selectivity methyl ethyl ketone catalyzed ammoniation hydrogenation to prepare the loaded type composite catalyst for sec-butylamine and its preparation method.
一种甲乙酮催化氨化加氢制备仲丁胺用催化剂，其特征在于催化剂载体为Al2O3-TiO2复合氧化物，活性组分由10-25％重量NiO，以及1-10％重量的CuO、Cr2O3、MgO、BaO中的两种组成。A catalyst for the preparation of sec-butylamine by catalytic hydrogenation of methyl ethyl ketone, characterized in that the catalyst carrier is Al 2 O 3 -TiO 2 composite oxide, the active component consists of 10-25% by weight NiO, and 1-10% by weight of Two compositions among CuO, Cr 2 O 3 , MgO, and BaO.
本发明的催化剂采用浸渍法制备，其特征在于先将Ni的盐溶液浸渍在Al2O3-TiO2氧化物上，于100-120℃干燥，450-600℃焙烧，再选择Cu、Mg、Ba、Cr中的两种的硝酸盐溶液，浸渍在载体上，并于100-120℃干燥，最后用氢气在250-300℃还原，制得催化剂。The catalyst of the present invention is prepared by an impregnation method, which is characterized in that the Ni salt solution is first impregnated on the Al 2 O 3 -TiO 2 oxide, dried at 100-120°C, calcined at 450-600°C, and then Cu, Mg, Ba and Cr nitrate solutions are impregnated on the carrier, dried at 100-120°C, and finally reduced with hydrogen at 250-300°C to obtain a catalyst.
本发明所用的Ni盐选自硝酸镍或醋酸镍。The Ni salt used in the present invention is selected from nickel nitrate or nickel acetate.
本发明的催化剂，在常压，反应温度170-200℃，甲乙酮与氨、氢气的摩尔比为1∶1.2∶1.2，甲乙酮转化率可达30-42％，选择性达70-97％。The catalyst of the present invention has a reaction temperature of 170-200 DEG C under normal pressure, a molar ratio of methyl ethyl ketone to ammonia and hydrogen of 1:1.2:1.2, a conversion rate of methyl ethyl ketone of 30-42%, and a selectivity of 70-97%.
具体实施方式Detailed ways
实施例1：Example 1:
选用20g直径为2-3毫米的Al2O3-TiO2颗粒为载体。将50ml浓度为20％的硝酸镍溶液，加热到75℃后，倒入上述Al2O3-TiO2载体中，于100-120℃干燥5小时，在450-600℃焙烧4小时，冷却后倒入25ml含有2.5g醋酸铜和含有2.4g硝酸铬的溶液，于100-120℃干燥5小时，最后用氢气在250-300℃还原3小时，制得催化剂。20 g of Al 2 O 3 -TiO 2 particles with a diameter of 2-3 mm are selected as the carrier. Heat 50ml of 20% nickel nitrate solution to 75°C, pour it into the above-mentioned Al 2 O 3 -TiO 2 carrier, dry at 100-120°C for 5 hours, bake at 450-600°C for 4 hours, and cool Pour 25ml of a solution containing 2.5g of copper acetate and 2.4g of chromium nitrate, dry at 100-120°C for 5 hours, and finally reduce with hydrogen at 250-300°C for 3 hours to obtain a catalyst.
将20ml上述催化剂装入Φ10的不锈钢反应器中，于180℃、常压下，甲乙酮与氨、氢气的摩尔比为1∶1.2∶1.2，反应的转化率为42％，选择性为97％。Put 20ml of the catalyst above into a Φ10 stainless steel reactor. At 180°C and normal pressure, the molar ratio of methyl ethyl ketone to ammonia and hydrogen is 1:1.2:1.2, the conversion rate of the reaction is 42%, and the selectivity is 97%.
实施例2：Example 2:
催化剂的制备方法同例1，不同的是第二次浸渍采用的是25ml含有2.5g醋酸铜和含有3.2g硝酸镁的溶液，在例1条件下干燥，并还原，制得所需催化剂。The preparation method of catalyzer is the same as example 1, and what difference is that second impregnation adopts is that 25ml contain 2.5g copper acetate and contain the solution of 3.2g magnesium nitrate, dry under example 1 condition, and reduction, make required catalyzer.
采用该催化剂20ml，使用与实例1相同的条件，反应转化率34％，选择性84％。Using 20ml of the catalyst, using the same conditions as Example 1, the reaction conversion rate was 34%, and the selectivity was 84%.
实施例3：Example 3:
催化剂的制备方法同例1，不同的是第二次浸渍采用的是25ml含有2.5g醋酸铜和含有1.5g硝酸钡的溶液，在例1条件下干燥，并还原，制得所需催化剂。The preparation method of catalyzer is the same as example 1, and what difference is that second time impregnation adopts is that 25ml contains 2.5g copper acetate and contains the solution of 1.5g barium nitrate, is dried under example 1 conditions, and reduction, makes required catalyzer.
采用该催化剂20ml，使用与实例1相同的条件，反应转化率35％，选择性86％。Using 20ml of the catalyst, using the same conditions as Example 1, the reaction conversion rate was 35%, and the selectivity was 86%.
实施例4：Example 4:
催化剂的制备方法同例1，不同的是第二次浸渍采用的是25ml含有3.25g硝酸铬和含有3.2g硝酸镁的溶液，在例1条件下干燥，并还原，制得所需催化剂。The preparation method of catalyzer is the same as example 1, and what difference is that second impregnation adopts is that 25ml contain 3.25g chromium nitrate and the solution that contains 3.2g magnesium nitrate, dry under example 1 condition, and reduction, make required catalyzer.
采用该催化剂20ml，使用与实例1相同的条件，反应转化率35％，选择性75％。Using 20ml of the catalyst, using the same conditions as Example 1, the reaction conversion rate was 35%, and the selectivity was 75%.
实施例5：Example 5:
催化剂的制备方法同例1，不同的是第二次浸渍采用的是25ml含有3.25g硝酸铬和含有1.5g硝酸钡的溶液，在例一条件下干燥，并还原，制得所需催化剂。The preparation method of catalyzer is the same as example 1, and what difference is that second impregnation adopts is that 25ml contain 3.25g chromium nitrate and the solution that contains 1.5g barium nitrate, dry under example 1 condition, and reduction, make required catalyzer.
采用该催化剂20ml，使用与实例1相同的条件，反应转化率37％，选择性81％。Using 20ml of this catalyst, using the same conditions as Example 1, the reaction conversion rate was 37%, and the selectivity was 81%.
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| CN100591418C (en) * | 2007-07-19 | 2010-02-24 | 武汉理工大学 | Co-precipitation preparation method of a nickel-based Claus tail gas hydrogenation catalyst |
| CN102553606B (en) * | 2010-12-30 | 2014-07-16 | 中国石油化工股份有限公司 | Nickel series hydrogenation catalyst, preparation method thereof and application thereof |
| CN102898312A (en) * | 2011-07-28 | 2013-01-30 | 泰州石油化工有限责任公司 | Method for preparing sec-butylamine through methyl ethyl ketone catalytic ammonization hydrogenation |
| CN102935370B (en) * | 2011-08-16 | 2015-09-16 | 中国石油化工股份有限公司 | A kind of C 5hydrogenation of petroleum resin catalyst, its preparation method and application thereof |
| CN110270279B (en) * | 2019-07-12 | 2021-10-08 | 江苏万盛大伟化学有限公司 | Fixed bed reactor for continuously producing diisotridecylamine and application thereof |
| CN110773175A (en) * | 2019-11-07 | 2020-02-11 | 江苏美思德化学股份有限公司 | Supported metal catalyst, preparation method and application thereof, and synthesis process of N-methylmorpholine |
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| US6111100A (en) * | 1999-01-14 | 2000-08-29 | Basf Aktiengesellschaft | Preparation of bis(2-morpholinoethyl) ether |
| US6111100C1 (en) * | 1999-01-14 | 2002-04-02 | Basf Ag | Preparation of bis(2-morpholinoethyl) ether |
| CN1351116A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Hydrocatalyst and its preparing process |
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