US20160207876A1 - Catalyst used for resource utilization of a fixed bed aniline distillation residue and method for preparing said catalyst - Google Patents

Catalyst used for resource utilization of a fixed bed aniline distillation residue and method for preparing said catalyst Download PDF

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US20160207876A1
US20160207876A1 US14/913,853 US201414913853A US2016207876A1 US 20160207876 A1 US20160207876 A1 US 20160207876A1 US 201414913853 A US201414913853 A US 201414913853A US 2016207876 A1 US2016207876 A1 US 2016207876A1
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catalyst
oxides
solution
temperature
sedimentation tank
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Hua Mei
Hao Chen
Dewei YU
Congying ZHANG
Hui Wang
Yuan Li
Zhongying Chen
Zilin Ni
Qingmei JIANG
Shanjian CAO
Zaigang YANG
Jun Qu
Jinhong SONG
Bingbo Hu
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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Assigned to WANHUA CHEMICAL (NINGBO) CO., LTD., WANHUA CHEMICAL GROUP CO., LTD. reassignment WANHUA CHEMICAL (NINGBO) CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CAO, Shanjian, CHEN, HAO, CHEN, ZHONGYING, HU, BINGBO, JIANG, Qingmei, LI, YUAN, MEI, HUA, NI, Zilin, QU, JUN, SONG, JINHONG, WANG, HUI, YANG, Zaigang, YU, DEWEI, ZHANG, Congying
Publication of US20160207876A1 publication Critical patent/US20160207876A1/en
Assigned to WANHUA CHEMICAL GROUP CO., LTD. reassignment WANHUA CHEMICAL GROUP CO., LTD. CORRECTIVE ASSIGNMENT TO REMOVE THE 2ND ASSIGNEE AND TO CORRECT THE ASSIGNEE ADDRESS PREVIOUSLY RECORDED AT REEL: 038419 FRAME: 0524. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Assignors: CAO, Shanjian, CHEN, HAO, CHEN, ZHONGYING, HU, BINGBO, JIANG, Qingmei, LI, YUAN, MEI, HUA, NI, Zilin, QU, JUN, SONG, JINHONG, WANG, HUI, YANG, Zaigang, YU, DEWEI, ZHANG, Congying
Priority to US15/720,103 priority Critical patent/US9926259B1/en
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Definitions

  • the present invention relates to a catalyst and preparation method thereof, and more particularly to a catalyst for fixed bed aniline rectification residue recycling and preparation method thereof.
  • Aniline is a colorless, oily liquid with a strong odor and toxicity. It is an important chemical intermediate, and thus is widely used for producing rubber processing aids, dyes, photographic chemicals, pharmaceuticals, pesticides, explosives, polyurethanes and the like.
  • the production methods of aniline comprise phenol ammoniation, iron powder reduction and catalytic hydrogenation of nitrobenzene.
  • the catalytic hydrogenation may be divided into two processes, i.e., the fixed bed gas phase hydrogenation and fluidized bed gas phase hydrogenation according to the different forms of the reactor used.
  • the fixed bed gas phase hydrogenation has the advantages of simple process, low maintenance cost, no need for separation of catalyst, low reaction temperature, good product quality and the like, but local overheating (hot spot) is prone to occur due to poor heat transfer of the fixed bed, which leads to side reactions and deactivation of the catalyst. Therefore, the activity cycle of the catalyst is shortened.
  • the fluidized bed reactor heat transfer is good, such that local overheating may be avoided, side reactions may be reduced and the service life of the catalyst may be prolonged.
  • the fluidized bed reactor has the disadvantages of complicated operation, remarkable catalyst abrasion, and high operation and maintenance costs.
  • the liquid phase hydrogenation comprises a gas phase reaction and a liquid phase reaction and achieves easy reaction heat removal, and has the advantages of simple equipment and low operation and maintenance costs, but the cost of technology introduction is high.
  • aniline is produced by the liquid phase catalytic hydrogenation process, wherein the raw material nitrobenzene is desulfurized and decarbonized by an oxidation system, the nitrobenzene and hydrogen gas are mixed and pretreated, and then reacted in a fluidized bed reactor and the used catalyst is recycled to the reactor for reuse. Since water is generated in the reaction, the crude product obtained after reaction is refined by extraction, the unreacted nitrobenzene is recovered, aniline is obtained by rectification, and aniline rectification residue is enriched in the rectification tower kettle.
  • the aniline rectification residue is primarily originated from the two aspects: (1) a part of high boiling components is produced from nitrobenzene due to the excess of hydrogen gas in the hydrogenation; (2) cyclohexanone intermediate produced in the hydrogenation reaction may be reacted with aniline to form Schiff base tar, which is black viscous liquid with a pungent smell and contains a lot of aromatic substances with negatively charged ⁇ -electron system, such as
  • aniline rectification residue have high viscosity and poor fluidity, and thus difficult to be reused. It is generally used for firewood material and waterproof material. The amount of aniline rectification residue used for the two uses is very small, based on the total amount of aniline rectification residue. Therefore, most of the aniline rectification residue, as waste liquid, is treated by incineration, but after incineration, it will produce nitrogen oxides and lead to acid rain and pollution environment, and further reduce the output of agriculture and fisheries.
  • the technical problem to be solved by the present invention is how to crack the aniline rectification residue sufficiently to obtain a certain amount of high economic value of product, in order to turn it from waste to treasure and reduce the pollution of the environment as far as possible.
  • Another object of the present invention is to provide a method of preparing the catalyst for fixed bed aniline rectification residue recycling. Said method is simple, and the prepared catalyst has good stability.
  • a yet another object of the present invention is to provide the use of said catalyst for fixed bed aniline rectification residue recycling.
  • a catalyst for fixed bed aniline rectification residue recycling which comprises the components described below based on the total weight of the catalyst:
  • NiO as an active component
  • the catalyst comprises the components described below:
  • NiO 15-30 wt % of NiO as the active component, 5-25 wt % of one or more selected from oxides of Fe, oxides of Mo, oxides of Cr and oxides of Co as the first cocatalyst component, 15-25 wt % of one or more selected from oxides of La, oxides of Zr, oxides of Y and oxides of Ce as the second cocatalyst component, the remaining portion being the support.
  • said support is SiO 2 .
  • a method of preparing the catalyst for fixed bed aniline rectification residue recycling which comprises:
  • the first cocatalyst component comprises the oxide of Mo
  • the precipitate of the components except Mo is immersed in ammonium molybdate solution, and then calcinated, molded and pulverized.
  • the concentration of the metal ions in said mixing solution of metal nitrates is controlled at 0.3-5 mol/L.
  • said alkali solution is aqueous Na 2 CO 3 solution, aqueous NaOH solution or aqueous solution of ammonia, and its concentration is 0.5-10 mol/L.
  • the concentration of said aqueous sodium silicate solution or the concentration of sodium silicate in alkali solution is 0.1-1 mol/L.
  • the temperature in the sedimentation tank is controlled at 50-70° C.
  • the calcination temperature is between 300-700° C., and the calcination time is 4-6 h.
  • said aging temperature is 60-80° C., and the aging time is 4-8 h; the drying temperature is 100-150° C., and the drying time is 8-15 h.
  • said molding comprises extrusion molding or compression molding the calcinated catalyst, and the pulverization comprises pulverizing the catalyst to 10-20 mesh.
  • the present invention additionally provides the use of the above-said catalyst or the catalyst prepared by the above-said method for aniline rectification residue recycling, wherein the aniline rectification residue is treated by gas phase hydrogenation to obtain cyclohexyl amine and dicyclohexyl amine, using monofunctional saturated alcohol as the diluent, under the catalysis of the catalyst, at a certain temperature and pressure.
  • Said monofunctional saturated alcohol is ethanol or methanol.
  • the monofunctional saturated alcohol/aniline rectification residue in mass ratio of 0.1-0.7:1 is injected to a fixed bed reactor with the catalyst loading capacity of 10 ml by a micro-metering pump, and is completely evaporated at the upper end of the reaction tube.
  • the liquid phase volume space velocity is 0.6-1.5 h ⁇ 1
  • the reaction pressure is 1-4 MPa
  • the reaction temperature is between 250-320° C.
  • the volume ratio of the hydrogen amount and the amount of aniline rectification residue is 500-3000:1
  • the hydrogen flow rate is 150-400 ml/min.
  • the catalyst Prior to initiation of the reaction, the catalyst needs to be reduced, and the reduction temperature and time are 350-500° C. and 4 h, respectively.
  • the reducing gas is H 2 (50 ml/min).
  • the resulting catalyst has high activity and high selectivity, based on the mass of the rectification residue, the cyclohexylamine and dicyclohexylamine yields are up to 36.8% and 40% respectively, and the catalyst has good stability and the product selectivity is still not decreased after 200 h reaction.
  • the reaction of the aniline rectification residue processed by the catalyst of the present invention belongs to hydrocracking.
  • hydrocracking the molecular chains C—C, C—N of the high molecular weight substances contained in the aniline rectification residue are broken, the molecular chains C ⁇ C are saturated, the viscosity of the system is decreased, and small molecular substances such as cyclohexyl amine, dicyclohexyl amine are obtained, such that the subsequent separation operation is facilitated.
  • the catalyst of the present invention will not cleave the ring of small molecules, and the reaction principle may refer to the following reaction schemes:
  • the components have a synergic effect among them, so that the catalyst has high activity and stability.
  • Ni catalyst has good catalytic activity, but is subjected to activity lowering due to the loss, sintering and coking of the active constituents in a high temperature reaction, and prone to sulfur poisoning.
  • the loss of the active constituents may be reduced, and the degree of carbon deposition and sintering may be alleviated, thereby enhance the stability of the catalyst and prolong the service life of the catalyst.
  • Y has effects of regulating the catalyst surface acidity, preventing carbon deposition and reducing ring opening reaction.
  • Fe has the role of stabilizing the catalyst, and Mo, Cr, Zr, Ce, La or Co has the functions of reducing carbon deposition on the catalyst and prolonging the life of the catalyst.
  • FIG. 1 is the gas chromatogram of the product of Example 1 of the present invention.
  • the fixed bed reactor used in the Examples have a size of length 100 cm and inner diameter 25 mm.
  • the reaction product is analyzed by Shimadzu GC-2014 gas chromatograph (hydrogen flame ionization (FID) detector) using internal standard method.
  • the detection conditions are as follows: analytical column SE-30, capillary column ( ⁇ 0.30 mm ⁇ 30 m), the gasification chamber 270° C., the detector 270° C.
  • the column temperature is 70° C. and maintained for 1 min, and then rise to 240° C. at the rate of 40° C./min and maintained for 5 min.
  • the aniline rectification residue used in the Examples is from the aniline rectification units of Ningbo Wanhua Polyurethane Co., Ltd.
  • solution A 16 g of nickel nitrate Ni(NO 3 ) 2 .6H 2 O, 20 g of ferric nitrate Fe(NO 3 ) 3 .9H 2 O and 11 g of lanthanum nitrate La(NO 3 ) 3 .6H 2 O are weighed respectively, and dissolved in 300 ml of distilled water, referred to as solution A.
  • solution B 15 mass % of aqueous ammonia solution (200 ml) is formulated, referred to as solution B.
  • solution C 17 g of sodium silicate (Na 2 SiO 3 ) is weighed and dissolved in 150 ml water, referred to as solution C.
  • solution A 20 g of nickel nitrate Ni(NO 3 ) 2 .6H 2 O, 8 g of cobalt nitrate Co (NO 3 ) 2 .6H 2 O and 15 g of cerium nitrate Ce (NO 3 ) 3 .6H 2 O are weighed respectively, and dissolved in 200 ml of distilled water, referred to as solution A.
  • solution B 1 mol/L of NaOH solution is formulated, 17 g of sodium silicate (Na 2 SiO 3 ) is dissolved in 200 ml NaOH solution, referred to as solution B.
  • the solution B is poured into a sedimentation tank and heated to 70° C., and the solution A is added dropwise to the sedimentation tank slowly.
  • the precipitation temperature is maintained at 70° C.
  • the stirring speed and precipitation temperature are kept unchanged, and the resulting precipitate is aged for 4 h, filtered and washed to neutral.
  • the precipitate is placed in an oven of 110° C. and dried for 12 h.
  • the precipitate is calcined under air atmosphere at 550° C. for 4 h, and then grinded, compression molded, pulverized and sieved to 10-20 mesh.
  • 24% NiO-10% Co 3 O 4 /39% SiO 2 -27% CeO 2 is prepared.
  • solution B 15 mass % of aqueous ammonia solution (200 ml) is formulated, referred to as solution B.
  • the solution A is poured into a sedimentation tank and heated to 70° C., and the solution B is added dropwise to the sedimentation tank slowly.
  • the precipitation temperature is maintained at 70° C.
  • the stirring speed and precipitation temperature are kept unchanged, and the resulting precipitate is aged for 4 h, filtered and washed to neutral.
  • the precipitate is placed in an oven of 110° C. and dried for 12 h. After the end of drying, the precipitate is calcined under air atmosphere at 600° C. for 4 h, and then grinded, compression molded, pulverized and sieved to 10-20 mesh.
  • 20% NiO-10% Co 3 O 4 /40% SiO 2 -30% CeO 2 is prepared.
  • solution A 18 g of nickel nitrate Ni(NO 3 ) 2 .6H 2 O, 18 g of cobalt nitrate Co(NO 3 ) 2 .6H 2 O and 10 g of yttrium nitrate Y(NO 3 ) 3 .6H 2 O are weighed respectively, and dissolved in 200 ml of distilled water, referred to as solution A.
  • solution B 200 ml of 1 mol/L of Na 2 CO 3 solution is formulated, and therein 14.6 g of sodium silicate (Na 2 SiO 3 ) is dissolved, referred to as solution B.
  • solution B 200 ml of 1 mol/L of Na 2 CO 3 solution is formulated, and therein 14 g of sodium silicate (Na 2 SiO 3 ) is dissolved, referred to as solution B.
  • solution B 250 ml of 1 mol/L of Na 2 CO 3 solution is formulated, and therein 16 g of sodium silicate (Na 2 SiO 3 ) is dissolved, referred to as solution B.
  • solution A 24 g of nickel nitrate Ni(NO 3 ) 2 .6H 2 O and 14 g of yttrium nitrate Y(NO 3 ) 3 .6H 2 O are weighed respectively, and dissolved in 300 ml of distilled water, referred to as solution A.
  • 300 ml of 0.7 mol/L of Na 2 CO 3 solution is formulated, and 17 g of sodium silicate (Na 2 SiO 3 ) is weighed and dissolved in the Na 2 CO 3 solution, referred to as solution B.
  • solution B 20 mass % of aqueous ammonia solution (150 ml) is formulated, referred to as solution B.
  • the solution A is poured into a sedimentation tank and heated to 70° C., and the solution B is added dropwise to the sedimentation tank slowly.
  • the precipitation temperature is maintained at 70° C.
  • the stirring speed and precipitation temperature are kept unchanged, and the resulting precipitate is aged for 4 h, filtered and washed to neutral.
  • the precipitate is placed in an oven of 110° C. and dried for 12 h. After the end of drying, the precipitate is calcined under air atmosphere at 600° C. for 3 h, and then grinded, compression molded, pulverized and sieved to 10-20 mesh.
  • 24.5% NiO-7.2% Cr 2 O 3 /39.9% SiO 2 -28.4% CeO 2 is prepared.
US14/913,853 2013-09-03 2014-03-07 Catalyst used for resource utilization of a fixed bed aniline distillation residue and method for preparing said catalyst Abandoned US20160207876A1 (en)

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CN107188329B (zh) * 2017-05-27 2020-06-26 南京工业大学 一种苯胺生产过程中工艺废水与精馏残液的联合净化方法
CN108047051B (zh) * 2017-12-12 2020-05-08 万华化学集团股份有限公司 复配分子筛催化剂用于催化裂化处理苯胺焦油的用途和方法
CN113149846A (zh) * 2021-05-31 2021-07-23 金城化学(江苏)有限公司 环己胺生产过程中副产物再次加氢工艺和装置

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