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

a technology of aniline distillation residue and catalyst, which is applied in the preparation of amino compounds, physical/chemical process catalysts, metal/metal-oxide/metal-hydroxide catalysts, etc., can solve the disadvantages of complicated operation of fluidized bed reactors, side reactions and deactivation of catalysts, and high heat generation (hot spot) prone to occur, and achieve good catalytic activity , high activity and stability

Inactive Publication Date: 2016-07-21
WANHUA CHEM GRP CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0006]It is an object of the present invention to provide a catalyst for fixed bed aniline rectification residue recycling, which can hydrocrack aniline rectification residue to break molecular chains C—C, C—N of the high molecular weight substances contained in the residue, to make the C═C molecular chains saturated, to decrease their molecular weight, to reduce the viscosity of the system, to enhance the fluidity, and also to obtain useful substances such as cyclohexyl amine, dicyclohexyl amine and the like such that the subsequent separation operation is facilitated.
[0007]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.
[0024]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. 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 H2 (50 ml / min). When the reduction is ended and the temperature drops to the reaction temperature, the feeding and reaction is initiated, and the resulting product is quantitatively analyzed by gas chromatograph. 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.
[0026]In the catalyst of the present invention, 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. By changing the support and adding the first and second cocatalyst components, 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.

Problems solved by technology

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.
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.
These factors make aniline rectification residue have high viscosity and poor fluidity, and thus difficult to be reused.
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.
At present, there is no effective method for the utilization of aniline rectification residue.

Method used

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

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0031]16 g of nickel nitrate Ni(NO3)2.6H2O, 20 g of ferric nitrate Fe(NO3)3.9H2O and 11 g of lanthanum nitrate La(NO3)3.6H2O are weighed respectively, and dissolved in 300 ml of distilled water, referred to as solution A.

[0032]15 mass % of aqueous ammonia solution (200 ml) is formulated, referred to as solution B.

[0033]17 g of sodium silicate (Na2SiO3) is weighed and dissolved in 150 ml water, referred to as solution C.

[0034]Firstly, 100 ml water in a sedimentation tank is heated to 50° C., and the solution A, B and C are added dropwise to the sedimentation tank. In the preparation process, pH and the precipitation temperature are maintained at 7.5 and 60° C. respectively. After the end of precipitation, the stirring speed and precipitation temperature are kept unchanged, and the resulting precipitate is aged for 4 h, filtered and washed to neutral. Thereafter, the precipitate is placed in an oven of 110° C. and dried for 12 h. After the end of drying, the precipitate is calcined un...

example 2

[0036]24 g of nickel nitrate Ni(NO3)2.6H2O, 20 g of ferric nitrate Fe(NO3)3.9H2O and 7 g of yttrium nitrate Y (NO3)3.6H2O are weighed respectively, and dissolved in 300 ml of distilled water, referred to as solution A. 0.7 mol / L of Na2CO3 solution is formulated, 17 g of sodium silicate (Na2SiO3) is weighed and dissolved in 300 ml Na2CO3 solution, referred to as solution B.

[0037]Firstly, water in the sedimentation tank is heated to 70° C., and the solution A and B are added dropwise to a sedimentation tank in a parallel flow. In the preparation process, pH and the precipitation temperature are maintained at 8 and 70° C. respectively. After the end of precipitation, the stirring speed and precipitation temperature are kept unchanged, and the resulting precipitate is aged for 4 h, filtered and washed to neutral. Thereafter, 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 500° C. for 4 h, an...

example 3

[0039]20 g of nickel nitrate Ni(NO3)2.6H2O, 8 g of cobalt nitrate Co (NO3)2.6H2O and 15 g of cerium nitrate Ce (NO3)3.6H2O are weighed respectively, and dissolved in 200 ml of distilled water, referred to as solution A.

[0040]1 mol / L of NaOH solution is formulated, 17 g of sodium silicate (Na2SiO3) is dissolved in 200 ml NaOH solution, referred to as solution B.

[0041]Firstly, 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. In the meantime, the precipitation temperature is maintained at 70° C. After the end of precipitation, the stirring speed and precipitation temperature are kept unchanged, and the resulting precipitate is aged for 4 h, filtered and washed to neutral. Thereafter, 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 550° C. for 4 h, and then grinded, compression molded, pulverized a...

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Abstract

The present invention relates to a catalyst for fixed bed aniline rectification residue recycling and preparation method thereof. Based on the total weight of the catalyst, the catalyst comprises the following components in percentage by weight: 5-40% of an active component, 2-30% of a first cocatalyst component, 10-30% of a second cocatalyst component and the balance of carrier, wherein the active component is NiO; the first cocatalyst component is one or more of Fe, Mo, Cr or Co oxide; and the second cocatalyst component is one or more of La, Zr, Y or Ce oxide. The catalyst is prepared through co-precipitation. The catalyst shows high activity and stability in the waste liquid treatment process, and can still maintain high rectification residue cracking rate after reaction of 200 hours.

Description

FIELD OF THE INVENTION[0001]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.BACKGROUND OF THE INVENTION[0002]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.[0003]Taking into account the source of raw materials, energy consumption, environmental protection and so on, most manufacturers use 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 t...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C07C209/62B01J23/75B01J23/887C07C209/72B01J37/03B01J37/02B01J37/08B01J23/83B01J23/86
CPCC07C209/62B01J23/83B01J23/75B01J23/8871C07C2101/14B01J37/031B01J37/0236B01J37/08C07C209/72B01J23/866B01J37/035B01J23/002B01J2523/00B01J37/03C07C2601/14Y02P20/584C07C211/35B01J2523/3706B01J2523/41B01J2523/842B01J2523/847B01J2523/36B01J2523/3712B01J2523/845B01J2523/48B01J2523/68B01J2523/67
Inventor MEI, HUACHEN, HAOYU, DEWEIZHANG, CONGYINGWANG, HUILI, YUANCHEN, ZHONGYINGNI, ZILINJIANG, QINGMEICAO, SHANJIANYANG, ZAIGANGQU, JUNSONG, JINHONGHU, BINGBO
Owner WANHUA CHEM GRP CO LTD
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