CN108786879B - Method for catalyzing selective hydrogenation of 1, 3-butadiene by PdAgNi/N-C catalyst - Google Patents

Method for catalyzing selective hydrogenation of 1, 3-butadiene by PdAgNi/N-C catalyst Download PDF

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CN108786879B
CN108786879B CN201810522176.1A CN201810522176A CN108786879B CN 108786879 B CN108786879 B CN 108786879B CN 201810522176 A CN201810522176 A CN 201810522176A CN 108786879 B CN108786879 B CN 108786879B
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butadiene
pdagni
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CN108786879A (en
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万超
许立信
叶明富
雷昭
王金刚
范立岩
张建伟
周伟
汪玉喜
罗贤进
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Anhui Gongda Chemical Technology Co ltd
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    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
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Abstract

The invention discloses a method for catalyzing selective hydrogenation of 1, 3-butadiene by using a PdAgNi/N-C catalyst, which is characterized by comprising the following steps: the method comprises the steps of firstly placing a PdAgNi/N-C catalyst in a tubular reactor, then raising the temperature of a catalyst bed layer to 30-60 ℃, and then introducing a mixed gas of 1, 3-butadiene and hydrogen into the reactor under the pressure of 1.5-3.2 MPa and the airspeed of 1.0-4.0 h‑1The reaction is carried out under the conditions of (1). The method takes PdAgNi/N-C as a catalyst, and uses the catalyst to carry out 1, 3-butadiene selective hydrogenation reaction, wherein the content of 1, 3-butadiene in a product is lower than 900ppb, the content of butane is lower than 2.3%, and the catalyst still keeps good catalytic activity after continuously running for 100 hours.

Description

Method for catalyzing selective hydrogenation of 1, 3-butadiene by PdAgNi/N-C catalyst
Technical Field
The invention relates to the technical field of chemistry and chemical engineering, in particular to a method for catalyzing selective hydrogenation of 1, 3-butadiene by using a PdAgNi/N-C catalyst.
Background
In petrochemical industry, naphtha steam cracking produces rich low chain C4Olefins, but in these C4Alkenes often contain small amounts of dienes or alkynes; in the downstream olefin polymerization process, diolefins or alkynes tend to be more easily adsorbed on the surface of the polymerization catalyst than monoolefins, so that the catalyst is poisoned and ineffective, and people often utilize selective hydrogenation of diolefins to generate monoolefins to solve the problem.
The development of highly efficient selective hydrogenation catalysts is the focus of current research, and the SHP process (Oil Gas J,1988,86(49)40-43) of the American Ring and Oil products corporation (UOP) uses noble metal catalysts, and the conversion rate of butadiene reaches 99.8%, but the production amount of n-butane reaches 35.7%. U.S. Pat. No. 4,47629 discloses a palladium-based catalyst for the selective hydrogenation of butadiene containing 0.025-1.0% Pd and 0.04-4% Sn or Pb, based on the weight of the catalyst, which is effective in increasing the selectivity of butadiene hydrogenation and inhibiting the isomerization of olefins. Chinese patent CN106582625A discloses a catalyst for selective hydrogenation of butadiene, which comprises the following components in parts by weight: (a) 0.05-0.5% of metal Pd or oxide thereof; (b)0.1-2 parts of a group IB metal or oxide thereof; (c)97.5-99.7 parts of carrier alumina, which effectively solves the technical problems of high loss of butene-1, higher cost of the catalyst and use of toxic and harmful raw materials in the preparation process in the prior art, but is slightly insufficient in controlling the content of butadiene in the product.
Disclosure of Invention
The invention aims to provide a method for catalyzing 1, 3-butadiene to be selectively hydrogenated by using a PdAgNi/N-C catalyst, which takes PdAgNi/N-C as the catalyst, has catalytic activity and stability, effectively reduces the content of 1, 3-butadiene and solves the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for catalyzing selective hydrogenation of 1, 3-butadiene by using a PdAgNi/N-C catalyst, which is characterized by comprising the following steps: the method comprises the steps of firstly placing a PdAgNi/N-C catalyst in a tubular reactor, then raising the temperature of a catalyst bed layer to 30-60 ℃, and then introducing a mixed gas of 1, 3-butadiene and hydrogen into the reactor under the pressure of 1.5-3.2 MPa and the airspeed of 1.0-4.0 h-1The reaction is carried out under the conditions of (1).
Preferably, the molar ratio of the 1, 3-butadiene to the hydrogen is 1: 1.2-2.5.
Preferably, the PdAgNi/N-C catalyst is prepared by the following steps:
(1) adding a certain molar amount of Pd salt, Ag salt, Ni salt and deionized water into a beaker, fully stirring in an ice bath at 0 ℃, adding an N-C material, and fully stirring;
(2) dropwise adding 0.1-0.4 mol/L sodium borohydride solution into the mixed solution prepared in the step (1), and stirring and reducing for 2 hours;
(3) and (3) filtering the solution obtained in the step (2) and drying to obtain the PAgNi/N-C catalyst.
Preferably, the Pd salt is palladium chloride, the Ag salt is silver nitrate, and the Ni salt is nickel chloride.
Preferably, the mole ratio of Pd to Ag to Ni is 1: 0.2-0.4: 0.1-0.3; the mole ratio of the Pd to the N-C material is 1: 500-800.
Preferably, in the step (1), the N-C material is prepared by roasting melamine and glucose according to a certain mass ratio, the mass ratio of the melamine to the glucose is 30-60: 1, the roasting temperature is 700-900 ℃, and the roasting time is 2-6 h.
Preferably, in the step (3), the drying temperature is 80-140 ℃, and the drying time is 10-20 h.
The invention discloses the following technical effects:
the method takes N-C material synthesized by melamine and glucose as precursors as a carrier, palladium chloride, silver nitrate and nickel chloride are used as precursors for preparing the catalyst, a dipping reduction method is adopted to prepare the PdAgNi/N-C catalyst, the catalyst has high activity and stability, the catalyst is used for carrying out 1, 3-butadiene selective hydrogenation reaction, wherein the content of 1, 3-butadiene in a product is lower than 900ppb, the content of butane is lower than 2.3%, and the catalyst still keeps good catalytic activity after continuously running for 100 hours.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be described in further detail with reference to specific embodiments in order to make the above objects, features and advantages more apparent and understandable.
Example 1
(1) Preparation of the catalyst
Adding 0.02mmol PdCl2、0.004mmolAgNO3And 0.002mmol NiCl2Dissolving the mixture in 10mL of distilled water, uniformly stirring the mixture in an ice bath at the temperature of 0 ℃, and then adding 10mmol of N-C material into the solution, wherein the N-C material is prepared by roasting melamine and glucose at the temperature of 700 ℃ for 2 hours according to the mass ratio of 30: 1; after fully stirring, dropwise adding 0.1mol/L sodium borohydride solution for reduction for 2h, filtering and drying in a drying oven at 80 ℃ for 20h to obtain the catalyst PdAg0.2Ni0.1/N-C500And (4) sealing and storing.
(2) Hydrogenation process
Filling 1.5mL of the catalyst prepared in the step (1) into a tubular reactor with the inner diameter of 8mm, raising the temperature of a catalyst bed layer to 30 ℃, introducing a mixed gas of 1, 3-butadiene and hydrogen with the molar ratio of 1:1.2 into the reactor, wherein the reaction pressure is 1.5MPa, and the reaction space velocity is 1.0h-1。
Analyzing the product obtained after the reaction for 2 hours in the step (2) by adopting gas chromatography and mass spectrometry, wherein the content of 1, 3-butadiene in the product is lower than 880ppb, and the content of butane is lower than 2.1%; after the catalyst is continuously operated for 100 hours, the gas chromatography and mass spectrometry analysis on the product show that the content of 1, 3-butadiene in the product is less than 895ppb, and the content of butane is less than 2.2%.
Example 2
(1) Preparation of the catalyst
Adding 0.02mmol PdCl2、0.008mmolAgNO3And 0.006mmol NiCl2Dissolving the mixture in 10mL of distilled water, uniformly stirring the mixture in an ice bath at the temperature of 0 ℃, and then adding 16mmol of N-C material into the solution, wherein the N-C material is prepared by roasting melamine and glucose at the temperature of 900 ℃ for 6 hours according to the mass ratio of 60: 1; after fully stirring, dropwise adding 0.4mol/L sodium borohydride solution for reduction for 2h, filtering and drying in a drying oven at 140 ℃ for 10h to obtain the catalyst PdAg0.4Ni0.3/N-C800And (4) sealing and storing.
(2) Hydrogenation process
Filling 1.5mL of the catalyst prepared in the step (1) into a tubular reactor with the inner diameter of 8mm, raising the temperature of a catalyst bed layer to 60 ℃, introducing a mixed gas of 1, 3-butadiene and hydrogen with the molar ratio of 1:2.5 into the reactor, wherein the reaction pressure is 3.2MPa, and the reaction space velocity is 4.0h-1。
Analyzing the product obtained after the reaction for 2 hours in the step (2) by adopting gas chromatography and mass spectrometry, wherein the content of 1, 3-butadiene in the product is lower than 790ppb, and the content of butane is lower than 1.8%; after the catalyst is continuously operated for 100 hours, the gas chromatography and mass spectrometry analysis on the product show that the butadiene content of the product 1, 3-is lower than 815ppb, and the butane content is lower than 2.0%.
Example 3
(1) Preparation of the catalyst
Adding 0.02mmol PdCl2、0.006mmolAgNO3And 0.004mmol NiCl2Dissolving the mixture in 10mL of distilled water, uniformly stirring the mixture in an ice bath at the temperature of 0 ℃, and then adding 14mmol of N-C material into the solution, wherein the N-C material is prepared by roasting melamine and glucose at the temperature of 800 ℃ for 4 hours according to the mass ratio of 50: 1; after fully stirring, dropwise adding 0.3mol/L sodium borohydride solution for reduction for 2h, filtering and drying in a drying oven at 120 ℃ for 15h to obtain the catalyst PdAg0.3Ni0.2/N-C700And (4) sealing and storing.
(2) Hydrogenation process
Filling 1.5mL of the catalyst prepared in the step (1) into a tubular reactor with the inner diameter of 8mm, raising the temperature of a catalyst bed layer to 50 ℃, introducing a mixed gas of 1, 3-butadiene and hydrogen with the molar ratio of 1:2.0 into the reactor, wherein the reaction pressure is 2.8MPa, and the reaction space velocity is 3h-1。
Analyzing the product obtained after the reaction for 2 hours in the step (2) by adopting gas chromatography and mass spectrometry, wherein the content of 1, 3-butadiene in the product is lower than 820ppb, and the content of butane is lower than 2.0%; after the catalyst is continuously operated for 100 hours, the gas chromatography and mass spectrometry analysis on the product show that the content of 1, 3-butadiene in the product is less than 840ppb, and the content of butane is less than 2.1%.
Example 4
(1) Preparation of the catalyst
Adding 0.02mmol PdCl2、0.006mmolAgNO3And 0.002mmol NiCl2Dissolving the mixture in 10mL of distilled water, stirring the mixture evenly in an ice bath at the temperature of 0 ℃, and then adding 12mmol of N-C material into the solution, wherein the N-C material is prepared by roasting melamine and glucose for 4 hours at the temperature of 850 ℃ according to the mass ratio of 40: 1; after fully stirring, dropwise adding 0.2mol/L sodium borohydride solution for reduction for 2h, filtering and drying in a drying oven at 100 ℃ for 18h to obtain the catalyst PdAg0.3Ni0.1/N-C600And (4) sealing and storing.
(2) Hydrogenation process
Filling 1.5mL of the catalyst prepared in the step (1) into a tubular reactor with the inner diameter of 8mm, raising the temperature of a catalyst bed layer to 40 ℃, introducing a mixed gas of 1, 3-butadiene and hydrogen with the molar ratio of 1:1.5 into the reactor, wherein the reaction pressure is 2.2MPa, and the reaction space velocity is 2.0h-1。
Analyzing the product obtained after the reaction for 2 hours in the step (2) by adopting gas chromatography and mass spectrometry, wherein the content of 1, 3-butadiene in the product is lower than 830ppb, and the content of butane is lower than 1.9%; after the catalyst is continuously operated for 100 hours, the gas chromatography and mass spectrometry analysis on the product show that the content of 1, 3-butadiene in the product is less than 850ppb, and the content of butane is less than 2.2%.
Example 5
(1) Preparation of the catalyst
Adding 0.02mmol PdCl2、0.004mmolAgNO3And 0.004mmol NiCl2Dissolving the mixture in 10mL of distilled water, stirring the mixture evenly in an ice bath at the temperature of 0 ℃, and then adding 11mmol of N-C material into the solution, wherein the N-C material is prepared by roasting melamine and glucose at the temperature of 750 ℃ for 3 hours according to the mass ratio of 45: 1; after fully stirring, dropwise adding 0.3mol/L sodium borohydride solution for reduction for 2h, filtering and drying in a drying oven at 90 ℃ for 12h to obtain the catalyst PdAg0.2Ni0.2/N-C550And (4) sealing and storing.
(2) Hydrogenation process
Filling 1.5mL of the catalyst prepared in the step (1) into a tubular reactor with the inner diameter of 8mm, raising the temperature of a catalyst bed layer to 35 ℃, introducing a mixed gas of 1, 3-butadiene and hydrogen with the molar ratio of 1:1.8 into the reactor, wherein the reaction pressure is 2.6MPa, and the reaction space velocity is 3.2h-1。
Analyzing the product obtained after the reaction for 2 hours in the step (2) by adopting gas chromatography and mass spectrometry, wherein the content of 1, 3-butadiene in the product is lower than 870ppb, and the content of butane is lower than 1.9%; after the catalyst is continuously operated for 100 hours, the gas chromatography and mass spectrometry analysis on the product show that the content of 1, 3-butadiene in the product is lower than 885ppb, and the content of butane is lower than 2.1%.
Example 6
(1) Preparation of the catalyst
Adding 0.02mmol PdCl2、0.008mmolAgNO3And 0.004mmol NiCl2Dissolving the mixture in 10mL of distilled water, uniformly stirring the mixture in an ice bath at the temperature of 0 ℃, and then adding 15mmol of N-C material into the solution, wherein the N-C material is prepared by roasting melamine and glucose at the temperature of 850 ℃ for 5 hours according to the mass ratio of 45: 1; after fully stirring, dropwise adding 0.2mol/L sodium borohydride solution for reduction for 2h, filtering and drying in a drying oven at 120 ℃ for 16h to obtain the catalyst PdAg0.4Ni0.2/N-C750And (4) sealing and storing.
(2) Hydrogenation process
Filling 1.5mL of the catalyst prepared in the step (1) into a tubular reactor with the inner diameter of 8mm, raising the temperature of a catalyst bed layer to 50 ℃, and then mixing 1, 3-butadiene and 1, 2.3 in a molar ratioIntroducing the mixed gas of hydrogen into the reactor, wherein the reaction pressure is 2.5MPa, and the reaction space velocity is 2.8h-1。
Analyzing the product obtained after the reaction for 2 hours in the step (2) by adopting gas chromatography and mass spectrometry, wherein the content of 1, 3-butadiene in the product is lower than 830ppb, and the content of butane is lower than 1.9%; after the catalyst is continuously operated for 100 hours, the gas chromatography and mass spectrometry analysis on the product show that the content of 1, 3-butadiene in the product is less than 850ppb, and the content of butane is less than 2.2%.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (5)

1. A method for catalyzing selective hydrogenation of 1, 3-butadiene by using a PdAgNi/N-C catalyst is characterized by comprising the following steps: the method comprises the steps of firstly placing a PdAgNi/N-C catalyst in a tubular reactor, then raising the temperature of a catalyst bed layer to 30-60 ℃, and then introducing a mixed gas of 1, 3-butadiene and hydrogen into the reactor under the pressure of 1.5-3.2 MPa and the airspeed of 1.0-4.0 h-1The reaction is carried out under the conditions of (1);
the PdAgNi/N-C catalyst is prepared by the following steps:
(1) adding a certain molar amount of Pd salt, Ag salt, Ni salt and deionized water into a beaker, fully stirring in an ice bath at 0 ℃, adding an N-C material, and fully stirring;
(2) dropwise adding 0.1-0.4 mol/L sodium borohydride solution into the mixed solution prepared in the step (1), and stirring and reducing for 2 hours;
(3) filtering the solution in the step (2) and drying to obtain a PAgNi/N-C catalyst;
in the step (1), the N-C material is prepared by roasting melamine and glucose according to a certain mass ratio, the mass ratio of the melamine to the glucose is 30-60: 1, the roasting temperature is 700-900 ℃, and the roasting time is 2-6 hours.
2. The method for the selective hydrogenation of 1, 3-butadiene catalyzed by PdAgNi/N-C catalyst according to claim 1, wherein: the molar ratio of the 1, 3-butadiene to the hydrogen is 1: 1.2-2.5.
3. The method for the selective hydrogenation of 1, 3-butadiene catalyzed by PdAgNi/N-C catalyst according to claim 1, wherein: the Pd salt is palladium chloride, the Ag salt is silver nitrate, and the Ni salt is nickel chloride.
4. The method for the selective hydrogenation of 1, 3-butadiene catalyzed by PdAgNi/N-C catalyst according to claim 3, wherein: the molar ratio of Pd to Ag to Ni is 1: 0.2-0.4: 0.1-0.3; the mole ratio of the Pd to the N-C material is 1: 500-800.
5. The method for the selective hydrogenation of 1, 3-butadiene catalyzed by PdAgNi/N-C catalyst according to claim 1, wherein: in the step (3), the drying temperature is 80-140 ℃, and the drying time is 10-20 h.
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