CN107999140B - Preparation method of mercury-free catalyst for reducing reaction temperature of vinyl chloride synthesis - Google Patents
Preparation method of mercury-free catalyst for reducing reaction temperature of vinyl chloride synthesis Download PDFInfo
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- CN107999140B CN107999140B CN201711220556.1A CN201711220556A CN107999140B CN 107999140 B CN107999140 B CN 107999140B CN 201711220556 A CN201711220556 A CN 201711220556A CN 107999140 B CN107999140 B CN 107999140B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
Abstract
The invention provides a preparation method of a mercury-free catalyst for reducing the reaction temperature of vinyl chloride synthesis, which comprises the steps of treating a carrier, selecting a catalyst raw material, adsorbing titanium tetrachloride, adsorbing 4-dimethylaminopyridine and adsorbing phosphomolybdic acid. The catalyst prepared by the invention comprises, by weight, 2.4% of titanium tetrachloride, 1.2% of copper chloride, 2.0% of phosphomolybdic acid, 1.6% of 4-dimethylaminopyridine, 1.5% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.2% of water. The catalyst of the invention does not contain noble metal, thereby saving the production cost. The catalyst of the invention reduces the reaction temperature of vinyl chloride synthesis to 100 ℃. The catalyst of the invention is used for vinyl chloride synthesis reaction, and the obtained crude product has the purity of the vinyl chloride reaching 97.2v%, the yield of the vinyl chloride reaching 98.4% and the selectivity of the vinyl chloride reaching 100% through chromatographic analysis.
Description
Technical Field
The invention relates to a preparation method of a mercury-free catalyst for reducing the reaction temperature of vinyl chloride synthesis, belonging to the technical field of catalysts.
Background
The industrial synthesis of vinyl chloride by acetylene method still adopts mercuric chloride catalyst using active carbon as carrier, with the development of social economy, the yield of polyvinyl chloride plastic is continuously increased, the consumption of catalyst is also continuously increased, the mercury resource in China is deficient, and the mercuric catalyst is easy to sublimate and run off to cause environmental pollution. The catalyst used in industry comprises high mercury catalyst and low mercury catalyst, the mercury chloride content of the high mercury catalyst is 10-12%, and the mercury chloride content of the low mercury catalyst is 4-6.5%. The development of a novel green and environment-friendly mercury-free catalyst is an urgent problem in the synthesis of vinyl chloride by a calcium carbide method.
In the prior art, in order to improve the conversion rate of acetylene and the yield of vinyl chloride, the reaction temperature is generally increased, or noble metal is adopted as the main component of the catalyst.
CN103894221A discloses a method for preparing vinyl chloride by using a molecular sieve mercury-free catalyst to catalyze acetylene hydrochlorination, wherein the adopted catalyst is FAU type molecular sieve and non-molecular sieve, cations which can be exchanged on the FAU type molecular sieve are one or more of hydrogen ions, sodium ions, calcium ions, potassium ions, lithium ions, magnesium ions, strontium ions and barium ions, the reaction temperature for carrying out acetylene hydrochlorination is 280-350 ℃, the conversion rate of acetylene is not lower than 80%, and the selectivity of vinyl chloride is not lower than 97%. The reaction temperature of the method is high.
CN106975500A discloses a mercury-free catalyst for producing chloroethylene by acetylene method and its preparation method, the active component of the catalyst is ruthenium trichloride, the auxiliary agents are cuprous chloride and bismuth chloride, the reaction temperature for synthesizing chloroethylene is 160 deg.C, and the space velocity is 50h-1The mol ratio of the hydrogen chloride to the acetylene is 1.15:1, and the conversion rate of the acetylene and the selectivity of the chloroethylene are both more than 99 percent. The method uses rare earth metals of ruthenium and bismuth, and has higher production cost and higher reaction temperature.
CN106215977A discloses a mercury-free catalyst with high catalytic activity for synthesizing chloroethylene and a preparation method thereof, wherein raw materials of the catalyst comprise platinum, stannic chloride, cuprous chloride, methyl rhenium trioxide and the like, the method can reduce the reaction temperature to 113 ℃, the yield of chloroethylene reaches more than 98%, the selectivity of chloroethylene reaches 100%, but the catalyst adopts noble metal platinum, so that the production cost is increased.
Disclosure of Invention
The invention provides a preparation method of a mercury-free catalyst for reducing the reaction temperature of vinyl chloride synthesis, aiming at solving the defects in the prior art and realizing the following purposes:
the reaction temperature is reduced, noble metal is not used as a catalyst raw material, and the conversion rate of acetylene and the yield of vinyl chloride are improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of mercury-free catalyst for reducing reaction temperature of vinyl chloride synthesis is characterized by comprising the following steps: the preparation method comprises the steps of treating a carrier, selecting a catalyst raw material, adsorbing titanium tetrachloride, adsorbing 4-dimethylaminopyridine and adsorbing phosphomolybdic acid.
The following is a further improvement of the above technical solution:
and (2) treating the carrier, namely soaking the carrier activated carbon in an acid solution, wherein the acid comprises succinic acid, polyacrylic acid and hydroxyethylidene diphosphonic acid in a mass ratio of 3:5:2, the mass content of the acid solution is 5%, and the mass ratio of the acid solution to the activated carbon is 3:1, and soaking for 2 hours.
The catalyst comprises the following raw materials in parts by weight: 2.5 parts of titanium tetrachloride, 1.2 parts of copper chloride, 2.0 parts of phosphomolybdic acid, 1.7 parts of 4-dimethylaminopyridine, 1.5 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 91.1 parts of a carrier.
The carrier adsorbing the titanium tetrachloride is prepared by heating the titanium tetrachloride to 150 ℃, mixing the gasified titanium tetrachloride with nitrogen, introducing the mixture into a chemical vapor deposition device, raising the temperature of the chemical vapor deposition device to 300 ℃ at the speed of 5 ℃/min, keeping the temperature for 30 minutes, raising the temperature to 450 ℃ at the speed of 3 ℃/min, keeping the temperature for 1 hour, cooling the chemical vapor deposition device to 200 ℃, purging with 100 ml/min of nitrogen for 2 hours, and cooling to room temperature.
The 4-dimethylaminopyridine is adsorbed, the 4-dimethylaminopyridine is dissolved in 10 times of ethanol by mass, desalted water is added to prepare an adsorption solution b, and the mass ratio of the 4-dimethylaminopyridine to the desalted water is 1: 100; putting the carrier into an adsorption solution b for vacuum adsorption, wherein the parameters of the vacuum adsorption are as follows: vacuumizing to-0.060 MPa and keeping for 20 s; then, the pressure is reduced to-0.040 MPa, the pressure is kept for 15s, the pressure is restored to normal pressure, and the soaking and adsorption are carried out for 1h under the normal pressure.
Adsorbing phosphomolybdic acid, dropwise adding an aqueous solution of phosphomolybdic acid at the temperature of 40 ℃, at the speed of 0.5ml/min, carrying out ultrasonic-assisted adsorption on the solution while dropwise adding, wherein the ultrasonic power density is 90W/L, the ultrasonic frequency is 75KHz, simultaneously introducing compressed air, the air pressure of the air flow is preferably 0.8MPa, the flow rate of the air flow is 20L/h, filtering after dropwise adding, and drying until the water content is 0.2%.
By adopting the technical scheme, the invention has the beneficial effects that:
(1) the catalyst prepared by the invention comprises, by weight, 2.4% of titanium tetrachloride, 1.2% of copper chloride, 2.0% of phosphomolybdic acid, 1.6% of 4-dimethylaminopyridine, 1.5% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.2% of water.
The catalyst of the invention does not contain noble metal, thereby saving the production cost.
(2) The catalyst of the invention reduces the reaction temperature of vinyl chloride synthesis to 100 ℃.
(3) The catalyst of the invention is used for vinyl chloride synthesis reaction, and the obtained crude product has the purity of the vinyl chloride reaching 97.2v%, the yield of the vinyl chloride reaching 98.4% and the selectivity of the vinyl chloride reaching 100% through chromatographic analysis.
After the crude product of the vinyl chloride is rectified, the purity of the obtained vinyl chloride reaches 99.999v%, and the acetylene content is less than 0.0001 v%.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
EXAMPLE 1 preparation of Mercury-free catalyst for lowering vinyl chloride Synthesis reaction temperature
The method comprises the following steps:
(1) selection of vectors
Active carbon is taken as a carrier, the iodine value of the active carbon is 1300mg/g, the methylene blue value is 125mg/g, the carbon tetrachloride adsorption value is 120 percent, the water content is 2 percent, the ash content is 1.5 percent, the bulk density is 380g/L, and the specific surface area is 1500m2(iv)/g, average pore diameter is 2.8-3.0nm, and average particle diameter of the carrier is 45 μm.
(2) Treatment of the support
Soaking activated carbon in an acid solution, wherein the acid comprises succinic acid, polyacrylic acid and hydroxyethylidene diphosphonic acid in a mass ratio of 3:5:2, the mass content of the acid solution is 5%, the mass ratio of the acid solution to the activated carbon is 3:1, soaking is carried out for 2 hours, the ultrasonic power density is controlled to be 100W/L during soaking, the ultrasonic frequency is 70KHz, and meanwhile, pressure is introducedCompressing air with pressure of 1.0-1.2MPa and flow rate of 25-30m3And h, after soaking, washing with water, and drying until the water content is below 1.5%.
(3) Selection of catalyst feedstock
The catalyst comprises the following raw material components in parts by weight: 2.5 parts of titanium tetrachloride, 1.2 parts of copper chloride, 2.0 parts of phosphomolybdic acid, 1.7 parts of 4-dimethylaminopyridine, 1.5 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 91.1 parts of a carrier.
Weighing the raw materials of the catalyst according to the formula.
(4) Adsorption of titanium tetrachloride
Placing the activated carbon carrier in a chemical vapor deposition device, heating to 200 ℃, purging for 2 hours under the protection of nitrogen of 150ml/min, removing moisture, heating titanium tetrachloride to 150 ℃, mixing the gasified titanium tetrachloride with the nitrogen, introducing the mixture into the chemical vapor deposition device, enabling the flow rate of titanium tetrachloride steam to be 1ml/min and the flow rate of the nitrogen to be 70ml/min, raising the temperature of the chemical vapor deposition device to 300 ℃ at the speed of 5 ℃/min, keeping the temperature for 30 minutes, raising the temperature to 450 ℃ at the speed of 3 ℃/min, keeping the temperature for 1 hour, cooling the chemical vapor deposition device to 200 ℃, purging for 2 hours with nitrogen of 100 ml/min, and reducing the temperature to room temperature to obtain the carrier adsorbing titanium tetrachloride.
(5) Adsorption of copper chloride and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride
Dissolving copper chloride and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in 100 times of weight of desalted water to prepare an adsorption liquid a;
putting the carrier for adsorbing titanium tetrachloride into the prepared adsorption solution a, wherein the mass ratio of the carrier to the adsorption solution a is 1:5, the adsorption temperature is 40 ℃, the adsorption time is 1 hour, a circulating pump is used for enabling the adsorption solution to continuously flow in the adsorption solution, and then the carrier is taken out, filtered and dried until the water content is less than 0.2%.
(6) Adsorption of 4-dimethylaminopyridine
Dissolving 4-dimethylamino pyridine in 10 times of ethanol, adding desalted water to obtain an adsorption solution b, putting the carrier containing part of the catalyst component obtained in the step (5) into the adsorption solution b, and performing vacuum adsorption.
The mass ratio of the 4-dimethylaminopyridine to the desalted water is 1: 100;
putting the adsorption solution b containing a carrier of a part of catalyst components into a stainless steel vacuum tank, vacuumizing by using a vacuum pump, and performing vacuum adsorption, wherein the parameters of the vacuum adsorption are as follows: vacuumizing to-0.060 MPa and keeping for 20 s; then, the pressure is reduced to-0.040 MPa, the pressure is kept for 15s, the pressure is restored to normal pressure, and the soaking and adsorption are carried out for 1h under the normal pressure.
The mass ratio of the carrier containing a part of the catalyst component to the adsorption liquid b was 1: 200.
(7) Adsorption of phosphomolybdic acid
And (3) dropwise adding an aqueous solution of phosphomolybdic acid into the mixed solution after adsorption in the step (6), wherein the dropwise adding temperature is 40 ℃, the dropwise adding speed is 0.5ml/min, ultrasonic-assisted adsorption is carried out on the solution while dropwise adding, the ultrasonic power density is 90W/L, the ultrasonic frequency is 75KHz, compressed air is introduced simultaneously, the air pressure of the air flow is preferably 0.8MPa, the flow rate of the air flow is 20L/h, and after dropwise adding, filtering and drying are carried out until the water content is 0.2% to obtain the catalyst.
The phosphomolybdic acid content of the aqueous solution of phosphomolybdic acid is 15%.
The catalyst prepared by the invention comprises, by weight, 2.4% of titanium tetrachloride, 1.2% of copper chloride, 2.0% of phosphomolybdic acid, 1.6% of 4-dimethylaminopyridine, 1.5% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 0.2% of water and the balance of a carrier.
Example 2 use of the above catalyst in vinyl chloride Synthesis reactions
The method comprises the following steps:
(1) catalyst-loaded catalyst
Before filling the catalyst, checking whether there is no leak point inside and outside the reactor, and the inner wall of the tube array is clean, dry and free of impurities; the catalyst of the invention is loaded into each tube array of the reactor immediately after the package is opened, and the catalyst loading is completed within 0.5h, and the reactor is protected against moisture.
(2) Preheating
Introducing dried HCl at the temperature of 90-100 ℃, and controlling the speed to be 5m3And/h, continuously discharging acid from the bottom of the reactor every 2h for 15 h.
(3) Reaction for synthesizing vinyl chloride
Controlling the molar ratio of acetylene to hydrogen chloride to be 1: 1.05 (100 percent purity), introducing mixed gas with the preheating temperature of more than 90 ℃ into a reactor, adjusting the introduction amount of acetylene gas according to the cooling capacity of the reactor during the culture period of 1 month, and controlling the temperature to be between 105 and 110 ℃;
after the culture period is finished, the introduction amount of acetylene gas is adjusted to 55h according to the cooling capacity of the reactor-1Controlling the molar ratio of acetylene to hydrogen chloride at 1: 1.05, the reaction temperature at 100 ℃ and the reaction pressure at 0.030 MPa;
the hydrogen chloride activation time was 40 minutes.
The mercury-free catalyst in embodiment 1 of the invention is used for vinyl chloride synthesis reaction, and the obtained crude product has the purity of vinyl chloride up to 97.2v%, the yield of vinyl chloride up to 98.4% and the selectivity of vinyl chloride up to 100% by chromatographic analysis;
after the crude product of the vinyl chloride is rectified, the purity of the obtained vinyl chloride reaches 99.999v%, and the acetylene content is less than 0.0001 v%.
The catalyst of the invention has low unit consumption, and the unit consumption of the catalyst is 0.0010-0.0011 g/ml of chloroethylene.
Unless otherwise stated, the percentages used in the present invention are percentages by weight, and the proportions described in the present invention are proportions by mass.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A preparation method of mercury-free catalyst for reducing reaction temperature of vinyl chloride synthesis is characterized by comprising the following steps: the preparation method comprises the steps of treating a carrier, selecting a catalyst raw material, adsorbing titanium tetrachloride, adsorbing copper chloride and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, adsorbing 4-dimethylaminopyridine and adsorbing phosphomolybdic acid;
treating the carrier, namely soaking the carrier activated carbon in an acid solution, wherein the acid comprises succinic acid, polyacrylic acid and hydroxyethylidene diphosphonic acid in a mass ratio of 3:5:2, the mass content of the acid solution is 5%, the mass ratio of the acid solution to the activated carbon is 3:1, and soaking for 2 hours;
the catalyst comprises the following raw materials in parts by weight: 2.5 parts of titanium tetrachloride, 1.2 parts of copper chloride, 2.0 parts of phosphomolybdic acid, 1.7 parts of 4-dimethylaminopyridine, 1.5 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 91.1 parts of a carrier.
2. The method for preparing a mercury-free catalyst for reducing the reaction temperature of vinyl chloride synthesis according to claim 1, wherein: the method comprises the steps of heating titanium tetrachloride to 150 ℃, mixing the gasified titanium tetrachloride with nitrogen, introducing the mixture into a chemical vapor deposition device, enabling the flow rate of titanium tetrachloride vapor to be 1mL/min and the flow rate of nitrogen to be 70mL/min, raising the temperature of the chemical vapor deposition device to 300 ℃ at the speed of 5 ℃/min, keeping the temperature for 30 minutes, raising the temperature to 450 ℃ at the speed of 3 ℃/min, keeping the temperature for 1 hour, cooling the chemical vapor deposition device to 200 ℃, purging the chemical vapor deposition device with 100 mL/min of nitrogen for 2 hours, and cooling the temperature to room temperature to obtain the carrier adsorbing titanium tetrachloride.
3. The method for preparing a mercury-free catalyst for reducing the reaction temperature of vinyl chloride synthesis according to claim 1, wherein: the 4-dimethylaminopyridine is adsorbed, the 4-dimethylaminopyridine is dissolved in 10 times of ethanol by mass, desalted water is added to prepare an adsorption solution b, and the mass ratio of the 4-dimethylaminopyridine to the desalted water is 1: 100; putting the carrier into an adsorption solution b for vacuum adsorption, wherein the parameters of the vacuum adsorption are as follows: vacuumizing to-0.060 MPa and keeping for 20 s; then regulating the pressure to-0.040 MPa, keeping the pressure for 15s, recovering to the normal pressure, and soaking and adsorbing for 1h at the normal pressure.
4. The method for preparing a mercury-free catalyst for reducing the reaction temperature of vinyl chloride synthesis according to claim 1, wherein: adsorbing phosphomolybdic acid, dropwise adding an aqueous solution of phosphomolybdic acid at the temperature of 40 ℃, at the speed of 0.5mL/min, carrying out ultrasonic-assisted adsorption on the solution while dropwise adding, wherein the ultrasonic power density is 90W/L, the ultrasonic frequency is 75KHz, simultaneously introducing compressed air, the air pressure of the air flow is preferably 0.8MPa, the flow rate of the air flow is 20L/h, filtering after dropwise adding, and drying until the water content is 0.2%.
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| DE3009520C2 (en) * | 1980-03-12 | 1986-09-04 | Wacker-Chemie GmbH, 8000 München | Process for the removal of acetylene from the reaction product of the thermal 1,2-dichloroethane cleavage |
| CN101747141A (en) * | 2009-12-22 | 2010-06-23 | 南通天海化工助剂有限公司 | Technology for producing trans-1,2-dichloroethylene |
| CN103191764B (en) * | 2013-04-23 | 2015-04-22 | 新疆天业（集团）有限公司 | Mercury-free catalyst for synthesizing vinyl chloride through acetylene hydrochlorination and preparation method thereof |
| CN104289254B (en) * | 2014-10-11 | 2017-02-01 | 中国科学院上海高等研究院 | Nitrogen-modified catalyst applied to preparation of vinyl chloride and preparation method of nitrogen-modified catalyst |
| CN104289246B (en) * | 2014-10-11 | 2017-03-15 | 中国科学院上海高等研究院 | A kind of catalyst without mercury and its application in synthesis vinyl chloride thereof |
| CN104437564A (en) * | 2014-11-03 | 2015-03-25 | 扬州大学 | Catalyst for environment-friendly catalytic production of chloroethylene and method for producing chloroethylene by using catalyst |
| CN106866349B (en) * | 2015-12-14 | 2022-07-08 | 中国科学院大连化学物理研究所 | Method for preparing vinyl chloride by low-temperature hydrochlorination of acetylene |
| CN105521801B (en) * | 2015-12-15 | 2020-11-03 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Application of catalyst in synthesis of vinyl chloride by hydrochlorination of acetylene |
| CN106378122A (en) * | 2016-08-26 | 2017-02-08 | 天津南化催化剂有限公司 | Silica gel loaded titanium catalyst, preparation method and application thereof |
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