CN113797942B - Phosphorus-modified copper-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof - Google Patents

Phosphorus-modified copper-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof Download PDF

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CN113797942B
CN113797942B CN202110964875.3A CN202110964875A CN113797942B CN 113797942 B CN113797942 B CN 113797942B CN 202110964875 A CN202110964875 A CN 202110964875A CN 113797942 B CN113797942 B CN 113797942B
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activated carbon
phosphorus
catalyst
acetylene
hydrochlorination
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CN113797942A (en
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徐小雷
牛强
解荣永
赵长森
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Ordos Hanbo Technology Co ltd
Inner Mongolia Erdos Electric Power Metallurgy Group Co Ltd
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Ordos Hanbo Technology Co ltd
Inner Mongolia Erdos Electric Power Metallurgy Group Co Ltd
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a phosphorus-modified copper-based catalyst for acetylene hydrochlorination, and a preparation method and application thereof, and relates to the technical field of chemical production. The method of the invention comprises the following steps: acid washing the activated carbon; loading the binder on the activated carbon, and roasting; immersing the calcined activated carbon in an aqueous solution of copper salt, phosphoric acid and/or phosphate; and drying the impregnated activated carbon to obtain the catalyst. The invention takes the active carbon as a carrier, takes non-noble metal as an active component, and adds the binder to prepare the phosphorus modified copper-based catalyst, thereby having the advantages of low cost, simple preparation process, high catalyst activity and stability, and the like, and having better industrial application prospect.

Description

Phosphorus-modified copper-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof
Technical Field
The invention relates to the technical field of chemical production, in particular to a phosphorus-modified copper-based catalyst for acetylene hydrochlorination, and a preparation method and application thereof.
Background
Vinyl chloride is used as an important thermoplastic plastic and is widely applied in various fields such as building materials, agriculture, national defense and the like. Vinyl chloride monomer is the main raw material for synthesizing polyvinyl chloride, and two main types of mature synthetic green wires of polyvinyl chloride are: calcium carbide process and ethylene process. Because China is a basic national condition of 'rich coal, lean oil and less gas', in China, a path of a calcium carbide method based on coal is a main flow process for producing polyvinyl chloride, and an activated carbon supported mercury chloride catalyst is adopted in a core catalytic link. However, mercury loss and volatilization can cause serious pollution damage to the environment and people. Therefore, it is highly desirable to develop a mercury-free catalyst for hydrochlorination of acetylene.
Research on mercury-free catalysts has been advanced in China, scientific researchers have mainly explored active components of mercury-free catalysts, carriers, assistants and the like, wherein the active components comprise noble metals (ruthenium, palladium, gold and the like) and non-noble metals (copper, bismuth, tin and the like), the carriers comprise active carbon (coal-based active carbon, coconut shell active carbon and the like), porous materials such as molecular sieves, silicon dioxide, aluminum oxide, carbon nanotubes and the like, and the assistants comprise potassium, barium, phosphorus and the like. Patent CN103962131a discloses a method for preparing a mercury-free catalyst for hydrochlorination of acetylene, which uses active carbon as a carrier and chlorides of noble metal elements such as palladium, rhodium, gold and the like as active components, and the prepared catalyst has good acetylene conversion rate and chloroethylene selectivity, but high cost limits the industrial application thereof. Non-noble metal catalysts are also one of the hot spots in acetylene hydrochlorination catalyst research. The non-noble metal catalyst is lower than the noble metal catalyst in cost, but the catalytic activity and stability of the non-noble metal catalyst cannot meet the industrial requirements.
Patent CN103007972a discloses a catalyst prepared by using copper salt as an active component and using an auxiliary agent as alkali metal and transition metal chloride for hydrochlorination of acetylene, and the catalyst has low acetylene conversion rate and cannot meet the industrial production requirement. The patent CN102441407A discloses that the active carbon is used as a carrier, the barium-loaded compound, the phosphorus-loaded compound and the water-based polymer monomer are used, the interaction between the synthesized catalyst metal and the carrier is strong, the active components are not easy to run off, and the catalytic effect and the stability are improved to a certain extent. The patent CN106492869A discloses that copper salt, ammonium salt and phosphoric acid or copper salt, ammonium salt and phosphoric acid are prepared into solution, and the solution is loaded on an active carbon carrier by an impregnation method, so that the catalyst prepared by the method can obtain better activity and stability under the low-temperature condition through the synergistic effect of multiple components. Under the pressure condition of 130 ℃ reaction temperature and current mercury catalyst operation and feeding strength, the once-through conversion rate of more than 96% and the vinyl chloride selectivity of more than 99% can be obtained. The patent CN103272619A discloses that phosphorus modified activated carbon or activated carbon after acid washing is taken as a carrier, and active components of copper or tin phosphate, sulfate, chloride and pyrophosphate are loaded on the carrier by a stepwise impregnation method. The catalyst is used in hydrochlorination of acetylene, and the selectivity of vinyl chloride is higher, but the conversion rate of acetylene is only 20-65%. The catalyst reported in the patent generally has the problems of short service life, high price and the like. Meanwhile, the existing non-noble metal catalyst has certain reactivity to acetylene hydrochlorination, but the stability and activity cannot completely meet the industrial requirements. Therefore, research and development of an economic, green and high-performance mercury-free catalyst for acetylene hydrochlorination become a key problem to be solved in the current polyvinyl chloride industry, and have very important research significance.
In view of the above, the present invention provides a phosphorus-modified copper-based catalyst for hydrochlorination of acetylene, and a preparation method and application thereof, aiming at the technical defects of the prior art.
Disclosure of Invention
The invention aims to provide a phosphorus-modified copper-based catalyst for acetylene hydrochlorination, a preparation method and application thereof, wherein active carbon is used as a carrier, non-noble metal is used as an active component, and a binder is added to prepare the phosphorus-modified copper-based catalyst.
In order to achieve the above object, the present invention has the following technical scheme:
in one aspect, the invention provides a method for preparing a phosphorus-modified copper-based catalyst for hydrochlorination of acetylene, comprising the following steps:
(1) Acid washing the activated carbon;
(2) Loading the binder on the activated carbon, and roasting;
(3) Immersing the calcined activated carbon in an aqueous solution of copper salt, phosphoric acid and/or phosphate;
(4) And drying the impregnated activated carbon to obtain the catalyst.
Preferably, in the step (1), the activated carbon is at least one selected from wood carbon, coal carbon and coconut shell carbon. Preferably, the specific surface area of the activated carbon is 300-2000m 2 Preferably 700 to 1500m 2 /g; ash of ashThe score is less than 10%, more preferably less than 6%.
Preferably, in step (1), the acid used for the acid washing is at least one of phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid.
Preferably, in the step (2), the binder is at least one of an aluminum sol, a silica sol or a titanium sol.
Preferably, in the step (2), the baking temperature is 200 to 800 ℃, and more preferably 400 to 600 ℃.
Preferably, in step (3), the copper salt is selected from CuCl 2 、CuSO 4 、Cu 3 (PO 4 ) 2 、Cu 2 P 2 O 7 、Cu(NO 3 ) 2 And Cu 2 (OH) 2 SO 4 At least one of them.
Preferably, in step (3), the phosphate is selected from Na 3 PO 4 、K 3 PO 4 And NH 4 H 2 PO 4 At least one of them.
Preferably, in the step (3), the content of the copper salt in the aqueous solution is 5-50wt%, preferably 10-30wt%, and the content of the phosphoric acid or the phosphate in the mixed solution is 1-5wt%, preferably 3-4wt%.
Preferably, in the step (3), the volume of the aqueous solution is 1.05 to 2 times of the volume of the activated carbon.
Preferably, in the step (3), the calcined activated carbon is acid-washed granular activated carbon, and the specific surface area is 700-1500m 2 And/g, ash value less than 6%.
Preferably, in the step (3), the temperature of the impregnation is 30-60 ℃; the soaking time is 8-30h.
In yet another aspect, the present invention provides a phosphorus-modified copper-based catalyst prepared by the above-described preparation method.
Finally, the invention provides application of the phosphorus-modified copper-based catalyst in acetylene hydrochlorination.
Preferably, the application comprises applying C 2 H 2 Filling the phosphorus modified copper into the mixed gas of HCl and the mixed gasAnd (3) carrying out acetylene hydrochlorination in a fixed bed reactor based on a catalyst.
Further preferably, the HCl and C 2 H 2 The molar ratio of (2) is 1.05:1-1.2:1.
Further preferably, the C 2 H 2 Airspeed of 20 to 260h -1 。
Further preferably, the temperature of the hydrochlorination of acetylene is 140-220 ℃.
The beneficial effects of the invention are as follows:
1) The catalyst does not contain noble metal, and the cost of the catalyst is low; the active components of the catalyst are cheap and easy to obtain, the binder in the catalyst can delay the loss of the active components of the catalyst in the use process in the hydrochlorination of acetylene, and the stability of the catalyst is good;
2) The phosphorus modification can improve the dispersity of active components and can effectively improve the activity of the prepared catalyst;
3) The catalyst prepared by the invention has simple preparation process and is easy for industrial mass production;
4) The catalyst does not contain toxic and harmful metals and has no pollution to the environment.
Detailed Description
In order to make the technical means, the creation features, the achievement of the purpose and the effect of the present invention easy to understand, the present invention will be further elucidated with reference to the specific embodiments, but the following embodiments are only preferred embodiments of the present invention, not all of them. Based on the examples in the embodiments, those skilled in the art can obtain other examples without making any inventive effort, which fall within the scope of the invention. In the following examples, unless otherwise specified, the methods of operation used were conventional, the equipment used was conventional, and the materials used in the examples were the same.
In the following embodiments, the pickling step specifically includes: the activated carbon is put into a HCl solution with the concentration of 1 mol/L for 2 hours, then washed to be neutral by water and dried for standby.
In the following examples, silica sol was purchased from the tetan platform: nanometer silica sol (Xianfeng nanometer)
In the following examples, the titanium sol was purchased from the tetan platform: nanometer titania sol (Xianfeng nanometer)
In the following examples, the alumina sol was purchased from the tetan platform: water and alumina sol (Xianfeng nanometer)
Example 1
(1) Weighing 2g of silica sol, uniformly loading the silica sol on 50g of activated carbon after pickling, and roasting the silica sol at 400 ℃ under the air condition;
(2) 17g of copper chloride dihydrate and 5.8g of 85% H are weighed out 3 PO 4 Dissolving in 50mL deionized water, stirring to dissolve thoroughly, and preparing into mixed solution;
(3) Adding the prepared solution into the pickled granular active carbon, wherein the volume of the active carbon and the mixed solution is 1:1.05, and soaking for 24 hours at the temperature of 40 ℃;
(4) Taking out the impregnated active carbon, and drying for 12 hours at 140 ℃ to obtain the required catalyst A1;
(5) Loading the catalyst into a fixed bed reactor, and introducing HCl/C 2 H 2 The mixed gas with the mole ratio of 1.08 is subjected to acetylene hydrochlorination, the reaction temperature is 180 ℃, and the acetylene airspeed is 30h -1 。
Example 2
(1) Weighing titanium sol containing 2g of titanium dioxide, uniformly loading the titanium sol on 50g of activated carbon after pickling, and roasting the titanium sol at 400 ℃ under the air condition;
(2) 17g of copper chloride dihydrate and 5.8g of 85% H 3 PO 4 Dissolving in 50mL deionized water, stirring to dissolve thoroughly, and preparing into mixed solution;
(3) Adding the prepared solution into the pickled granular active carbon, wherein the volume of the active carbon and the mixed solution is 1:1.05, and soaking for 24 hours at the temperature of 40 ℃;
(4) Taking out the impregnated active carbon, and drying for 12 hours at 140 ℃ to obtain the required catalyst A2;
(5) Loading the catalyst into a fixed bedIn the reactor, HCl/C was introduced 2 H 2 The mixed gas with the mole ratio of 1.08 is subjected to acetylene hydrochlorination, the reaction temperature is 150 ℃ and the acetylene airspeed is 30h -1 。
Example 3
(1) Weighing 2g of alumina sol, uniformly loading the alumina sol on 50g of activated carbon after pickling, and roasting the alumina sol at 400 ℃ under the air condition;
(2) 17g of copper chloride dihydrate is weighed and dissolved in 50mL of deionized water, and stirred to be fully dissolved, so as to prepare a mixed solution;
(3) Adding the prepared solution into the pickled granular active carbon, wherein the volume of the active carbon and the mixed solution is 1:1.05, and soaking for 24 hours at the temperature of 40 ℃;
(4) Taking out the impregnated active carbon, and drying for 12 hours at 140 ℃ to obtain the required catalyst A3;
(5) Loading the catalyst into a fixed bed reactor, and introducing HCl/C 2 H 2 The mixed gas with the mole ratio of 1.08 is subjected to hydrochlorination, the reaction temperature is 180 ℃, and the acetylene airspeed is 30h -1 。
Example 4
(1) Weighing alumina sol containing 0.5g of alumina, uniformly loading the alumina sol on 50g of activated carbon after pickling, and roasting the alumina sol at 400 ℃ under the air condition;
(2) 17g copper chloride dihydrate and 4.6g NH 4 H 2 PO 4 Dissolving in 50mL deionized water, stirring to dissolve thoroughly, and preparing into mixed solution;
(3) Adding the prepared solution into the pickled granular active carbon, wherein the volume of the active carbon and the mixed solution is 1:1.05, and soaking for 24 hours at the temperature of 40 ℃;
(4) Taking out the impregnated active carbon, and drying for 12 hours at 140 ℃ to obtain the required catalyst A4;
(5) Loading the catalyst into a fixed bed reactor, and introducing HCl/C 2 H 2 The mixed gas with the mole ratio of 1.08 is subjected to hydrochlorination, the reaction temperature is 180 ℃, and the acetylene airspeed is 30h -1 。
Example 5
(1) 17g copper chloride dihydrate and 9.2g NH 4 H 2 PO 4 Dissolving in 50mL deionized water, adding aluminum sol containing 3.5g of aluminum oxide, stirring to fully dissolve, and preparing into mixed solution;
(2) Adding the prepared solution into the pickled granular active carbon, wherein the volume of the active carbon and the mixed solution is 1:1.05, and soaking for 24 hours at the temperature of 40 ℃;
(3) Taking out the impregnated active carbon, and drying for 12 hours at 140 ℃ to obtain a required catalyst A5;
(4) Loading the catalyst into a fixed bed reactor, and introducing HCl/C 2 H 2 The mixed gas with the mole ratio of 1.08 is subjected to hydrochlorination, the reaction temperature is 180 ℃, and the acetylene airspeed is 30h -1 。
Example 6
To further investigate the stability of the catalysts of the present invention, the catalysts prepared in the above examples 1 and 5 were respectively selected and charged into a fixed bed reactor, and HCl/C was introduced 2 H 2 The mixed gas with the mole ratio of 1.08 is subjected to hydrochlorination, and the acetylene airspeed is 30h at the reaction temperature of 150 DEG C -1 The catalyst is subjected to long-period performance evaluation, and after long-time stability evaluation, the catalyst can meet the industrial production requirements, and the evaluation results are shown in the following table.
Table 1.
Comparative example 1
The difference from example 1 is that the activated carbon is not acid washed.
The other preparation steps and the addition amounts of the raw materials were the same as in example 1.
Comparative example 2
The difference from example 1 is that the activated carbon in step (1) was not subjected to the 400 ℃ calcination treatment.
The other preparation steps and the addition amounts of the raw materials were the same as in example 1.
Comparative example 3
The difference from example 1 is that the deionized water solvent in step (2) was changed to the same volume of absolute ethanol solvent.
The other preparation steps and the addition amounts of the raw materials were the same as in example 1.
Comparative example 4
The difference from example 4 is that the impregnation with the activated carbon and the mixed solution in step (3) was changed to an equal volume impregnation with a volume of 1:1.05.
The other preparation steps and the addition amounts of the raw materials were the same as in example 4.
Comparative example 5
The difference from example 4 is that the activated carbon impregnated in step (3) was dried at 140℃for 12 hours and dried at 140℃for 12 hours in vacuo.
The other preparation steps and the addition amounts of the raw materials were the same as in example 4.
Acetylene conversion and vinyl chloride selectivity results of the hydrochlorination of acetylene for the example to produce the A1-A5 catalysts and comparative example to produce the B1-B5 catalysts are shown in Table 2.
TABLE 2
According to the evaluation results of the acetylene hydrochlorination reaction of the catalyst in the table, the doping of phosphorus and the binder is beneficial to improving the catalytic activity of the catalyst and the selectivity of vinyl chloride, while in the comparative case, the catalytic performance of the catalyst is reduced by changing the impregnation method, the solvent type, the drying condition, the acid washing condition of the activated carbon and the like in the process of preparing the catalyst.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The preparation method of the phosphorus-modified copper-based catalyst for the hydrochlorination of acetylene is characterized by comprising the following steps of:
(1) Acid washing the activated carbon;
(2) Loading the binder on the activated carbon, and roasting;
(3) Immersing the calcined activated carbon in an aqueous solution of copper salt and phosphoric acid;
(4) Drying the impregnated activated carbon to obtain the catalyst;
wherein in the step (3), the copper salt is CuCl 2 ；
In the step (3), the volume of the aqueous solution is 1.05 times of the volume of the activated carbon;
in the step (2), the roasting temperature is 400 ℃.
2. The method according to claim 1, wherein in the step (1), the activated carbon is at least one selected from wood charcoal, coal charcoal, and coconut shell charcoal, and the specific surface area of the activated carbon is 300-2000m 2 /g; the ash value of the activated carbon is less than 10%.
3. The method according to claim 2, wherein in the step (1), the activated carbon has a specific surface area of 700 to 1500m 2 And/g, the ash value of the activated carbon is less than 6%.
4. The method according to claim 1, wherein in the step (1), the acid used for the acid washing is at least one of phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid.
5. The method of claim 1, wherein in step (2), the binder is at least one of an aluminum sol, a silica sol, or a titanium sol.
6. The method according to claim 1, wherein in step (2), the copper salt content in the aqueous solution is 5 to 50wt%; the content of phosphoric acid or phosphate in the mixed solution is 1-5wt%; the temperature of the impregnation is 30-60 ℃; the soaking time is 8-30h.
7. The method according to claim 6, wherein in the step (3), the copper salt content in the aqueous solution is 10 to 30wt% and the phosphoric acid or phosphate content in the mixed solution is 3 to 4wt%.
8. A phosphorus-modified copper-based catalyst prepared according to the preparation method of any one of claims 1 to 7.
9. The use of the phosphorus-modified copper-based catalyst of claim 8 in hydrochlorination of acetylene.
10. The use according to claim 9, comprising the step of adding C to the composition 2 H 2 Introducing the mixed gas of HCl and the phosphorus-modified copper-based catalyst into a fixed bed reactor filled with the phosphorus-modified copper-based catalyst, and performing acetylene hydrochlorination; the HCl and C 2 H 2 The molar ratio of C is 1.05:1-1.2:1 2 H 2 Is at a space velocity of 20-260h -1 The temperature of the hydrochlorination reaction of acetylene is 140-220 ℃.
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Publication number Priority date Publication date Assignee Title
CN103272619A (en) * 2013-06-07 2013-09-04 天津大学 Anion modified mercury-free catalyst for ethyne hydrochlorination reaction, and preparation method thereof
CN105251502A (en) * 2014-12-02 2016-01-20 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) Mercury-free catalyst for acetylene hydrochlorination
WO2018049820A1 (en) * 2016-09-18 2018-03-22 天津大学 Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination
CN111389441A (en) * 2020-04-17 2020-07-10 鄂尔多斯市瀚博科技有限公司 Catalyst for acetylene hydrochlorination reaction and preparation method and application thereof
CN111389423A (en) * 2020-04-30 2020-07-10 鄂尔多斯市瀚博科技有限公司 Modified copper-based catalyst for acetylene hydrochlorination and preparation method thereof

Patent Citations (5)

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CN103272619A (en) * 2013-06-07 2013-09-04 天津大学 Anion modified mercury-free catalyst for ethyne hydrochlorination reaction, and preparation method thereof
CN105251502A (en) * 2014-12-02 2016-01-20 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) Mercury-free catalyst for acetylene hydrochlorination
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CN111389423A (en) * 2020-04-30 2020-07-10 鄂尔多斯市瀚博科技有限公司 Modified copper-based catalyst for acetylene hydrochlorination and preparation method thereof

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