CN111389426A - Cu-based acetylene hydrochlorination mercury-free catalyst - Google Patents

Cu-based acetylene hydrochlorination mercury-free catalyst Download PDF

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CN111389426A
CN111389426A CN202010316553.3A CN202010316553A CN111389426A CN 111389426 A CN111389426 A CN 111389426A CN 202010316553 A CN202010316553 A CN 202010316553A CN 111389426 A CN111389426 A CN 111389426A
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catalyst
inorganic salt
activated carbon
drying
solution
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朱瑞波
赵长森
颜艺专
牛强
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Ordos Hanbo Technology Co ltd
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Ordos Hanbo Technology 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
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B01J27/055—Sulfates with alkali metals, copper, gold or silver
    • 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
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/122—Halides of copper
    • 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
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • 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
    • B01J27/24—Nitrogen compounds
    • 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

Abstract

The invention relates to the field of metal catalysts, in particular to a Cu-based acetylene hydrochlorination mercury-free catalyst. The catalyst comprises a carrier, an active component and an auxiliary agent; the carrier is modified activated carbon, the active component is inorganic salt of Cu, and the auxiliary agent is a non-noble metal component; the non-noble metal component is at least one of inorganic salt of K, inorganic salt of Ti, inorganic salt of Mg and inorganic salt of Sn, and inorganic salt of Ce. The catalyst has the advantages of simple operation, high catalytic activity, high conversion rate, good selectivity to vinyl chloride, small harm and toxic action to the environment, and is beneficial to large-scale production and use.

Description

Cu-based acetylene hydrochlorination mercury-free catalyst
Technical Field
The invention relates to the field of metal catalysis, in particular to a Cu-based acetylene hydrochlorination mercury-free catalyst.
Background
At present, polyvinyl chloride (PVC) resin has very wide market demand all over the world, the annual output of the Chinese polyvinyl chloride is close to 2000 ten thousand tons, and the vinyl chloride is a monomer for synthesizing the PVC and is one of important chemical raw materials; the industrial production process of vinyl chloride mainly comprises an ethylene method and an acetylene method, wherein the ethylene resource is lack and the price is very high, so that the energy structure characteristic of rich coal, less oil and less gas shortage is combined, the acetylene method is the main source of most of the yield of vinyl chloride in China, the production of vinyl chloride by the acetylene method adopts a mercury catalyst which has high volatility and toxicity, the loss and volatilization of mercury in the use process of the mercury catalyst can cause serious pollution damage to the environment and people, and the low-mercury and mercury-free catalysis has become necessary trend along with the emergence of international water guarantee convention, the increasing attention of the country and the gradual improvement of environmental protection consciousness of people. Therefore, the research and development of mercury-free catalysts to replace mercury-containing catalysts are imperative in the production of PVC by acetylene method.
The research and development of the metal mercury-free catalyst mainly comprise noble metals such as Au, Pd and Ru and non-noble metals such as Bi, Sn and Cu. The noble metal catalyst is generally expensive in price and high in operation cost, and the application of the noble metal catalyst in industrialization is restrained; the patent application CN 102029189A takes chloroauric acid as an active component, the auxiliary agent is halide of Ka, Ba and Cu, the catalyst is high in activity and selectivity, but no stability test result exists, and Au is taken as the active component of the catalyst, so that the industrial consumption of Au is large, the cost is too high, and the industrial difficulty is high. The non-noble metal catalyst has low cost, is simple and easy to obtain, but has the problem of poor activity and selectivity.
In patent application CN 107952453A, Cu or Bi metal salt is used as an active component, coal and coconut shell activated carbon are selected as carriers, and the activity of the prepared catalyst can not meet the requirement of an industrial acetylene hydrochlorination catalyst.
Patent application CN 103007972 a discloses a non-noble metal mercury-free catalyst for hydrochlorination of acetylene and a preparation method thereof, wherein the catalyst mainly contains an active component Cu element, an anion chlorine element and metal elements for promoting the catalysis of lithium, potassium, strontium, cobalt, zinc, chromium, manganese and nickel; the catalyst and the preparation method thereof have the advantages of low cost and small harm to the environment, and the problem of mercury pollution in vinyl chloride production by an acetylene method is solved by providing a relatively economic method, but the catalyst also has the problems of poor stability and short service life.
Patent application CN 102380380 a discloses a non-mercury catalyst system for hydrochlorination of acetylene, which is composed of an active component of one or more mixed salts of oxides, nitrates, chlorides, phosphates and acetates of copper, zinc, bismuth, nickel, manganese, molybdenum and tin metal elements and a carrier, and has the characteristics of high economic benefit, stable composition and environmental friendliness, but the catalyst system also has the problems of low conversion rate and poor activity.
Based on the above, the Cu-based acetylene hydrochlorination mercury-free catalyst has great economic and environmental benefits when being applied to industrial preparation of vinyl chloride.
Disclosure of Invention
On the basis of the prior art, the invention aims to provide a Cu-based acetylene hydrochlorination mercury-free catalyst with industrial value, which is an acetylene hydrochlorination non-noble metal mercury-free catalyst, and can solve the problems of poor stability and high environmental hazard of the currently researched metal catalyst in the acetylene hydrochlorination process so as to meet the requirement standard of the acetylene hydrochlorination catalyst in industry.
The specific technical scheme of the invention is as follows:
the Cu-based acetylene hydrochlorination mercury-free catalyst comprises a carrier, an active component and an auxiliary agent, wherein the carrier is modified activated carbon, the active component is an inorganic salt of Cu, and the auxiliary agent is a non-noble metal component;
the modified activated carbon is wood or coconut shell activated carbon and is prepared by immersing a modifier, filtering, drying and roasting.
Preferably, the immersion time is 2 h.
Preferably, the drying condition is drying at 80-100 ℃ for 2-6 h.
Preferably, the roasting condition is 200-300 ℃ for 3-15 h.
Preferably, the modifier is at least one of hydrogen peroxide, hydrochloric acid solution and sulfuric acid solution.
Preferably, the mass concentration of the modifier is 5-10%.
Preferably, the mass volume ratio of the wood or coconut shell activated carbon to the modifier is 1:2-6g/m L.
Preferably, the inorganic salt of Cu is one or more of chloride, nitrate and sulfate of Cu.
Preferably, the mass of the inorganic salt of Cu accounts for 10-25% of the total mass of the catalyst.
Preferably, the non-noble metal component is a mixture of at least one of an inorganic salt of K, an inorganic salt of Ti, an inorganic salt of Mg and an inorganic salt of Sn, and an inorganic salt of Ce.
More preferably, the inorganic salt of K is preferably at least one of chloride, sulfate and nitrate of K.
More preferably, the inorganic salt of Ti is preferably at least one of chloride, sulfate and nitrate of Ti.
More preferably, the inorganic salt of Mg is preferably at least one of chloride, sulfate and nitrate of Mg.
More preferably, the inorganic salt of Sn is at least one of chloride, sulfate and nitrate of Sn.
More preferably, the inorganic salt of Ce is preferably at least one of chloride, sulfate and nitrate of Ce.
The invention also relates to a preparation method of the Cu-based acetylene mercury-free hydrochlorination catalyst, which comprises the following steps:
(1) preparing a precursor I by a chemical precipitation method: adding modified activated carbon into Ce inorganic salt solution, stirring, precipitating with chemical precipitant, filtering, and drying the filter residue at 90-150 deg.C to obtain precursor I;
(2) preparation of catalyst by excess impregnation: and mixing the rest of the auxiliary agent and the inorganic salt solution of Cu to obtain a mixed solution II, adding the precursor I into the mixed solution II, excessively soaking at normal temperature, standing for 5-15h, and drying at 80-150 ℃ to obtain the copper-aluminum alloy.
Preferably, the chemical precipitant is NaOH or ammonia.
Preferably, the concentration of the chemical precipitant is 0.1 to 0.5 mol/ml.
Preferably, the mass of the inorganic salt of Ce is 1-5% of the mass of the catalyst.
More preferably, the mass of the inorganic salt of Ce is 2-3% of the mass of the catalyst.
Preferably, the mass of the residual auxiliary agent in the step (2) accounts for 0.1-10% of the mass of the catalyst.
The invention also relates to the application of the catalyst or the catalyst prepared by the preparation method in acetylene hydrochlorination.
The evaluation conditions in the application of the catalyst in the hydrochlorination of acetylene are as follows: t is 110-170 ℃, normal pressure and C2H2(GHSV)＝30～50h-1、n(HCl)：n(C2H2)＝1.05～1.45。
The catalyst prepared by the invention has the following beneficial effects:
1. the active components and the auxiliary agent adopted by the catalyst are low-toxicity metal compounds, so that the catalyst is more environment-friendly.
2. The catalyst of the invention adopts modified active carbon as a carrier and various non-noble metal components as auxiliaries, thereby effectively improving the conversion rate, selectivity and stability of the catalyst.
3. The invention further improves the conversion rate and stability of the catalyst by optimizing the composition of the active component.
4. The invention optimizes the type of the modifier in the preparation process of the modified activated carbon, and further improves the conversion rate and the stability of the catalyst.
5. The preparation method of the catalyst adopts a method of respectively impregnating a plurality of components in the auxiliary agent, thereby further improving the conversion rate, the selectivity and the stability of the catalyst.
6. The initial conversion rate of the catalyst reaches 95.5-98.6%, the selectivity of chloroethylene is more than 99.5%, and the conversion rate of acetylene still can reach 86.6-94.4% after 6000h of 500-fluid reaction, which shows that the prepared catalyst has the characteristics of high conversion rate, good stability and longer service life.
Detailed Description
The technical solutions in the embodiments of the present invention are further clearly described, and the described embodiments are only a part of the present invention, and are used for explaining the present invention, but not for limiting the present invention, so that other embodiments obtained by other persons skilled in the art without any inventive work belong to the scope of the present invention. The following is a more specific example description of the catalyst.
In the embodiment of the present invention, unless otherwise specified, the raw material gas C is used as the evaluation condition of the catalyst2H2And the ratio of HCl is a molar ratio.
Example 1:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 2 hours by using a 5 wt% hydrochloric acid solution of 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 2 hours at 80 ℃, and adding N2Roasting at 200 ℃ for 5h in atmosphere, weighing 3.8g of hydrated cerium nitrate, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, putting into a 120 ℃ oven, drying for 8h, weighing 16g of hydrated copper chloride and 2.5g of magnesium chloride, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 6h, and drying at 120 ℃ for 12h to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 97.6%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 89.5%.
Example 2:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 2 hours by using 7 percent of wt hydrochloric acid solution 200m L, washing the activated carbon by using deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 6 hours at 100 ℃, and adding N into the aqueous solution2Calcining at 300 deg.C for 5 hr under atmosphere, weighing 3.8g hydrateDissolving cerium nitrate in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, putting into a 150 ℃ oven, drying for 8h, weighing 16g of hydrated copper chloride and 2.5g of magnesium chloride, dissolving into 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 6h, and drying for 12h at 120 ℃ to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 97.4%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 89.7%.
Example 3:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 2 hours by using 10 percent wt hydrochloric acid solution 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 10 hours in atmosphere, weighing 1.9g of hydrated cerium nitrate, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12 hours, putting into a 130 ℃ oven, drying for 8 hours, weighing 16g of hydrated copper chloride and 2.5g of magnesium chloride, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 6 hours, and drying at 120 ℃ for 12 hours to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 97.4%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 89.5%.
Example 4:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 2 hours by using 10 percent wt hydrochloric acid solution 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 15h under the atmosphere, weighing 0.8g of hydrated cerium nitrate, dissolving in 200m L deionized water, putting the pretreated activated carbon into the cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, and drying in a 90 ℃ oven for 8h(ii) a Weighing 16g of hydrated copper chloride and 2.5g of magnesium chloride, dissolving the hydrated copper chloride and the magnesium chloride in 60g of deionized water, uniformly mixing, putting the active carbon containing Ce into the solution, stirring and soaking for 6 hours, and drying at 120 ℃ for 12 hours to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 97.5%, vinyl chloride selectivity of greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 88.9%.
Example 5:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 2 hours by using 10 percent wt hydrochloric acid solution 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 15h in the atmosphere, weighing 0.8g of hydrated cerium chloride, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, putting into a 120 ℃ oven, drying for 8h, weighing 16g of hydrated copper chloride and 2.5g of magnesium chloride, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 6h, and drying at 120 ℃ for 12h to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 96.8%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 86.6%.
Example 6:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 2 hours by using 10 percent wt hydrochloric acid solution 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 15h in the atmosphere, weighing 1.8g of hydrated cerium chloride, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, putting into a 120 ℃ oven, drying for 8h, weighing 16g of hydrated copper chloride and 2.5g of potassium chloride, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 6h, and drying at 120 ℃ for 12h to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 96.8%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 86.6%.
Example 7:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 2 hours by using 10 percent wt hydrochloric acid solution 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 15h in the atmosphere, weighing 3.7g of hydrated cerium chloride, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, putting into a 120 ℃ oven, drying for 8h, weighing 16g of hydrated copper chloride and 2.5g of stannic chloride, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 6h, and drying at 120 ℃ for 12h to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 98.1%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 87.3%.
Example 8:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 2 hours by using 10 percent wt hydrochloric acid solution 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 15h in the atmosphere, weighing 3.7g of hydrated cerium sulfate, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, drying in a 120 ℃ oven for 8h, weighing 16g of hydrated copper chloride and 2.5g of titanium sulfate, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 6h, and drying at 120 ℃ for 12h to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H21:1.06 HCl with initial acetylene conversion95.7 percent, the selectivity of chloroethylene is more than 99.5 percent, the reaction is run for 600 hours, and the acetylene conversion rate is 87.6 percent.
Example 9:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 2 hours by using 10 percent wt hydrochloric acid solution 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 15h in the atmosphere, weighing 1.0g of hydrated cerium sulfate, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, drying in a 120 ℃ oven for 8h, weighing 16g of hydrated copper chloride and 2.5g of potassium sulfate, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 15h, and drying at 80 ℃ for 12h to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 95.4%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 87.1%.
Example 10:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 2 hours by using 7 percent of wt hydrochloric acid solution 200m L, washing the activated carbon by using deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N into the aqueous solution2Roasting at 250 ℃ for 5h in the atmosphere, weighing 3.8g of hydrated cerium nitrate, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, drying in a 120 ℃ oven for 8h, weighing 16g of hydrated copper sulfate and 2.5g of potassium nitrate, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 14h, and drying at 140 ℃ for 12h to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 97.4%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 89.5%.
Example 11:
firstly, weighing 58g of wood activated carbon, immersing the activated carbon for 2 hours by using 7 percent of wt hydrochloric acid solution 200m L, washing the activated carbon by using deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N into the aqueous solution2Roasting at 250 ℃ for 5h in the atmosphere, weighing 3.8g of hydrated cerium nitrate, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, putting into a 120 ℃ oven, drying for 8h, weighing 8g of hydrated copper sulfate and 2.5g of magnesium nitrate, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 5h, and drying for 12h at 150 ℃ to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 95.5%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 87.5%.
Example 12:
firstly, weighing 54g of wood activated carbon, immersing the activated carbon for 2 hours by using 7 percent wt hydrochloric acid solution 200m L, washing the activated carbon by using deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 5h in the atmosphere, weighing 3.8g of hydrated cerium nitrate, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, putting into a 120 ℃ oven, drying for 8h, weighing 12g of hydrated copper sulfate and 2.5g of tin nitrate, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 8h, and drying for 12h at 100 ℃ to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 96.2%, vinyl chloride selectivity of greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 87.7%.
Example 13:
firstly, weighing 54g of wood activated carbon, immersing the activated carbon for 2 hours by using 7 percent wt hydrochloric acid solution 200m L, washing the activated carbon by using deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 5h in the atmosphere, weighing 3.8g of hydrated cerium nitrate, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, drying in an oven at 120 ℃ for 8h, weighing 12g of hydrated copper sulfate and 5g of tin nitrate, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 6h, and drying at 80 ℃ for 12h to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 96.6%, vinyl chloride selectivity of greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 88.1%.
Example 14:
firstly, weighing 54g of wood activated carbon, immersing the activated carbon for 2 hours by using 7 percent wt hydrochloric acid solution 200m L, washing the activated carbon by using deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 5h in the atmosphere, weighing 3.8g of hydrated cerium nitrate, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, putting into a 120 ℃ oven, drying for 8h, weighing 12g of hydrated copper sulfate and 7.4g of tin nitrate, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 6h, and drying for 12h at 150 ℃ to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 160 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 95.8%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 87.1%.
Example 15:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 5 hours by using a 7 wt% sulfuric acid solution of 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Calcining at 250 deg.C for 5h under atmosphere, weighing 3.8g cerous nitrate hydrate, dissolving in 200m L deionized water, adding pretreated activated carbon into cerous nitrate solution, stirring, dripping 0.5 mol/L NaOH solution 50m L, and filteringFiltering, standing for 12h, and drying in an oven at 120 deg.C for 8 h; weighing 16g of hydrated copper chloride and 2.31g of stannic chloride, dissolving in 60g of deionized water, uniformly mixing, putting the Ce-containing activated carbon into the solution, stirring and soaking for 6 hours, and drying at 120 ℃ for 12 hours to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 150 ℃, and the space velocity is 30h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 98.6%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 91.5%.
Example 16:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 5 hours by using a 7 wt% sulfuric acid solution of 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 13h in the atmosphere, weighing 3.8g of hydrated cerium nitrate, dissolving in 200m L deionized water, putting the pretreated activated carbon into a cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, putting into a 120 ℃ oven, drying for 8h, weighing 16g of hydrated copper chloride, 1.3g of tin chloride and 1.65g of titanium sulfate, dissolving in 60g of deionized water, uniformly mixing, putting the activated carbon containing Ce into the solution, stirring, soaking for 10h, and drying for 12h at 120 ℃ to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 150 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 95.4%, vinyl chloride selectivity greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 93.1%.
Example 17:
firstly, weighing 50g of wood activated carbon, immersing the activated carbon for 5 hours by using a 5 wt% hydrochloric acid solution of 200m L, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, drying the activated carbon for 5 hours at 100 ℃, and adding N2Roasting at 250 ℃ for 5h under atmosphere, weighing 3.8g of hydrated cerium nitrate, dissolving in 200m L deionized water, putting the pretreated activated carbon into the cerium nitrate solution, stirring, dropwise adding 0.5 mol/L NaOH solution 50m L, filtering, standing for 12h, drying in a 120 ℃ oven for 8h, weighing 16g of hydrated copper chloride, 1.43g of potassium chloride and 1.65g of titanium sulfate, dissolving in 60g of deionized water, uniformly mixing, and dissolving the active cerium in 60g of deionized waterPutting the charcoal into the solution, stirring and dipping for 6h, and drying at 120 ℃ for 12h to obtain the catalyst.
The evaluation conditions of the catalyst were: the temperature is 170 ℃, and the space velocity is 35h-1The feed gas C2H2HCl 1:1.06, with an initial acetylene conversion of 97.4%, vinyl chloride selectivity of greater than 99.5%, and a reaction run of 600h with an acetylene conversion of 94.4%.
Comparative example 1
The only difference from example 17 is that the hydrated cerium nitrate was replaced with an equal amount of nickel nitrate and the remaining conditions were the same. The catalyst thus prepared was evaluated under the evaluation conditions of example 17 of the present invention, and as a result, the initial acetylene conversion was 92.5%, the vinyl chloride selectivity was 99.5%, the reaction was run for 600 hours, and the acetylene conversion was 66.8%.
Comparative example 2
The difference from example 17 was only that the 5% by weight hydrochloric acid solution was replaced with an equal volume of 5% by weight nitric acid solution, and the other conditions were the same. The catalyst thus prepared was evaluated under the evaluation conditions of example 17 of the present invention, and as a result, the initial acetylene conversion was 97.4%, the vinyl chloride selectivity was 99.5%, the reaction was run for 600 hours, and the acetylene conversion was 65.2%.
Comparative example 3
The catalyst prepared was evaluated according to the evaluation conditions of example 17 of the present invention, and as a result, the initial acetylene conversion was 84.9%, the vinyl chloride selectivity was 99.5%, the reaction was carried out for 600 hours, and the acetylene conversion was 63.3%.
In conclusion, the novel Cu-based acetylene hydrochlorination mercury-free catalyst has the characteristics of good selectivity, high stability and small environmental hazard, can realize industrial production, and has potential application prospects and profound research significance in the aspects of acetylene hydrochlorination and metal catalysis.
The above detailed description is specific to preferred embodiments of the present invention, and the embodiments are not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.

Claims (10)

1. The Cu-based acetylene hydrochlorination mercury-free catalyst is characterized by comprising a carrier, an active component and an auxiliary agent, wherein the carrier is modified activated carbon, the active component is an inorganic salt of Cu, and the auxiliary agent is a non-noble metal component;
the modified activated carbon is wood or coconut shell activated carbon and is prepared by immersing a modifier, filtering, drying and roasting.
2. The catalyst as claimed in claim 1, wherein the immersion time is 2-10h, the drying condition is drying at 80-100 ℃ for 2-6h, and the calcination condition is calcination at 200-300 ℃ for 3-15 h.
3. The catalyst of claim 1, wherein the modifier is at least one of hydrogen peroxide solution, hydrochloric acid solution and sulfuric acid solution, and the mass concentration of the modifier is 5-10%.
4. The catalyst of claim 1, wherein the inorganic salt of Cu is one or more of a chloride, a nitrate, and a sulfate of Cu; the mass of the inorganic salt of Cu accounts for 10-25% of the total mass of the catalyst.
5. The catalyst of claim 1, wherein the non-noble metal component is at least one of an inorganic salt of K, an inorganic salt of Ti, an inorganic salt of Mg, and an inorganic salt of Sn, and an inorganic salt of Ce; the inorganic salt of K is preferably at least one of chloride, sulfate and nitrate of K; the inorganic salt of Ti is preferably at least one of chloride, sulfate and nitrate of Ti; the inorganic salt of Mg is preferably at least one of chloride, sulfate and nitrate of Mg; the inorganic salt of Sn is preferably at least one of chloride, sulfate and nitrate of Sn; the inorganic salt of Ce is preferably at least one of chloride, sulfate and nitrate of Ce.
6. The method for preparing a Cu-based acetylene mercury-free hydrochlorination catalyst of claim 5, comprising the steps of:
(1) preparing a precursor I by a chemical precipitation method: adding modified activated carbon into Ce inorganic salt solution, stirring, precipitating with chemical precipitant, filtering, and drying the filter residue at 90-150 deg.C to obtain precursor I;
(2) preparation of catalyst by excess impregnation: and mixing the rest of the auxiliary agent and the inorganic salt solution of Cu to obtain a mixed solution II, adding the precursor I into the mixed solution II, excessively soaking at normal temperature, standing for 5-15h, and drying at 80-150 ℃ to obtain the copper-aluminum alloy.
7. The method according to claim 6, wherein the chemical precipitant is NaOH or ammonia water, and the concentration of the chemical precipitant is 0.1 to 0.5 mol/ml.
8. The process according to claim 6, wherein the amount of the inorganic salt of Ce is 1-5%, preferably 2-3% by mass of the catalyst.
9. The process according to claim 6, wherein the mass of the remaining auxiliary in the step (2) is 0.1 to 10% of the mass of the catalyst.
10. Use of the catalyst according to any one of claims 1 to 5 or the catalyst prepared by the preparation process according to any one of claims 6 to 9 in the hydrochlorination of acetylene.
CN202010316553.3A 2020-04-21 2020-04-21 Cu-based acetylene hydrochlorination mercury-free catalyst Pending CN111389426A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113634265A (en) * 2021-07-26 2021-11-12 内蒙古鄂尔多斯电力冶金集团股份有限公司 Catalyst for synthesizing vinyl chloride by hydrochlorinating Cu-Ru acetylene and preparation method thereof
CN114146728A (en) * 2021-11-29 2022-03-08 内蒙古鄂尔多斯电力冶金集团股份有限公司 Composite carrier Cu-based acetylene hydrochlorination catalyst and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113634265A (en) * 2021-07-26 2021-11-12 内蒙古鄂尔多斯电力冶金集团股份有限公司 Catalyst for synthesizing vinyl chloride by hydrochlorinating Cu-Ru acetylene and preparation method thereof
CN113634265B (en) * 2021-07-26 2023-10-27 内蒙古鄂尔多斯电力冶金集团股份有限公司 Catalyst for synthesizing chloroethylene by hydrochlorination of Cu-Ru acetylene and preparation method thereof
CN114146728A (en) * 2021-11-29 2022-03-08 内蒙古鄂尔多斯电力冶金集团股份有限公司 Composite carrier Cu-based acetylene hydrochlorination catalyst and preparation method thereof
CN114146728B (en) * 2021-11-29 2023-12-05 内蒙古鄂尔多斯电力冶金集团股份有限公司 Composite carrier Cu-based acetylene hydrochlorination catalyst and preparation method thereof

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