An ultra-low noble metal content mercury-free catalyst for acetylene hydrochlorination reaction and a preparation method thereof

Abstract

The application discloses a catalyst, which comprises an active component, an auxiliary A, an auxiliary B and a catalyst carrier, the active component comprises a noble metal element and a copper element, the auxiliary A is an organic phosphorus compound, and the auxiliary B is a sulfur-containing compound and / or a nitrogen-containing compound, wherein the active component, the auxiliary A and the auxiliary B are directly loaded on the catalyst carrier. The catalyst has good acetylene conversion rate, excellent vinyl chloride selectivity and better stability in the process of preparing vinyl chloride monomer through acetylene hydrochlorination reaction, and has a good industrial application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to a mercury-free catalyst for acetylene hydrochlorination reaction and a preparation method thereof, and belongs to the field of catalysts and their preparation in chemical production. BACKGROUND

[0002] PVC, as one of the five general-purpose plastics, plays an important role in national economic construction and is widely used in various industries such as automobiles, building materials, pipes, wires and cables, toys, and food packaging. Acetylene method (acetylene hydrochlorination method), ethylene method and ethane method are the main methods for the industrial synthesis of vinyl chloride monomer. At present, the catalyst used in the acetylene method in industry is activated carbon supported mercury chloride catalyst. However, the high volatility and toxicity of mercury chloride pose a great threat to the environment and human beings; the loading of mercury chloride in the industrial catalyst is 10-15 wt.%, and the production capacity of the catalyst is 1000 kg (VCM) / kg (cat.) About 25% of HgCl2 is lost during the catalytic cycle. Therefore, to achieve green and sustainable development of the acetylene method PVC industry, the development of mercury-free catalysts with excellent performance is imminent. Researchers at home and abroad have made a lot of research on the development of mercury-free catalysts and have made some progress:

[0003] G.J. Hutchings et al. conducted a series of studies on single metals such as gold, palladium and platinum, and found that all single metal elements could exhibit certain catalytic activity in acetylene hydrochlorination reaction, but had poor stability, short service life and common problems such as temperature runaway during the reaction.

[0004] Chinese patent CN101947465A discloses a low-noble metal mercury-free catalyst system, which uses gold, platinum, rhodium, ruthenium, palladium and other noble metals and copper, zinc, potassium, barium, nickel and other non-noble metals as active components, and active carbon, molecular sieve, silica gel, carbon nanotube and the like as carriers. The mass content of noble metals is 0.05-0.5%.

[0005] Chinese patent CN102029189A discloses a mercury-free catalyst system, which has gold salt as the main active component, which can be gold halide, complex and the like. The gold content in the gold salt accounts for 0.1-10% of the weight of the catalyst; the auxiliary active component is non-noble metal salt, which can be potassium, barium, lanthanum, copper halide, acetate, phosphate, complex and the like. The content of non-noble metal salt accounts for 0.1-10% of the weight of the catalyst; and the carrier is active carbon, including coconut shell carbon, coal carbon, fruit shell carbon, or silica gel.

[0006] Chinese patent CN101716508A discloses a mercury-free catalyst system. The catalyst is a granular catalyst prepared by impregnation method using activated carbon as carrier, chloride containing 2-15% of palladium or gold as active component, and 1-5% of rare earth chloride as cocatalyst component.

[0007] Chinese patent CN114029069A discloses a gold-copper ethyne hydrochlorination catalyst modified by ionic liquid. The catalyst uses activated carbon as carrier, gold salt as active component, and copper salt and ionic liquid as catalyst additives. The weight of gold accounts for 0.05-0.2% of the catalyst, the weight of copper accounts for 0.5-2% of the catalyst, and the weight of ionic liquid accounts for 1-10% of the gold-copper ethyne hydrochlorination catalyst.

[0008] Chinese patent CN108993596A discloses a copper complex catalyst for ethyne hydrochlorination reaction. The catalyst is complexed by copper salt and organic phosphorus-containing acid ligand. The mass fraction of copper in the copper complex catalyst is 1-15%, and the mass fraction of organic phosphorus-containing acid ligand is 1-50%.

[0009] Chinese patent CN111774094A discloses a copper-based mercury-free catalyst. The catalyst uses activated carbon modified by trimethylaluminum or silicon tetrachloride as carrier, zinc chloride or iron chloride as additive, and complex formed by copper chloride and nitrogen-containing or carbonyl-containing ligand as active component. The mass fraction of copper chloride in the catalyst is 5-40%, and the molar ratio of copper chloride to additive is 1.0:0.05-0.5.

[0010] Chinese patent CN111672525A discloses a copper-based ethyne hydrochlorination catalyst modified by in-situ synthesis of layered mesoporous zirconium phosphate on activated carbon and its preparation method. The catalyst uses activated carbon as carrier, is modified by in-situ synthesis of mesoporous zirconium phosphate, and then loaded with copper salt and dried. The mass percentage composition of the catalyst is 5-50% of copper salt and 0.1-20% of mesoporous zirconium phosphate.

[0011] From the current patent and literature reports, the existing system and characteristics of mercury-free catalyst are as follows: the single noble metal system, such as gold, palladium, ruthenium, platinum, etc., has high activity, and when assisted by specific ligands, adjuvants, etc., the activity and life are greatly improved, and the content of noble metal is generally more than 0.1%, so the most important problem of these catalysts is that the cost is extremely high, which seriously hinders its industrial application; as a representative of non-noble metal catalyst, copper-based catalyst, after being assisted by specific phosphorus compound ligands, the activity and stability reach a certain level, but there is still a certain gap with noble metal catalyst; the noble metal and copper-based composite catalyst, although the activity has been significantly improved, but the stability of the catalyst still has serious defects, and the content of noble metal needs to be more than 0.05%, although the cost is reduced, but it is still much higher than that of copper-based catalyst; other non-metallic catalysts, such as carbon-based catalyst, ionic liquid catalyst, molecular sieve catalyst, etc., cannot compare with copper-based and noble metal catalysts in activity and stability. SUMMARY

[0012] One of the purposes of the present application is to solve the environmental pollution problem caused by the use of high-toxicity mercury catalyst in the production of calcium carbide acetylene method polyvinyl chloride; the second purpose is to solve the problem of high noble metal loading and high cost of the current activated carbon supported noble metal catalyst; the third purpose is to solve the problems of poor stability, short life and the common phenomenon of overshoot in the reaction process of the current acetylene hydrochlorination reaction catalyst.

[0013] The characteristics of the present application are that copper, noble metal (gold, ruthenium, etc.) are used as the main active component, and phosphorus compounds, thiosulfate and other coordination compounds are used as the auxiliary active component, and activated carbon is used as the carrier to form a new type of efficient four-component composite mercury-free catalyst. The most significant feature of the catalyst is that through the four-component composite, the content of noble metal is greatly reduced while maintaining the high activity and high stability of the catalyst, and the content can be as low as 100 ppm. The catalyst described in the present application completely inherits the advantages of high activity and high stability of noble metal catalysts, and at the same time has the low cost advantage of copper-based catalysts, and has a broad application prospect.

[0014] Therefore, the present application develops an acetylene hydrochlorination reaction ultra-low noble metal content mercury-free catalyst and a preparation method thereof.

[0015] The catalyst comprises an active component, an adjuvant A, an adjuvant B and a catalyst carrier, the active component comprises a noble metal element and a copper element, the adjuvant A is an organic phosphorus compound, and the adjuvant B is a sulfur-containing compound and / or a nitrogen-containing compound, wherein the active component, the adjuvant A and the adjuvant B are directly loaded on the catalyst carrier.

[0016] Optionally, the noble metal element is from a noble metal salt; the noble metal salt comprises at least one of chloroauric acid, ruthenium chloride, palladium chloride, chloroplatinic acid.

[0017] Optionally, the copper element is from a copper salt; the copper salt comprises at least one of copper chloride, copper sulfate, and copper acetate.

[0018] Optionally, the organic phosphorus compound comprises at least one of dimethylphosphine oxide, diphenylphosphine oxide, (methoxymethyl)diphenylphosphine oxide, di(p- methylphenyl)phosphine oxide, tricyclohexylphosphine oxide, cyclohexyldiphenylphosphine oxide, tri(4-methylphenyl)phosphine oxide, methyl-diphenylphosphine oxide, triphenylphosphine oxide, tri-n-butylphosphine oxide, and tri-n-octylphosphine oxide.

[0019] Optionally, the auxiliary agent B comprises at least one of sodium thiosulfate, thiourea, potassium thiocyanate, and trichloroisocyanuric acid.

[0020] Optionally, the catalyst carrier is activated carbon, and a specific surface area of the activated carbon is 800-1400 m 2 / g.

[0021] Optionally, the activated carbon comprises at least one of coconut shell carbon, wood carbon, and coal carbon.

[0022] Optionally, a mass percentage of the noble metal element to the catalyst carrier is 0.0005-0.01%. Optionally, the mass percentage of the noble metal element to the catalyst carrier is 0.0005%, 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, or 0.01%, and a range value between any two numerical values.

[0023] Optionally, a mass percentage of the copper element to the catalyst carrier is 5-25%. Optionally, the mass percentage of the copper element to the catalyst carrier is 5%, 10%, 15%, 20%, or 25%, and a range value between any two numerical values.

[0024] Optionally, a mass percentage of the phosphorus element in the organic phosphorus compound to the catalyst carrier is 0.5-2.5%. Optionally, the mass percentage of the phosphorus element in the organic phosphorus compound to the catalyst carrier is 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, or 2.5%, and a range value between any two numerical values.

[0025] Optionally, the mass percentage of the additive B to the catalyst carrier is 1-8%.

[0026] Optionally, the catalyst does not contain mercury element.

[0027] More particularly, the present application develops an acetylene hydrochlorination reaction ultra-low noble metal content mercury-free catalyst, which comprises an active component, an additive A, an additive B and a catalyst carrier, the active component comprises a noble metal salt and a copper salt, the additive A is an organic phosphorus, wherein the active component is directly loaded on the catalyst carrier. The mass percentage of the noble metal element to the catalyst carrier is 0.0005-0.01%, the mass percentage of the copper element in the copper salt to the catalyst carrier is 5-25%, the mass percentage of the phosphorus element in the organic phosphorus to the catalyst carrier is 0.5-2.5%, and the mass percentage of the additive B to the catalyst carrier is 1-8%.

[0028] In a preferred embodiment, the carrier of the catalyst is activated carbon, the specific surface area of the activated carbon is 800-1400 m 2 / g, and the activated carbon carrier of the catalyst is at least one of coconut shell carbon, coal carbon and wood carbon.

[0029] In a preferred embodiment, the noble metal salt comprises at least one of chloroauric acid, ruthenium chloride, palladium chloride and chloroplatinic acid.

[0030] In a preferred embodiment, in the catalyst, the mass percentage of the noble metal element to the carrier is 0.001-0.009%.

[0031] In a preferred embodiment, the copper salt comprises at least one of copper chloride, copper sulfate and copper acetate.

[0032] In a preferred embodiment, in the catalyst, the mass percentage of the copper element in the copper salt to the catalyst carrier is 7-20%.

[0033] In a preferred embodiment, the organic phosphorus comprises at least one of dimethyl phosphine oxide, diphenyl phosphine oxide, (methoxymethyl) diphenyl phosphine oxide, di(p-methylphenyl) phosphine oxide, tricyclohexyl phosphine oxide, cyclohexyl diphenyl phosphine oxide, tri(4-methylphenyl) phosphine oxide, methyl diphenyl phosphine oxide, triphenyl phosphine oxide, tri-n-butyl phosphine oxide and tri-n-octyl phosphine oxide.

[0034] In a preferred embodiment, in the catalyst, the mass percentage of phosphorus element in the organic phosphorus to the carrier is 0.7-2%.

[0035] In a preferred embodiment, the auxiliary agent B comprises at least one of sodium thiosulfate, thiourea, potassium thiocyanate and trichloroisocyanuric acid.

[0036] In a preferred embodiment, in the catalyst, the mass percentage of auxiliary agent B to the carrier is 2-5%.

[0037] According to another aspect of the present application, a preparation method of the catalyst described in any of the above is provided, comprising the following steps:

[0038] (1) impregnating a catalyst carrier in a solution containing a copper element and an organic phosphorus compound, drying to obtain a catalyst precursor;

[0039] (2) adding a solution containing a noble metal element and an auxiliary agent B to the catalyst precursor, impregnating, drying to obtain the catalyst.

[0040] Optionally, in step (1), in the solution containing a copper element and an organic phosphorus compound, the copper element is from a copper salt; the copper salt comprises at least one of copper chloride, copper sulfate and copper acetate; the organic phosphorus compound comprises at least one of dimethyl phosphine oxide, diphenyl phosphine oxide, (methoxymethyl) diphenyl phosphine oxide, di(p-methylphenyl) phosphine oxide, tricyclohexyl phosphine oxide, cyclohexyl diphenyl phosphine oxide, tris(4-methylphenyl) phosphine oxide, methyl diphenyl phosphine oxide, triphenyl phosphine oxide, tri-n-butyl phosphine oxide and tri-n-octyl phosphine oxide.

[0041] Optionally, in step (2), in the solution containing a noble metal element and an auxiliary agent B, the noble metal element is from a noble metal salt; the noble metal salt comprises at least one of chloroauric acid, ruthenium chloride, palladium chloride and chloroplatinic acid; the auxiliary agent B comprises at least one of sodium thiosulfate, thiourea, potassium thiocyanate and trichloroisocyanuric acid.

[0042] Optionally, step (1) is equal-volume impregnation.

[0043] Optionally, step (2) is equal-volume impregnation.

[0044] Optionally, in step (1), the temperature of the impregnation is 20-50°C, and the impregnation time is 12-24h.

[0045] Optionally, in step (2), the temperature of the impregnation is room temperature, and the impregnation time is 12-24h.

[0046] Optionally, in steps (1) and (2), the drying is vacuum drying, the temperature of the vacuum drying is 100-120℃, and the time is 24-48h.

[0047] Specifically, the present application develops a preparation method of an ethyne hydrochlorination reaction ultra-low noble metal content mercury-free catalyst, comprising the following steps:

[0048] (1) Take activated carbon for crushing and screening;

[0049] (2) Prepare a mixed solution of copper salt and organic phosphorus, use the mixed solution to impregnate the activated carbon in equal volume, and vacuum dry to obtain a copper-phosphorus catalyst;

[0050] (3) Prepare a mixed solution of noble metal salt and additive B, use the mixed solution to impregnate the copper-phosphorus catalyst in equal volume, and vacuum dry to obtain an ultra-low noble metal content mercury-free catalyst.

[0051] The temperature of the equal volume impregnation in the above step (2) is 20-50℃, and the impregnation time is 12-24h; the equal volume impregnation temperature in the above step (3) is room temperature, and the impregnation time is 12-24h; the vacuum drying temperature is 100-120℃, and the drying time is 24-48h.

[0052] According to another aspect of the present application, a method for ethyne hydrochlorination reaction is provided, comprising the following steps: contacting a raw material containing ethyne and hydrogen chloride with a catalyst, reacting, and preparing chloroethylene;

[0053] The catalyst is selected from at least one of the catalysts described in any of the above, and the catalyst prepared according to the preparation method described in any of the above.

[0054] Optionally, the ethyne space velocity is 30-180h -1 , and the reaction temperature is 150-200℃.

[0055] In the present application, "room temperature" refers to 10-50℃.

[0056] Compared with the prior art, the present application has the following beneficial effects:

[0057] 1) The present application develops an ethyne hydrochlorination ultra-low noble metal content mercury-free catalyst, which breaks through the noble metal usage, can be less than 0.01%, greatly reduces the catalyst cost, and realizes the unity of high activity, high selectivity and high stability of the mercury-free catalyst.

[0058] 2) The mercury-free catalyst provided in the present application has a simple and easy preparation method, is used for preparing chloroethylene by ethyne hydrochlorination reaction, and avoids the environmental pollution and other problems caused by traditional mercury chloride catalyst in ethyne hydrochlorination reaction.

[0059] 3) The invention develops an ethyne hydrochlorination ultra-low noble metal content mercury-free catalyst, which has excellent catalytic performance, a relatively long service life and a good industrial application prospect. DETAILED DESCRIPTION

[0060] In order to better illustrate the present invention, the following examples are given. However, the scope of the present invention is not limited to the examples only, and the scope of the claimed invention is described in the claims.

[0061] The endpoints of the ranges and any values disclosed in this application are not limited to the precise values recited. The ranges or values should be interpreted as being approximate, meaning values near the recited values are also within the scope of the ranges or values, unless the context clearly indicates otherwise. For numeric values, the endpoints of each range and individual points can be combined with one another to generate one or more new numeric ranges, which should be considered as being specifically disclosed herein.

[0062] First, prepare chloroauric acid, ruthenium chloride, palladium chloride, and chloroplatinic acid solutions respectively: take 1 g of chloroauric acid, ruthenium chloride, palladium chloride, and chloroplatinic acid respectively, and prepare 100 ml of solution in a respective volumetric flask. Prepare for subsequent sample preparation.

[0063] Example 1

[0064] (1) Weigh 26.63 g of hydrated copper chloride and 8.97 g of triphenylphosphine oxide into 60 g of anhydrous ethanol, take 50 g of coconut charcoal, add it to the above solution, stir uniformly, immerse for 12 h, and then transfer to a vacuum drying oven at 120℃ for 48 h to obtain a copper-phosphorus catalyst;

[0065] (2) Weigh 0.95 g of chloroauric acid solution and 2.50 g of sodium thiosulfate, add 34 g of deionized water, and dropwise add the above copper-phosphorus catalyst, immerse for 12 h, and then transfer to a vacuum oven at 120℃ for 48 h to obtain an ultra-low gold content mercury-free catalyst. The composition of the ultra-low gold content mercury-free catalyst is gold element: copper element: phosphorus element: sodium thiosulfate: coconut charcoal mass ratio = 0.009%: 20%: 2%: 5%: 1.

[0066] (3) The catalyst is used for ethyne hydrochlorination reaction, when the ethyne space velocity is 180 h -1 , and the reaction temperature is 180℃, the initial conversion rate of ethyne is 94.6%, and the selectivity of chloroethylene is 98%. The catalyst ethyne conversion rate is 89.2% and the chloroethylene selectivity is 98% after running for 100 h.

[0067] Example 2

[0068] (1) Take 19.97 g of hydrated copper chloride and 5.28 g of tri-n-butyl phosphine oxide, dissolve in 60 g of anhydrous ethanol, take 50 g of coconut shell charcoal, add to the above solution, stir uniformly, immerse for 24 h, then transfer to a vacuum drying oven at 120°C for drying for 48 h to obtain a copper-phosphorus catalyst;

[0069] (2) Take 0.84 g of chloroauric acid solution and 4.00 g of sodium thiosulfate, add 30 g of deionized water, dropwise add to the above copper-phosphorus catalyst, immerse for 24 h, then transfer to a vacuum oven at 120°C for drying for 24 h to obtain a mercury-free catalyst with ultra-low gold content. The composition of the mercury-free catalyst with ultra-low gold content is gold element: copper element: phosphorus element: sodium thiosulfate: coconut shell charcoal mass ratio = 0.008%: 15%: 1.5%: 8%: 1.

[0070] (3) The catalyst is used for acetylene hydrochlorination reaction, when the acetylene space velocity is 180 h -1 , and the reaction temperature is 180°C, the initial acetylene conversion rate is 93.2%, and the chloroethylene selectivity is 98%. The catalyst acetylene conversion rate is 87.3% and the chloroethylene selectivity is 98% after reaction for 100 h.

[0071] Example 3

[0072] (1) Take 19.97 g of hydrated copper chloride and 5.28 g of tri-n-butyl phosphine oxide, dissolve in 60 g of anhydrous ethanol, take 50 g of coconut shell charcoal, add to the above solution, stir uniformly, immerse for 24 h, then transfer to a vacuum drying oven at 120°C for drying for 48 h to obtain a copper-phosphorus catalyst;

[0073] (2) Take 0.84 g of chloroauric acid solution and 4.00 g of sodium thiosulfate, add 30 g of deionized water, dropwise add to the above copper-phosphorus catalyst, immerse for 24 h, then transfer to a vacuum oven at 120°C for drying for 24 h to obtain a mercury-free catalyst with ultra-low gold content. The composition of the mercury-free catalyst with ultra-low gold content is gold element: copper element: phosphorus element: sodium thiosulfate: coconut shell charcoal mass ratio = 0.008%: 15%: 1.5%: 8%: 1.

[0074] (3) The catalyst is used for acetylene hydrochlorination reaction, when the acetylene space velocity is 180 h -1 , and the reaction temperature is 180°C, the initial acetylene conversion rate is 93.2%, and the chloroethylene selectivity is 98%. The catalyst acetylene conversion rate is 87.3% and the chloroethylene selectivity is 98% after reaction for 100 h.

[0075] Example 4

[0076] (1) Take 26.63 g of hydrated copper chloride and 7.94 g of (methoxymethyl) diphenyl phosphine oxide, dissolve in 60 g of anhydrous ethanol, take 50 g of coconut shell charcoal, add to the above solution, stir uniformly, immerse for 12 h, then transfer to a vacuum drying oven at 120 °C for drying for 48 h to obtain a copper phosphorus catalyst;

[0077] (2) Take 0.74 g of chloroauric acid solution and 2.50 g of trichloroisocyanuric acid, add 34 g of deionized water, dropwise add to the above copper phosphorus catalyst, immerse for 12 h, then transfer to a vacuum oven at 120 °C for drying for 48 h to obtain a mercury-free catalyst with ultra-low gold content. The composition of the mercury-free catalyst with ultra-low gold content is gold element: copper element: phosphorus element: trichloroisocyanuric acid: coconut shell charcoal mass ratio = 0.007%: 20%: 2%: 5%: 1.

[0078] (3) The catalyst is used for acetylene hydrochlorination reaction, when the acetylene space velocity is 30 h -1 , and the reaction temperature is 180 °C, the initial acetylene conversion rate is 99.5%, and the chloroethylene selectivity is 98%. After 100 h of reaction, the acetylene conversion rate and the chloroethylene selectivity remain unchanged.

[0079] Example 5

[0080] (1) Take 26.63 g of hydrated copper chloride and 7.94 g of (methoxymethyl) diphenyl phosphine oxide, dissolve in 60 g of anhydrous ethanol, take 50 g of coconut shell charcoal, add to the above solution, stir uniformly, immerse for 12 h, then transfer to a vacuum drying oven at 120 °C for drying for 48 h to obtain a copper phosphorus catalyst;

[0081] (2) Take 0.74 g of chloroauric acid solution and 2.50 g of trichloroisocyanuric acid, add 34 g of deionized water, dropwise add to the above copper phosphorus catalyst, immerse for 12 h, then transfer to a vacuum oven at 120 °C for drying for 48 h to obtain a mercury-free catalyst with ultra-low gold content. The composition of the mercury-free catalyst with ultra-low gold content is gold element: copper element: phosphorus element: trichloroisocyanuric acid: coconut shell charcoal mass ratio = 0.007%: 20%: 2%: 5%: 1.

[0082] (3) The catalyst is used for acetylene hydrochlorination reaction, when the acetylene space velocity is 30 h -1 , and the reaction temperature is 180 °C, the initial acetylene conversion rate is 99.5%, and the chloroethylene selectivity is 98%. After 100 h of reaction, the acetylene conversion rate and the chloroethylene selectivity remain unchanged.

[0083] Example 6

[0084] (1) Weigh 19.97g of hydrated copper chloride and 7.75g of tris(4-methylphenyl)phosphine oxide and dissolve them in 35g of anhydrous ethanol. Take 50g of wood charcoal and add it to the above solution. Stir well and soak for 12h. Then transfer it to a vacuum drying oven and dry at 120℃ for 48h to obtain a copper-phosphorus catalyst.

[0085] (2) Weigh 1.29 g of ruthenium chloride solution and 1.00 g of sodium thiosulfate, add 12 g of deionized water, and add dropwise to the above copper-phosphorus catalyst. After soaking for 12 h, transfer to a vacuum oven and dry at 120 °C for 48 h to obtain a mercury-free catalyst with ultra-low ruthenium content. The composition of the mercury-free catalyst with ultra-low ruthenium content is ruthenium: copper: phosphorus: sodium thiosulfate: charcoal mass ratio = 0.01%: 15%: 1.5%: 2%: 1.

[0086] (3) This catalyst was used in the acetylene hydrochlorination reaction at an acetylene space velocity of 180 h⁻¹. -1 At a reaction temperature of 180℃, the initial acetylene conversion rate was 88.2%, and the vinyl chloride selectivity was 98%. After 100 hours of reaction, the catalyst achieved an acetylene conversion rate of 84.6% and a vinyl chloride selectivity of 98%.

[0087] Example 7

[0088] (1) Weigh 48.75g of hydrated copper sulfate and 2.39g of tricyclohexylphosphine oxide and dissolve them in 70g of anhydrous ethanol. Heat the solution to 50°C. Take 50g of coconut shell charcoal and add it to the above solution. Stir well and soak for 12h. Then transfer it to a vacuum drying oven and dry at 120°C for 48h to obtain a copper-phosphorus catalyst.

[0089] (2) Weigh 0.65g of ruthenium chloride solution and 2.50g of trichloroisocyanuric acid, add 10g of deionized water, and add dropwise to the above copper-phosphorus catalyst. After impregnation for 12h, transfer to a vacuum oven and dry at 120℃ for 48h to obtain a mercury-free catalyst with ultra-low ruthenium content. The composition of the mercury-free catalyst with ultra-low ruthenium content is ruthenium:copper:phosphorus:trichloroisocyanuric acid:coconut shell carbon mass ratio = 0.005%:25%:0.5%:5%:1.

[0090] (3) This catalyst was used in the acetylene hydrochlorination reaction at an acetylene space velocity of 30 h⁻¹. -1 At a reaction temperature of 180℃, the initial acetylene conversion rate was 96.2%, and the vinyl chloride selectivity was 98%. After 100 hours of reaction, the catalyst achieved an acetylene conversion rate of 92.5% and a vinyl chloride selectivity of 98%.

[0091] Example 8

[0092] (1) Take 15.60 g of hydrated copper acetate and 3.49 g of methyl diphenyl phosphine oxide, dissolve in 35 g of anhydrous ethanol, take 50 g of coal carbon, add to the above solution, stir uniformly, immerse for 12 h, then transfer to a vacuum drying oven at 120°C for drying for 48 h to obtain a copper phosphorus catalyst;

[0093] (2) Take 0.04 g of palladium chloride solution and 1.00 g of sodium thiosulfate, add 14 g of deionized water, dropwise add to the above copper phosphorus catalyst, immerse for 12 h, then transfer to a vacuum oven at 120°C for drying for 48 h to obtain a mercury-free catalyst with ultra-low palladium content. The composition of the mercury-free catalyst with ultra-low palladium content is: palladium element: copper element: phosphorus element: sodium thiosulfate: coal carbon mass ratio = 0.0005%: 10%: 1%: 2%: 1. -1 (3) The catalyst is used for acetylene hydrochlorination reaction, when the acetylene space velocity is 180 h-1 and the reaction temperature is 180°C, the initial acetylene conversion rate is 81.4%, and the chloroethylene selectivity is 98%. The catalyst runs for 100 h, the acetylene conversion rate is 76.9%, and the chloroethylene selectivity is 98%.

[0094] Example 9

[0095] (1) Take 6.66 g of hydrated copper chloride and 1.86 g of di(p-methylphenyl) phosphine oxide, dissolve in 60 g of anhydrous ethanol, take 50 g of coconut shell carbon, add to the above solution, stir uniformly, immerse for 12 h, then transfer to a vacuum drying oven at 100°C for drying for 48 h to obtain a copper phosphorus catalyst;

[0096] (2) Take 0.75 g of palladium chloride solution and 2.50 g of trichloroisocyanuric acid, add 30 g of deionized water, dropwise add to the above copper phosphorus catalyst, immerse for 12 h, then transfer to a vacuum oven at 100°C for drying for 48 h to obtain a mercury-free catalyst with ultra-low palladium content. The composition of the mercury-free catalyst with ultra-low palladium content is: palladium element: copper element: phosphorus element: trichloroisocyanuric acid: coconut shell carbon mass ratio = 0.009%: 5%: 0.5%: 5%: 1.

[0097] (3) The catalyst is used for acetylene hydrochlorination reaction, when the acetylene space velocity is 180 h -1 , the reaction temperature is 180°C, the initial acetylene conversion rate is 91.8%, and the chloroethylene selectivity is 98%. The catalyst runs for 100 h, the acetylene conversion rate is 81.3%, and the chloroethylene selectivity is 98%.

[0098] Example 10

[0099] (1) Take 9.32 g of hydrated copper chloride and 3.21 g of cyclohexyl diphenyl phosphine oxide, dissolve in 60 g of anhydrous ethanol, take 50 g of coconut shell carbon, add to the above solution, stir uniformly, immerse for 12 h, then transfer to a vacuum drying oven at 120°C for drying for 48 h to obtain a copper phosphorus catalyst;

[0100] (2) Weigh 1.20 g of chloroplatinic acid solution and 2.00 g of sodium thiosulfate, add 31 g of deionized water, and dropwise add to the above copper-phosphorus catalyst, immerse for 12 h, and then transfer to a vacuum oven to dry at 120°C for 48 h to obtain a mercury-free catalyst with ultra-low platinum content. The composition of the mercury-free catalyst with ultra-low platinum content is platinum element: copper element: phosphorus element: sodium thiosulfate: coconut shell charcoal mass ratio = 0.009%: 7%: 0.7%: 4%: 1. (3) The catalyst is used for acetylene hydrochlorination reaction, when the acetylene space velocity is 180 h -1 , the initial acetylene conversion rate is 90.1%, and the selectivity of chloroethylene is 98%. The acetylene conversion rate of the catalyst is 85.6% and the selectivity of chloroethylene is 98% after 100 h of reaction.

[0101] Example 11

[0102] (1) Weigh 13.32 g of hydrated copper chloride and 3.24 g of diphenylphosphine oxide into 60 g of anhydrous ethanol, take 50 g of coconut shell charcoal, add to the above solution, stir uniformly, immerse for 12 h, and then transfer to a vacuum drying oven to dry at 120°C for 48 h to obtain a copper-phosphorus catalyst;

[0103] (2) Weigh 0.67 g of chloroplatinic acid solution and 2.00 g of trichloroisocyanuric acid, add 33 g of deionized water, and dropwise add to the above copper-phosphorus catalyst, immerse for 12 h, and then transfer to a vacuum oven to dry at 120°C for 48 h to obtain a mercury-free catalyst with ultra-low platinum content. The composition of the mercury-free catalyst with ultra-low platinum content is platinum element: copper element: phosphorus element: trichloroisocyanuric acid: coconut shell charcoal mass ratio = 0.005%: 10%: 1%: 4%: 1. (3) The catalyst is used for acetylene hydrochlorination reaction, when the acetylene space velocity is 180 h -1 , the initial acetylene conversion rate is 89.3%, and the selectivity of chloroethylene is 98%. The acetylene conversion rate of the catalyst is 84.6% and the selectivity of chloroethylene is 98% after 100 h of reaction.

[0104] Comparative Example 1

[0105] (1) Weigh 26.63 g of hydrated copper chloride and 0.95 g of chloroauric acid solution into 60 g of deionized water, take 50 g of coconut shell charcoal, add to the above solution, stir uniformly, immerse for 12 h, and then transfer to a vacuum drying oven to dry at 120°C for 48 h to obtain a mercury-free gold-copper catalyst;

[0106] (2) The catalyst is used for acetylene hydrochlorination reaction, when the acetylene space velocity is 180 h -1At a reaction temperature of 180℃, the initial acetylene conversion rate was 85.6%, and the vinyl chloride selectivity was 98%. After 100 hours of reaction, the catalyst achieved an acetylene conversion rate of 54.6% and a vinyl chloride selectivity of 98%.

[0107] Comparative Example 2

[0108] (1) Weigh 8.97g of triphenylphosphine oxide and dissolve it in 60g of anhydrous ethanol. Take 50g of coconut shell charcoal and add it to the above solution. Stir well and soak for 12h. Then transfer it to a vacuum drying oven and dry at 120℃ for 48h to obtain the phosphorus catalyst.

[0109] (2) Weigh 0.95g of chloroauric acid solution, add 34g of deionized water, add dropwise to the above phosphorus catalyst, soak for 12h, then transfer to a vacuum oven and dry at 120℃ for 48h to obtain a mercury-free catalyst for gold phosphorus.

[0110] (3) This catalyst was used in the acetylene hydrochlorination reaction at an acetylene space velocity of 180 h⁻¹. -1 At a reaction temperature of 180℃, the initial acetylene conversion rate was 37.2%, and the vinyl chloride selectivity was 98%. After 100 hours of reaction, the catalyst achieved an acetylene conversion rate of 21.3% and a vinyl chloride selectivity of 98%.

[0111] Comparative Example 3

[0112] (1) Weigh 26.63g of hydrated copper chloride, 2.50g of sodium thiosulfate and 0.95g of chloroauric acid solution and dissolve them in 60g of deionized water. Take 50g of coconut shell charcoal and add it to the above solution. Stir evenly and soak for 12h. Then transfer it to a vacuum drying oven and dry at 120℃ for 48h to obtain a gold-copper mercury-free catalyst.

[0113] (2) This catalyst was used in the acetylene hydrochlorination reaction at an acetylene space velocity of 180 h⁻¹. -1 At a reaction temperature of 180℃, the initial acetylene conversion rate was 88.2%, and the vinyl chloride selectivity was 98%. After 100 hours of reaction, the catalyst achieved an acetylene conversion rate of 67.3% and a vinyl chloride selectivity of 98%.

[0114] Comparing Example 1 with Comparative Examples 1 and 3, it can be concluded that: when organophosphorus compounds and auxiliary agent B are missing or one of them is missing, gold salts and copper salts, as active components, have high initial activity in the acetylene hydrochlorination reaction, but the conversion rate decreases rapidly and the stability is poor.

[0115] Comparing Example 1 and Comparative Example 2, it can be concluded that: in the absence of copper salt active components, gold salt and organophosphorus are used as catalysts for active components, and the initial activity of the acetylene hydrochlorination reaction is not high, indicating that copper salt is also the main source of activity when the content of precious metals is extremely low.

[0116] The above merely describes several embodiments of the present application, and does not limit the present application in any form. Although the present application is disclosed with the preferred embodiments, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the disclosed technical contents without departing from the scope of the technical solutions of the present application, and the equivalent embodiments are equivalent to the equivalent embodiments, which are within the scope of the technical solutions.

Claims

1. A catalyst characterized in that, The catalyst comprises an active component, an auxiliary A, an auxiliary B and a catalyst carrier, the active component comprises a noble metal element and a copper element, the auxiliary A is an organic phosphorus compound, wherein the active component, the auxiliary A and the auxiliary B are directly loaded on the catalyst carrier; The catalyst does not contain mercury element; The organic phosphorus compound comprises at least one of dimethyl phosphine oxide, diphenyl phosphine oxide, (methoxymethyl) diphenyl phosphine oxide, di(p-methylphenyl) phosphine oxide, tricyclohexyl phosphine oxide, cyclohexyl diphenyl phosphine oxide, tri(4-methylphenyl) phosphine oxide, methyl diphenyl phosphine oxide, triphenyl phosphine oxide, tri-n-butyl phosphine oxide and tri-n-octyl phosphine oxide; The auxiliary B comprises at least one of sodium thiosulfate, thiourea, potassium thiocyanate and trichloroisocyanuric acid; The mass percentage of the noble metal element in the catalyst carrier is 0.001-0.009%.

2. The catalyst according to claim 1, characterized in that, The noble metal element is from a noble metal salt; the noble metal salt comprises at least one of chloroauric acid, ruthenium chloride, palladium chloride and chloroplatinic acid; The copper element is from a copper salt; the copper salt comprises at least one of copper chloride, copper sulfate and copper acetate.

3. The catalyst of claim 1, wherein The catalyst carrier is activated carbon, the specific surface area of the activated carbon is 800-1400 m 2 / g; The active carbon comprises at least one of coconut shell carbon, wooden carbon and coal carbon.

4. The catalyst according to claim 1, wherein, The mass percentage of the copper element in the catalyst carrier is 5-25%; The mass percentage of the phosphorus element in the organic phosphorus compound in the catalyst carrier is 0.5-2.5%; The mass percentage of the auxiliary B in the catalyst carrier is 1-8%.

5. Process for the preparation of the catalyst according to any one of claims 1 to 4, characterized in that, The preparation method comprises the following steps: (1) immersing the catalyst carrier in a solution containing a copper element and an organic phosphorus compound, drying to obtain a catalyst precursor; (2) adding a solution containing a noble metal element and an auxiliary B to the catalyst precursor, immersing and drying to obtain the catalyst.

6. The preparation method according to claim 5, wherein, In step (1), the copper element in the solution containing a copper element and an organic phosphorus compound is from a copper salt; the copper salt comprises at least one of copper chloride, copper sulfate and copper acetate; and the organic phosphorus compound comprises at least one of dimethyl phosphine oxide, diphenyl phosphine oxide, (methoxymethyl) diphenyl phosphine oxide, di(p-methylphenyl) phosphine oxide, tricyclohexyl phosphine oxide, cyclohexyl diphenyl phosphine oxide, tri(4-methylphenyl) phosphine oxide, methyl diphenyl phosphine oxide, triphenyl phosphine oxide, tri-n-butyl phosphine oxide and tri-n-octyl phosphine oxide; In step (2), the noble metal element in the solution containing a noble metal element and an auxiliary B is from a noble metal salt; the noble metal salt comprises at least one of chloroauric acid, ruthenium chloride, palladium chloride and chloroplatinic acid; and the auxiliary B comprises at least one of sodium thiosulfate, thiourea, potassium thiocyanate and trichloroisocyanuric acid; Step (1) is equal-volume immersion; Step (2) is equal-volume immersion.

7. The method of claim 5, wherein: In step (1), the temperature of the immersion is 20-50°C, and the immersion time is 12-24 h; In step (2), the temperature of the immersion is room temperature, and the immersion time is 12-24 h; In steps (1) and (2), the drying is vacuum drying, and the temperature of the vacuum drying is 100-120 °C, and the time is 24-48 h.

8. A process for the hydrochlorination of acetylene, characterized in that, Includes the following steps: Vinyl chloride is prepared by reacting raw materials containing acetylene and hydrogen chloride with a catalyst. The catalyst is selected from at least one of the catalysts according to any one of claims 1 to 4 and the catalysts prepared by the preparation method according to any one of claims 5 to 7.

9. The method of claim 8, wherein, acetylene space velocity of 30 to 180 h -1 at a reaction temperature of 150 to 200 °C.