CN110586200B - Regeneration method of gold-carbon catalyst for acetylene hydrochlorination - Google Patents
Regeneration method of gold-carbon catalyst for acetylene hydrochlorination Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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- B01J38/70—Wet oxidation of material submerged in liquid
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- C—CHEMISTRY; METALLURGY
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- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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Abstract
The invention discloses a regeneration method of a gold-carbon catalyst for acetylene hydrochlorination, which comprises the following three steps: firstly, roasting at high temperature under the protection of nitrogen; secondly, the aqua regia is boiled; and thirdly, soaking potassium permanganate, potassium dichromate, hydrogen peroxide and other oxidants. And (4) obtaining the regenerated catalyst after the three steps of treatment. The method can recover the activity of the gold-carbon catalyst after the hydrochlorination of acetylene to a great extent, and the regenerated catalyst can keep good performance in continuous operation. The regeneration method is simple and easy to amplify, and the regeneration of the catalyst can greatly reduce the use cost of the gold-carbon catalyst, so that the gold-carbon catalyst becomes a recyclable green and environment-friendly product.
Description
Technical Field
The invention belongs to the technical field of catalyst regeneration, and particularly relates to a regeneration method of a gold-carbon catalyst for acetylene hydrochlorination.
Background
The synthesis of vinyl chloride monomer by addition of acetylene and hydrogen chloride is the earliest industrialized vinyl chloride production process and has always occupied an important position in China. However, the process adopts a mercury chloride catalyst which is extremely toxic and easy to sublimate and lose, so that the process not only seriously harms human health and pollutes the environment, but also influences the product quality of the vinyl chloride monomer. How to reduce the catalyst pollution brought in the process of producing chloroethylene so as to better meet the national requirements for building a resource-saving and environment-friendly society becomes a problem to be solved urgently in the whole industry for producing polyvinyl chloride by a calcium carbide acetylene method.
In 2017, 8, 16, water guarantee convention, the convention of China is in force, and new vinyl chloride monomer production processes using mercury-containing catalysts are forbidden. The elimination of the mercury-containing catalyst is imperative, so the development of the environment-friendly nontoxic mercury-free catalyst becomes a problem to be solved urgently in the whole PVC industry, and the extensive attention of scholars at home and abroad is also aroused. Gold catalysts are considered to be the most promising mercury-free catalysts for the application of acetylene hydrochlorination instead of mercury chloride catalysts. Scholars at home and abroad have made a great deal of research on the hydrochlorination of the gold-catalyzed acetylene and have obtained certain experimental results.
In summary, the supported gold catalyst has good selectivity and activity, but high cost and stability are the most critical factors for preventing the industrial application.
Disclosure of Invention
The invention aims to provide a regeneration method of a gold-carbon catalyst for acetylene hydrochlorination, which can greatly reduce the catalyst cost, prolong the service life of the catalyst and realize the recycling of the catalyst, and is an important ring for realizing industrialization and industrial application of gold-carbon.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. and roasting the inactivated gold carbon catalyst after acetylene hydrochlorination at 350-650 ℃ for 2-6 h in a nitrogen atmosphere.
2. And (3) soaking the catalyst roasted in the step (1) in aqua regia, heating to boil, keeping boiling for 0.5-2 h, cooling to room temperature, washing with water and drying.
3. Soaking the catalyst dried in the step 2 in an oxidant aqueous solution at normal temperature for 6-12 h, washing with water after soaking, and drying to obtain a regenerated catalyst; wherein, the oxidant is any one or mixture of more of potassium permanganate, potassium dichromate, hydrogen peroxide and potassium hypochlorite.
In the step 1, the deactivated gold carbon catalyst after acetylene hydrochlorination is preferably roasted for 4-5 h at 450-550 ℃ in a nitrogen atmosphere, wherein the roasting temperature rise rate is preferably 3-8 ℃/min.
In the step 2, the volume ratio of the catalyst to the aqua regia is 1: 2.5-5.0, and the preferred volume ratio of the catalyst to the aqua regia is 1: 4.0-5.0.
In the step 2, the boiling time is more preferably 1.5 to 2 hours.
In the step 3, the volume ratio of the catalyst to the oxidant aqueous solution is 1: 1.2-3.0, and the mass concentration of the oxidant in the oxidant aqueous solution is 5% -25%; preferably, the volume ratio of the catalyst to the oxidant aqueous solution is 1: 1.5-2.5, and the mass concentration of the oxidant in the oxidant aqueous solution is 10-25%.
In the step 3, the soaking is preferably carried out at normal temperature for 10-12 hours.
The invention has the following beneficial effects:
according to the method, firstly, carbon deposition attached to the catalyst is removed through high-temperature roasting, and then the catalyst is treated by using aqua regia and an oxidant, so that the activity of the gold-carbon catalyst after acetylene hydrochlorination can be recovered to a great extent, and the regenerated catalyst can keep good performance in continuous operation. The invention can greatly reduce the catalyst cost, prolong the service life of the catalyst and realize the recycling of the catalyst through the regeneration of the catalyst.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
The fresh catalyst described in the following examples was prepared according to the method of example 3 in the invention patent application having publication No. CN 109876864a entitled "an ultra-low content noble metal composite catalyst for acetylene hydrochlorination and a method for preparing the same", wherein the deactivated gold-carbon catalyst (deactivated catalyst) refers to the deactivated catalyst recovered after being used for acetylene hydrochlorination according to the method in the application.
Example 1
1. 20g of gold carbon catalyst inactivated after acetylene hydrochlorination is placed in an atmosphere furnace, the temperature is raised to 500 ℃ at the temperature rise rate of 5 ℃/min under the nitrogen atmosphere, the mixture is roasted for 3h at constant temperature, and the mixture is taken out after cooling.
2. And (2) soaking the catalyst roasted in the step (1) in aqua regia, wherein the volume ratio of the catalyst to the aqua regia is 1:5.0, heating to boil, keeping boiling for 2h, cooling to room temperature, washing with water and drying.
3. And (3) soaking the dried catalyst in the step (2) in a potassium permanganate aqueous solution with the mass concentration of 10%, wherein the volume ratio of the catalyst to the potassium permanganate aqueous solution is 1:2.0, soaking at normal temperature for 12 hours, and washing and drying after soaking to obtain the regenerated catalyst.
Example 2
1. 20g of gold carbon catalyst inactivated after acetylene hydrochlorination is placed in an atmosphere furnace, the temperature is raised to 500 ℃ at the temperature rise rate of 5 ℃/min under the nitrogen atmosphere, the mixture is roasted for 3h at constant temperature, and the mixture is taken out after cooling.
2. And (2) soaking the catalyst roasted in the step (1) in aqua regia, wherein the volume ratio of the catalyst to the aqua regia is 1:5.0, heating to boil, keeping boiling for 2h, cooling to room temperature, washing with water and drying.
3. And (3) soaking the dried catalyst in the step (2) in a potassium dichromate aqueous solution with the mass concentration of 25%, wherein the volume ratio of the catalyst to the potassium dichromate aqueous solution is 1:1.2, soaking at normal temperature for 12h, and washing and drying after soaking to obtain the regenerated catalyst.
Example 3
1. 20g of gold carbon catalyst inactivated after acetylene hydrochlorination is placed in an atmosphere furnace, the temperature is raised to 650 ℃ at the heating rate of 8 ℃/min under the nitrogen atmosphere, the mixture is roasted for 2h at constant temperature, and the mixture is taken out after cooling.
2. And (2) soaking the catalyst roasted in the step (1) in aqua regia, wherein the volume ratio of the catalyst to the aqua regia is 1:2.5, heating to boil, keeping boiling for 0.5h, cooling to room temperature, washing with water and drying.
3. And (3) soaking the dried catalyst in the step (2) in a 5% hydrogen peroxide aqueous solution at a volume ratio of 1:3.0, soaking at normal temperature for 6h, washing with water and drying after soaking to obtain the regenerated catalyst.
Example 4
1. 20g of the gold-carbon catalyst inactivated after the hydrochlorination of acetylene is placed in an atmosphere furnace, the temperature is raised to 350 ℃ at the heating rate of 3 ℃/min under the nitrogen atmosphere, the mixture is roasted for 6 hours at constant temperature, and the mixture is taken out after being cooled.
2. And (2) soaking the catalyst roasted in the step (1) in aqua regia, wherein the volume ratio of the catalyst to the aqua regia is 1:2.5, heating to boil, keeping boiling for 0.5h, cooling to room temperature, washing with water and drying.
3. And (3) soaking the catalyst dried in the step (2) in a potassium hypochlorite aqueous solution with the mass concentration of 10%, wherein the volume ratio of the catalyst to the potassium hypochlorite aqueous solution is 1:2.0, soaking at normal temperature for 6 hours, and washing and drying after soaking to obtain the regenerated catalyst.
Example 5
1. 20g of gold carbon catalyst inactivated after acetylene hydrochlorination is placed in an atmosphere furnace, the temperature is raised to 500 ℃ at the temperature rise rate of 5 ℃/min under the nitrogen atmosphere, the mixture is roasted for 3h at constant temperature, and the mixture is taken out after cooling.
2. And (2) soaking the catalyst calcined in the step (1) in aqua regia with the volume ratio of the catalyst to the aqua regia of 1:5.0, heating to boil, keeping boiling for 2 hours, cooling to room temperature, washing with water and drying.
3. And (3) soaking the catalyst dried in the step (2) in a mixed aqueous solution of potassium permanganate and hydrogen peroxide, wherein the mass concentration of potassium permanganate is 10%, the mass concentration of hydrogen peroxide is 5%, and the volume ratio of the catalyst to the mixed aqueous solution is 1:2.0, soaking at normal temperature for 12h, and washing and drying after soaking to obtain the regenerated catalyst.
To demonstrate the advantageous effects of the present invention, the inventors prepared the regenerated catalysts, the fresh catalysts and the deactivated catalysts obtained in examples 1 to 5The method is used for acetylene hydrochlorination, and a fixed bed reactor is adopted to continuously evaluate the acetylene hydrochlorination. Raw materials of acetylene gas and hydrogen chloride gas come from a high-pressure steel cylinder, the flow rate of the raw materials is regulated by a mass flow meter, the raw materials are mixed and enter a reactor, the temperature of the reactor is controlled by a temperature program controller, and reaction products are absorbed by alkali liquor and then are subjected to online monitoring analysis by a gas chromatograph. The test is carried out at the acetylene volume space velocity of 250h -1 The flow rate ratio of hydrogen chloride to acetylene was 1.1, and the temperature was 180 ℃, and the test results are shown in table 1.
Table 1 results of testing different catalysts
| Catalyst and process for preparing same | Initial acetylene conversion (%) | Initial vinyl chloride selectivity (%) | Acetylene conversion after 10h reaction (%) |
| Example 1 | 83.8 | 99.7 | 82.3 |
| Example 2 | 80.1 | 98.9 | 77.8 |
| Example 3 | 76.3 | 99.5 | 73.7 |
| Example 4 | 68.9 | 99.2 | 65.5 |
| Example 5 | 85.5 | 98.6 | 82.2 |
| Fresh catalyst | 92.2 | 99.9 | 91.4 |
| Deactivated catalyst | 31.4 | 97.1 | 18.9 |
It can be seen from table 1 that, after the gold-carbon catalyst obtained by hydrochlorination of acetylene is regenerated according to the regeneration method of the present invention, the catalytic activity is greatly recovered, and the regenerated catalyst can maintain good performance during continuous operation, so as to improve the service life of the catalyst.
Claims (4)
1. A regeneration method of a gold-carbon catalyst for acetylene hydrochlorination is characterized by comprising the following steps:
(1) roasting the inactivated gold carbon catalyst after acetylene hydrochlorination at 450-550 ℃ for 4-5 h in a nitrogen atmosphere;
(2) soaking the catalyst roasted in the step (1) in aqua regia, heating to boil, keeping boiling for 0.5-2 h, cooling to room temperature, washing with water and drying; wherein the volume ratio of the catalyst to the aqua regia is 1: 4.0-5.0;
(3) soaking the dried catalyst in the step (2) in an oxidant aqueous solution at normal temperature for 6-12 h, washing with water after soaking, and drying to obtain a regenerated catalyst; the oxidizing agent is any one or mixture of more of potassium permanganate, potassium dichromate, hydrogen peroxide and potassium hypochlorite, the volume ratio of the catalyst to the oxidizing agent aqueous solution is 1: 1.5-2.5, and the mass concentration of the oxidizing agent in the oxidizing agent aqueous solution is 10-25%.
2. The method for regenerating a gold-carbon catalyst for hydrochlorination of acetylene according to claim 1, characterized in that: in the step (1), the temperature rise rate of the roasting is 3-8 ℃/min.
3. The method for regenerating a gold-carbon catalyst for hydrochlorination of acetylene according to claim 1, characterized in that: in the step (2), the boiling time is kept to be 1.5-2 h.
4. The method for regenerating a gold-carbon catalyst for hydrochlorination of acetylene according to claim 1, characterized in that: and (3) soaking for 10-12 hours at normal temperature.
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| CN111203281A (en) * | 2019-09-05 | 2020-05-29 | 浙江工业大学 | Regeneration method of acetylene hydrochlorination non-mercury catalyst |
| CN112221489A (en) * | 2020-11-18 | 2021-01-15 | 西安凯立新材料股份有限公司 | Regeneration method of gold carbon catalyst for preparing VCM |
| CN114029052B (en) * | 2021-12-03 | 2023-12-05 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Regeneration method of mercury-free noble metal catalyst for hydrochlorination of acetylene |
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