CN114029052B - Regeneration method of mercury-free noble metal catalyst for hydrochlorination of acetylene - Google Patents

Regeneration method of mercury-free noble metal catalyst for hydrochlorination of acetylene Download PDF

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CN114029052B
CN114029052B CN202111466297.7A CN202111466297A CN114029052B CN 114029052 B CN114029052 B CN 114029052B CN 202111466297 A CN202111466297 A CN 202111466297A CN 114029052 B CN114029052 B CN 114029052B
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catalyst
mercury
regeneration
noble metal
metal catalyst
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CN114029052A (en
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徐小雷
牛强
解荣永
赵长森
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Ordos Hanbo Technology Co ltd
Inner Mongolia Erdos Electric Power Metallurgy Group Co Ltd
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Ordos Hanbo Technology Co ltd
Inner Mongolia Erdos Electric Power Metallurgy Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The application discloses a regeneration method of an acetylene hydrochlorination mercury-free noble metal catalyst, and relates to the technical field of catalyst regeneration. The method of the application comprises the following steps: and (3) putting the deactivated mercury-free noble metal catalyst into a regeneration reagent, heating to 40-75 ℃ and carrying out dipping treatment to obtain the regenerated mercury-free noble metal catalyst. The method effectively regenerates the catalyst, prolongs the service life of the catalyst and reduces the cost; by selecting specific regeneration reagent and regeneration temperature, the recovery rate of the initial conversion rate is greatly improved, and the catalytic activity of the catalyst is recovered to the original performance to the greatest extent.

Description

Regeneration method of mercury-free noble metal catalyst for hydrochlorination of acetylene
Technical Field
The application relates to the technical field of catalyst regeneration, in particular to a regeneration method of an acetylene hydrochlorination mercury-free noble metal catalyst.
Background
Polyvinyl chloride (PVC) industry has developed over sixty years and, despite the intense competition from environmental ecological protection, petroleum crisis and other plastic varieties, market demands continue to grow as PVC production technology continues to advance and varieties continue to update. Polyvinyl chloride is a high molecular compound polymerized by vinyl chloride monomer (VCM for short), the production method of the VCM mainly comprises the steps of preparing the VCM by ethylene method, ethane method and acetylene method, the research and development work of the VCM by oxychlorination of ethylene, ethane and the like in countries and regions with abundant natural gas resources such as Europe, russia, america and the like is very active, petroleum resources in China are short, and the monomer vinyl chloride for synthesizing the polyvinyl chloride is mainly synthesized by hydrochlorination of acetylene, but the technology adopts a mercury chloride catalyst which is extremely toxic and easy to sublimate and lose, so that the human health and the environment are seriously endangered, and therefore, finding a non-mercury catalyst to replace the traditional mercury catalyst is an urgent problem to be solved for the whole PVC industry of the acetylene method of calcium carbide. Numerous works are carried out by domestic and foreign scientific researchers, no substitute for mercury chloride catalyst is found so far, and once mercury resources are exhausted, the production of the calcium carbide method VCM cannot be carried out. In order to reduce the pollution of mercury chloride to the environment and the harm degree to human bodies as much as possible, and the production of the calcium carbide VCM can survive and move on longer and more far, the mercury resource consumption is required to be reduced. Therefore, it is urgently needed to develop an environment-friendly mercury-free catalyst production route to realize efficient and clean production of PVC.
In recent years, noble metal catalysts have the advantages of high activity, good stability and the like, and are attracting more and more attention in the field of acetylene hydrochlorination. These studies have focused mainly on noble metal catalysts such as Au, ru, pt, etc., but the noble metal catalysts have high cost and short life, which increases the difficulty of industrialization. Therefore, the deactivated noble metal catalyst is regenerated to restore its activity to some extent, prolong the service life of the catalyst and lower the cost of the catalyst.
At present, the research on noble metal catalyst regeneration methods at home and abroad is less, namely Wang Qinqin, zhu Mingyuan, bin generation, university of stone and river, and natural science and science, namely 2015,33 (1), finds that the main reason for the deactivation of the Au-based catalyst is the active component Au in the reaction process 3+ Reduced to AuO, the reduction of the active component results in a reduction of the catalyst activity.
In view of the above, the application provides a method for regenerating an acetylene hydrochlorination mercury-free noble metal catalyst, which uses a reagent with strong oxidizing property to treat the deactivated catalyst at a specific temperature to recover the activity of the catalyst, thereby greatly reducing the cost of the catalyst and having simple operation process.
Disclosure of Invention
The application aims to provide a regeneration method of an acetylene hydrochlorination mercury-free noble metal catalyst, and the inventor finds that the activity recovery capability of the catalyst can be greatly improved by adjusting the types and the regeneration temperature of specific regeneration reagents in the experimental process, thereby being beneficial to overcoming the problem of high catalytic activity cost of the existing mercury-free noble metal catalyst and realizing the purpose of prolonging the service life of the catalyst.
In order to achieve the above object, the present application has the following technical scheme:
the regeneration method of the mercury-free noble metal catalyst for hydrochlorination of acetylene comprises the following steps:
and (3) putting the deactivated mercury-free noble metal catalyst into a regeneration reagent, heating to 40-75 ℃ and carrying out dipping treatment to obtain the regenerated mercury-free noble metal catalyst.
Preferably, the deactivated mercury-free noble metal catalyst is also subjected to a drying treatment prior to being placed in the regeneration reagent.
Preferably, the mercury-free noble metal catalyst contains at least one of Au, ru, rh, pd, os, ir, pt, ag.
Preferably, the regeneration reagent is at least one of hydrogen peroxide, nitric acid, dichromic acid, perchloric acid, hypochlorous acid, iodic acid, hypoiodic acid, bromic acid, perbromic acid, hypobromous acid, chlorous acid, hydrochloric acid, peroxodisulfuric acid, potassium permanganate, formic acid, and tartaric acid. When the regeneration reagent is any one of hydrogen peroxide, nitric acid, dichromic acid, perchloric acid, hypochlorous acid, iodic acid, hypoiodic acid, bromic acid, hydrobromic acid, hypobromous acid, chlorous acid, hydrochloric acid, peroxodisulfuric acid and potassium permanganate, the concentration is 2-40%; when the regeneration reagent is any one of formic acid and tartaric acid, the concentration is 10-95%. Here, "concentration" refers to mass concentration.
Further preferably, the regenerating agent is at least one selected from nitric acid, perchloric acid, peroxodisulfuric acid, hypobromous acid. Still more preferably, the regenerating agent is a mixed solution of nitric acid and perchloric acid. Still further preferably, the regeneration reagent is nitric acid and perchloric acid in a volume ratio of 1-5: 1. Most preferably, the regeneration reagent is nitric acid and perchloric acid according to a volume ratio of 3: 1.
Preferably, the temperature of the impregnation is 40-70 ℃, further preferably 50 ℃.
Preferably, the time of the impregnation is 6 to 36 hours, more preferably 18 to 24 hours.
Preferably, after the impregnation treatment, the method further comprises the following steps:
washing the impregnated mercury-free noble metal catalyst with deionized water, and then drying.
Compared with the prior art, the application has the beneficial effects that:
(1) The method effectively regenerates the catalyst, prolongs the service life of the catalyst and reduces the cost;
(2) By selecting specific regeneration reagent and regeneration temperature, the recovery rate of the initial conversion rate is greatly improved, and the catalytic activity of the catalyst is recovered to the original performance to the greatest extent.
Detailed Description
In order to make the technical means, the creation features, the achievement of the purpose and the effect of the present application easy to understand, the present application will be further elucidated with reference to the specific embodiments, but the following embodiments are only preferred embodiments of the present application, not all of them. Based on the examples in the embodiments, those skilled in the art can obtain other examples without making any inventive effort, which fall within the scope of the application. In the following examples, unless otherwise specified, the methods of operation used were conventional, the equipment used was conventional, and the materials used in the examples were the same.
Au catalyst preparation and deactivation
The first step: soaking wood activated carbon in 1mol/L HCl for 2 hr, removing part of ash and impurity ions (Fe 3+ 、Zn 2+ Etc.), filtering, and washing until the filtrate is substantially neutral. And finally, drying at 120 ℃ for standby. And a second step of: to meter HAuCl 4 ·4H 2 O is prepared into aqua regia solution by newly prepared aqua regia solution, and is immersed into the aqua regia solutionSoaking the active carbon carrier obtained in the first step for 8 hours, heating in water bath until the liquid is basically evaporated, and then putting the active carbon carrier into an oven for drying at 120 ℃ to obtain the Au catalyst.
Filling the prepared Au catalyst into an industrial lateral line evaluation device for hydrochlorination activity test, wherein T=180 ℃, normal pressure and C 2 H 2 (GHSV)＝90h -1 、n(HCl)：n(C 2 H 2 ) Under the evaluation conditions of =1.15, the continuous operation was carried out for 2000 hours, and the acetylene conversion was reduced to 41.2%, which became an inactive catalyst. And disassembling the deactivated catalyst for later use.
Ru catalyst preparation and deactivation
2.5g of ruthenium trichloride trihydrate is dissolved in 28.3g of deionized water under stirring, after complete dissolution, the solution is completely immersed on 50g of wood active carbon for 8 hours, and after the immersion is completed, the solution is filtered and dried, so that the loading amount of ruthenium trichloride is 5%.
Filling the prepared Ru-based catalyst into an industrial lateral line evaluation device for hydrochlorination activity test, wherein T=170 ℃, normal pressure and C are adopted 2 H 2 (GHSV)＝90h -1 、n(HCl)：n(C 2 H 2 ) Under the evaluation conditions of =1.15, the continuous operation was carried out for 2000 hours, and the acetylene conversion was reduced to 44%, which became an inactive catalyst. And disassembling the deactivated catalyst for later use.
Example 1
Mixing nitric acid and perchloric acid according to a volume ratio of 3:1 (15 ml of nitric acid and 5ml of perchloric acid) to obtain a mixed solution, heating to 40 ℃, respectively taking 10g of the deactivated Au catalyst and 10g of the Ru-based catalyst, respectively placing the deactivated Au catalyst and the Ru-based catalyst in the prepared mixed solution for soaking for 24 hours, filtering, washing to be neutral, drying, and finally carrying out hydrochlorination activity test in a fixed bed evaluation device.
Example 2
20ml of 25% perchloric acid solution was prepared, heated to 50 ℃, 10g of each of the above deactivated Au catalyst and Ru-based catalyst was immersed in the solution for 18 hours, filtered, washed to neutrality, dried, and tested for hydrochlorination activity in a fixed bed evaluation device.
Example 3
15ml of a peroxodisulfuric acid solution with a concentration of 15% was prepared, heated to 65 ℃, 10g of each of the above-mentioned deactivated Au catalyst and Ru-based catalyst was taken and immersed in the solution for 18 hours, filtered, washed to neutrality, dried, and tested for hydrochlorination activity in a fixed bed evaluation device.
Example 4
15ml of hypobromous acid solution with the concentration of 15% is prepared and heated to 50 ℃, 10g of each of the deactivated Au catalyst and the Ru-based catalyst is taken and respectively placed in the solution for soaking for 18 hours, filtered, washed to be neutral and dried, and hydrochlorination activity test is carried out in a fixed bed evaluation device.
Example 5
Mixing nitric acid and perchloric acid according to a volume ratio of 3:1 (15 ml of nitric acid and 5ml of perchloric acid) to obtain a mixed solution, heating to 50 ℃, respectively taking 10g of the deactivated Au catalyst and 10g of the Ru-based catalyst, respectively placing the deactivated Au catalyst and the Ru-based catalyst in the prepared mixed solution for soaking for 24 hours, filtering, washing to be neutral, drying, and finally carrying out hydrochlorination activity test in a fixed bed evaluation device.
Example 6
Mixing nitric acid and perchloric acid according to a volume ratio of 5:1 (15 ml of nitric acid and 3ml of perchloric acid) to obtain a mixed solution, heating to 50 ℃, respectively taking 10g of the deactivated Au catalyst and 10g of the Ru-based catalyst, respectively placing the deactivated Au catalyst and the Ru-based catalyst in the prepared mixed solution for soaking for 24 hours, filtering, washing to be neutral, drying, and finally carrying out hydrochlorination activity test in a fixed bed evaluation device.
Example 7
Mixing nitric acid and perchloric acid according to a volume ratio of 1:1 (10 ml of nitric acid and 10ml of perchloric acid) to obtain a mixed solution, heating to 50 ℃, respectively soaking 10g of the deactivated Au catalyst and 10g of the Ru-based catalyst in the prepared mixed solution for 24 hours, filtering, washing to be neutral, drying, and finally carrying out hydrochlorination activity test in a fixed bed evaluation device.
Comparative example 1
Mixing nitric acid and perchloric acid according to a volume ratio of 3:1 (15 ml of nitric acid and 5ml of perchloric acid) to obtain a mixed solution, heating to 35 ℃, respectively taking 10g of the deactivated Au catalyst and 10g of the Ru-based catalyst, respectively placing the deactivated Au catalyst and the Ru-based catalyst in the prepared mixed solution for soaking for 24 hours, filtering, washing to be neutral, drying, and finally carrying out hydrochlorination activity test in a fixed bed evaluation device.
Comparative example 2
Mixing nitric acid and perchloric acid according to a volume ratio of 3:1 (15 ml of nitric acid and 5ml of perchloric acid) to obtain a mixed solution, heating to 80 ℃, respectively taking 10g of the deactivated Au catalyst and 10g of the Ru-based catalyst, respectively placing the deactivated Au catalyst and the Ru-based catalyst in the prepared mixed solution for soaking for 24 hours, filtering, washing to be neutral, drying, and finally carrying out hydrochlorination activity test in a fixed bed evaluation device.
Result detection
Catalyst performance evaluation device: the catalyst was evaluated for its performance by means of a stainless steel fixed bed reactor having an inner diameter of 8-15 mm.
The feed gas hydrogen chloride and acetylene are controlled by respective mass flow controllers, and nitrogen is introduced for 30-60min before the reaction to sweep out moisture and air. After the cleaning, the raw material gas is mixed by various mass flow meters and enters a fixed bed reaction tube for reaction, and the temperature in the fixed bed is detected by a thermocouple. The tail gas is analyzed by a gas chromatograph after being absorbed by NaOH solution in an absorption bottle to remove hydrogen chloride.
The regenerated catalyst obtained in the examples and the comparative examples is activated by hydrogen chloride for 30min and the space velocity of acetylene is 90h -1 Reaction temperature 180 ℃, raw material gas ratio n (HCl): n (C) 2 H 2 ) Evaluation under the condition of=1.15, the acetylene initial conversion, vinyl chloride selectivity and performance comparison before and after catalyst deactivation in the present application compared with the original noble metal catalyst were respectively tested, and the results are shown in tables 1 to 2.
TABLE 1 Au catalyst regeneration test results
TABLE 2 results of Ru catalyst regeneration test
It can be seen that the examples greatly improve the recovery rate of the initial conversion rate by selecting a specific regeneration reagent and a specific regeneration temperature, so that the catalytic activity of the catalyst is maximally recovered to the original performance. Comparative examples 1 and 2 show that the temperature of the regeneration solvent has a significant effect on the catalyst regeneration result.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.

Claims (7)

1. The regeneration method of the mercury-free noble metal catalyst for hydrochlorination of acetylene is characterized by comprising the following steps of: placing the deactivated mercury-free noble metal catalyst into a regeneration reagent, heating to 40 ℃ or 50 ℃ for soaking treatment to obtain a regenerated mercury-free noble metal catalyst; wherein, the regeneration reagent is nitric acid and perchloric acid according to the volume ratio of 3: 1.
2. The regeneration process according to claim 1, wherein the deactivated mercury-free noble metal catalyst is further subjected to a drying treatment before being placed in the regeneration reagent.
3. The regeneration process according to claim 1, wherein the mercury-free noble metal catalyst contains at least one of Au, ru, rh, pd, os, ir, pt, ag.
4. The regeneration process according to claim 1, characterized in that the temperature of the impregnation is 50 ℃.
5. The regeneration process according to claim 1, characterized in that the time of the impregnation is between 6 and 36 hours.
6. The regeneration process according to claim 5, characterized in that the impregnation time is 18-24 hours.
7. The regeneration method according to claim 1, further comprising the steps of, after the impregnation treatment: washing the impregnated mercury-free noble metal catalyst with deionized water, and then drying.
CN202111466297.7A 2021-12-03 2021-12-03 Regeneration method of mercury-free noble metal catalyst for hydrochlorination of acetylene Active CN114029052B (en)

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CN115837277A (en) * 2022-11-15 2023-03-24 鄂尔多斯市瀚博科技有限公司 Regeneration method of gold catalyst in vinyl chloride production process

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