CN105536885A - Regeneration method of noble metal catalyst for preparing vinyl chloride - Google Patents

Regeneration method of noble metal catalyst for preparing vinyl chloride Download PDF

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Publication number
CN105536885A
CN105536885A CN201511015313.5A CN201511015313A CN105536885A CN 105536885 A CN105536885 A CN 105536885A CN 201511015313 A CN201511015313 A CN 201511015313A CN 105536885 A CN105536885 A CN 105536885A
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China
Prior art keywords
noble metal
metal catalyst
catalyst
vinyl chloride
renovation
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CN201511015313.5A
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Chinese (zh)
Inventor
王雅玲
王伟国
刘红霞
宋志刚
孔范录
郝涛
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新疆中泰化学股份有限公司
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Priority to CN201511015313.5A priority Critical patent/CN105536885A/en
Publication of CN105536885A publication Critical patent/CN105536885A/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42Platinum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44Palladium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12Treating with free oxygen-containing gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/42Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/48Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/07Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Abstract

The invention relates to the technical field of catalyst regeneration and particularly relates to a regeneration method of a noble metal catalyst for preparing vinyl chloride. The method comprises the following steps: (I) performing nitrogen treatment; (II) treating the regeneration gas; and (III) cooling to normal temperature in a nitrogen atmosphere and performing hot reflux treatment. According to the method provided by the invention, the regenerated noble metal catalyst is equivalent to the fresh noble metal catalyst in activity and approaches traditional low-mercury catalysts in performance, thus the noble metal catalyst obtained by the method can be recycled, and the preparation cost of hydrogen chloride is remarkably reduced; and furthermore, the implementation process is non-toxic and harmless, the poison to the environment and organisms thereof is eliminated, and a basis is laid for replacing the low-mercury catalyst with the noble metal catalyst and realizing industrial popularization and application.

Description

For the preparation of the renovation process of the noble metal catalyst of vinyl chloride

Technical field

the present invention relates to catalyst regeneration techniques field, is a kind of renovation process of the noble metal catalyst for the preparation of vinyl chloride.

Background technology

vCM is mainly used in synthesizing polyvinyl chloride (PVC), based on the energy resource structure that China's coal heavy wool weak breath is poor, the factor such as integrated cost, technique, carbide acetylene hydrochlorinate method will be still the main technique that China PVC produces within longer a period of time in future.

the acetylene hydrochlorination method that China adopts is in fixed bed reactors, the catalyst of activated carbon supported mercury is utilized to carry out gas-solid phase reaction, but, the scarcity of mercury pollution and mercury resource is the key issue of current calcium carbide acetylene method PVC industry, therefore, seeking alternative is the study hotspot in this field without low-mercury catalyst.Current noble metal catalyst substitutes low-mercury catalyst and has obtained comparatively considerable achievement, employing noble metal is high as main active component activity, good stability, performance is close to traditional low-mercury catalyst, but the active component of noble metal catalyst is easily reduced and causes catalytic activity to decline, and noble metal catalyst just cannot recycle once inactivation, make to adopt noble metal catalyst to there is the high problem of production cost, therefore commercial introduction application still has a segment distance.

Summary of the invention

the invention provides a kind of renovation process of the noble metal catalyst for the preparation of vinyl chloride, overcome the deficiency of above-mentioned prior art, it cannot recycle the problem causing production cost high after effectively solving noble metal catalyst inactivation.

technical scheme of the present invention is realized by following measures: a kind of renovation process of the noble metal catalyst for the preparation of vinyl chloride, carry out in the steps below: the first step, the noble metal catalyst of inactivation is placed in fixed bed reactors, little of 3 hours by nitrogen treatment 1 under temperature is 80 DEG C to 120 DEG C conditions; Second step, is fixed the intensification of bed bioreactor bed temperature under nitrogen atmosphere, and after temperature stabilization, cut out nitrogen, incision regeneration gas processes, process 3 is little after 5 hours, then cuts out regeneration gas, incision nitrogen; 3rd step, is down to normal temperature by the bed temperature of fixed bed reactors under nitrogen atmosphere.

here is the further optimization and/or improvements to foregoing invention technical scheme:

in above-mentioned 3rd step, after the bed temperature of bed bioreactor to be fixed is down to normal temperature, less of 24 hours by acid solution heating reflow treatment 12.

above-mentioned acid solution is more than one in red fuming nitric acid (RFNA), concentrated hydrochloric acid and SPA, red fuming nitric acid (RFNA), concentrated hydrochloric acid and SPA be analyze pure; Or/and the quality of acid solution is 2 times to 3 times of the noble metal catalyst water absorption rate of inactivation selected in the first step; Or/and the temperature adding hot reflux is 50 DEG C to 80 DEG C.

above-mentioned regeneration gas is more than one in air, oxygen and hydrogen chloride gas; Or/and the flow of the regeneration gas in incision fixed bed reactors is 10mL/min to 20mL/min.

in above-mentioned second step, the bed temperature of fixed bed reactors is warming up to 150 DEG C to 180 DEG C.

above-mentioned take internal diameter as the fixed bed reactors of 13mm, and the order number of inactivation noble metal catalyst is 20 order to 60 orders, and loadings is 10ml to 20mL; Or/and noble metal catalyst is palladium-based catalyst or platinum based catalyst or Au-based catalyst.

the activity of the recover precious metals catalyst noble metal catalyst fresh with it that the present invention obtains is suitable, its performance is close to traditional low-mercury catalyst, therefore the noble metal catalyst obtained according to the inventive method can recycle, the hydrogen chloride cost of preparing being significantly reduces, further, nontoxic in the invention process process, stopped the murder by poisoning that environment and biology thereof are caused, for noble metal catalyst substitute low-mercury catalyst, realize commercial introduction application lay a good foundation.

Detailed description of the invention

the present invention by the restriction of following embodiment, can not determine concrete embodiment according to technical scheme of the present invention and actual conditions.

below in conjunction with embodiment, the invention will be further described:

embodiment 1, should carry out for the preparation of the renovation process of the noble metal catalyst of vinyl chloride: the first step, is placed in fixed bed reactors by the noble metal catalyst of inactivation in the steps below, little of 3 hours by nitrogen treatment 1 under temperature is 80 DEG C to 120 DEG C conditions; Second step, is fixed the intensification of bed bioreactor bed temperature under nitrogen atmosphere, and after temperature stabilization, cut out nitrogen, incision regeneration gas processes, process 3 is little after 5 hours, then cuts out regeneration gas, incision nitrogen; 3rd step, is down to normal temperature by the bed temperature of fixed bed reactors under nitrogen atmosphere.The object of nitrogen, for purging, is conducive to the foreign material on Cementation of Precious Metals catalyst and gas.

embodiment 2, should carry out for the preparation of renovation process of the noble metal catalyst of vinyl chloride: the first step, is placed in fixed bed reactors by the noble metal catalyst of inactivation in the steps below, by nitrogen treatment 1 hour or 3 hours under temperature is 80 DEG C or 120 DEG C of conditions; Second step, is fixed the intensification of bed bioreactor bed temperature under nitrogen atmosphere, after temperature stabilization, cuts out nitrogen, incision regeneration gas processes, process after 3 hours or 5 hours, then cuts out regeneration gas, incision nitrogen; 3rd step, is down to normal temperature by the bed temperature of fixed bed reactors under nitrogen atmosphere.

embodiment 3, as the optimization of embodiment 1 and embodiment 2, in the 3rd step, after the bed temperature of bed bioreactor to be fixed is down to normal temperature, less of 24 hours by acid solution heating reflow treatment 12.Acid solution is as the active component in the noble metal catalyst of the further Oxidative inactivation of Oxygen in Liquid agent, and the activity of the noble metal catalyst obtained by acid solution heating reflow treatment is got a promotion again.

embodiment 4, preferred as embodiment 3, acid solution is more than one in red fuming nitric acid (RFNA), concentrated hydrochloric acid and SPA, red fuming nitric acid (RFNA), concentrated hydrochloric acid and SPA be analyze pure.

embodiment 5, preferred as embodiment 3 and embodiment 4, the quality of acid solution is 2 times to 3 times of the noble metal catalyst water absorption rate of inactivation selected in the first step.

embodiment 6, preferred as embodiment 3, embodiment 4 and embodiment 5, the temperature adding hot reflux is 50 DEG C to 80 DEG C.

embodiment 7, preferred as above-described embodiment, regeneration gas is more than one in air, oxygen and hydrogen chloride gas.Regeneration gas has oxidisability, is oxidized the active component be reduced as gaseous oxidizing agent.

embodiment 8, preferred as above-described embodiment, the flow of the regeneration gas in incision fixed bed reactors is 10mL/min to 20mL/min.

embodiment 9, preferred as above-described embodiment, in second step, the bed temperature of fixed bed reactors is warming up to 150 DEG C to 180 DEG C.Under this bed temperature, carry out the regeneration of inactivation noble metal catalyst, the effect obtained is best.

embodiment 10, preferred as above-described embodiment, take internal diameter as the fixed bed reactors of 13mm, the order number of inactivation noble metal catalyst is 20 order to 60 orders, and loadings is 10ml to 20mL.

embodiment 11, preferred as above-described embodiment, noble metal catalyst is palladium-based catalyst or platinum based catalyst or Au-based catalyst.

embodiment 12, should carry out in the steps below for the preparation of the renovation process of the noble metal catalyst of vinyl chloride: the first step, the noble metal catalyst of inactivation is placed in fixed bed reactors, be the fixed bed reactors of 13mm by internal diameter, the order number of inactivation noble metal catalyst is 40 orders, loadings is 15mL, under temperature is 100 DEG C of conditions, use nitrogen treatment 1 hour, second step, be fixed the intensification of bed bioreactor bed temperature under nitrogen atmosphere, the bed temperature of fixed bed reactors is warming up to 160 DEG C, after temperature stabilization, cut out nitrogen, incision regeneration gas processes, the flow of regeneration gas is 15mL/min, and regeneration gas process after 3.5 hours, then cuts out regeneration gas, incision nitrogen, 3rd step, under nitrogen atmosphere the bed temperature of fixed bed reactors is down to normal temperature, after the bed temperature of bed bioreactor to be fixed is down to normal temperature, reflow treatment is heated 12 hours again by acid solution, wherein, the temperature adding hot reflux is 60 DEG C, wherein, acid solution is red fuming nitric acid (RFNA), more than one in concentrated hydrochloric acid and SPA, red fuming nitric acid (RFNA), it is pure that concentrated hydrochloric acid and SPA are analysis, the quality of acid solution is 2 times of the noble metal catalyst water absorption rate of inactivation selected in the first step, regeneration gas is air, more than one in oxygen and hydrogen chloride gas, noble metal catalyst is palladium-based catalyst or platinum based catalyst or Au-based catalyst.

embodiment 13, should carry out in the steps below for the preparation of the renovation process of the noble metal catalyst of vinyl chloride: the first step, the noble metal catalyst of inactivation is placed in fixed bed reactors, be the fixed bed reactors of 13mm by internal diameter, the order number of inactivation noble metal catalyst is 60 orders, and loadings is that 15mL uses nitrogen treatment 2 hours under temperature is 120 DEG C of conditions, second step, be fixed the intensification of bed bioreactor bed temperature under nitrogen atmosphere, the bed temperature of fixed bed reactors is warming up to 180 DEG C, after temperature stabilization, cut out nitrogen, incision regeneration gas processes, the flow of regeneration gas is 20mL/min, and regeneration gas process after 5 hours, then cuts out regeneration gas, incision nitrogen, 3rd step, under nitrogen atmosphere the bed temperature of fixed bed reactors is down to normal temperature, after the bed temperature of bed bioreactor to be fixed is down to normal temperature, reflow treatment is heated 24 hours again by acid solution, wherein, the temperature adding hot reflux is 80 DEG C, wherein, acid solution is red fuming nitric acid (RFNA), more than one in concentrated hydrochloric acid and SPA, red fuming nitric acid (RFNA), it is pure that concentrated hydrochloric acid and SPA are analysis, the quality of acid solution is 2 times of the noble metal catalyst water absorption rate of inactivation selected in the first step, regeneration gas is air, more than one in oxygen and hydrogen chloride gas, noble metal catalyst is palladium-based catalyst or platinum based catalyst or Au-based catalyst.

the recover precious metals catalyst performance that the above embodiment of the present invention obtains measures:

being loaded in fixed bed reactors by the recover precious metals catalyst obtained according to the above embodiment of the present invention 1, is 60h in acetylene air speed -1 to 100h -1 , V (HCl): V (C 2 h 2 )=1 to 1.1, reaction temperature are 100 DEG C to 200 DEG C, react under normal pressure, reaction afterproduct gas is after saturated NaOH solution absorbs, by chromatography, the activity quality of the recover precious metals obtained by conversion of alkyne and vinyl chloride selective evaluation the above embodiment of the present invention, analysis result shows: conversion of alkyne is 94% to 95%, and vinyl chloride is selective is 97% to 98%;

being loaded in fixed bed reactors by the recover precious metals catalyst obtained according to the above embodiment of the present invention 12, is 60h in acetylene air speed -1 to 100h -1 , V (HCl): V (C 2 h 2 )=1 to 1.1, reaction temperature are 140 DEG C to 180 DEG C, react under normal pressure, reaction afterproduct gas is after saturated NaOH solution absorbs, by chromatography, the activity quality of the recover precious metals obtained by conversion of alkyne and vinyl chloride selective evaluation the above embodiment of the present invention; Analysis result shows conversion of alkyne average out to 94%, and vinyl chloride average selectivity is 97%;

being loaded in fixed bed reactors by the recover precious metals catalyst obtained according to the above embodiment of the present invention 13, is 60h in acetylene air speed -1 to 100h -1 , V (HCl): V (C 2 h 2 )=1 to 1.1, reaction temperature are 140 DEG C to 180 DEG C, react under normal pressure, reaction afterproduct gas is after saturated NaOH solution absorbs, by chromatography, the activity quality of the recover precious metals obtained by conversion of alkyne and vinyl chloride selective evaluation the above embodiment of the present invention; Analysis result shows conversion of alkyne average out to 95%, and vinyl chloride average selectivity is 98%;

and the conversion of alkyne of fresh noble metal catalyst is 98%, vinyl chloride is selective is 99%; The conversion of alkyne of low-mercury catalyst is 98%, and vinyl chloride is selective is 99%;

illustrate that the activity of recover precious metals catalyst of the present invention and its fresh catalyst is suitable, its performance is close to even exceeding traditional low-mercury catalyst.

in sum, the activity of the recover precious metals catalyst noble metal catalyst fresh with it that the renovation process carried out according to the embodiment of the present invention obtains is suitable, its performance is close to traditional low-mercury catalyst, therefore the noble metal catalyst obtained according to the inventive method can recycle, make to prepare hydrogen chloride cost significantly to reduce, further, nontoxic in the invention process process, stopped the murder by poisoning that environment and biology thereof are caused, for noble metal catalyst substitute low-mercury catalyst, realize commercial introduction application lay a good foundation.

above technical characteristic constitutes embodiments of the invention, and it has stronger adaptability and implementation result, can increase and decrease non-essential technical characteristic according to actual needs, meet the demand of different situations.

Claims (10)

1. the renovation process for the preparation of the noble metal catalyst of vinyl chloride, it is characterized in that carrying out in the steps below: the first step, the noble metal catalyst of inactivation is placed in fixed bed reactors, little of 3 hours by nitrogen treatment 1 under temperature is 80 DEG C to 120 DEG C conditions; Second step, is fixed the intensification of bed bioreactor bed temperature under nitrogen atmosphere, and after temperature stabilization, cut out nitrogen, incision regeneration gas processes, process 3 is little after 5 hours, then cuts out regeneration gas, incision nitrogen; 3rd step, is down to normal temperature by the bed temperature of fixed bed reactors under nitrogen atmosphere.
2. the renovation process of the noble metal catalyst for the preparation of vinyl chloride according to claim 1, is characterized in that in the 3rd step, after the bed temperature of bed bioreactor to be fixed is down to normal temperature, less of 24 hours by acid solution heating reflow treatment 12.
3. the renovation process of the noble metal catalyst for the preparation of vinyl chloride according to claim 2, is characterized in that acid solution is more than one in red fuming nitric acid (RFNA), concentrated hydrochloric acid and SPA, red fuming nitric acid (RFNA), concentrated hydrochloric acid and SPA be analyze pure; Or/and the quality of acid solution is 2 times to 3 times of the noble metal catalyst water absorption rate of inactivation selected in the first step; Or/and the temperature adding hot reflux is 50 DEG C to 80 DEG C.
4. the renovation process of the noble metal catalyst for the preparation of vinyl chloride according to claim 1 or 2 or 3, is characterized in that regeneration gas is more than one in air, oxygen and hydrogen chloride gas; Or/and the flow of the regeneration gas in incision fixed bed reactors is 10mL/min to 20mL/min.
5. the renovation process of the noble metal catalyst for the preparation of vinyl chloride according to claim 1 or 2 or 3, is characterized in that in second step, and the bed temperature of fixed bed reactors is warming up to 150 DEG C to 180 DEG C.
6. the renovation process of the noble metal catalyst for the preparation of vinyl chloride according to claim 4, is characterized in that in second step, and the bed temperature of fixed bed reactors is warming up to 150 DEG C to 180 DEG C.
7. the renovation process of the noble metal catalyst for the preparation of vinyl chloride according to claim 1 or 2 or 3, it is characterized in that taking internal diameter as the fixed bed reactors of 13mm, the order number of inactivation noble metal catalyst is 20 order to 60 orders, and loadings is 10ml to 20mL; Or/and noble metal catalyst is palladium-based catalyst or platinum based catalyst or Au-based catalyst.
8. the renovation process of the noble metal catalyst for the preparation of vinyl chloride according to claim 4, it is characterized in that taking internal diameter as the fixed bed reactors of 13mm, the order number of inactivation noble metal catalyst is 20 order to 60 orders, and loadings is 10ml to 20mL; Or/and noble metal catalyst is palladium-based catalyst or platinum based catalyst or Au-based catalyst.
9. the renovation process of the noble metal catalyst for the preparation of vinyl chloride according to claim 5, it is characterized in that taking internal diameter as the fixed bed reactors of 13mm, the order number of inactivation noble metal catalyst is 20 order to 60 orders, and loadings is 10ml to 20mL; Or/and noble metal catalyst is palladium-based catalyst or platinum based catalyst or Au-based catalyst.
10. the renovation process of the noble metal catalyst for the preparation of vinyl chloride according to claim 6, it is characterized in that taking internal diameter as the fixed bed reactors of 13mm, the order number of inactivation noble metal catalyst is 20 order to 60 orders, and loadings is 10ml to 20mL; Or/and noble metal catalyst is palladium-based catalyst or platinum based catalyst or Au-based catalyst.
CN201511015313.5A 2015-12-31 2015-12-31 Regeneration method of noble metal catalyst for preparing vinyl chloride CN105536885A (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN106582895A (en) * 2016-10-27 2017-04-26 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) Ethyne hydrochlorination precious metal mercury-free catalyst regeneration method
CN106732827A (en) * 2017-01-03 2017-05-31 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) A kind of acetylene hydrochlorination noble metal catalyst without mercury regeneration method
CN107344100A (en) * 2016-05-06 2017-11-14 北京华宇同方化工科技开发有限公司 One kind inactivation HgCl2The renovation process of/AC catalyst

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107344100A (en) * 2016-05-06 2017-11-14 北京华宇同方化工科技开发有限公司 One kind inactivation HgCl2The renovation process of/AC catalyst
CN106582895A (en) * 2016-10-27 2017-04-26 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) Ethyne hydrochlorination precious metal mercury-free catalyst regeneration method
CN106732827A (en) * 2017-01-03 2017-05-31 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) A kind of acetylene hydrochlorination noble metal catalyst without mercury regeneration method

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