CN102357366A - Non-mercury catalyst used for acetylene hydrochlorination - Google Patents
Non-mercury catalyst used for acetylene hydrochlorination Download PDFInfo
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- CN102357366A CN102357366A CN2011102576962A CN201110257696A CN102357366A CN 102357366 A CN102357366 A CN 102357366A CN 2011102576962 A CN2011102576962 A CN 2011102576962A CN 201110257696 A CN201110257696 A CN 201110257696A CN 102357366 A CN102357366 A CN 102357366A
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Abstract
The invention discloses a supported non-mercury catalyst used for acetylene hydrochlorination and a preparation method thereof. The active component of the catalyst is a noble metal, mainly a halide and complex of palladium. 0.1-5wt% of the active component is supported on the carrier. The catalyst carriers are HZSM-5 type, NaZSM-5 type, mordenite, Hbeta type and HY type molecular sieves. The catalyst is prepared by carrier pretreatment-dipping method. Under the conditions of a raw gas space velocity of 90-200h<-1>, a raw gas ratio V(HC1): V(C2H2) of 1-3, a normal pressure and a reaction temperature of 100-200DEG C, a test on acetylene hydrochlorination activity is conducted. The invention has the advantages that: the catalyst of a vinyl chloride monomer is synthesized in a green way with good environmental benefits; the catalyst has simple composition and high catalytic activity, with an acetylene conversion rate up to 90-98% and vinyl chloride selectivity over 98%.
Description
(1) technical field
The present invention relates to a kind of support type non-mercury catalyst that is used for acetylene hydrochlorination reaction synthesizing chloroethylene and preparation method thereof and application, belong to catalyst preparation technology and application in the organic synthesis.
(2) background technology
Vinyl chloride (VCM) is the monomer of synthesizing polyvinyl chloride, is mainly used in synthesizing polyvinyl chloride resin (PVC).Corvic is one of the world's five large-engineering plastics, a large amount of demands is arranged in the world.The commercial production of VCM mainly contains three kinds of methods at present: acetylene method, ethylene process and ethane method.External main employing comes from the ethylene process of petrochemical industry route, and the many national conditions of the few coal of China's oil are occupied an leading position the acetylene method that comes from the Coal Chemical Industry route in the production of VCM.Promptly begun by coal, to acetylene, reaction finally obtains VCM through acetylene hydrochlorination again through calcium carbide.Yet, the HgCl that adopts in this method
2/ activated-carbon catalyst has severe toxicity; Be prone to distillation, contaminated environment not only, harm humans is healthy; And affect the product quality of VCM; Therefore mercury catalyst can not be applicable to that China builds the target of resource-conserving, environmentally friendly production, so it is extremely urgent that the non-mercury catalyst of research high-performance environment protection type replaces traditional mercuric chleride catalyst.Though the researcher does a lot in the improvement of mercuric chleride catalyst and the research of substitute both at home and abroad, in industry, does not still have great breakthrough so far.
Existing both at home and abroad report about the research of acetylene hydrochlorination reaction non-mercury catalyst.In recent years, the activated carbon supported metal of the most employing of acetylene method preparing chloroethylene is main.It is carrier that Chinese invention patent application number 101249451A discloses with the active carbon, and precious metal chloride and base metal chloride are the non-mercury catalyst of active component, document [Wei Xiaobo; Wei Fei, hold high up big in. process engineering journal, 8 (2008) 1288-1222] reported that with base metal bismuth salt be active component; Silica is the composite catalyst of carrier; In addition, it is carrier with multiple molecular sieves such as 13X and MCM-4 that Chinese invention patent application number 201010246013.9 discloses a kind of, with HgCl
2Be active component, add the new catalyst that multiple metallic compound is an auxiliary agent.But in open source literature, not seeing as yet with the molecular sieve at present is carrier, and noble metal is that the loaded catalyst of active component is used for the acetylene hydrochlorination reaction, does not also see the report that improves catalyst performance with the mode of pretreatment molecular sieves carrier.
Therefore, the present invention provides a kind of non-mercury catalyst that is used for the acetylene hydrochlorination reaction and preparation method thereof, acetylene method is produced vinyl chloride have crucial meaning.
(3) summary of the invention
The present invention is to be purpose to eliminate the chlor-alkali industry mercury emissions, to the harm of existing industrial mercuric chleride catalyst to environment, is provided for preparing vinyl chloride by hydrochlorination of acetylene with support type catalyst without mercury and preparation method thereof.
Ultrasonic-dipping or rotary evaporation immersion process for preparing that catalyst provided by the invention is taked.With the load capacity is that 0.1-5wt% precious metal palladium salt is active component, and molecular sieve is a carrier, comprises HZSM-5 type, NaZSM-5 type, modenite, H β type and HY type molecular sieve.
Detailed process is: a certain amount of palladium bichloride is dissolved into after wetting with distilled water in an amount of concentrated hydrochloric acid, is made into certain density H
2PdCl
4Maceration extract.Solution impregnation to the 1～50g that gets above-mentioned 10～100mL is on the pretreatment molecular sieves carrier, with ultrasonic or rotary evaporation dipping 2～8h.The gained macerate is through 110～120 ℃ of drying 3～10h.
The present invention carries out preliminary treatment with reagent corresponding to molecular sieve carrier.Pretreating reagent is hydrochloric acid, nitric acid, phosphoric acid, potassium permanganate, hydrogen peroxide, NaOH, potassium hydroxide, ammoniacal liquor, the organic acid of respective concentration.Detailed process is following:
Method one: get pretreating reagent; Its mass fraction concentration is about 5-50%; It is slowly joined in the round-bottomed flask that the good molecular sieve carrier of drying is housed; In 50～100 ℃ of water-baths, heat magnetic agitation, dipping, cooling for reflux 3～8h,, dry 3～10h down for 105 ℃ after filter, wash to faintly acid.
Method two: molecular sieve is immersed in the pretreating reagent of respective concentration, the about 1～6h of sonicated filters, and distilled water is washed till to 105 ℃ of following oven dry 3～10h of faintly acid.
The invention has the advantages that: the molecular sieve carrier pretreatment unit is simple, and the catalyst environment is profitable, and catalyst is formed simple, and method for preparing catalyst is simple, and activity component load quantity is little, and catalytic performance is good.
(4) specific embodiment
For further the present invention being specifically described, introduce several instances below, but can not think research restriction of the present invention.The present invention realizes that by following technical measures technical scheme is following:
Embodiment 1:
Take by weighing the H beta-molecular sieve of the drying of 5～20g, place 30% hydrochloric acid solution to stir.In 50～80 ℃ of water-baths, heat magnetic agitation, dipping, cooling for reflux 3～8h, filter, wash to faintly acid, 105 ℃ oven dry 2～8h is subsequent use down.H with 10～30mL
2PdCl
4Maceration extract is impregnated on the above-mentioned molecular sieve, and behind ultrasonic or rotary evaporation dipping 2～8h, the gained macerate is in 110～120 ℃ of drying 3～10h, and the load capacity of the Pd in this catalyst on carrier is 2wt%.
With the above-mentioned catalyst 1-5g internal diameter of packing into is in the fixed bed reactors (quartz glass material) of 10mm.At unstripped gas air speed 120h
-1, the unstripped gas ratio is V (HCl): V (C
2H
2)=1.15, normal pressure carries out the test of acetylene hydrochlorination reactivity to this catalyst under 160 ℃ of conditions of reaction temperature, and analytical reactions tail gas, the conversion of alkyne of catalyst are 81.24%, and the vinyl chloride selectivity is 95.33%.
Embodiment 2:
Take by weighing the dry HZSM-5 molecular sieve carrier of 5～20g, be placed in 20% the phosphoric acid solution and stir.In 50～80 ℃ of water-baths, heat magnetic agitation, dipping, cooling for reflux 3～8h, filter, wash to faintly acid, 105 ℃ oven dry 3～10h is subsequent use down.H with 10～30mL
2PdCl
4Maceration extract is impregnated on the above-mentioned molecular sieve, and behind ultrasonic or rotary evaporation dipping 2～8h, the gained macerate is in 110～120 ℃ of drying 3～10h, and the load capacity of the Pd in this catalyst on carrier is 0.7wt%.
With the above-mentioned catalyst 1-5g internal diameter of packing into is in the fixed bed reactors (quartz glass material) of 10mm, at unstripped gas air speed 120h
-1, the unstripped gas ratio is V (HCl): V (C
2H
2)=1.15, normal pressure carries out the test of acetylene hydrochlorination reactivity to this catalyst under 160 ℃ of conditions of reaction temperature, and analytical reactions tail gas, the conversion of alkyne of catalyst are 93.75%, and the vinyl chloride selectivity is 85.16%.
Embodiment 3:
The HY molecular sieve carrier of the drying of 5～20g is immersed in 15% the salpeter solution, adopts the about 1～6h of sonicated, filter then, be washed till faintly acid with distilled water, 105 ℃ oven dry 3～10h are subsequent use down.H with 10～30mL
2PdCl
4Maceration extract is impregnated on the above-mentioned molecular sieve, and behind ultrasonic or rotary evaporation dipping 2～8h, the gained macerate is in 110～120 ℃ of drying 3～10h.The load capacity of Pd in this catalyst on carrier is 1.2%.
The catalyst of above-mentioned 1-5g is packed in the fixed bed reactors (quartz glass material) of 10mm, at unstripped gas air speed 120h
-1, the unstripped gas ratio is V (HCl): V (C
2H
2)=1.15, normal pressure carries out the test of acetylene hydrochlorination reactivity to this catalyst under 160 ℃ of conditions of reaction temperature, and analytical reactions tail gas, the conversion of alkyne of catalyst are 98.32%, and the vinyl chloride selectivity is 92.86%.
Embodiment 4:
Take by weighing the modenite of the drying of 5～20g, be placed in 10% the hydrogenperoxide steam generator and stir.In 50～80 ℃ of water-baths, heat magnetic agitation, dipping, cooling for reflux 3～8h, filter, wash to faintly acid, 105 ℃ oven dry 3～10h is subsequent use down.H with 10～30mL
2PdCl
4Maceration extract is impregnated on the above-mentioned molecular sieve, and behind ultrasonic or rotary evaporation dipping 3～5h, the gained macerate is in 110～120 ℃ of drying 3～6h.The load capacity of Pd in this catalyst on carrier is 3%.
With the above-mentioned catalyst 1-5g internal diameter of packing into is in the fixed bed reactors (quartz glass material) of 10mm, at unstripped gas air speed 120h
-1, the unstripped gas ratio is V (HCl): V (C
2H
2)=1.15, normal pressure carries out the test of acetylene hydrochlorination reactivity to this catalyst under 160 ℃ of conditions of reaction temperature, and analytical reactions tail gas, the conversion of alkyne of catalyst are 89.78%, and the vinyl chloride selectivity is 98.62%.
Claims (7)
1. one kind can be used for preparing chloroethylene by acetylene hydrochlorination with support type catalyst without mercury and preparation method thereof.It is characterized in that catalyst comprises noble metal active component and carrier.
2. catalyst according to claim 1 is characterized in that active component is the halide and the complex compound of palladium, and the load capacity of active component on carrier is 0.1-5wt%.
3. catalyst according to claim 1 is characterized in that carrier selects wherein a kind of in HZSM-5, NaZSM-5, modenite, H β, the HY equimolecular sieve for use.
4. according to claim 1; 2 and 3 described catalyst; The preprocess method that it is characterized in that catalyst carrier, this method comprises (1): molecular sieve is placed certain density pretreating reagent, and filter the back of in pretreatment unit, stirring, flood, reflux; Be washed with distilled water to faintly acid, oven dry obtains molecular sieve carrier.(2): in an amount of molecular sieve carrier, add and carry out behind the corresponding pretreating reagent ultrasonicly, under ultrasound environments, flood, be washed till faintly acid with distilled water then, oven dry obtains molecular sieve carrier.
5. according to the described catalyst of claim 1,2 and 3, the pretreating reagent that it is characterized in that the carrier of catalyst is hydrochloric acid, nitric acid, phosphoric acid, potassium permanganate, hydrogen peroxide, NaOH, potassium hydroxide, ammoniacal liquor, organic acid.
6. according to the described catalyst of claim 1,2 and 3, ultrasonic-dipping or rotary evaporation flood to it is characterized in that the Preparation of catalysts method adopts.
7. according to using catalyst described in the claim 1-6, it is characterized in that preparing under the certain reaction condition vinyl chloride: the unstripped gas air speed is 90-200h
-1, the unstripped gas ratio is V (HCl): V (C
2H
2)=1-3, pressure are 1-1.5 * 10
5Pa, reaction temperature 100-180 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110257696.2A CN102357366B (en) | 2011-09-02 | 2011-09-02 | For the non-mercury catalyst of acetylene hydrochlorination reaction |
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| CN201110257696.2A CN102357366B (en) | 2011-09-02 | 2011-09-02 | For the non-mercury catalyst of acetylene hydrochlorination reaction |
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| CN102357366B CN102357366B (en) | 2016-05-18 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415793A (en) * | 2013-08-27 | 2015-03-18 | 天津大学 | Oxygen-modified catalyst carrier, and preparation method and application thereof |
| CN106916048A (en) * | 2017-03-07 | 2017-07-04 | 铜仁学院 | A kind of method that use photocatalysis prepares vinyl chloride |
| CN109201105A (en) * | 2018-08-24 | 2019-01-15 | 中国石油大学(华东) | A kind of preparation method of deep desulfurization catalyst |
| CN111250117A (en) * | 2020-02-07 | 2020-06-09 | 新疆大学 | Supported mercury-free catalyst, preparation method thereof and application thereof in catalyzing hydrochlorination of acetylene |
| CN111744538A (en) * | 2019-03-28 | 2020-10-09 | 新疆大学 | Molecular sieve non-noble metal catalyst for hydrochlorination of acetylene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786939A (en) * | 2010-03-04 | 2010-07-28 | 大连化工研究设计院 | Method for preparing vinyl chloride by reacting ammonium chloride with acetylene |
-
2011
- 2011-09-02 CN CN201110257696.2A patent/CN102357366B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786939A (en) * | 2010-03-04 | 2010-07-28 | 大连化工研究设计院 | Method for preparing vinyl chloride by reacting ammonium chloride with acetylene |
Non-Patent Citations (1)
| Title |
|---|
| 王声洁等，: "乙炔氢氯化PdCl2/C催化剂失活原因分析", 《石油化工》, vol. 38, no. 3, 31 December 2009 (2009-12-31), pages 249 - 253 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415793A (en) * | 2013-08-27 | 2015-03-18 | 天津大学 | Oxygen-modified catalyst carrier, and preparation method and application thereof |
| CN104415793B (en) * | 2013-08-27 | 2016-12-28 | 天津大学 | A kind of oxygen modified catalyst supports and preparation method and application |
| CN106916048A (en) * | 2017-03-07 | 2017-07-04 | 铜仁学院 | A kind of method that use photocatalysis prepares vinyl chloride |
| CN109201105A (en) * | 2018-08-24 | 2019-01-15 | 中国石油大学(华东) | A kind of preparation method of deep desulfurization catalyst |
| CN109201105B (en) * | 2018-08-24 | 2021-12-07 | 山东法恩泰科技工程有限公司 | Preparation method of deep desulfurization catalyst |
| CN111744538A (en) * | 2019-03-28 | 2020-10-09 | 新疆大学 | Molecular sieve non-noble metal catalyst for hydrochlorination of acetylene |
| CN111250117A (en) * | 2020-02-07 | 2020-06-09 | 新疆大学 | Supported mercury-free catalyst, preparation method thereof and application thereof in catalyzing hydrochlorination of acetylene |
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| CN102357366B (en) | 2016-05-18 |
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