CN102357366B - For the non-mercury catalyst of acetylene hydrochlorination reaction - Google Patents
For the non-mercury catalyst of acetylene hydrochlorination reaction Download PDFInfo
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- CN102357366B CN102357366B CN201110257696.2A CN201110257696A CN102357366B CN 102357366 B CN102357366 B CN 102357366B CN 201110257696 A CN201110257696 A CN 201110257696A CN 102357366 B CN102357366 B CN 102357366B
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Abstract
The invention discloses a kind of support type non-mercury catalyst that can be used for acetylene hydrochlorination reaction and preparation method thereof. The Active components of catalyst is noble metal, is mainly halide and the complex compound of palladium, and the load capacity of active component on carrier is 0.1-5wt%; Catalyst carrier is molecular sieve, comprises HZSM-5 type, NaZSM-5 type, modenite, H β type and HY type. Catalyst adopts the preparation of carrier pretreatment-infusion process, is 90-200h in unstripped gas air speed-1, unstripped gas ratio is V (HCl): V (C2H2)=1-3, normal pressure, has carried out the test of acetylene hydrochlorination reactivity under reaction temperature 100-200 DEG C of condition. The invention has the advantages that it is the catalyst of green synthesizing chloroethylene monomer, environmental benefit is good; Catalyst composition is simple, and catalytic activity is high: conversion of alkyne can reach 90-98%, selectively can the reaching more than 98% of vinyl chloride.
Description
(1) technical field
The present invention relates to a kind of support type non-mercury catalyst for acetylene hydrochlorination reaction synthesizing chloroethylene and preparation method thereof and answerWith, belong to catalyst preparation technology and application in organic synthesis.
(2) background technology
Vinyl chloride (VCM) is the monomer of synthesizing polyvinyl chloride, is mainly used in synthesizing polyvinyl chloride resin (PVC). CorvicBe one of the world's five large-engineering plastics, have a large amount of demands in the world. The industrial production of VCM mainly contains at presentThree kinds of methods: acetylene method, ethylene process and ethane method. External main employing comes from the ethylene process of petrochemical industry route, and China's oilThe many national conditions of few coal are occupied an leading position the acetylene method that comes from Coal Chemical Industry Route in the production of VCM. Started by coal,Arrive acetylene through calcium carbide, then reaction finally obtains VCM through acetylene hydrochlorination. But, the HgCl adopting in this method2/ liveProperty Pd/carbon catalyst have severe toxicity, easily distillation, not only contaminated environment, harm humans health, and affect the product of VCMProduct quality, therefore mercury catalyst can not be applicable to the target of China's Resources for construction economizing type, 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. Although researcher both at home and abroadDo a lot in the improvement of mercuric chleride catalyst and the research of substitute, but still there is no a great breakthrough industrial so far.
The existing report about the research of acetylene hydrochlorination reaction non-mercury catalyst both at home and abroad. In recent years, acetylene method preparing chloroethylene is mostIt is main adopting activated carbon supported metal. Chinese invention patent application 101249451A discloses taking active carbon as carrier, your goldThe non-mercury catalyst that to belong to chloride and base metal chloride be active component, document [Wei little Bo, Wei Fei, hold high up big in. process engineeringReport, 8 (2008) 1288-1222] report taking base metal bismuth salt as active component, the composite catalyst that silica is carrier,In addition, Chinese invention patent application numbers 201010246013.9 discloses and has a kind ofly sieved with the different kinds of molecules such as 13X and MCM-4For carrier, with HgCl2For active component, add the new catalyst that various metals compound is auxiliary agent. But at present openIn document, there is not yet taking molecular sieve as carrier, the loaded catalyst that noble metal is active component reacts for acetylene hydrochlorination,Also have no the report that improves catalyst performance by the mode of pretreatment molecular sieves carrier.
Therefore, the invention provides a kind of non-mercury catalyst for acetylene hydrochlorination reaction and preparation method thereof, acetylene method is producedVinyl chloride tool is of great significance.
(3) summary of the invention
The present invention is that to eliminate chlor-alkali industry mercury emissions be object, the harm for existing industrial mercuric chleride catalyst to environment,Be provided for preparing vinyl chloride by hydrochlorination of acetylene support type catalyst without mercury and preparation method thereof.
Catalyst provided by the invention is taked ultrasonic-dipping or the preparation of rotary evaporation infusion process. Taking load capacity as 0.1-5wt% noble metalPalladium salt is active component, and molecular sieve is carrier, comprises HZSM-5 type, NaZSM-5 type, modenite, H β type and HYType molecular sieve.
Detailed process is: after a certain amount of palladium bichloride is wetting with distilled water, be dissolved in appropriate concentrated hydrochloric acid, be made into necessarily denseThe H of degree2PdCl4Maceration extract. Get solution impregnation to 1～50g of above-mentioned 10～100mL on pretreatment molecular sieves carrier, with superSound or rotary evaporation dipping 2～8h. Gained macerate is through 110～120 DEG C of dry 3～10h.
The present invention carries out pretreatment with corresponding reagent to molecular sieve carrier. Pretreating reagent be respective concentration hydrochloric acid, nitric acid,Phosphoric acid, potassium permanganate, hydrogen peroxide, NaOH, potassium hydroxide, ammoniacal liquor, organic acid. Detailed process is as follows:
Method one: get pretreating reagent, its mass fraction concentration is about 5-50%, slowly joins it dried dividing is housedIn the round-bottomed flask of son sieve carrier, in 50～100 DEG C of water-baths, heat magnetic agitation, dipping, cooling for reflux 3～8h, after throughFilter, wash to faintly acid, dry 3～10h at 105 DEG C.
Method two: molecular sieve is immersed in the pretreating reagent of respective concentration, approximately 1～6h of ultrasonic processing, filters distilled waterBe washed till to 105 DEG C of faintly acids and dry 3～10h.
The invention has the advantages that: molecular sieve carrier pretreatment unit is simple, catalyst environment is profitable, and catalyst composition is simple,Method for preparing catalyst is simple, and activity component load quantity is little, and catalytic performance is good.
(4) detailed description of the invention
For further the present invention being specifically described, introducing several examples below, but can not think research limit of the present inventionSystem. The present invention is realized by following technical measures, and technical scheme is as follows:
Embodiment 1:
Take the dry H beta-molecular sieve of 5～20g, be placed in 30% hydrochloric acid solution and stir. In 50～80 DEG C of water-bathsHeating magnetic agitation, dipping, cooling for reflux 3～8h, filter, wash to faintly acid, dries 2～8h at 105 DEG C for subsequent use. WillThe H of 10～30mL2PdCl4Maceration extract is impregnated on above-mentioned molecular sieve, and with after ultrasonic or rotary evaporation dipping 2～8h, gained soaksStain thing is in 110～120 DEG C of dry 3～10h, and the load capacity of the Pd in this catalyst on carrier is 2wt%.
Above-mentioned catalyst 1-5g is packed in the fixed bed reactors that internal diameter is 10mm (quartz glass material). In unstripped gas air speed120h-1, unstripped gas ratio is V (HCl): V (C2H2)=1.15, normal pressure, carries out this catalyst under 160 DEG C of conditions of reaction temperatureThe test of acetylene hydrochlorination reactivity, analytical reactions tail gas, the conversion of alkyne of catalyst is 81.24%, vinyl chloride is selectiveBe 95.33%.
Embodiment 2:
Take the dry HZSM-5 molecular sieve carrier of 5～20g, be placed in 20% phosphoric acid solution and stir. 50～80In DEG C water-bath, heat magnetic agitation, dipping, cooling for reflux 3～8h, filter, wash to faintly acid, dry 3～10h at 105 DEG CFor subsequent use. By the H of 10～30mL2PdCl4Maceration extract is impregnated on above-mentioned molecular sieve, with after ultrasonic or rotary evaporation dipping 2～8h,Gained macerate is in 110～120 DEG C of dry 3～10h, and the load capacity of the Pd in this catalyst on carrier is 0.7wt%.
Above-mentioned catalyst 1-5g is packed in the fixed bed reactors that internal diameter is 10mm (quartz glass material), in unstripped gas air speed 120h-1, unstripped gas ratio is V (HCl): V (C2H2)=1.15, normal pressure, carries out this catalyst under 160 DEG C of conditions of reaction temperatureThe test of acetylene hydrochlorination reactivity, analytical reactions tail gas, the conversion of alkyne of catalyst is 93.75%, vinyl chloride is selectiveBe 85.16%.
Embodiment 3:
The dry HY molecular sieve carrier of 5～20g is immersed in 15% salpeter solution, adopts approximately 1～6h of ultrasonic processing,Then filter, be washed till faintly acid with distilled water, dry 3～10h at 105 DEG C for subsequent use. By the H of 10～30mL2PdCl4Maceration extractBe impregnated on above-mentioned molecular sieve, with after ultrasonic or rotary evaporation dipping 2～8h, gained macerate is in 110～120 DEG C of dry 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, in unstripped gas air speed 120h-1, unstripped gas ratio is V (HCl): V (C2H2)=1.15, normal pressure, carries out acetylene to this catalyst under 160 DEG C of conditions of reaction temperatureThe test of hydrochlorination activity, analytical reactions tail gas, the conversion of alkyne of catalyst is 98.32%, vinyl chloride is selectively92.86％。
Embodiment 4:
Take the dry modenite of 5～20g, be placed in 10% hydrogenperoxide steam generator and stir. At 50～80 DEG CIn water-bath, heat magnetic agitation, dipping, cooling for reflux 3～8h, filter, wash to faintly acid, dry 3～10h at 105 DEG CFor subsequent use. By the H of 10～30mL2PdCl4Maceration extract is impregnated on above-mentioned molecular sieve, with after ultrasonic or rotary evaporation dipping 3～5h,Gained macerate is in 110～120 DEG C of dry 3～6h. The load capacity of Pd in this catalyst on carrier is 3%.
Above-mentioned catalyst 1-5g is packed in the fixed bed reactors that internal diameter is 10mm (quartz glass material), in unstripped gas air speed120h-1, unstripped gas ratio is V (HCl): V (C2H2)=1.15, normal pressure, carries out this catalyst under 160 DEG C of conditions of reaction temperatureThe test of acetylene hydrochlorination reactivity, analytical reactions tail gas, the conversion of alkyne of catalyst is 89.78%, vinyl chloride is selectiveBe 98.62%.
Claims (3)
1. one kind can be used for the preparation method of preparing chloroethylene by acetylene hydrochlorination support type catalyst without mercury, it is characterized in that: taking load capacity as 0.1-5wt% precious metal palladium salt is as active component, taking the wherein one in HZSM-5 type, modenite, H β type and HY type molecular sieve as carrier, take ultrasonic-dipping or the preparation of rotary evaporation infusion process;
Concrete grammar is: after a certain amount of palladium bichloride is wetting with distilled water, be dissolved in appropriate concentrated hydrochloric acid, be made into certain density H2PdCl4Maceration extract, the maceration extract of getting above-mentioned 10～l00mL is impregnated into 1～50g on pretreated molecular sieve carrier, and with ultrasonic or rotary evaporation dipping 2～8h, gained macerate, through 110～120 DEG C of dry 3～l0h, obtains catalyst finished product;
Described molecular sieve carrier is carried out to pretreated method be: hydrochloric acid, nitric acid, phosphoric acid or hydrogen peroxide that pretreating reagent is respective concentration, concrete grammar is as follows:
Get pretreating reagent, its mass fraction concentration is 5-50%, it is slowly joined in the round-bottomed flask that dried molecular sieve carrier is housed, in 50～100 DEG C of water-baths, heat magnetic agitation, dipping, cooling for reflux 3～8h, by filtering, washing to faintly acid, at 105 DEG C, dry 3～l0h, obtain molecular sieve carrier; Or
Molecular sieve is immersed in the pretreating reagent of respective concentration, ultrasonic processing 1～6h, filters, and distilled water is washed till faintly acid, dries 3～l0h at 105 DEG C, obtains molecular sieve carrier.
2. the catalyst that prepared by preparation method claimed in claim 1, is characterized in that: active component is precious metal palladium salt, and the load capacity of active component on carrier is 0.1-5wt%; Carrier is the wherein one in HZSM-5, modenite, H β, HY type molecular sieve.
3. right to use requires catalyst described in 2 to prepare the method for vinyl chloride, it is characterized in that: under following reaction condition, prepare vinyl chloride: unstripped gas air speed is 90-200h-1, unstripped gas ratio is V (HCl): V (C2H2)=1-3, pressure is 1-1.5 × 105Pa, reaction temperature 100-180 DEG C.
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| 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 |
| 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 |
| CN111250117B (en) * | 2020-02-07 | 2022-12-16 | 新疆大学 | Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in catalyzing acetylene hydrochlorination reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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 |
|---|
| 乙炔氢氯化PdCl2/C催化剂失活原因分析;王声洁等，;《石油化工》;20091231;第38卷(第3期);249-253 * |
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