CN102755888A - Preparation and application of synthesizing chloroethylene mercury free catalyst through acetylene method - Google Patents
Preparation and application of synthesizing chloroethylene mercury free catalyst through acetylene method Download PDFInfo
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- CN102755888A CN102755888A CN2012102382834A CN201210238283A CN102755888A CN 102755888 A CN102755888 A CN 102755888A CN 2012102382834 A CN2012102382834 A CN 2012102382834A CN 201210238283 A CN201210238283 A CN 201210238283A CN 102755888 A CN102755888 A CN 102755888A
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Abstract
The invention provides a preparation method of synthesizing chloroethylene mercury free catalyst through an acetylene method. The mercury free catalyst comprises a main active ingredient, a promoter and a carrier, the method comprises the steps of: pre-treating the carrier, preparing impregnation mother liquor, impregnating and microwave radiating, and the like, and the microwave radiating step comprises the steps: processing through microwave with power of 100-1000 W and frequency of 2450+/-50 MHz under the protection of a shielding gas. The impregnation assisted microwave radiating method of preparing heavy metal loaded type catalyst in the invention has the advantages of energy saving, high efficiency and fastness, and the active ingredients are uniformly loaded on the carrier within a short period to improve the catalytic performance of the catalyst, improve the action activity and prolong the service life.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to a kind of preparation method who is used for the non-mercury catalyst of acetylene method synthesizing chloroethylene, also relate to a kind of method of using non-mercury catalyst by hydrogen chloride and acetylene reaction synthesizing chloroethylene.
Background technology
Vinyl chloride is important organic synthesis raw material, and main purposes is to produce polyvinyl chloride.At present, method for synthesizing chloroethylene mainly contains two kinds: acetylene method and ethylene process.The VCM production capacity more than 95% adopts ethylene process technology in the world wide at present.Because the few oil of the rich coal of China adds the high position operation of international oil price in recent years, is main with the acetylene method of Coal Chemical Industry route equally still at the VC in China monomer.
At present, acetylene method vinyl chloride is made catalyst with activated carbon supported mercury chloride mostly, in fixed bed reactors, carries out, and the mercury chloride load capacity is 10%～12%.Because mercury chloride has very high toxicity, and stability is very poor, and distillation is run off easily, causes environmental pollution.Along with the attention to mercury pollution of the exhaustion of China's mercury ore resource and the world, low mercury catalyst and non-mercury catalyst cause showing great attention to of people.The domestic low mercury catalyst mercury chloride load capacity of promoting the use of is about 6%, still fundamentally do not eliminate mercury pollution, thereby the exploitation of non-mercury catalyst seems particularly urgent.Through making great efforts for many years, the exploitation of non-mercury catalyst has obtained certain progress, finds that the acetylene hydrochlorination activity of part metals is superior to mercury chloride, but still unsatisfactory at aspects such as stability, the requirement of unmet heavy industrialization still.
The proposition of NEC chemical industry Co., Ltd. as active component, has been attempted multiple tin halides, wherein with SnCl with tin halides
4Effect is best, but because of SnCl
4Volatilization is run off and is made catalyst stability not good enough easily.Nankai University Deng state just waits and proposes to adopt three component catalyst CuCl-BiCl
3-SnCl
2/ C, the life-span can reach 120h, though far above the single component catalyst of stanniferous, the commercial Application difficulty is bigger.A kind of low precious metal content catalyst without mercury that is used for the acetylene hydrochlorination reaction of propositions such as Tsing-Hua University sieve state China, but its initial activity is too low, and a large amount of unreacted acetylene have increased the difficulty of subsequent treatment, are not suitable for suitability for industrialized production.
Noble metal catalyst has good activity in the reaction of acetylene method synthesizing chloroethylene, in order to increase the service life, research before this mainly concentrates on the selection of catalyst promoter and carrier, and the preparation method generally is simple infusion process.The degree of scatter of catalyst activity component on carrier directly has influence on its activity, selectivity and life-span.In the technology of preparing of the existing non-mercury catalyst of acetylene method synthesizing chloroethylene, all adopt traditional outside heat conduction technology, such as adopting baking oven to carry out drying; The particle external temperature is higher than inside; So evaporation of water earlier begins with the aperture and forms moist gradient from particle is outside, make solution from granule interior to the outside migration and cause active component to redistribute, cause component skewness inside and outside particle; Cause catalytic activity not high, the life-span is short.
Summary of the invention
The objective of the invention is, not enough to prior art, a kind of preparation method who is used for acetylene method synthesizing chloroethylene non-mercury catalyst is provided.Adopt the method for microwave radiation in this catalyst preparation process, effectively avoided the gathering of molecules of active components.
Another object of the present invention is, provides a kind of use above-mentioned catalyst, makes the method for acetylene with high conversion ratio prepared in reaction vinyl chloride.This catalyst is used for acetylene method synthesizing chloroethylene reaction and has that reactivity height, selectivity are good, the advantage of long service life, and the loss that do not distil, and has avoided the pollution to environment.
The present invention proposes a kind of new catalyst preparation technology, adopt the method for the auxiliary microwave radiation of infusion process, active component is loaded on the carrier equably, and improve its catalytic performance greatly.The microwave radiation is different with traditional heating mode; Traditional heating is thermal source conduction-type heating from outward appearance to inner essence, and microwave field is heated whole medium simultaneously, so heating using microwave is called " the body heating " of no thermograde again; Under the microwave energy field action of high frequency conversion; Molecular motion becomes orderly dither by rambling state, thereby makes molecular kinetic energy become heat energy, reaches the purpose of even heating.
The present invention realizes through following technical scheme:
A kind of preparation method who is used for the non-mercury catalyst of acetylene method synthesizing chloroethylene, this catalyst comprises main active component, co-catalyst and carrier, this method comprises the preliminary treatment of carrier, preparation, dipping and the microwave radiation of dipping mother liquor.
Among the present invention, it is preferred 0.01%～10% that said main reactive metal element accounts for total catalyst weight, and more preferably 0.2%～3%; It is preferred 0.1%～10% that the promoter metal element accounts for total catalyst weight, and more preferably 1%～5%; All the other are inert carrier.
The pre-treatment step of said carrier is: pickling, filter washing, drying.Carrier is carried out pickling deash to remove, said sour preferred concentration is the hydrochloric acid of 1～10mol/L, 20～100 ℃ of pickling temperatures, pickling time 0.5h～8h.
The preparation process of said dipping mother liquor is: a certain amount of main active component and co-catalyst are dissolved in deionized water, hydrochloric acid or the chloroazotic acid, stir to such an extent that mother liquor is flooded in clarification.The concentration of dipping mother liquor makes main activity component metal element account for 0.01%～10% of catalyst gross weight, and the promoter metal element accounts for 0.1%～10% of catalyst gross weight.
Said impregnation steps is: above-mentioned dipping mother liquor is added in the carrier, and normal temperature is down more than the dipping 0.5h.Said impregnation method can be incipient impregnation, excess solution dipping, any one in dipping and the vacuum impregnation repeatedly.
Said microwave irradiation step is: will flood the gained catalyst and place micro-wave oven or microwave reactor; Under the protection gas shiled; Adopting power 100～1000W, frequency is the microwave treatment of 2450 ± 50MHz; Form stable loaded catalyst, described protection gas is any one among N2, He, the Ar.Preferred 300～the 800W of microwave power, processing time 1～30min.
Further, the inventive method can comprise activation step: to feeding hydrogen chloride gas through the catalyst of microwave radiation, under 100～200 ℃ of temperature more than the activation 0.5h.
In the embodiment preferred, said main active component and co-catalyst all exist with the acid of metal or the form of salt.Said main active component is one or more metallic elements that are selected from gold, silver and the platinum group metal.Said co-catalyst is one or more metallic elements that are selected from cobalt, copper, potassium, lanthanum, cerium, the nickel.Said metallic element can be forms such as chloride, nitrate, acetate, phosphate or ammonium salt, is best especially with the chloride.
In the embodiment preferred, described carrier is material with carbon element, oxide or molecular sieve.Wherein the material with carbon element carrier can be one or more in active carbon, NACF, mesoporous charcoal and the CNT; Said oxide carrier comprises aluminium oxide, silica and titanium oxide; Molecular sieve comprises MCM series, ZSM is serial and SBA is serial.
In another embodiment preferred, said absorbent charcoal carrier is any one in the following active carbon: wood activated charcoal, comprising cocoanut active charcoal, apricot shell active carbon, activated carbon from bamboo; The mineral raw material active carbon is that raw material, oil are that raw material, PETROLEUM PROCESSING product are the active carbon that raw material is processed comprising coal; The active carbon that scrap rubber or waste plastics are processed.
Active carbon according to the invention can obtain through any one method among the following preparation method: chemical method, physics method, chemistry-physical set is legal or the physical-chemical combined method.
Active carbon according to the invention comprises any one in granular active carbon, Alveolate activated carbon capable, the active carbon slab.
According to the present invention, a kind of like this method also is provided, wherein under the condition that above-mentioned non-mercury catalyst exists, through hydrogen chloride and acetylene reaction synthesizing chloroethylene.
In a kind of embodiment preferred, the operating condition that the above-mentioned non-mercury catalyst that obtains is used for the acetylene method synthesizing chloroethylene is: feed gas volume is than being V (HCl): V (C
2H
2)=1: 1～1.3, reaction temperature are 130～200 ℃, and the acetylene air speed is 30～480h
-1, reaction pressure is 0.1～1MPa.
Compared with prior art, the invention has the beneficial effects as follows:
1, method for preparing catalyst is simple, and active component is nontoxic, environmentally safe;
2, adopt microwave radiation processing, compare with the conventional external mode of heating, the catalyst that makes has bigger specific area, and active component is more evenly distributed in the carrier duct, has improved reactivity, has prolonged service life.
3, adopt the microwave radiation to compare with the conventional external mode of heating, have energy-conservation, efficiently, advantage fast, energy consumption is about the half the of traditional heating mode.
The specific embodiment
Below the present invention will be described in more detail through specific embodiment.Embodiment only is to a kind of explanation of the present invention, and is not construed as limiting the invention.
Embodiment 1
With the 10g active carbon with the hydrochloric acid of 2mol/L in 70 ℃ of stirred in water bath 4h, filter, deionized water repeatedly washs to filtrating neutral, in 120 ℃ of dry 12h.0.2654g chloroplatinic acid, 0.5212g lanthanum chloride are dissolved in the 15ml 2mol/L hydrochloric acid, are added dropwise in pretreated active carbon normal temperature dipping 4h after the clarification; To flood the gained catalyst then and place microwave reactor, 1000W, 2450MHz microwave treatment 5min under nitrogen protection get Pt content 1%, the catalyst of La content 2%.
Adopt this catalyst to estimate: it is the stainless steel fixed bed reactors of 10mm, long 40cm that catalyst is placed internal diameter, and the electrical heating temperature control is warming up to 180 ℃, feeds hydrogen chloride activation 1h, feeds acetylene again, and the unstripped gas ratio is V (HCl): V (C
2H
2)=1.15, acetylene air speed 100h
-1, reaction pressure 0.1MPa.Reaction end gas feeds sodium hydroxide solution and absorbs to remove unreacted hydrogen chloride, and online gas-chromatography is carried out the product composition analysis.Catalytic performance is seen table 1.
Embodiment 2
With the 10g active carbon with the hydrochloric acid of 5mol/L in 70 ℃ of stirred in water bath 4h, filter, deionized water repeatedly washs to filtrating neutral, in 120 ℃ of dry 12h.0.2091g gold chloride, 0.0265g chloroplatinic acid, 0.4050g nickel chloride are dissolved in the 15ml chloroazotic acid; Be added dropwise to after the clarification in pretreated active carbon, normal temperature dipping 4h will flood the gained catalyst then and place microwave reactor; 500W, 2450MHz microwave treatment 15min under nitrogen protection; Get Au content 1%, Pt content 0.1%, the catalyst of Ni content 1%.
The method of pressing embodiment 1 is estimated the reactivity worth of its acetylene method synthesizing chloroethylene, and wherein changing the reaction temperature control is 160 ℃, and the unstripped gas ratio is V (HCl): V (C
2H
2)=1.2, acetylene air speed 40h
-1The result sees table 1.
Embodiment 3
With the 10g active carbon with the hydrochloric acid of 1mol/L in 70 ℃ of stirred in water bath 4h, filter, deionized water repeatedly washs to filtrating neutral, in 120 ℃ of dry 12h.With 0.1666g palladium bichloride, 0.5369g copper chloride, 0.1653g potassium chloride is dissolved in the 15ml 1mol/L hydrochloric acid, is added dropwise to after the clarification in pretreated active carbon; Normal temperature dipping 4h; To flood the gained catalyst then and place microwave reactor, 700W, 2450MHz microwave treatment 10min under nitrogen protection get Pd content 1%; Cu content 2%, the catalyst of K content 1%.
The method of pressing embodiment 1 is estimated the reactivity worth of its acetylene method synthesizing chloroethylene, and wherein changing the reaction temperature control is 170 ℃, and the unstripped gas ratio is V (HCl): V (C
2H
2)=1.2, acetylene air speed 30h
-1The result sees table 1.
Embodiment 4
With 10g MCM-41 molecular sieve with the hydrochloric acid of 1mol/L in 30 ℃ of stirred in water bath 1h, filter, deionized water repeatedly washs to filtrating neutral, in 120 ℃ of dry 12h.0.2091g gold chloride, 0.1653g potassium chloride, 0.1342g copper chloride are dissolved in the 15ml 1mo/L hydrochloric acid; Be added dropwise to after the clarification in pretreated MCM-41 molecular sieve, normal temperature dipping 4h will flood the gained catalyst then and place microwave reactor; 300W, 2450MHz microwave treatment 15min under nitrogen protection; Get Au content 1%, K content 1%, the catalyst of Cu content 0.5%.
The method of pressing embodiment 1 is estimated the reactivity worth of its acetylene method synthesizing chloroethylene, and wherein changing the reaction temperature control is 180 ℃, and the unstripped gas ratio is V (HCl): V (C
2H
2)=1.1, acetylene air speed 30h
-1The result sees table 1.
Comparative Examples 1～4
Behind the catalyst normal temperature dipping, without microwave radiation processing, in 120 ℃ of baking oven baking 12h, other catalyst preparation process and evaluation procedure are identical with embodiment 1～4 respectively.The result sees table 1.
Table 1 different catalysts is in synthesizing chloroethylene by acetylene product evaluation result
Can find out from table 1; The catalyst that adopts the microwave radiation to make among the embodiment 1～4; Have bigger specific area than the catalyst through oven in the Comparative Examples 1～4, thereby conversion of alkyne improves obviously, and along with the prolongation in reaction time; Reactivity descends slower, has longer service life.
Claims (10)
1. preparation method who is used for the non-mercury catalyst of acetylene method synthesizing chloroethylene; It is characterized in that; Said non-mercury catalyst comprises main active component, co-catalyst and carrier, and said method comprises the preliminary treatment of carrier, preparation, dipping and the microwave radiation of dipping mother liquor.
2. according to the preparation method of the said non-mercury catalyst of claim 1, it is characterized in that the pre-treatment step of said carrier is: pickling; Filter; Washing, drying, the hydrochloric acid of said acid cleaning process preferred concentration 1～10mol/L is handled 0.5～8h under 20～100 ℃ of temperature.
3. according to the preparation method of the said non-mercury catalyst of claim 1, it is characterized in that the preparation process of said dipping mother liquor is: main active component and co-catalyst are dissolved in deionized water, hydrochloric acid or chloroazotic acid make the dipping mother liquor.
4. according to the preparation method of the said non-mercury catalyst of claim 1; It is characterized in that; Said impregnation steps is: will flood mother liquor and add in the carrier, normal temperature is down more than the dipping 0.5h, and said impregnation method is incipient impregnation, excess solution dipping, any one in dipping and the vacuum impregnation repeatedly.
5. according to the preparation method of the said non-mercury catalyst of claim 1; It is characterized in that; Said microwave irradiation step is: will flood the gained catalyst and place micro-wave oven or microwave reactor, under the protection gas shiled, adopting power 100～1000W, frequency is the microwave treatment of 2450 ± 50MHz; Form stable loaded catalyst, said protection gas is any one in nitrogen, helium and the argon gas.
6. according to the preparation method of the said non-mercury catalyst of claim 5, it is characterized in that said microwave radiation is for adopting microwave treatment 1～30min of frequency 2450 ± 50MHz.
7. according to the preparation method of the said non-mercury catalyst of claim 1, it is characterized in that, further comprise activation step: to feeding hydrogen chloride gas, under 100～200 ℃ of temperature more than the activation 0.5h through the catalyst of microwave radiation.
8. according to the preparation method of the said non-mercury catalyst of claim 1, it is characterized in that said main active component, co-catalyst all exist with the acid of metal or the form of salt; Said main active component is one or more metallic elements that are selected from gold, silver and the platinum group metal; Said co-catalyst is one or more metallic elements that are selected from cobalt, copper, potassium, lanthanum, cerium and the nickel; Said metallic element can be chloride, nitrate, acetate, phosphate or ammonium salts, preferred chloride form.
9. according to the preparation method of the said non-mercury catalyst of claim 1; It is characterized in that; Said carrier is material with carbon element, oxide or molecular sieve; Said material with carbon element carrier is selected from active carbon, NACF, mesoporous charcoal or CNT, and said active carbon can be any one in granular active carbon, Alveolate activated carbon capable or the active carbon slab; The preferred aluminium oxide of said oxide carrier, silica or titanium oxide; The preferred MCM of said molecular sieve carrier is serial, ZSM is serial or SBA is serial.
10. the method for a synthesizing chloroethylene is wherein in the requirement 1～9 of having the right in the presence of the catalyst of each said method preparation, through hydrogen chloride and acetylene reaction synthesizing chloroethylene; Preferably, the volume ratio of unstripped gas hydrogen chloride and acetylene is 1: 1～1.3, and reaction temperature is 130～200 ℃, and the acetylene air speed is 30～480h
-1, reaction pressure is 0.1～1MPa.
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| CN110465279B (en) * | 2019-08-21 | 2022-10-18 | 福建省鑫森炭业股份有限公司 | Mercury-free catalyst carrier activated carbon for PVC production and preparation method thereof |
| CN112570043A (en) * | 2020-12-08 | 2021-03-30 | 西安凯立新材料股份有限公司 | Catalyst for acetylene hydrochlorination and application thereof |
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