CN101670293A - Method for synthesizing and regenerating mercury-free catalyst for hydrochlorination of acetylene and application thereof - Google Patents
Method for synthesizing and regenerating mercury-free catalyst for hydrochlorination of acetylene and application thereof Download PDFInfo
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- CN101670293A CN101670293A CN200910079509A CN200910079509A CN101670293A CN 101670293 A CN101670293 A CN 101670293A CN 200910079509 A CN200910079509 A CN 200910079509A CN 200910079509 A CN200910079509 A CN 200910079509A CN 101670293 A CN101670293 A CN 101670293A
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- 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
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Abstract
The invention relates to a method for synthesizing and regenerating a mercury-free catalyst for hydrochlorination of acetylene and an application thereof, which belongs to the technical field of preparation of the mercury-free catalysts. The catalyst contains bismuth, phosphorous, a component for promoting catalysis and a carrier. The content of bismuth element accounts for 0.1-68.8wt% of the weight of the catalyst, the content of phosphorous element accounts for 0.1-40.8wt% of the weight of the catalyst, the content of the component for promoting the catalysis accounts for 0.1-63.6wt%, and the content of the carrier accounts for 50-99.5%. The coke-burning regeneration is carried out on the catalyst in hydrogen, water vapor, oxygen, air or other oxygen-containing oxidative atmosphere at the temperature of 300-600 DEG C after the inactivation. The catalyst is prepared by the impregnation method, the co-precipitation method or the spray granulation method. The catalyst provided by the invention has the advantages of good activity, high selectivity, high strength and regeneration, and can be used for producing vinyl chloride by the hydrochlorination of the acetylene.
Description
Technical field
The invention belongs to catalyst preparation technology and range of application, particularly a kind of hydrochlorinate catalyst and application thereof specifically, relate to the catalyst and preparation and the renovation process that are used for acetylene and hydrogen chloride preparing chloroethylene.
Background technology
Pvc material is purposes one of general-purpose plastics the most widely in the world because it in many-sided excellent performance such as physical property, chemical stability, is applied in the field of industry-by-industry.(vinyl chloride's polyvinyl chloride VCM) is polymerized by VCM.The VCM industrial production process is mainly acetylene carbide and process for oxychlorination of ethylene, and the acetylene carbide because its raw material is a coal, is more suitable for producing in the countries and regions of rich coal resources, petroleum resources shortage.Since two thousand, China's Production of PVC ability goes up more than 20% every year on average, and China PVC output in 2005 surpasses the U.S. and leaps to the No. 1 in the world, and wherein the polyvinyl chloride amount of acetylene carbide production accounts for more than 70% of total growth.
The key reaction that carbide is produced vinyl chloride is
C
2H
2+HCl＝C
2H
3Cl
Its industrial catalyst has been HgCl since the forties in 20th century always
2The catalyst of/active carbon, the temperature of reaction are 140～180 ℃, because HgCl
2The characteristics that vapour pressure is higher, it is volatilization gradually in course of reaction, and HgCl
2Very big toxicity is arranged, the HgCl of volatilization again
2The environmental pollution influence is bigger.And since catalyst to have adopted active carbon be carrier, determined the unrenewable characteristics of its catalyst.In addition, the intensity of active carbon is also low, has caused it not to be suitable for large-scale fluid bed production, and can only adopt small fixed to produce.
Owing to the acetylene hydrochlorination method has very big economic advantages and energy advantages with respect to process for oxychlorination of ethylene, therefore the catalyst that can look for for mercuric chloride catalyst is all being developed in the whole world always, developed country even attempting replacing mercuric chloride catalyst with noble metal catalysts such as platinum, gold, its effect is still undesirable.Human HAuCl such as the Graham J.Hutchings of Britain
4As active constituent, active carbon is that carrier has made active higher catalyst, but the cost of catalyst is very high, and there is inactivation in catalyst, and the catalyst behind the inactivation is not easy regeneration.
It the present invention proposes a kind of acetylene hydrochlorination catalyst and preparation and renovation process in above-mentioned background, specifically, relates to the catalyst and preparation and the renovation process that are used for acetylene and hydrogen chloride preparing chloroethylene.In the hope of solving high toxicity catalyst problem in the acetylene preparing chloroethylene process.
Summary of the invention
The present invention be directed to HgCl
2The toxicity of/activated-carbon catalyst is big, and characteristics such as can not regenerate provide the catalyst of a kind of bismuth-containing and phosphorus.
Technical scheme of the present invention is as follows:
By a large amount of catalyst screenings and research work, the catalyst that content of the present invention relates to the oxide of bismuth and phosphorus or salt as main active component, add one or more again and help catalyst component, help catalyst component can be chromium, molybdenum, tungsten, manganese, ruthenium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, indium, tin, the mixture of one or more of the oxide of one or more metallic elements in the lead or salt, also can add a kind of catalyst again and stablize component, the catalyst stable elements can be lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium, scandium, yttrium, one or more metallic elements in the lanthanum.Preferred element is copper, chromium, zinc, nickel.The catalytic component that can reduce oxidizing temperature is preferably arranged,, burning carbon temperature is descended greatly, and reduce the loss of volatile components in the catalyst as copper.
The catalyst without mercury of the acetylene hydrochlorination reaction usefulness that the present invention proposes is characterized in that this catalyst contains bismuth and phosphorus, helps catalyst component and carrier.
State in the catalyst above-mentioned, the content of described bismuth element accounts for catalyst weight 0.1～68.8wt%, the content of described P elements accounts for catalyst weight 0.1～40.8wt/%, and the described content of catalyst component that helps accounts for 0.1～63.6wt%, and the content of described carrier accounts for 50～99.5%.
State in the catalyst above-mentioned, the content of described bismuth element accounts for catalyst weight 2～20wt%, and the content of described P elements accounts for catalyst weight 1%～20wt%, and the described content of catalyst component that helps accounts for 1～10wt%, and the content of described carrier accounts for 50～90%.
State in the catalyst above-mentioned, described bismuth exists with oxide, inorganic salts or organic salt.
State in the catalyst above-mentioned, it is characterized in that, described phosphorus is with phosphoric acid, pyrophosphoric acid, polyphosphoric acids, metaphosphoric acid, phosphorous acid, and the mixture of one or more in the oxide of phosphate, pyrophosphate, polyphosphate, metaphosphate, phosphite, phosphorus exists.
State in the catalyst above-mentioned, describedly help that catalyst component comprises, one or more metallic elements in molybdenum, tungsten, manganese, ruthenium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, indium, tin or the lead, can also comprise one or more metallic elements in lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium, scandium, yttrium, the lanthanum.
State in the catalyst above-mentioned, described to help the metallic element of catalyst component be copper, chromium, zinc, nickel.
State in the catalyst above-mentioned, described metallic element is one or more a mixture of the oxide of each metallic element or its esters.
State in the catalyst above-mentioned, described carrier is one or more the mixture in active carbon, silica, silica gel, aluminium oxide, diatomite, vanadine or the molecular sieve.
State in the catalyst above-mentioned, described catalyst makes by infusion process, coprecipitation or spray granulation.
State in the catalyst above-mentioned, described catalyst can be used for fixing bed, moving bed or fluidized-bed reactor.
State in the catalyst above-mentioned, by under 300～600 ℃, in hydrogen, steam, oxygen, air or other oxygen containing oxidizing atmosphere, carry out coke-burning regeneration behind the described catalysqt deactivation.
The catalyst without mercury renovation process of the acetylene hydrochlorination reaction usefulness that the present invention proposes is characterized in that the regeneration condition of described catalyst is, oxygen volume space velocity 300～1200, the volume space velocity 300～1200 of steam, 200～600 ℃ of temperature, pressure 0.05～0.6MPa.0.001-10 hour regenerative response time.
In above-mentioned catalyst without mercury renovation process, the regeneration condition of described catalyst is 300～500 ℃, pressure 0.05～0.2MPa.0.1-2 hour regenerative response time.
The application of the catalyst without mercury of the acetylene hydrochlorination reaction usefulness that the present invention proposes, it is characterized in that described reaction condition is: 80～600 ℃ of temperature, pressure 0.05～0.6MPa, the mol ratio of acetylene and hydrogen chloride is 1: 3～3: 1, and the weight space velocity of acetylene is 0.01～5h
-1Preferred reaction condition is: 150～350 ℃, and pressure 0.05～0.2MPa.
Catalyst provided by the invention is used for the course of reaction of acetylene hydrochlorination preparing chloroethylene, has actively high, and selectivity is good, near or surpass the technic index of mercuric chleride catalyst, and high temperature resistant, can regenerate, the intensity height can be used for fixing bed and fluidized-bed reactor.
Description of drawings
Fig. 1 is Cu-Bi-PO of the present invention
4/ SiO
2The circular regeneration result of the test.
The specific embodiment
With instantiation the present invention is described below:
In order to make catalyst that bigger specific area be arranged, active constituent can be by more efficient use, preferably catalyst activity component can be carried on the bigger carrier of specific area, carrier can preferably be used silica, aluminium oxide or molecular sieve for one or more the mixture in active carbon, silica, aluminium oxide, diatomite, vanadine and the molecular sieve.
Following more detailed description technical scheme of the present invention:
Raw material as the bismuth composition can use bismuth salt such as bismuth nitrate, bismuth chloride, waltherite, bismuth sulfate, permolybdic acid bismuth, bismuth phosphate, or bismuth oxide or bismuth metal, preferably uses bismuth nitrate and bismuth chloride.
Raw material as phosphorus composition can use phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acids, diphosphorus trioxide, five oxidations, three phosphorus or elemental phosphorous, preferably uses phosphoric acid or pyrophosphoric acid.
Acetylene hydrochlorination catalyst of the present invention, general preparation method is, soluble compounds such as first chloride with bismuth, nitrate are dissolved in the watery hydrochloric acid, the soluble compound that will contain aiding catalytic component and stable component again is dissolved in aforementioned solution, the phosphoric acid that adds phosphoric acid and the corresponding molal quantity of metal cation again, add catalyst carrier then and carry out incipient impregnation,, under 200～800 ℃ temperature, carry out roasting afterwards afterwards 90～135 ℃ of oven dry.
This catalyst also can directly prepare with the phosphate of bismuth and the phosphate of other metal, earlier be dissolved in dilute hydrochloric acid solution with the phosphate of bismuth or with the mixed phosphate of other metal, add catalyst carrier then and carry out incipient impregnation, 90～135 ℃ of oven dry, under 200～800 ℃ temperature, carry out roasting afterwards afterwards.
This catalyst also can be prepared by the method for co-precipitation, soluble compounds such as the chloride of bismuth, nitrate are dissolved in the watery hydrochloric acid, the soluble compound that will contain aiding catalytic component and stable component again is dissolved in aforementioned solution, the phosphoric acid that adds phosphoric acid and the corresponding molal quantity of metal cation again, the presoma that adds catalyst carrier then adds precipitating reagent then, and precipitated solid is filtered, after 90～135 ℃ of oven dry, under 200～800 ℃ temperature, carry out roasting.
This catalyst also can be prepared by the method for mist projection granulating, soluble compounds such as the chloride of bismuth, nitrate are dissolved in the watery hydrochloric acid, the soluble compound that will contain aiding catalytic component and stable component again is dissolved in aforementioned solution, the phosphoric acid that adds phosphoric acid and the corresponding molal quantity of metal cation again, the presoma that adds catalyst carrier then, carry out mist projection granulating then, under 200～800 ℃ temperature, carry out roasting at last.
By choosing suitable carriers or presoma, this catalyst can be used for multiple reactor.The granular catalyst that makes can be directly used in fluidized-bed reactor.Also can make fine catalyst, make the fixed bed catalyst by former extruding slivering.
The carrier of choosing can be one or more the mixture in active carbon, silica, aluminium oxide, diatomite, vanadine and the molecular sieve, preferred carrier is silica, Alpha-alumina and molecular sieve, carrier is preferably the carrier of high temperature oxidation resisting, so that carrier structure is not destroyed in catalyst coke-burning regeneration process.
This catalyst is in use because the volatilization meeting of bismuth inactivation gradually, and the catalyst behind the inactivation can be regenerated by the form of adding bismuth, and the bismuth of volatilization can reclaim by the mode of alternating temperature absorption.Preferred reactor types is the multicompartment fluidized bed reactor, and subregion in the course of reaction can make the distillation of bismuth add, course of reaction, and the recovery of bismuth etc. is finished jointly.
Followingly describe the present invention in detail according to embodiment and Comparative Examples.But the present invention is confined to this never in any form.The composition ratio of the respective element in the gained catalyst is calculated with the material quantity of corresponding formation element.Same a kind of formation element of supposing to be included in the initiation material that is used for Preparation of Catalyst enters this catalyst same as before.
Embodiment 1:
1g bismuth chloride, 0.05g palladium bichloride are dissolved in the phosphate aqueous solution that the 10g mass content is 10% hydrochloric acid and 10%, and stir, treat that solid is all after the dissolving.With the 6g specific area is 350-400m
2/ g, 100～200 purpose SiO
2Add in the solution make, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 450 ℃ of following roasting 8h.
Embodiment 2:
0.3g bismuth chloride, 0.05g manganese chloride, 0.2g cesium chloride are dissolved in the phosphate aqueous solution that the 10g mass content is 10% hydrochloric acid and 6%, and stir, treat that solid is all after the dissolving.With the 6g specific area is 350-400m
2/ g, 100～200 purpose SiO
2Add in the solution make, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 400 ℃ of following roasting 8h.
Embodiment 3:
0.3g bismuth phosphate, 0.2g chromium chloride hexahydrate, 0.1g potassium chloride are dissolved in the phosphate aqueous solution that the 10g mass content is 10% hydrochloric acid and 6%, and stir, treat that solid is all after the dissolving.With the 7g specific area is 150-200m
2/ g, 100～200 purpose α-Al
2O
3Add in the solution make, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 800 ℃ of following roasting 8h.
Embodiment 4:
0.5g bismuth nitrate, 1g copper nitrate, 0.4g barium nitrate are dissolved in the phosphate aqueous solution that the 10g mass content is 10% hydrochloric acid and 10%, and stir, treat that solid is all after the dissolving.With the 7g specific area is 150-200m
2/ g, 100～200 purpose α-Al
2O
3Add in the solution make, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 500 ℃ of following roasting 8h.
Embodiment 5:
0.1g bismuth chloride, 0.1g six water nickel chlorides, 0.1g sodium chloride are dissolved in the phosphate aqueous solution that the 10g mass content is 10% hydrochloric acid and 3%, and stir, treat that solid is all after the dissolving.With the 7g specific area is 150-200m
2/ g, 100～200 purpose α-Al
2O
3Add in the solution make, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 300 ℃ of following roasting 8h.
Embodiment 6:
0.3g bismuth chloride, 0.05g zinc chloride, 0.2g lanthanum chloride are dissolved in the phosphate aqueous solution that the 10g mass content is 10% hydrochloric acid and 6%, and stir, treat that solid is all after the dissolving.With the 7g specific area is 150-200m
2/ g, 100～200 purpose α-Al
2O
3Add in the solution make, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 500 ℃ of following roasting 8h.
Embodiment 7:
0.8g bismuth chloride, 0.1g gold trichloride, 0.8g strontium chloride are dissolved in the phosphate aqueous solution that the 10g mass content is 10% hydrochloric acid, 10% nitric acid and 6%, and stir, treat that solid is all after the dissolving.With the 5g specific area is 300-340m
2/ g, 100～200 purpose ZSM5 molecular sieves add in the solution that makes, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 230 ℃ of following roasting 8h.
Embodiment 8:
0.05g bismuth chloride, 0.3g platinum chloride, 0.2g calcium chloride are dissolved in the phosphate aqueous solution that the 10g mass content is 10% hydrochloric acid, 6% nitric acid and 3.3%, and stir, treat that solid is all after the dissolving.With the 5g specific area is 300-340m
2/ g, 100～200 purpose ZSM5 molecular sieves add in the solution that makes, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 280 ℃ of following roasting 8h.
Embodiment 9:
1g bismuth chloride, 0.5g hydrate ruthenium trichloride, 0.2g rubidium chloride are dissolved in the phosphate aqueous solution that the 10g mass content is 10% hydrochloric acid and 10%, and stir, treat that solid is all after the dissolving.With the 6g specific area is 120-180m
2/ g, 100～200 purpose terra silicea purificatas add in the solution that makes, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 500 ℃ of following roasting 8h.
Embodiment 10:
0.4g bismuth chloride, 1g hydration lead chloride, 0.5g magnesium chloride are dissolved in the phosphate aqueous solution that the 10g mass content is 10% hydrochloric acid and 10%, and stir, treat that solid is all after the dissolving.With the 6g specific area is 120-180m
2/ g, 100～200 purpose terra silicea purificatas add in the solution that makes, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 500 ℃ of following roasting 8h.
Embodiment 11:
It is in 15% the hydrochloric acid that 0.02g bismuth phosphate, 1g stannous pyrophosphate are dissolved in the 10g mass content, and stirs, and treats that solid is all after the dissolving.With the 6g specific area is 120-180m
2/ g, 100～200 purpose terra silicea purificatas add in the solution that makes, leave standstill 5h after, earlier at 120 ℃ of oven dry 5h down, then at 500 ℃ of following roasting 8h.
Comparative Examples 1:
With the 10g specific surface is 800-1000m2/g, 100-200 purpose activated carbon granule, 5g mercury chloride and 100g water place enclosed system to be heated to 95～100 ℃ and keep the dip time of 6h, after treating the system cooling, activated carbon granule is separated with the method for filtering, after 100～120 ℃ of oven dry, place enclosed system with 5g mercury chloride and 100g water again, the step of dipping, filtration, oven dry is repeated once, make mercury chloride/activated-carbon catalyst, this method for making and industrial mercury chloride method for making are similar, and catalyst that makes and industrial catalyst character are approaching.
The catalyst that makes carries out the mensuration of catalyst activity according to following method:
Get the catalyst 0.5g that example 1～11, Comparative Examples 1 make successively and mix with 5g quartz sand, place small-sized quartz tube reactor, quartz tube reactor is placed the heating furnace of controllable temperature, treat to feed unstripped gas after the temperature constant, unstripped gas adopts the C of 5ml/min
2H
2(purity＞99%) and 5ml/min (purity＞99.9%) HCl gas, reaction pressure 1.1atm (absolute pressure), when catalyst was the catalyst of prepared in laboratory, reaction temperature was 200 ℃; Reactor outlet connects the detection that gas-chromatography is carried out product.
Evaluation result to catalyst sees Table 1:
The evaluation result of table 1 catalyst in hydrochlorination
The catalyst of example 1～12 reacts after 1～30 hour again tangible inactivation, and the main cause of inactivation is a catalyst surface knot charcoal.The regeneration of catalyst is coke-burning regeneration in hydrogen, steam, oxygen and other oxygen-containing atmosphere mainly.With instantiation this patent is described below, but this patent is not limited thereto.
The regeneration of catalyst among the present invention is described with instantiation below:
Embodiment 13:
The catalyst reaction of example 1～12 is after 2～20 hours, is that 360～2400 nitrogen comes the acetylene in the metathesis reactor, 20 minutes no acetylene gas of post-reactor outlet with volume space velocity.Be that 300～1200 oxygen carries out coke-burning regeneration with volume space velocity under 200～600 ℃ of temperature, made charcoal fully, and finished the regeneration of catalyst in 5～60 minutes.
Embodiment 14:
The catalyst reaction of example 1～12 is after 2～20 hours, and the nitrogen with 360～2400 comes the acetylene in the metathesis reactor, 20 minutes no acetylene gas of post-reactor outlet.With volume space velocity is that 300～1200 oxygen and volume space velocity are that 300～1200 steam carries out coke-burning regeneration under 200～600 ℃ of temperature, makes charcoal fully, and finishes the regeneration of catalyst in 5～60 minutes.
To regenerating, the regeneration rear catalyst is undertaken by example 1～12 activity of such catalysts investigation method by the method for example 13,14.Regeneration rear catalyst activity rating result such as Fig. 1:
Claims (15)
1, the catalyst without mercury of acetylene hydrochlorination reaction usefulness is characterized in that this catalyst contains bismuth and phosphorus, helps catalyst component and carrier.
2, catalyst according to claim 1, it is characterized in that, the content of described bismuth element accounts for catalyst weight 0.1～68.8wt%, the content of described P elements accounts for catalyst weight 0.1～40.8wt/%, the described content of catalyst component that helps accounts for 0.1～63.6wt%, and the content of described carrier accounts for 50～99.5%.
3, catalyst according to claim 1, it is characterized in that the content of described bismuth element accounts for catalyst weight 2～20wt%, the content of described P elements accounts for catalyst weight 1%-20wt%, the described content of catalyst component that helps accounts for 1～10wt%, and the content of described carrier accounts for 50～90%.
4, catalyst according to claim 1 is characterized in that, described bismuth exists with oxide, inorganic salts or organic salt.
5, catalyst according to claim 1, it is characterized in that, described phosphorus is with phosphoric acid, pyrophosphoric acid, polyphosphoric acids, metaphosphoric acid, phosphorous acid, and the mixture of one or more in the oxide of phosphate, pyrophosphate, polyphosphate, metaphosphate, phosphite, phosphorus exists.
6, catalyst according to claim 1, it is characterized in that, describedly help that catalyst component comprises, one or more metallic elements in molybdenum, tungsten, manganese, ruthenium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, indium, tin or the lead, can also comprise one or more metallic elements in lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium, scandium, yttrium, the lanthanum.
According to claim 1 or 6 described catalyst, it is characterized in that 7, described to help the metallic element of catalyst component be copper, chromium, zinc, nickel.
According to the described catalyst of claim 1 or 6, it is characterized in that 8, described metallic element is one or more a mixture of the oxide of each metallic element or its esters.
9, catalyst according to claim 1 is characterized in that, described carrier is one or more the mixture in active carbon, silica, silica gel, aluminium oxide, diatomite, vanadine or the molecular sieve.
10, catalyst according to claim 1 is characterized in that, described catalyst makes by infusion process, coprecipitation or spray granulation.
11, catalyst according to claim 1 is characterized in that, described catalyst can be used for fixing bed, moving bed or fluidized-bed reactor.
12, catalyst according to claim 1 is characterized in that, by under 300～600 ℃, carries out coke-burning regeneration in hydrogen, steam, oxygen, air or other oxygen containing oxidizing atmosphere behind the described catalysqt deactivation.
13, the catalyst without mercury renovation process of acetylene hydrochlorination reaction usefulness is characterized in that the regeneration condition of described catalyst is oxygen volume space velocity 300～1200, the volume space velocity 300～1200 of steam, 200～600 ℃ of temperature, pressure 0.05～0.6MPa.0.001-10 hour regenerative response time.
14, catalyst without mercury renovation process according to claim 13 is characterized in that, the regeneration condition of described catalyst is 300～500 ℃, pressure 0.05～0.2MPa.0.1-2 hour regenerative response time.
15, the application of the catalyst without mercury of acetylene hydrochlorination reaction usefulness is characterized in that described reaction condition is: 80～600 ℃ of temperature, and pressure 0.05～0.6MPa, the mol ratio of acetylene and hydrogen chloride is 1: 3～3: 1, the weight space velocity of acetylene is 0.01～5h
-1Preferred reaction condition is: 150～350 ℃, and pressure 0.05～0.2MPa.
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2009
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