CN102489225B - Slurry bubble column technology for preparing ethylene through acetylene hydrogenation and device thereof - Google Patents
Slurry bubble column technology for preparing ethylene through acetylene hydrogenation and device thereof Download PDFInfo
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- CN102489225B CN102489225B CN201110413397.3A CN201110413397A CN102489225B CN 102489225 B CN102489225 B CN 102489225B CN 201110413397 A CN201110413397 A CN 201110413397A CN 102489225 B CN102489225 B CN 102489225B
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Provided are slurry bubble column technology for preparing ethylene through acetylene hydrogenation and a device thereof. The slurry bubble column technology includes adding water and then catalyst into a reactor, filling inert gases for replacing, heating, leading gas mixture of acetylene and hydrogen to enter in the reactor for reacting from the bottom of the reactor through a gas distributor, finally exhausting reaction products and unreacted feed gases from the top of the reactor, and separating to obtain the ethylene. The unreacted feed gases and the feed gases are mixed and then enter the reactor again for reacting. The reactor comprises a reaction gas inlet at the bottom, the gas distributor and a material liquid exhaust port, a reactor barrel body is arranged on an expended section on the upper portion of a slurry bubble column reactor, and a catalyst feeding port and a gas outlet are arranged at the top of the reactor. The slurry bubble column for preparing the ethylene through the acetylene hydrogenation is simple in structure, overcomes the phenomenon of temperature runaway in a fixed bed reactor and improves the conversion rate and selectivity of the reaction, and the operation is easy to control.
Description
Technical field
The present invention is relevant with reactor and method thereof that a kind of acetylene hydrogenation is prepared ethene, is a kind of for starching technique and the device thereof of state bed middle and high concentration producing ethylene with acetylene hydrogenation further.
Background technology
Ethene is to produce three large synthetic material and the most basic raw materials of Organic chemical products, and its product is widely used in the fields such as national economy, people's lives, national defence, is " mother of organic synthesis ".The production of ethene is mainly made by the method for cracking petroleum hydrocarbon, and ethylene yield has become the mark of weighing a national petrochemical industry development level, and its production capacity is counted as the embodiment of a national economic strength.Face the shortage of petroleum resources and riseing of international oil price, raw material sources become the bottleneck of development ethylene industry, are also the problems of pendulum necessary solution in face of people.Therefore, research and develop a kind of new source and process and prepare the new technology of preparing that ethene petroleum replacing is raw material, can alleviate the dependence to oil.
In coal chemical technology, because petroleum resources are day by day in short supply and oil price is growing, development, take coal as the route of raw material substitution oil becomes the significant process in chemical field, gets the attention, and has obtained fast development.Wherein, enrich coal, limestone resource having, have the area of abundant electric power resource simultaneously, development is a kind of clean coal technology that has very much development potentiality take coal as raw material by calcium carbide acetylene processed.Although carbide acetylene process route is simple, added value of product is high, good in economic efficiency, realize large-scale industrial production, but compared with the organic synthesis route that is raw material with oil ethene, the industrial chain of the downstream product of acetylene is too short, rich wretched insufficiency, its main downstream product polyvinyl chloride (PVC) industry quality is not good, profit is not high, is badly in need of expanding the industrial chain of acetylene downstream product.Based on this, the present invention is take high concentration calcium carbide acetylene as unstripped gas passes through catalytic hydrogenation reaction, and a kind of new ethene method of preparing is provided, and can further expand Coal Chemical Industry Route.This is for rich coal resources and the flourishing area of carbide acetylene industry, and technique and the technology of exploitation high concentration producing ethylene with acetylene hydrogenation, have broad application prospects.
Low concentration acetylene gas solid catalysis hydrogen addition technology is very ripe in petroleum industry, is mainly used in removing in ethene acetylene impurity.In petrochemicals deep processing, during by hydrocarbon cracking ethene processed, pyrolysis furnace is normal trace (approximately 1%) acetylene that exists in working off one's feeling vent one's spleen.The existence of acetylene, can reduce the activity of ethylene rolymerization catalyst, makes polymer performance variation, therefore acetylene content should be controlled to 1 × 10
-7below.In industrial process, remove acetylene a small amount of in ethene and adopt fixed-bed process, take Pd or Ni as catalyst, under 30 ~ 100 ℃ of conditions, react.But because acetylene activity is high, hydrogenation reaction fuel factor is large, even there is a small amount of acetylene in cracking gas, traditional fixed bed hydrogenation reactor still exists the serious problems such as green oil generating amount is large, the catalyst circulation cycle is short, reactor easy " temperature runaway ".Therefore, while removing acetylene, when conventionally adopting millisecond pyrolysis furnace, change original one-stage hydrogenation technique into three series connection, intersegmental cooling multistage hydrogenation technique in petroleum industry, reaction process is comparatively complicated.
Above-mentioned analysis is known, for the hydrogenation technique of a small amount of acetylene in ethene, is not suitable for high concentration acetylene catalytic hydrogenation process of producing ethylene at present, and reason is:
(1) acetylene hydrogenation is strong exothermal reaction.The concentration of reactant acetylene is higher, and reaction speed is faster, and exothermic heat of reaction is more, and reactor is " temperature runaway " easily, and bed temperature can not effectively be controlled, and catalyst is prone to the serious problems such as sintering;
(2) adopt fixed-bed catalytic hydrogenation to react, exchange capability of heat is poor.For high concentration acetylene hydrogenation technique, the temperature control of fixed bed is more difficult, and technique will be more complicated;
(3), in acetylene hydrogenation process, because the easy polymerization reaction take place of unsaturated hydro carbons generates " green oil ", cover catalyst surface and make catalysqt deactivation.The catalyst regeneration time is increased in fixed bed reactors for removing " green oil ", have a strong impact on bed disposal ability.
Summary of the invention
In order to address the above problem, the invention provides a kind of slurry state bed process and device thereof of producing ethylene with acetylene hydrogenation, take carbide acetylene gas as raw material, in the situation that not adding any carrier gas, adopt paste state bed reactor to select hydrogenation to realize the technique of ethene processed.
Above-mentioned purpose of the present invention is achieved through the following technical solutions: a kind of slurry state bed process of high concentration producing ethylene with acetylene hydrogenation, and described in it, technique comprises following steps:
(1) in paste state bed reactor, adding volume is the water of reactor volume 1/5, after add catalyst, and pass into inert gas N
2carry out atmosphere displacement;
(2) paste state bed reactor is heated to 60-90 ℃;
(3) admixture of gas of acetylene and hydrogen is passed in paste state bed reactor through gas distributor by paste state bed reactor bottom, 80-100 ℃ of reaction;
(4) product and unreacted unstripped gas are discharged by paste state bed reactor top, after entering segregation section and separating, make ethylene product, and unreacted unstripped gas reenters reactor after mixing with fresh feed gas and reacts.
In above-mentioned technique, described catalyst is loaded catalyst, and the active component of this catalyst is one or more the combination in Pd, Pt and Ni, and its load capacity is: 0.03-1 wt%, its carrier is Al
2o
3, SiO
2with the one in active carbon, its particle diameter is 50-300mm.
In above-mentioned technique, described raw material acetylene is: carbide acetylene gas; In described unstripped gas, the volume ratio of hydrogen and acetylene is: 1
:1-6
:1; Described operation air speed is: 1000-20000mL/ (g-cath).
The device of a kind of slurry state bed process of realizing above-mentioned producing ethylene with acetylene hydrogenation of the present invention, comprises paste state bed reactor; Described in it, paste state bed reactor also comprises the reaction gas entrance, gas distributor and the feed liquid outlet that are positioned at paste state bed reactor bottom; Described paste state bed reactor cylindrical shell and the expanding reach that is positioned at paste state bed reactor top; Described paste state bed reactor top is provided with catalyst charging hole and gas vent.Wherein, the cylindrical shell height of described device with diameter ratio is: 10-15
:1.
Slurry state bed process and the device thereof of a kind of producing ethylene with acetylene hydrogenation provided by the present invention, compared with prior art, the advantage and the good effect that have are: device of the present invention can be realized high concentration acetylene and prepare in a large number production ethylene product, have further expanded the downstream fine chemical product of acetylene; Paste state bed reactor of the present invention, compared with fixed bed, adopts slurry state bed can effectively remove reaction heat, the accurate control of realization response temperature; In slurry state bed process process of the present invention, " green oil " generating can be dissolved in liquid phase, effectively avoided the activated centre of catalyst capped, reduced the regeneration times of catalyst, and reaction production capacity has obtained improving further.
Slurry state bed process and the device thereof of a kind of producing ethylene with acetylene hydrogenation provided by the present invention, there is structure of reactor simple, operation is easy to control, can effectively overcome " temperature runaway " problem in fixed bed reactors, and reaction temperature is even, reactor continuous operating time is long, can be by operating parameters such as temperature, gas holdup, solid holdup, gas residence time and structure of distributor in adjusting course of reaction, control hydrogenation reaction degree, improve reaction conversion ratio and the advantage such as selective.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation of starching state bed process and device thereof of the present invention.
In figure: 1: reaction gas entrance; 2: gas distributor; 3: feed liquid outlet; 4: paste state bed reactor cylindrical shell; 5: expanding reach; 6: catalyst charging hole; 7: gas vent.
The specific embodiment
Below the specific embodiment of the present invention is made an explanation:
Implement slurry state bed process and the device thereof of a kind of producing ethylene with acetylene hydrogenation provided by the present invention, the enforcement of a kind of producing ethylene with acetylene hydrogenation technique described in it realizes in existing slurry reactor apparatus, this device comprises paste state bed reactor, and described in it, paste state bed reactor mainly comprises the reaction gas entrance 1, gas distributor 2 and the feed liquid outlet 3 that are positioned at paste state bed reactor bottom; Wherein, paste state bed reactor cylindrical shell 4 and the expanding reach 5 that is positioned at paste state bed reactor top; Be provided with catalyst charging hole 6 and gas vent 7 at the top of paste state bed reactor.The cylindrical shell height of this device is 10-15 with diameter ratio
:between 1, be suitable for and realize technique of the present invention.
The slurry state bed process of implementing a kind of producing ethylene with acetylene hydrogenation of the present invention, is to realize in above-mentioned slurry reactor apparatus, by specific embodiment, the specific embodiment of the present invention is described in further detail below in conjunction with accompanying drawing:
(1) at height and diameter than in the paste state bed reactor of 11:1, add 80ml water from reactor top charge door 6, and then to add particle diameter be that 50mm, carrier are Al
2o
3, load P d amount is the 4g catalyst granules of 0.3 wt%, and passes into inert gas N from reaction gas entrance 1
2carry out atmosphere displacement;
(2) paste state bed reactor is heated to 60 ℃;
(3) be that acetylene and the hydrogen mixture that 5000mL/ (g-cath), volume ratio are 1:1 passes into paste state bed reactor from the reaction gas entrance 1 of paste state bed reactor bottom through gas distributor by air speed, 90 ℃ of reactions;
(4) product and unreacted unstripped gas are discharged from paste state bed reactor top, enter centrifugal station and separate, and obtain ethylene product, and unreacted unstripped gas reenters reactor after mixing with fresh feed gas and recycles.
After stable reaction, sample from the gas vent 7 at paste state bed reactor top that to analyze its conversion of alkyne by gas chromatograph be 38.6%, ethylene selectivity is 28.7%, and yield is 25.4%.
(1) at height and diameter than being the paste state bed reactor of 14:1, add 120ml water from reactor top charge door 6, and then to add particle diameter be that 100mm, carrier are SiO
2, supporting Pt amount is the 6g catalyst granules of 0.03 wt%, and passes into inert gas N from reaction gas entrance 1
2carry out atmosphere displacement;
(2) paste state bed reactor is heated to 80 ℃;
(3) be that acetylene and the hydrogen mixture that 1000mL/ (g-cath), volume ratio are 1:2 passes into paste state bed reactor from the reaction gas entrance 1 of paste state bed reactor bottom through gas distributor by air speed, 80 ℃ of reactions;
(4) product and unreacted unstripped gas are discharged from paste state bed reactor top, enter centrifugal station and separate, and obtain ethylene product, and unreacted unstripped gas reenters reactor after mixing with fresh feed gas and recycles.
After stable reaction, sample from the gas vent 7 at paste state bed reactor top that to analyze its conversion of alkyne by gas chromatograph be 35.6%, ethylene selectivity is 24.5%, and yield is 19.6%.
(1) paste state bed reactor that is 15:1 at height and diameter ratio, add 200ml water from reactor top charge door 6, and then to add particle diameter be that 200mm, carrier are that active carbon, load Ni amount is the 12g catalyst granules of 1.0 wt%, and pass into inert gas N from reaction gas entrance 1
2carry out atmosphere displacement;
(2) paste state bed reactor is heated to 90 ℃;
(3) be that acetylene and the hydrogen mixture that 10000mL/ (g-cath), volume ratio are 1:3 passes into paste state bed reactor from the reaction gas entrance 1 of paste state bed reactor bottom through gas distributor by air speed, 100 ℃ of reactions;
(4) product and unreacted unstripped gas are discharged from paste state bed reactor top, enter centrifugal station and separate, and obtain ethylene product, and unreacted unstripped gas reenters reactor after mixing with fresh feed gas and recycles.
After stable reaction, sample from the gas vent 7 at paste state bed reactor top that to analyze its conversion of alkyne by gas chromatograph be 41.6%, ethylene selectivity is 27.5%, and yield is 22.6%.
(1) at height and diameter than being the paste state bed reactor of 15:1, add 100ml water from reactor top charge door 6, and then to add particle diameter be that 300mm, carrier are Al
2o
3, load P d amount is the 25g catalyst granules of 0.6 wt%, and passes into inert gas N from reaction gas entrance 1
2carry out atmosphere displacement;
(2) paste state bed reactor is heated to 70 ℃;
(3) be that acetylene and the hydrogen mixture that 20000mL/ (g-cath), volume ratio are 1:5 passes into paste state bed reactor from the reaction gas entrance 1 of paste state bed reactor bottom through gas distributor by air speed, 95 ℃ of reactions;
(4) product and unreacted unstripped gas are discharged from paste state bed reactor top, enter centrifugal station and separate, and obtain ethylene product, and unreacted unstripped gas reenters reactor after mixing with fresh feed gas and recycles.
After stable reaction, sample from the gas vent 7 at paste state bed reactor top that to analyze its conversion of alkyne by gas chromatograph be 100%, ethylene selectivity is 54.8%, and yield is 44.3%.
(1) at height and diameter than being the paste state bed reactor of 13:1, add 150ml water from reactor top charge door 6, and then to add particle diameter be that 70mm, carrier are SiO
2, load Ni amount is the 20g catalyst granules of 1.0 wt%, and passes into inert gas N from reaction gas entrance 1
2carry out atmosphere displacement;
(2) paste state bed reactor is heated to 80 ℃;
(3) be that acetylene and the hydrogen mixture that 1000mL/ (g-cath), volume ratio are 1:6 passes into paste state bed reactor from the reaction gas entrance 1 of paste state bed reactor bottom through gas distributor by air speed, 85 ℃ of reactions;
(4) product and unreacted unstripped gas are discharged from paste state bed reactor top, enter centrifugal station and separate, and obtain ethylene product, and unreacted unstripped gas reenters reactor after mixing with fresh feed gas and recycles.
After stable reaction, sample from the gas vent 7 at paste state bed reactor top that to analyze its conversion of alkyne by gas chromatograph be 87.6%, ethylene selectivity is 34.5%, and yield is 25.9%.
(1) at height and diameter than being the paste state bed reactor of 14:1, add 100ml water from reactor top charge door 6, and then to add particle diameter be that 60mm, carrier are Al
2o
3, load ratio be 1:1 Pd and Ni, its load capacity is the 30g catalyst granules of 0.08 wt%, and passes into inert gas N from reaction gas entrance 1
2carry out atmosphere displacement;
(2) paste state bed reactor is heated to 90 ℃;
(3) be that acetylene and the hydrogen mixture that 8000mL/ (g-cath), volume ratio are 1:4 passes into paste state bed reactor from the reaction gas entrance 1 of paste state bed reactor bottom through gas distributor by air speed, 100 ℃ of reactions;
(4) product and unreacted unstripped gas are discharged from paste state bed reactor top, enter centrifugal station and separate, and obtain ethylene product, and unreacted unstripped gas reenters reactor after mixing with fresh feed gas and recycles.
After stable reaction, sample from the gas vent 7 at paste state bed reactor top that to analyze its conversion of alkyne by gas chromatograph be 94.7%, ethylene selectivity is 58.5%, and yield is 38.6%.
Claims (2)
1. a slurry state bed process for producing ethylene with acetylene hydrogenation, described in it, technique follows these steps to carry out:
(1) in paste state bed reactor, adding volume is the water of reactor volume 1/5, after add loaded catalyst, and pass into inert gas N
2carry out atmosphere displacement;
(2) paste state bed reactor is heated to 60-90 ℃;
(3) by the volume ratio of hydrogen in raw material and acetylene be: 1
:1-6
:1 admixture of gas is passed in paste state bed reactor through gas distributor by paste state bed reactor bottom, and operation air speed is: 1000-20000mL/ (g-cath), 80-100 ℃ of reaction;
(4) product and unreacted unstripped gas are discharged by paste state bed reactor top, after entering segregation section and separating, make ethylene product, and unreacted unstripped gas reenters reactor after mixing with fresh feed gas and reacts;
The active component of described loaded catalyst is one or more the combination in Pd, Pt and Ni; Its load capacity is: 0.03-1 wt%; Its carrier is: Al
2o
3, SiO
2with the one in active carbon, its particle diameter is: 50-300mm;
Described paste state bed reactor also comprises the reaction gas entrance (1), gas distributor (2) and the feed liquid outlet (3) that are positioned at paste state bed reactor bottom; Described paste state bed reactor cylindrical shell (4) and the expanding reach (5) that is positioned at paste state bed reactor top; Described paste state bed reactor top is provided with catalyst charging hole (6) and gas vent (7); The cylindrical shell height of described device with diameter ratio is: 10-15
:1.
2. technique as claimed in claim 1, described in it, raw material acetylene is: carbide acetylene gas.
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| CN102489225B true CN102489225B (en) | 2014-05-21 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044179A (en) * | 2012-12-19 | 2013-04-17 | 清华大学 | Method for preparing ethylene through liquid-phase selective hydrogenation of acetylene in slurry reactor |
| CN103418378B (en) * | 2013-08-01 | 2016-04-27 | 济南开发区星火科学技术研究院 | A kind of cracking c_4 fraction selective hydrogenation palladium-based catalyst |
| CN105152842B (en) * | 2015-08-07 | 2017-06-16 | 北京华福工程有限公司 | A kind of acetylene hydrogenation prepares the reaction system and method for ethene |
| CN105056844B (en) * | 2015-08-07 | 2017-04-12 | 北京华福工程有限公司 | Gas distributor for acetylene hydrogenation to ethylene slurry reactor and application thereof |
| CN105170035A (en) * | 2015-08-28 | 2015-12-23 | 北京神雾环境能源科技集团股份有限公司 | Hydrogenation reactor and method for preparing ethylene |
| CN105879792B (en) * | 2016-06-14 | 2018-06-08 | 神雾科技集团股份有限公司 | It is a kind of using prepared in slurry bed reactor for the reaction system and method for ethylene |
| CN106902861A (en) * | 2017-02-27 | 2017-06-30 | 北京神雾环境能源科技集团股份有限公司 | Preparation and its application process for preparing the catalyst of ethene |
| CN106944070A (en) * | 2017-02-27 | 2017-07-14 | 北京神雾环境能源科技集团股份有限公司 | A kind of synthesis of non-precious metal catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene and application process |
| CN106902820A (en) * | 2017-02-27 | 2017-06-30 | 北京神雾环境能源科技集团股份有限公司 | A kind of synthesis of graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene and application process |
| CN108126741A (en) * | 2017-12-05 | 2018-06-08 | 北京华福工程有限公司 | A kind of preparation method of composite carried catalyst and low-carbon olefine |
| CN114225668B (en) * | 2021-11-26 | 2023-01-13 | 山东大学 | Reaction device, method and application for preparing formic acid by capturing carbon dioxide and hydrogenating |
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| CN101391198A (en) * | 2008-10-31 | 2009-03-25 | 神华集团有限责任公司 | Slurry bed ft synthetic reactor and technique |
| CN101402541A (en) * | 2008-11-21 | 2009-04-08 | 清华大学 | Fluidized bed process and apparatus for producing ethylene with acetylene hydrogenation |
| CN101898929A (en) * | 2009-05-25 | 2010-12-01 | 代斌 | Reaction process for producing ethylene by selectively hydrogenating acetylene of calcium carbide process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391198A (en) * | 2008-10-31 | 2009-03-25 | 神华集团有限责任公司 | Slurry bed ft synthetic reactor and technique |
| CN101402541A (en) * | 2008-11-21 | 2009-04-08 | 清华大学 | Fluidized bed process and apparatus for producing ethylene with acetylene hydrogenation |
| CN101898929A (en) * | 2009-05-25 | 2010-12-01 | 代斌 | Reaction process for producing ethylene by selectively hydrogenating acetylene of calcium carbide process |
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