CN103121905B - Recovery method of hydrocarbon fuel gas rich in alkyne - Google Patents
Recovery method of hydrocarbon fuel gas rich in alkyne Download PDFInfo
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- CN103121905B CN103121905B CN201110366904.2A CN201110366904A CN103121905B CN 103121905 B CN103121905 B CN 103121905B CN 201110366904 A CN201110366904 A CN 201110366904A CN 103121905 B CN103121905 B CN 103121905B
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Abstract
The invention relates to a method for recovering and utilizing hydrocarbon fuel gas rich in alkyne by catalytic hydrogenation and mainly solves the problem that alkyne-enriched hydrocarbon fuel gas in a butadiene device is sent to a torch to be burned and fails to be effectively utilized. Gaseous hydrocarbon fuel gas is absorbed by solvent into liquid, absorbed liquid is mixed with hydrogen to enter a catalytic selective hydrogenation reactor, and alkyne selective hydrogenation is allowed under the catalytic action of nickel, copper, silver and palladium, catalytic hydrogenation product cools and enters a stripper, and alkyne-enriched mixture is obtained from the top of the stripper and is sent into the butadiene device to obtain the high-purity butadiene product. Bottom residue is mainly solvent and is sent to an absorption tower for recovery. The problem that the fuel gas in the butadiene device fails to be effectively utilized is solved well by the application of the technical scheme. The recovery method is widely applicable to industrial productions to achieve hydrocarbon fuel gas recovery and butadiene yield increasing.
Description
Technical field
The present invention relates to a kind of recovery method being rich in the hydrocarbon fuel gas of alkynes.
Background technology
Divinyl is a kind of important basic petrochemical organic raw material and synthetic rubber monomer, and be one of most important component in C 4 fraction, the status in petrochemical complex olefin feedstock is only second to ethene and propylene.Owing to containing conjugated diolefine in its molecule, can replace, addition, the reaction such as cyclisation and polymerization, its tool in synthetic rubber and organic synthesis etc. is had been widely used, cis-1,4-polybutadiene rubber (BR) can be synthesized, styrene-butadiene rubber(SBR) (SBR), paracril, SBS elastomer (SBS), the multiple rubber products such as acrylonitrile-butadiene-styrene (ABS) (ABS) resin, can be used in addition producing adiponitrile, hexanediamine, nylon66 fiber, 1, the Organic chemical products such as 4-butyleneglycol and be used as caking agent, gasoline dope etc., purposes is very extensive.
At present, the source of world's divinyl mainly contains two kinds, and one is from refinery C
4cut dehydrogenation obtains, and a few countries that the method is only enriched at some butane, Butene at present adopts.Another is the mixed C from ethylene cracker by-product
4in cut, extracting obtains, and this method is cheap, preponderates economically, is the main mode of production of divinyl in the world at present.In recent years, American UOP and BASF AG's joint development go out extracting process integration, combine, first by C by the selective acetylene hydrocarbon hydrogenation technique (KLP technique) of UOP and the Butadiene Extraction distil process of BASF AG
4selective acetylene hydrocarbon hydrogenation in cut, then adopts extractive distillation technology to reclaim 1,3-butadiene from butane and butylene.
Cracking petroleum hydrocarbon vapor produces cracking C
4cut, wherein containing a large amount of divinyl, is separated by extraction plant and obtains highly purified product butadiene.At the alkynes cut such as the second extracting rectifying part and the isolated methylacetylene of direct rectifying part, ethylacetylene, vinylacetylene of extraction plant, its alkyne concentration is higher, general between 20 ~ 43%, these cuts being rich in alkynes there is no industrial utility value at present, deliver to torch process as fuel gas.But, because high density alkynes is easily polymerized blast, vinylacetylene concentration is more than 45%, or concentration be 20% and gaseous phase partial pressure reaches 0.25MPa time, decomposable asymmetric choice net is revealed, therefore this part alkynes cut just can send torch burning after first must utilizing the cut dilutions such as safer butane or butylene, causes the very large wasting of resources.If this part alkynes material is processed, make alkynes be converted into the diolefine extracting utilization again of high added value, will greatly improve economic benefit and the Environmental Protection Level of butadiene extraction unit.
Document CN1590513A describes a kind of use bimetal or multimetallic catalyst, residual fraction butadiene product equipment being contained to alkynes directly carries out selec-tive hydrogenation, alkynes is converted into divinyl and monoolefine sends butadiene extraction unit back to again, content relates generally to the composition of catalyzer and the method for hydrogenation reaction.The hydrogenation reaction that the document describes needs reaction product to loop back reactor inlet, internal circulating load is larger, there is the problem that reaction member energy consumption is high, butadiene yield is low (some butadiene is hydrogenated to butylene), and the document does not relate to the treatment process of alkynes cut before entering reactor to high density, easily polymerization self-destruction.
Summary of the invention
Technical problem to be solved by this invention is that the hydrocarbon fuel gas being rich in alkynes in existing butadiene product equipment is sent to torch and burns, and the problem that can not be utilized effectively, provides a kind of recovery method being rich in the hydrocarbon fuel gas of alkynes newly.The method has the advantage that effectively can utilize the alkynes such as ethylacetylene, vinylacetylene in hydrocarbon fuel gas.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of recovery method being rich in the hydrocarbon fuel gas of alkynes, comprises the following steps:
(1) enter bottom absorption tower from the hydrocarbon fuel gas raw material being rich in alkynes out-of-bounds come, solvent self-absorption top of tower adds, and is absorbed by fuel gas and forms liquid phase scrubbing liquid;
(2) absorption liquid sends into hydrogenator after mixing with hydrogen, carries out alkynes selective hydrogenation reaction in liquid phase and obtains hydrogenation products;
(3) hydrogenation products enters Analytic Tower after heat exchange, is separated the material feeding butadiene product equipment separation of being rich in divinyl obtained obtains high purity butylene diene products from tower top; Solvent is analytically separated at the bottom of tower tower, is back to top, absorption tower and recycles.
In technique scheme, in raw material, alkynes weight content preferable range is 0.1 ~ 45%; Hydrogen preferred version is for being reformer hydrogen, hydrogen psa or cracking hydrogen, and concentration is greater than 95%; Carry out heat exchange between the charging and discharging of hydrogenator, reclaim heat.Hydrogenator type preferred version is bubbling bed reactor.Hydrogenator preferred version is two sections or multi-segment structure, is intersegmentally provided with interchanger, or at intersegmental feeding thinner.Reaction pressure preferable range in hydrogenator is 0.8 ~ 2.0MPa, and hydrocarbon material volume space velocity preferable range is 2 ~ 3 hours
-1; The temperature in preferable range of hydrogenator is 30 ~ 80 DEG C, and the mol ratio preferable range of hydrogen and alkynes is 1.2 ~ 3.Liquid phase preferred version at the bottom of Analytic Tower tower is for circulation is as absorption tower lyosorption.Absorption tower preferred version is valve tray column, packing tower or sieve-tray tower.The lyosorption preferred version adopted in absorption tower is C
5~ C
12alkane.Adopt in absorption tower lyosorption more preferably scheme be hexanaphthene.Selective hydrogenation catalyst preferred version is nickel palladium copper multimetallic catalyst or nickel palladium copper silver polymetallic catalyzer.
In the inventive method, the hydrocarbon fuel gas being rich in alkynes in butadiene extraction unit, by recycling after shortening, avoids and burns because delivering to torch the wasting of resources and environmental pollution that bring, improve the overall efficiency of butadiene extraction unit.In the method, selec-tive hydrogenation is carried out to the alkynes such as ethylacetylene, vinylacetylene in hydrocarbon fuel gas, alkynes is hydrogenated into diolefin, thus butene-1 output can be improved.The method, by the method for solvent absorbing, solves the danger that high density alkynes is easily polymerized self-destruction; Meanwhile, lower by alkyne concentration in the liquid phase after solvent absorbing, avoid use hydrogenation after product and dilute the butadiene hydrogenation loss caused; Lyosorption can be recycled after resolving in addition.
The inventive method adopts the mode of absorption, parsing, selec-tive hydrogenation, solves operability and the security of high density alkynes hydrogenation process, and has good combinableness with butadiene extraction unit, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the inventive method process flow diagram;
Fig. 2 is document CN 1590513A process flow diagram;
In Fig. 1 or Fig. 2, A is absorption tower, and B is alkyne hydrogenation reactor, and C is interchanger, D is Analytic Tower, and E is gas-liquid separator, and 1 is the hydrocarbon material being rich in alkynes from butadiene extraction unit, 2 is lyosorption, and 3 is hydro carbons absorption liquid, and 4 is material after hydrotreatment, 5 is Analytic Tower charging, 6 are rich in divinyl material for what return butadiene extraction unit, and 7 is circulating solvent, and 8 is hydrogen, 9 is outer row's non-condensable gas, and 10 is reaction product cycle stock.
In Fig. 1, the hydrocarbon material 1 being rich in alkynes from butadiene extraction unit utilizes solvent 2 to absorb in the A of absorption tower, absorption liquid enters alkyne hydrogenation reactor B and carries out selective acetylene hydrocarbon hydrogenation after mixing with hydrogen 8, hydrogenation products 4 enters Analytic Tower D after interchanger C cools, resolving tower top is that butadiene extraction unit separation sent into by the material being rich in divinyl, be isolated lyosorption at the bottom of Analytic Tower, deliver to absorption tower circulation on probation.
Below by embodiment, the present invention is further elaborated.
Embodiment
[comparative example 1]
Shown in Fig. 2, charging is for being rich in alkynes material, and adopt document CN 1590513A technical process, reaction temperature in is 20 DEG C, and reaction pressure is 2.0MPa, hydrocarbon material volume space velocity 2.0 hours
-1, the mol ratio of hydrogen and alkynes is 1: 1 ~ 2: 1, and recycle ratio is 8: 1.Adopt palladium copper bimetallic catalyst, its content is palladium 0.2wt%, copper 10.9wt%, and support of the catalyst is aluminum oxide, and hydrogenator is single stage adiabatic formula fixed bed, and test proves that alkynes transformation efficiency is about 98.5%, and butadiene yield is 98%.1 is seen the following form into and out of material composition:
Material composition before and after table 1 reacts
| wt％ | Divinyl | Propine | Vinylacetylene | Ethylacetylene |
| Raw material | 25.62 | 7.81 | 19.94 | 9.08 |
| Product (500 hours) | 25.15 | - | 0.3 | 0.22 |
| Product (1000 hours) | 25.1 | - | 0.42 | 0.25 |
[comparative example 2]
Shown in Fig. 2, charging is for being rich in alkynes material, and adopt document CN 1590513A technical process, reaction temperature in is 25 DEG C, and reaction pressure is 2.5MPa, hydrocarbon material volume space velocity 2.0 hours
-1, the mol ratio of hydrogen and alkynes is 1: 1 ~ 2: 1, and recycle ratio is 12: 1.Adopt palladium copper silver polymetallic catalyzer, its content is palladium 0.2wt%, copper 9.5wt%, silver 0.2wt%, support of the catalyst is aluminum oxide, and hydrogenator is two sections of heat-insulating fixed beds, test proves that alkynes transformation efficiency is about 98%, and butadiene yield is 103 ~ 105%.2 are seen the following form into and out of material composition:
Material composition before and after table 2 reacts
| wt％ | 1-butylene | Divinyl | Propine | Vinyl second | Ethylacetylene |
| Raw material | 17.66 | 27.22 | 7.11 | 23.85 | 9.1 |
| Product (500 hours) | 41.05 | 28.61 | - | 0.49 | 0.26 |
| (1000 is little for product | 41.65 | 27.95 | - | 0.52 | 0.26 |
[embodiment 1]
Shown in Fig. 1, adopt present invention process flow process, charging is the hydrocarbon material being rich in alkynes, and adopt nickel palladium copper multimetallic catalyst, its content is nickel 10wt%, palladium 0.3wt%, copper 1.1wt%; Temperature of reaction is 40 DEG C, and reaction pressure is 1.5MPa, hydrocarbon material volume space velocity 2.5 hours
-1, the mol ratio of hydrogen and alkynes is 1.2: 1 ~ 3: 1, and hydrogenator is bubbling bed, and test proves that alkynes transformation efficiency is about 98.6%, and butadiene yield is 189%.3 are seen the following form into and out of material composition:
Material composition before and after table 3 reacts
| wt％ | Butylene | Divinyl | Propine | Vinyl second | Ethylacetylene |
| Raw material | 13.63 | 37.62 | 0.07 | 35.33 | 6.88 |
| Product | 17.85 | 71.06 | - | 0.49 | 0.09 |
[embodiment 2]
Shown in Fig. 1, adopt present invention process flow process, charging is the hydrocarbon material being rich in alkynes, and adopt nickel palladium copper silver polymetallic catalyzer, its content is nickel 10wt%, palladium 0.3wt%, copper 1.1wt%, silver-colored 0.2wt%; Temperature of reaction is 65 DEG C, and reaction pressure is 1.8MPa, hydrocarbon material volume space velocity 3 hours
-1, the mol ratio of hydrogen and alkynes is 1.2: 1 ~ 3: 1, and hydrogenator is bubbling bed, and test proves that alkynes transformation efficiency is about 99%, and butadiene yield is 205%.4 are seen the following form into and out of material composition:
Material composition before and after table 4 reacts
| wt％ | Butylene | Divinyl | Propine | Vinyl second | Ethylacetylene |
| Raw material | 0.27 | 45.53 | 0.03 | 42.95 | 9.28 |
| Product | 7.51 | 93.49 | - | 0.43 | 0.08 |
Claims (6)
1. be rich in a recovery method for the hydrocarbon fuel gas of alkynes, comprise the following steps:
(1) enter bottom absorption tower from the hydrocarbon fuel gas raw material being rich in alkynes that out-of-bounds butadiene extraction unit is come, solvent self-absorption top of tower adds, and is absorbed by fuel gas and forms liquid phase scrubbing liquid;
(2) absorption liquid sends into hydrogenator after mixing with hydrogen, carries out alkynes selective hydrogenation reaction in liquid phase and obtains hydrogenation products;
(3) hydrogenation products enters Analytic Tower after heat exchange, is separated the material feeding butadiene product equipment separation of being rich in divinyl obtained obtains high purity butylene diene products from tower top; Solvent is analytically separated at the bottom of tower tower, is back to top, absorption tower and recycles;
In described raw material, alkynes weight content is 0.1 ~ 45%; Hydrogen is reformer hydrogen, hydrogen psa or cracking hydrogen, and concentration is greater than 95%; Carry out heat exchange between the charging and discharging of hydrogenator, reclaim heat;
Lyosorption is adopted to be hexanaphthene in described absorption tower;
Described selective hydrogenation catalyst is nickel palladium copper multimetallic catalyst or nickel palladium copper silver polymetallic catalyzer.
2. be rich in the recovery method of the hydrocarbon fuel gas of alkynes according to claim 1, it is characterized in that hydrogenator type is bubbling bed reactor.
3. be rich in the recovery method of the hydrocarbon fuel gas of alkynes according to claim 1, it is characterized in that hydrogenator is two sections or multi-segment structure, be intersegmentally provided with interchanger, or at intersegmental feeding thinner.
4. be rich in the recovery method of the hydrocarbon fuel gas of alkynes according to claim 1, it is characterized in that the reaction pressure in hydrogenator is 0.8 ~ 2.0MPa, hydrocarbon material volume space velocity is 2 ~ 3 hours
-1; The temperature in of hydrogenator is 30 ~ 80 DEG C, and the mol ratio of hydrogen and alkynes is 1.2 ~ 3.
5. be rich in the recovery method of the hydrocarbon fuel gas of alkynes according to claim 1, it is characterized in that at the bottom of Analytic Tower tower, liquid phase circulation is as absorption tower lyosorption.
6. be rich in the recovery method of the hydrocarbon fuel gas of alkynes according to claim 1, it is characterized in that absorption tower is valve tray column, packing tower or sieve-tray tower.
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| CN103121905B true CN103121905B (en) | 2015-06-10 |
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| CN108786879B (en) * | 2018-05-28 | 2021-03-26 | 安徽工大化工科技有限公司 | Method for catalyzing selective hydrogenation of 1, 3-butadiene by PdAgNi/N-C catalyst |
| CN111732076A (en) * | 2020-07-06 | 2020-10-02 | 中国石油化工股份有限公司 | Method for catalytically cracking hydrocarbons by using liquid catalyst |
| US20240076559A1 (en) | 2020-10-26 | 2024-03-07 | China Petroleum & Chemical Corporation | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation apparatus thereof |
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| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Acetylene hydrocarbon selective hydrogenation method |
| CN101821361A (en) * | 2008-07-17 | 2010-09-01 | Sk能源株式会社 | Process for 1,3-butadiene separation from crude C4 stream with acetylene converter |
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| US7045670B2 (en) * | 2003-09-03 | 2006-05-16 | Synfuels International, Inc. | Process for liquid phase hydrogenation |
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| CN101821361A (en) * | 2008-07-17 | 2010-09-01 | Sk能源株式会社 | Process for 1,3-butadiene separation from crude C4 stream with acetylene converter |
| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Acetylene hydrocarbon selective hydrogenation method |
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