CN103121904A - Utilization method for hydrocarbon fuel gas rich in alkyne - Google Patents
Utilization method for hydrocarbon fuel gas rich in alkyne Download PDFInfo
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- CN103121904A CN103121904A CN2011103694222A CN201110369422A CN103121904A CN 103121904 A CN103121904 A CN 103121904A CN 2011103694222 A CN2011103694222 A CN 2011103694222A CN 201110369422 A CN201110369422 A CN 201110369422A CN 103121904 A CN103121904 A CN 103121904A
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Abstract
The invention relates to a utilization method for hydrocarbon fuel gas rich in alkyne, which mainly solves the problem that the hydrocarbon fuel gas rich in alkyne in a butadiene device cannot be used effectively due to being sent to a torch to be burned up. According to the utilization method for hydrocarbon fuel gas rich in alkyne, gaseous phase hydrocarbon fuel gas is absorbed as a liquid phase through the adoption of a solvent, the absorption liquid and hydrogen are mixed and then enter into a one-stage process catalysis selectivity hydrogenation reactor, under multiple metals catalyst reaction of nickel, palladium, copper and silver, alkyne selective hydrogenation reaction is carried out, the alkyne is changed into diolefin through hydrogenation, the product enters into an analysis tower so as to separate the solvent and C4 olefin, the material at the bottom of the tower returns back to an absorption tower for recycling, the material at the top of the tower and hydrogen are mixed and then enter into a two-stage process catalysis hydrogenation reactor, under the metal catalyst reaction of nickel and molybdenum, the diolefin is changed into monoolefine through hydrogenation, then the monoolefine is sent to a butene-1 device for separation so as to obtain the product of butane-1. The utilization method better solves the problem, and can be widely applied to recycling hydrocarbon fuel gas and industrial increase production of butene-1.
Description
Technical field
The present invention relates to a kind of butadiene extraction unit remnants be rich in alkynes hydrocarbon fuel gas utilize method.The present invention makes butadiene extraction unit remnants be rich in the hydrocarbon fuel gas of alkynes by solvent absorbing, and selects hydrogenation under the effect of catalyzer, and the butene-1 in the recovery product and the method for other monoene.
Background technology
Butene-1 is a kind of important industrial chemicals, and chemical property is more active, is the important component of refining plant C 4 and c4 cleavage hydro carbons.High-purity butylene-1 is mainly used in monomer, poly 1-butene plastics, the high density polyethylene(HDPE) (HDPE) of copolymerization linear low density of polyethylene (LLDPE).From the Asia, the appearance of the butene-1 of one of LLDPE raw materials for production is serious, and supply falls short of demand.The Asia only has the manufacturer of minority butene-1 externally to sell product, along with the rapid growth of existing LLDPE manufacturer demand, will be stronger to the demand of butene-1.
The butene-1 production line mainly contains two kinds, and a kind of is oligomerization process take ethene as raw material, and another kind is with C
4Hydrocarbon is extracting or the separating technology of raw material, and the latter accounts for 64.5% of aggregated capacity.In the last few years, because the ethene imbalance between supply and demand is very outstanding, and price was higher, and the technological line that adopts ethylene dimerization to produce butene-1 faces the higher immense pressure of production cost, and progressively withdraws from the market.C-4-fraction obtains the technological line of butene-1 by separating technology, common first extracting divinyl or hydrogenation are removed divinyl, then after removing iso-butylene by the iso-butylene etherificate, obtain the higher butene-1 product of purity after accurate the separation again, obtain simultaneously being rich in the hydrocarbon mixture (being mainly butene-2 and normal butane) of butene-2.In addition, also have Shanghai Petroleum Chemical Engineering Institute isomerization of butene technology newly developed, having uniqueness optionally under the solid acid catalyst effect, butene-2 is converted into butene-1.
Cracking petroleum hydrocarbon vapor produces cracking C
4Cut wherein contains a large amount of divinyl, separates obtaining highly purified product butadiene by extraction plant.The second extracting rectifying part and the alkynes cuts such as the direct isolated methylacetylene of rectifying part, ethylacetylene, vinylacetylene at extraction plant, its alkynes concentration is higher, generally between 20～43%, these cuts that are rich in alkynes there is no at present industrial utilization and are worth, and the pneumatic transmission that acts as a fuel is processed to torch.But, due to the easy polymerization blast of high density alkynes, vinylacetylene concentration surpasses 45%, or concentration is 20% and gaseous phase partial pressure when reaching 0.25MPa, can decompose self-destruction, therefore this part alkynes cut just can send torch burning after must first utilizing the cut dilutions such as safer butane or butylene, has caused the very large wasting of resources.If this part alkynes material is processed, make alkynes be converted into divinyl or the butene-1 of high added value, will greatly improve economic benefit and the Environmental Protection Level of butadiene extraction unit.
Summary of the invention
Technical problem solved by the invention is that the hydrocarbon fuel gas that is 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 method of utilizing of the new hydrocarbon fuel gas that is rich in alkynes.The method has advantages of can effectively 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 hydrocarbon fuel gas that is rich in alkynes utilize method, comprise the following steps:
(1) enter the bottom, absorption tower from the hydrocarbon fuel gas raw material that is rich in alkynes that out-of-bounds comes, solvent self-absorption top of tower adds, and fuel gas is absorbed obtain the liquid phase absorption liquid;
(2) absorption liquid and hydrogen are that diolefin obtains the one-stage hydrogenation product with selective acetylene hydrocarbon hydrogenation in the one-stage hydrogenation reactor;
(3) one-stage hydrogenation product gas-liquid separation after cooling separates the gas phase that obtains and is mainly unreacting hydrogen, delivers to second-stage hydrogenation reactor; Separate the liquid phase that obtains and enter Analytic Tower, separate obtaining being rich in C from the Analytic Tower tower top
4The material of alkene, solvent is separated at the bottom of the Analytic Tower tower, is back to the top, absorption tower and recycles;
(4) Analytic Tower tower top material and hydrogen in second-stage hydrogenation reactor, are butene-1 with selective hydrogenation of diolefin as, and after product was cooling, liquid phase was delivered to the separation of butene-1 device and obtained the high-purity butylene-1 product.
In technique scheme, in raw material, alkynes weight content preferable range is 0.1～45%; The hydrogen preferred version is reformer hydrogen, hydrogen psa, cracking hydrogen or unreacting hydrogen, and concentration is greater than 95%; Carry out heat exchange between the charging and discharging of hydrogenator, reclaim heat; Adopt the unstripped gas that solvent will be rich in alkynes to be absorbed as liquid phase, the service temperature preferable range is 20～80 ℃, and the working pressure preferable range is 1barG; Adopting the lyosorption preferred version in the absorption tower is C
5～C
12Alkane.Adopt in the absorption tower lyosorption more preferably scheme be hexanaphthene.The hydrogenator preferred version is two sections or multi-segment structure, intersegmentally is provided with interchanger or at the intersegmental thinner of sending into; Reaction pressure preferable range in one section selective hydrogenation reaction device is 0.8～2.5MPa, and more preferably scope is 1.2～2.0MPa, and hydrocarbon material volume space velocity preferable range is 2.5～4 hours
-1One section selective hydrogenation reaction device preferred version is bubbling bed reactor; Analytic Tower tower top pressure preferable range is 0.6～2.0MPaG, and the feeding temperature preferable range is 30～60 ℃; Reaction pressure preferable range in two sections selective hydrogenation reaction devices is 1.5～3.0MPa, and more preferably scope is 2.0～2.5MPa; Hydrocarbon material volume space velocity preferable range is 1～2 hour
-1The temperature in preferable range of one section selective hydrogenation reaction device is 30～80 ℃, and the mol ratio preferable range of hydrogen and alkynes is 1.5～3.5; The temperature in preferable range of two sections selective hydrogenation of butadiene reactors is 160～180 ℃, and the mol ratio preferable range of hydrogen and alkynes is 450～550; Two sections selective hydrogenation of butadiene reactor preferred versions are the gas phase fixed-bed reactor.The absorption tower preferred version is valve tray column, packing tower or sieve-tray tower.In one section selective hydrogenation reaction device, the selective hydrogenation catalyst preferred version is nickel palladium copper multimetallic catalyst or nickel palladium copper silver multimetallic catalyst.In two sections selective hydrogenation reaction devices, the selective hydrogenation catalyst preferred version is nickel molybdenum catalyst.
In the inventive method, the hydrocarbon fuel gas that is rich in alkynes in butadiene extraction unit is recycled after by shortening, has avoided burning because delivering to torch the wasting of resources and the environmental pollution that brings, and has improved the overall efficiency of butadiene extraction unit.The method is carried out secondary hydrogenation to the alkynes such as ethylacetylene, vinylacetylene in hydrocarbon fuel gas, at first select hydrogenation for one section, alkynes is hydrogenated into diolefin, and then carries out secondary hydrogenation, the further hydrogenation of diolefin is become butene-1, thereby improve butene-1 output.The method has solved the danger of the easy polymerization self-destruction of high density alkynes by the method for solvent absorbing; Simultaneously, lower by alkynes concentration in the liquid phase after solvent absorbing, avoided the butadiene hydrogenation loss of using the dilution of hydrogenation after product to cause; Lyosorption can be recycled after resolving in addition.
The inventive method adopts absorption, parsing, two sections modes of selecting hydrogenation, operability and the security of high density alkynes hydrogenation process have been improved, and have good combinableness with butadiene extraction unit and the accurate tripping device of butene-1, obtained technique effect preferably.
Description of drawings
Fig. 1 is the inventive method process flow diagram;
in Fig. 1, A is the absorption tower, B is one section selective hydrogenation reaction device, C, G is interchanger, D, H is gas-liquid separator, E is Analytic Tower, F is two sections selective hydrogenation reaction devices, 1 is lyosorption, 2 are the hydrocarbon material that is rich in alkynes from butadiene extraction unit, 3 is the hydro carbons absorption liquid, 4 is hydrogen, 5, 6 is the one-stage hydrogenation product, 7 is the Analytic Tower charging, 8 is two sections selective hydrogenation reaction device hydrogen feed, 9 is the discharging of Analytic Tower tower top, 10 is circulating solvent, 11, 12 are two sections selects hydrogenation products, 13 for removing butene-1 device material, 14 is the circulation diluted material of two sections selective hydrogenation reaction devices, 15, 16 for effluxing non-condensable gas.
in Fig. 1, the hydrocarbon fuel gas material 1 that is rich in alkynes from butadiene extraction unit utilizes solvent 2 to absorb in the A of absorption tower, absorption liquid with enter one section selective hydrogenation reaction device B after hydrogen 4 mixes and carry out selective acetylene hydrocarbon hydrogenation, hydrogenation products 5 carries out gas-liquid separation in gas-liquid separator D after interchanger C is cooling, gas phase is mainly unreacting hydrogen, deliver to two sections selective hydrogenation reaction devices, liquid phase enters Analytic Tower E, the discharging of Analytic Tower tower top is to be rich in the material of diolefin 9 to send into two sections selective hydrogenation reaction device F, it is isolated lyosorption 10 at the bottom of Analytic Tower, being circulated to the absorption tower uses, select hydrogenation products 11 through cooling for two sections, after gas-liquid separation, the Partial Liquid Phase product is delivered to the separation of butene-1 device and is obtained highly purified butene-1 product, Partial Liquid Phase loops back two sections selective hydrogenation reaction devices.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
By shown in Figure 1, adopt technical process of the present invention, charging is the hydrocarbon material that is rich in alkynes, one section selective hydrogenation reaction device adopts nickel palladium copper multimetallic catalyst; Temperature of reaction is 45 ℃, and reaction pressure is 2.0MPa, hydrocarbon material volume space velocity 2.5 hours-1, and the mol ratio of hydrogen and alkynes is 1.5: 1, the one-stage hydrogenation reactor is bubbling bed.Two sections selective hydrogenation reaction devices adopt nickel molybdenum multi-metal catalyzer; Temperature of reaction is 160 ℃, and reaction pressure is 2.5MPa, hydrocarbon material volume space velocity 1 hour-1, and the mol ratio of hydrogen and alkynes is 450: 1, second-stage hydrogenation reactor is fixed bed,
Evidence alkynes transformation efficiency is 98.1% left and right, and main ingredient sees the following form 1 into and out of the material composition:
| wt％ | Butylene | Divinyl | Propine | Vinyl second | Ethylacetylene |
| Raw material | 8.46 | 29.58 | 0.02 | 25.55 | 7.01 |
| Product | 71.31 | 0.53 | - | 0.42 | 0.21 |
[embodiment 2]
By shown in Figure 1, adopt technical process of the present invention, charging is the hydrocarbon material that is rich in alkynes, one section selective hydrogenation reaction device adopts nickel palladium copper multimetallic catalyst; Temperature of reaction is 67 ℃, and reaction pressure is 2.0MPa, hydrocarbon material volume space velocity 4 hours-1, and the mol ratio of hydrogen and alkynes is 3.5: 1, the one-stage hydrogenation reactor is bubbling bed.Two sections selective hydrogenation reaction devices adopt nickel molybdenum multi-metal catalyzer; Temperature of reaction is 180 ℃, and reaction pressure is 2.5MPa, hydrocarbon material volume space velocity 2 hours-1, and the mol ratio of hydrogen and alkynes is 550: 1, second-stage hydrogenation reactor is fixed bed.
Evidence alkynes transformation efficiency is 97.5% left and right, and main ingredient sees the following form 2 into and out of the material composition:
| wt％ | Butylene | Divinyl | Propine | Vinyl second | Ethylacetylene |
| Raw material | 6.59 | 41.45 | 0.05 | 32.83 | 8.08 |
| Product | 89.21 | 0.93 | - | 0.84 | 0.26 |
Claims (7)
- A hydrocarbon fuel gas that is rich in alkynes utilize method, comprise the following steps:(1) enter the bottom, absorption tower from the hydrocarbon fuel gas raw material that is rich in alkynes that out-of-bounds comes, solvent self-absorption top of tower adds, and fuel gas is absorbed obtain the liquid phase absorption liquid;(2) absorption liquid and hydrogen are that diolefin obtains the one-stage hydrogenation product with selective acetylene hydrocarbon hydrogenation in the one-stage hydrogenation reactor;(3) one-stage hydrogenation product gas-liquid separation after cooling separates the gas phase that obtains and is mainly unreacting hydrogen, delivers to second-stage hydrogenation reactor; Separate the liquid phase that obtains and enter Analytic Tower, separate obtaining being rich in C from the Analytic Tower tower top 4The material of alkene, solvent is separated at the bottom of the Analytic Tower tower, is back to the top, absorption tower and recycles;(4) Analytic Tower tower top material and hydrogen in second-stage hydrogenation reactor, are butene-1 with selective hydrogenation of diolefin as, and after product was cooling, liquid phase was delivered to the separation of butene-1 device and obtained the high-purity butylene-1 product.
- 2. be rich according to claim 1 alkynes hydrocarbon fuel gas utilize method, it is characterized in that in raw material, the alkynes weight content is 0.1～45%; Hydrogen is reformer hydrogen, hydrogen psa, cracking hydrogen or unreacting hydrogen, and concentration is greater than 95%; Carry out heat exchange between the charging and discharging of hydrogenator, reclaim heat; Adopt the unstripped gas that solvent will be rich in alkynes to be absorbed as liquid phase, 20～80 ℃ of service temperatures, working pressure is 1barG; Adopting lyosorption in the absorption tower is C 5～C 12Alkane.
- 3. be rich according to claim 2 alkynes hydrocarbon fuel gas utilize method, it is characterized in that adopting lyosorption in the absorption tower is hexanaphthene.
- 4. be rich according to claim 1 alkynes hydrocarbon fuel gas utilize method, it is characterized in that hydrogenator is two sections or multi-segment structure, intersegmentally be provided with interchanger or at the intersegmental thinner of sending into; Reaction pressure in one section selective hydrogenation reaction device is 0.8～2.5MPa, and the hydrocarbon material volume space velocity is 2.5～4 hours-1; One section selective hydrogenation reaction device is bubbling bed reactor; The Analytic Tower tower top pressure is 0.6～2.0MPaG, and feeding temperature is 30～60 ℃; Reaction pressure in two sections selective hydrogenation reaction devices is 1.5～3.0MPa, and the hydrocarbon material volume space velocity is 1～2 hour -1The temperature in of one section selective hydrogenation reaction device is 30～80 ℃, and the mol ratio of hydrogen and alkynes is 1.5～3.5; The temperature in of two sections selective hydrogenation of butadiene reactors is 160～180 ℃, and the mol ratio of hydrogen and alkynes is 450～550; Two sections selective hydrogenation of butadiene reactors are the gas phase fixed-bed reactor.
- 5. be rich according to claim 1 alkynes hydrocarbon fuel gas utilize method, it is characterized in that the absorption tower is valve tray column, packing tower or sieve-tray tower.
- 6. be rich according to claim 1 alkynes hydrocarbon fuel gas utilize method, it is characterized in that in one section selective hydrogenation reaction device, selective hydrogenation catalyst is nickel palladium copper multimetallic catalyst or nickel palladium copper silver multimetallic catalyst.
- 7. be rich according to claim 1 alkynes hydrocarbon fuel gas utilize method, it is characterized in that in two sections selective hydrogenation reaction devices, selective hydrogenation catalyst is nickel molybdenum catalyst.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622317A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Method used for preparing cyclohexane via benzene hydrogenation, and applications and device thereof |
| CN106588541A (en) * | 2016-12-09 | 2017-04-26 | 大连福佳·大化石油化工有限公司 | System for recycling condensate of extraction torch tank |
| CN109485534A (en) * | 2017-09-12 | 2019-03-19 | 中国石化扬子石油化工有限公司 | A kind of method of DMF method butadiene extraction device tail gas hydrogenation |
| CN116178093A (en) * | 2022-12-15 | 2023-05-30 | 惠州宇新化工有限责任公司 | Alkyne hydrogenation feeding optimization method |
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| US4831200A (en) * | 1986-12-30 | 1989-05-16 | Labofina, S.A. | Process for the selective hydrogenation of alkynes |
| CN1590353A (en) * | 2003-08-26 | 2005-03-09 | 中国石化集团齐鲁石油化工公司 | Utilization method of butadiene extraction device residue |
| 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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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4831200A (en) * | 1986-12-30 | 1989-05-16 | Labofina, S.A. | Process for the selective hydrogenation of alkynes |
| CN1590353A (en) * | 2003-08-26 | 2005-03-09 | 中国石化集团齐鲁石油化工公司 | Utilization method of butadiene extraction device residue |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622317A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Method used for preparing cyclohexane via benzene hydrogenation, and applications and device thereof |
| CN105622317B (en) * | 2014-11-03 | 2018-06-15 | 中国石油化工股份有限公司 | The method of preparing cyclohexane by hydrogenating benzene and its application and device |
| CN106588541A (en) * | 2016-12-09 | 2017-04-26 | 大连福佳·大化石油化工有限公司 | System for recycling condensate of extraction torch tank |
| CN106588541B (en) * | 2016-12-09 | 2019-04-16 | 大连福佳·大化石油化工有限公司 | A kind of extracting torch tank lime set recycle device |
| CN109485534A (en) * | 2017-09-12 | 2019-03-19 | 中国石化扬子石油化工有限公司 | A kind of method of DMF method butadiene extraction device tail gas hydrogenation |
| CN109485534B (en) * | 2017-09-12 | 2021-08-20 | 中国石化扬子石油化工有限公司 | Tail gas hydrogenation method for butadiene extraction device by DMF (dimethyl formamide) method |
| CN116178093A (en) * | 2022-12-15 | 2023-05-30 | 惠州宇新化工有限责任公司 | Alkyne hydrogenation feeding optimization method |
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