CN105566032B - The selection hydrogenation technique of rich alkynes carbon four - Google Patents
The selection hydrogenation technique of rich alkynes carbon four Download PDFInfo
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Abstract
The present invention relates to a kind of hydrogenation technique, and in particular to a kind of selection hydrogenation technique of rich alkynes carbon four.C 4 materials containing alkynes are come out from extraction device or tank field, are introduced into rectifying column, and the impurity of entrainment and carbon four are separated, and carbon four enters return tank, impurity goes fuel tank by bottom of towe extraction by overhead extraction after condensed device condensation；The hydrogenated raw material pump supercharging of carbon four, a part return to rectifying column as phegma, and another part is mixed into hydrogenation reactor with H2；Material enters qi leel tank after cooler cools down after hydrogenation, and on-condensible gas removes torch, and liquid produces through three roads of circulating pump point, and the first via returns to rectifying column charging aperture, and the second tunnel returns to hydrogenation reactor entrance, and the 3rd tunnel goes out device as hydrogenated products.The present invention solves the aggregation problem of alkadienes and alkynes in catalyst easy in inactivation and course of reaction, not only increases the butadiene of extraction device and the rate of recovery of butylene, and effectively extends the service life of hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of hydrogenation technique, and in particular to a kind of selection hydrogenation technique of rich alkynes carbon four.
Background technology
The process that hydrocarbon vapours crack alkene processed can generate the saturated hydrocarbons such as ethane, propane, butane；Ethene, propylene, butylene,
The unsaturated hydrocarbons such as butadiene；The height unsaturated hydrocarbons such as acetylene, propine, butine, vinylacetylene.
1,3-butadiene containing 40-50% in cracking mixing carbon four, is the primary raw material for producing rubber and resin, remaining
Main component is alkane and alkene, also a small amount of alkynes, and these alkynes include allylene, ethyl acetylene and vinylacetylene.
1,3-butadiene in cracking c_4 hydrocarbon is typically obtained by two sections of solvent extractions, and solvent is generally acetonitrile, dimethyl formyl
Amine and 1-METHYLPYRROLIDONE.Butane, butylene and separate butadiene are extracted butane, butylene by first paragraph；Second segment is by alkynes
With separate butadiene, the alkynes of carbon four is removed, 1,3-butadiene rectifying obtains product.In residual fraction caused by extraction device, alkynes
Hydrocarbon concentration is generally higher than 20wt%, and highest can exceed 40wt%, and these residual fractions rich in alkynes fail effectively to utilize, and because
High concentration alkynes easily polymerize blast, safety problem be present, therefore safer butane, fourth must be first used when handling these cuts
The cuts such as alkene are diluted, and subsequent treatment could be carried out as fuel etc. after reducing alkyne concentration.Recently as cracking severity
Increase, alkynes content is stepped up in C-4-fraction, and the amount rich in alkynes cut is also significantly increased caused by extraction device.Such as
Fruit, which is carried out processing and alkynes is converted into valuable cut, to be used, it will greatly improves the economic valency of this partial material
Value.
At present, a kind of conventional method is front-end hydrogenation, and it is carried out before cracking c_4 enters BEU
Selection hydrogenation, it is therefore an objective to save the second abstraction distillation system, shortcoming is that hydrogenation device for treatment amount is big, and inevitable loss section
Divide butadiene.The technique it is representative be French IFP technologies and the KLP technologies in the U.S..
Another technology is back end hydrogenation, selection hydrogenation is directly carried out to the rich alkynes C 4 materials after Butadiene Extraction, by alkynes
Hydrocarbon is converted into 1,3-butadiene and monoolefine, then returns again to BEU, reclaims butadiene and monoolefine therein.
Because alkynes content is too high in material, and the impurity such as extractant unavoidably taken out of in extractive process, general technology warp
After running after a while, solvent, impurity and a small amount of hydrocarbon polymer in Catalyst Adsorption material catalyst surface deposition,
Catalyst can gradually lose activity, and the life-span is shorter, and the polymerization ratio of unsaturated hydrocarbons in the reaction is more serious, therefore back end hydrogenation skill
Art report is less.
CN1590513A discloses a kind of hydrocarbon material flow selection hydrogenation technique rich in alkynes, the process selection single hop or more
Section fixed bed adiabatic formula bubbling reactor, is equipped with heat exchanger, hydrogenation pressure 1.5-4.0MPa, inlet temperature 10- between reactor
40 DEG C, liquid volume air speed 0.5-5h-1, internal circulating load is 6 with inlet amount weight ratio:1-30:1, alkynes conversion ratio 98% or so, fourth
Diene yield highest 105%.The technique butadiene yield is not high, fails impurity and hydrocarbon polymer in clearly solution material and is being catalyzed
The problem of being deposited in agent.
CN102285860A discloses a kind of selection hydrogenation technique of high alkynes content C4 logistics, the process selection one
Individual or multiple fixed bed adiabatic formula bubbling hydrogenation reactors (I) with pipeloop, then pass through the end without pipeloop
Reactor (II) is held, alkyne concentration is up to 20-50wt%C4 logistics, alkynes content can be down to below 1.5wt% after hydrogenation, can make
For the raw material of BEU.The technique, which fails to solve impurity and polymer to deposit on a catalyst, causes catalyst inactivation
The problem of.
CN103086832A discloses a kind of raising butadiene yield and the butadiene production system of raffinate yield and side
Method.The technique sets front-end hydrogenation reactor before gas-liquid separation device, and back end hydrogenation device is set after extraction device.Cracking mixing
Carbon four after removing part alkynes, carries out gas-liquid separation, liquid phase obtains fourth two into extraction device after extracting rectifying through front-end hydrogenation
Alkene product, high alkynes tail gas caused by extraction device obtain olefin product after back end hydrogenation reacts.After the technique richness alkynes cut fraction hydrogenation
What is mainly obtained is olefin product.
Prior art is not handled the impurity in raw material, fails effectively solve what catalyst longtime running was faced
Activity decay problem.The loss of butadiene is inevitably resulted in hydrogenation process, butadiene yield does not obtain maximum
The raising of degree.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of selection hydrogenation technique of rich alkynes carbon four, not only
The butadiene of extraction device and the rate of recovery of butylene are improved, and effectively extends the service life of hydrogenation catalyst.
The selection hydrogenation technique of rich alkynes carbon four of the present invention, comprises the following steps：
(1) C 4 materials containing alkynes come out from extraction device or tank field, are introduced into rectifying column, by the impurity and carbon of entrainment
Four separate, and carbon four enters return tank, impurity goes fuel tank by bottom of towe extraction by overhead extraction after condensed device condensation；
(2) the hydrogenated raw material pump supercharging of carbon four, a part return to rectifying column, another part and H as phegma2It is mixed into
Enter hydrogenation reactor；
(3) material enters qi leel tank after cooling after being hydrogenated with, and liquid produces through three roads of circulating pump point, and the first via returns to rectifying
Tower charging aperture, the second tunnel return to hydrogenation reactor entrance, and the 3rd tunnel goes out device as hydrogenated products.
Wherein：
Rectification column pressure control is in 0.3-2.0MPa, and at 30-120 DEG C, bottom temperature is controlled in 50- for tower top temperature control
140℃。
Impurity is the heavy things such as light dydrocarbon, extractant and polymer in step (1).
The hydrogenated raw material pump supercharging of carbon four, a part return to rectifying column, backflow volume and tower as phegma in step (2)
The mass ratio for ejecting doses is 0.1-1.0:1.
The hydrogenated raw material pump supercharging of carbon four, another part and H in step (2)2Be mixed into hydrogenation reactor, hydrogen with it is anti-
The mol ratio for answering total alkynes of device entrance is 1.0-4.0：1.
Hydrogenation reactor is adiabatic bubble type fixed bed, and reaction temperature is 10-90 DEG C in hydrogenation reactor, reaction pressure
1.0-4.0MPa liquid volume air speed is 6-30h-1。
Material enters qi leel tank after cooler cools down after being hydrogenated with step (3), and on-condensible gas removes torch.
Material enters qi leel tank after cooler cools down after being hydrogenated with step (3), and it is 0.3- to control qi leel pressure tank
2.0MPa。
The first via returns to rectifying column charging aperture, and the mixing quality ratio with charging is in 0.5-3.0:1；The first via is as dilution
Material returns to rectifying column charging aperture, to reduce the alkyne concentration in tower, controls the matter of alkynes on any one block of column plate in rectifying column
Measure concentration and be less than 15%, reduce alkadienes and polymerization amount of the alkynes in tower.
Second tunnel returns to hydrogenation reactor entrance, is controlled with the rich alkynes quality of material ratio that return tank comes out in 2-30:1,
Second tunnel returns to hydrogenation reactor entrance as hydrogenation reactor recycle stock.
3rd tunnel goes out device as hydrogenated products, and residual acetylenes hydrocarbon mass fraction is less than 0.5%.
Catalyst used in hydrogenation technique includes alumina catalyst support, main active component and helps active component, with catalyst group
Into weight：Main active component 0.15-0.5%, helps active component 0.1-1.0%.Main active component is containing palladium
Bimetallic or multimetal reforming catalyst, palladium content in 0.15-0.5%, help active component for potassium, sodium, lithium, calcium, magnesium, barium, copper,
The mixture of silver, one or both of the compound of gold, zinc, lanthanum, caesium, molybdenum, tungsten, antimony, strontium, arsenic, vanadium and the above；
The specific surface area 25-150m of catalyst2/ g, specific pore volume 0.2-1.0ml/g.
The preparation of catalyst used in the hydrogenation technique of the present invention can use method well known to those skilled in the art to prepare,
It is preferred that prepared using following methods：
First the predecessor of alkali metal or alkaline-earth metal is added in alumina support, can be the carbonate of alkali metal,
Can also be nitrate, through 120-300 DEG C it is dry 3-6h, 800-1200 DEG C roasting 3-14h modified support；Then prepare and live
Property component palladium soluble chloride or the itrated compound aqueous solution, adjust solution ph 1.5-4.0, be immersed in modified aluminium oxide supports
On, through 120-300 DEG C of dry 3-6h, catalyst precarsor is made；Again with the obtained aqueous solution for helping active component, help active metal can
To be the carbonate or nitrate of the metal, as long as water-soluble, its amount reaches the content requirement of needs, leaching
Stain is on catalyst precarsor.Through 120-300 DEG C of dry 3-6h, 300-600 DEG C of roasting 3-6h, finished product catalyst.
The present invention is selected the residual fraction rich in alkynes of the C 4 materials rich in alkynes or BEU
Hydrogenation is selected, alkynes is converted into monoolefine and butadiene, returns again to BEU recovery butadiene and monoolefine.This work
The content of alkynes is higher in skill raw material, but after the operation of hydrogenation plant long period, the activity of hydrocatalyst used does not reduce,
Active component palladium is not lost in substantially, and the content of alkadienes and alkyne polymer is extremely low in the product after hydrogenation, and alkynes total amount is low
In 0.5%.
In summary, the present invention has advantages below：
(1) rich alkynes C 4 materials are introduced into rectifying column, can be by the light dydrocarbon remained in C 4 materials, extractant and polymer
Removed by bottom of towe, make the material into hydrogenation reactor that there is relatively low impurity content, ensure that the longtime running of catalyst.
(2) partial material after being hydrogenated with returns to rectifying column, reduces the concentration of alkynes and alkadienes in rectifying column, reduces
The formation of polymer, loss of material is reduced, while reduce the alkynes content into hydrogenation reactor.
(3) partial hydrogenation product is back to hydrogenation reactor entrance, reduces the alkynes content into reactor, reduces
Alkadienes and polymer growing amount of the alkynes in reactor.
(4) partial material after being hydrogenated with returns to rectifying column, by the alkynes in hydrogenation process and the polymer of alkadienes generation
Part is removed by rectifying column, and the amount of polymers in hydrogenation reaction system can be maintained to relatively low level, ensure that catalyst
Longtime running.
(5) catalyst selected of the present invention be bimetallic or multimetal reforming catalyst, between metal, between metal and carrier by force
Strong reciprocation inhibits absorption of the alkynes to palladium, effectively inhibits the loss of palladium, extends the life-span of catalyst.
(6) catalyst selected is changed by the way that the predecessor of alkali metal or alkaline-earth metal is added in alumina support
The surface acidity of catalyst, reduce the growing amount of polymer on a catalyst；Meanwhile the bimetallic or multimetal reforming catalyst of selection
Metal composites have higher butadiene selective, can effectively improve the butadiene yield in hydrogenation products.
(7) present invention solve due to alkynes in rich alkynes raw material and diene hydrocarbon content is higher and raw material in easily entrainment it is a small amount of
A kind of aggregation problem of alkadienes and alkynes in catalyst easy in inactivation and course of reaction caused by extractant, there is provided fourth two
The selection hydrogenation technique of the rich alkynes C 4 materials of alkene extraction device discharge, not only increase the butadiene and butylene of extraction device
The rate of recovery, and effectively extend the service life of hydrogenation catalyst.
Brief description of the drawings
Fig. 1 is the process chart of the selection hydrogenation technique of rich alkynes carbon four of the present invention；
In figure：1st, rectifying column；2nd, condenser；3rd, return tank；4th, it is hydrogenated with feed pump；5th, hydrogenation reactor；6th, cooler；7、
Qi leel tank；8th, circulating pump；9th, fuel tank.
Embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
Using hydrogenation technique chosen below：
(1) C 4 materials containing alkynes come out from extraction device or tank field, are introduced into rectifying column, and Rectification column pressure control exists
0.5MPa, at 59 DEG C, bottom temperature is controlled at 120 DEG C, the impurity of entrainment and carbon four is separated, carbon four is by tower for tower top temperature control
Top extraction, enters return tank after condensed device condensation, impurity goes fuel tank by bottom of towe extraction；
(2) the hydrogenated raw material pump supercharging of carbon four, a part return to rectifying column as phegma, and backflow volume discharges with tower top
The mass ratio of amount is 0.5:1, another part and H2It is mixed into hydrogenation reactor, total alkynes of hydrogen and reactor inlet
Mol ratio is 2.0：1；Hydrogenation reactor is adiabatic bubble type fixed bed, 30 DEG C of bed inlet, pressure 1.5MPa, high alkynes raw material
Liquid air speed is 1.0h-1, plus internal circulating load, liquid air speed is in 15h-1, recycle ratio 14:1, the mol ratio of hydrogen and alkynes is
1.5:1；
(3) material enters qi leel tank after cooler cools down after being hydrogenated with, and it is 0.4MPa to control qi leel pressure tank；On-condensible gas
Torch is removed, liquid produces through three roads of circulating pump point, and the first via returns to rectifying column charging aperture, and the mixing quality ratio with charging is 1:
1, rectifier column reflux ratio is 0.2；The first via returns to rectifying column charging aperture as diluted material, to reduce the alkyne concentration in tower,
The mass concentration of alkynes on any one block of column plate in rectifying column is controlled to be less than 15%, reduction alkadienes polymerizeing in tower with alkynes
Amount；Second tunnel returns to hydrogenation reactor entrance, is controlled with the rich alkynes quality of material ratio that return tank comes out 14:1, the second tunnel is made
Hydrogenation reactor entrance is returned for hydrogenation reactor recycle stock；3rd tunnel goes out device, residual acetylenes hydrocarbonaceous amount as hydrogenated products
Fraction is less than 0.5%.
Alkyne hydrogenation reactor loads palladium copper potassium multimetal reforming catalyst, and its content is palladium 0.2wt%, copper 13.0wt%, potassium
1.0wt%, catalyst carrier are aluminum oxide.
Table 1 lists the front and rear composition of reaction.
Table 1 reacts front and rear material composition
It is also few in addition to vinylacetylene is hydrogenated generation 1,3-butadiene because internal circulating load is larger in hydrogenation process
Amount butadiene is hydrogenated generation 1- butylene, and butine is hydrogenated to 1- butylene.A small amount of 1- butylene tautomerizes to 2- butylene.Transported by 200h
Turn, palladium copper potassium multimetal reforming catalyst activity does not have significant change, and solvent residues amount is less than 1ppm, and the growing amount of polymer does not have yet
Significant change.Butadiene yield is 155%, alkynes conversion ratio more than 98%.
Embodiment 2
The present embodiment charging is the raw material rich in alkynes, and for raw material with embodiment 1, it is more that alkyne hydrogenation reactor loads palladium lead potassium
Metallic catalyst, its content are palladium 0.3wt%, lead 0.5wt%, potassium 0.5wt%, and catalyst carrier is aluminum oxide, hydrogenation reaction
Device is insulation fix bed reactor, and 30 DEG C of bed inlet, pressure 1.5MPa, high alkynes raw material liq air speed is 1.0h-1, recycle ratio
For 14:1, the mol ratio of hydrogen and alkynes is 1.2:1, return to the first via hydrogenation material of rectifying column and enter the ratio of tower height alkynes material
It is worth for 2:1, rectifier column reflux ratio is 0.2.Table 2 lists the front and rear composition of reaction.
Table 2 reacts front and rear material composition
From table 2, operated by 200h, palladium lead potassium multimetal reforming catalyst activity does not have significant change, solvent residues amount
Less than 1ppm, the growing amount of polymer does not have significant change yet.Butadiene yield is 171%, alkynes conversion ratio more than 97%.
Comparative example
With embodiment 1, alkyne hydrogenation reactor loads the more metals of palladium copper potassium same as Example 1 and urged this comparative example raw material
Agent, hydrogenation reactor are insulation fix bed reactor, 30 DEG C of bed inlet, pressure 1.5MPa, high alkynes raw material liq air speed
For 1.0h-1, recycle ratio 14:1, the mol ratio of hydrogen and alkynes is 1.5:1, hydrogenation products do not return to rectifying column and enter tower height alkynes
Material mixes, and rectifier column reflux ratio is 0.2.Table 3 lists the front and rear composition of reaction.
Table 3 reacts front and rear material composition
From table 3, without rectifying column removing impurities matter, solvent residues amount is not reduced, and the growing amount of polymer substantially increases
Add.Polymer gum level after 100h in material is operated i.e. in 0.18wt%, under palladium copper potassium multimetal reforming catalyst activity is obvious
Drop, less than embodiment 1, butadiene yield and alkynes conversion ratio substantially reduce.
Claims (7)
- A kind of 1. selection hydrogenation technique of rich alkynes carbon four, it is characterised in that：Comprise the following steps：（1）C 4 materials containing alkynes are come out from extraction device or tank field, are introduced into rectifying column, and the impurity of entrainment and carbon four are divided Open, carbon four enters return tank, impurity goes fuel tank by bottom of towe extraction by overhead extraction after condensed device condensation；（2）The hydrogenated raw material pump supercharging of carbon four, a part return to rectifying column, another part and H as phegma2It is mixed into and adds Hydrogen reactor；（3）Material enters qi leel tank after cooling after hydrogenation, and liquid produces through three roads of circulating pump point, and the first via returns to rectifying column and entered Material mouth, the second tunnel return to hydrogenation reactor entrance, and the 3rd tunnel goes out device as hydrogenated products；Step（2）The middle hydrogenated raw material pump supercharging of carbon four, a part return to rectifying column as phegma, and backflow volume goes out with tower top The mass ratio of doses is 0.1-1.0:1；The first via returns to rectifying column charging aperture, and the mixing quality ratio with charging is in 0.5-3.0:1；Second tunnel returns to hydrogenation reactor entrance, is controlled with the rich alkynes quality of material ratio that return tank comes out in 2-30:1.
- 2. the selection hydrogenation technique of rich alkynes carbon four according to claim 1, it is characterised in that：Rectification column pressure control exists 0.3-2.0MPa, at 30-120 DEG C, bottom temperature is controlled at 50-140 DEG C for tower top temperature control.
- 3. the selection hydrogenation technique of rich alkynes carbon four according to claim 1, it is characterised in that：Step（2）Middle carbon four is through adding Hydrogen feedstock pump is pressurized, another part and H2It is mixed into hydrogenation reactor, the mol ratio of total alkynes of hydrogen and reactor inlet For 1.0-4.0：1.
- 4. the selection hydrogenation technique of rich alkynes carbon four according to claim 1, it is characterised in that：Hydrogenation reactor is lagged drum Bubble fixed bed, reaction temperature is 10-90 DEG C, reaction pressure 1.0-4.0MPa in hydrogenation reactor, and liquid volume air speed is 6- 30 h-1。
- 5. the selection hydrogenation technique of rich alkynes carbon four according to claim 1, it is characterised in that：Step（3）Thing after middle hydrogenation Material enters qi leel tank after cooler cools down, and it is 0.3-2.0MPa to control qi leel pressure tank.
- 6. the selection hydrogenation technique of rich alkynes carbon four according to claim 1, it is characterised in that：Catalysis used in hydrogenation technique Agent includes alumina catalyst support, main active component and helps active component, and main active component is the bimetallic containing palladium or more metal catalytics Agent, active component is helped as potassium, sodium, lithium, calcium, magnesium, barium, copper, silver, gold, zinc, lanthanum, caesium, molybdenum, tungsten, antimony, strontium, arsenic, the compound of vanadium One or both of and the above mixture.
- 7. the selection hydrogenation technique of rich alkynes carbon four according to claim 1, it is characterised in that：The specific surface area of catalyst 25-150m2/ g, specific pore volume 0.2-1.0ml/g.
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| CN108779045A (en) * | 2016-03-31 | 2018-11-09 | 日本瑞翁株式会社 | Method for hydrogenation |
| CN109096031B (en) * | 2017-06-21 | 2022-07-12 | 中国石油化工股份有限公司 | Method for producing isopropyl benzene |
| CN109096030A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The synthetic method of isopropylbenzene |
| CN107382652A (en) * | 2017-08-01 | 2017-11-24 | 山东滨庆新能源开发有限公司 | Rich alkynes carbon four decolourizes, removing impurities matter technique |
| 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 |
| CN110002938A (en) * | 2018-01-05 | 2019-07-12 | 中国石油化工股份有限公司 | A kind of method of C 4 fraction selective hydrogenation |
| CN114478176B (en) * | 2020-10-26 | 2024-07-02 | 中国石油化工股份有限公司 | Butadiene extraction tail gas selective hydrogenation device and selective hydrogenation method |
| CN114478164B (en) * | 2020-10-26 | 2023-09-08 | 中国石油化工股份有限公司 | Butadiene extraction tail gas selective hydrogenation device and selective hydrogenation method |
| CN113236974B (en) * | 2021-04-28 | 2022-05-24 | 新疆天利高新石化股份有限公司 | Safe pipeline conveying method for high-concentration vinyl acetylene-rich alkyne carbon four |
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