CN103768896B - A kind of BEU exhaust gas recovery system and method - Google Patents
A kind of BEU exhaust gas recovery system and method Download PDFInfo
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Abstract
The invention discloses a kind of BEU exhaust gas recovery system and method.System includes: absorption tower, I section of hydrogenation reactor and Analytic Tower, top, absorption tower is provided with absorbent entrance, bottom, absorption tower is provided with butadiene gas inlet, after absorption tower outlet at bottom connects pump, is connected bottom I section of hydrogenation reactor after merging with hydrogen gas lines；I section of hydrogenation reactor top exit connects in the middle part of Analytic Tower, connects the absorbent entrance on absorption tower bottom Analytic Tower, and Analytic Tower top connects out-of-bounds.Method includes: butadiene tail gas is through absorption, I section of hydrogenation reaction, parsing.The present invention can the recycling of application solutions butadiene tail gas.
Description
Technical field
The present invention relates to the comprehensive utilization of carbon four resource, furtherly, relate to a kind of BEU exhaust gas recovery system and method.
Background technology
The substantial amounts of mixing carbon four of cracking petroleum hydrocarbon vapor ethylene unit by-product, containing the 1 of 40-60wt% in cracking mixing C-4-fraction, 3-butadiene, the allylene (MA) of 0.5-2.0wt%, ethyl acetylene (EA) and vinylacetylene (VA), all the other components are butane, butylene and a small amount of 1，2-butadiene, carbon three, carbon five.The mode of industrial usual employing two-stage extraction rectification extracts butadiene therein, but also produces the waste gas containing a large amount of high unsaturated hydrocarbons simultaneously, is commonly called as butadiene tail gas.In butadiene tail gas, alkyne concentration is higher, is generally higher than 20wt%, the highest more than 50wt%, and mainly vinylacetylene, also includes 20-60wt%1,3-butadiene simultaneously.Except the butadiene tail gas pressure adopting N-Methyl pyrrolidone (NMP) extraction process to produce is high, BASF AG has developed beyond the method for recycling, most butadiene tail gas containing high unsaturated C_4 hydrocarbon adopting dimethylformamide (DMF) and acetonitrile (ACN) method to produce butadiene generation are relatively low because of pressure, there is no effective Application way at present, torch burning disposal can only be sent.Owing to high concentration carbon four alkynes has the danger of polymerization blast, consider for safety factors, it is necessary to torch just can be sent after being diluted with the raffinate containing butane, butylene to process, thus cause waste and the environmental pollution of C_4 hydrocarbon.Recently as being continuously increased of the steam cracking degree of depth, in cracking mixing C-4-fraction, alkynes content increases therewith, and the produced tail gas rich in high alkynes of BEU is also significantly increased accordingly, causes the load of BEU to increase, energy consumption rises, and danger coefficient increases.If this strand of waste gas is recycled, alkynes therein, diolefin are hydroconverted into valuable butylene or butane, will can reduce butadiene production cost, be greatly improved the economic benefit of enterprise.
The hydrotreatment of alkynes in mixing C-4-fraction is divided into both front and back, and it, with the KLP technology of the U.S. for representative, is namely carried out hydrotreatment before C-4-fraction enters BEU, does not repeat here by front-end hydrogenation；High alkynes tail gas produced by BEU is carried out hydrotreatment and is referred to as back end hydrogenation, prior art is typically with increasing the mode of Matter Transfer ratio and is reduced to by alkyne concentration in the scope that reaction allows, enter back into fixed bed hydrogenation and be converted into butadiene or butylene, be then back to BEU.Owing in butadiene tail gas, alkynes and diolefin are dense, polyreaction is serious, so general back end hydrogenation catalyst life is very short, operating cost is higher.
Chinese patent CN1590513 discloses a kind of method BEU being made directly rich in the residue of alkynes and selecting hydrogenation, by the fixed bed adiabatic hydrogenation reactor with circulating device, adopt palladium copper bi-metal or palladium copper silver polymetallic catalyst, at 1.5-4.0MPa, reaction entrance 10-40 DEG C, liquid volume air speed is 0.5-5h-1Carrying out hydrogenation reaction under condition, after hydrogenation, material returns BEU.
Chinese patent CN101434508 discloses a kind of Application way for the rich alkynes residue after Butadiene Extraction, adopts palladium system Cu-contained catalyst, at reaction entrance 30-70 DEG C, pressure 1.0-2.5MPa, liquid air speed 10-20h-1Carry out hydrogenation reaction under condition, be characterized in adopting single hop or multistage isotherm formula bubbling bed reactor, shift a large amount of reaction heat in time, it is suppressed that the generation of polymer, extend the service life of catalyst.
Although above-mentioned prior art discloses the method for hydrotreating of butadiene tail gas, but to put into practice the method, still have following obstacle:
1. the liquefaction of butadiene tail gas and reactor feed problem.Owing to being hydrogenated to liquid phase reactor, pressure is within the scope of 1.0-3.0MPa, and butadiene tail gas is gas phase, and pressure is close to normal pressure, owing in butadiene tail gas, alkyne concentration is high, it is easy to occur polymerization to set off an explosion, and the mode of routine therefore can not be adopted to liquefy, boost.How the phase feed containing high alkynes being liquefied, boost, being then fed into reactor is the key point realizing butadiene waste gas utilization.
2. safety operation problem.Owing to butadiene tail gas containing the vinylacetylene of high concentration, when pressure, concentration, variations in temperature, it is susceptible to polyreaction, sets off an explosion, how to ensure to be liquefied by material under the premise of safety, boosting is the major issue first having in butadiene waste gas utilization process especially consider.
The hydrogenation reaction of carbon four alkynes and diolefin is strong exothermal reaction, course of reaction is released substantial amounts of heat and can cause that reaction temperature rises suddenly, additionally, the matter-poles such as carbon four alkynes and diolefin are unstable, on a catalyst it also occur that polyreaction, the polymer produced can be deposited in catalyst surface, causes catalysqt deactivation；The raising of the thermally-induced reaction temperature of hydrogenation reaction, the lifting of reaction temperature can further speed up again the speed of polymer deposition, so this with high concentration alkynes be raw material hydrogenation technique operation there is potential unsafe factor.Develop highly active hydrogenation catalyst no doubt important, but in butadiene waste gas utilization process, select suitable hydrogenation technique, to resolve safely above-mentioned problem on obstacle even more important.
Summary of the invention
The problem on obstacle that aspects such as being difficult to liquefaction, boosting and the safety operation of low pressure height alkynes tail gas reclaimed produced by butadiene exists is produced for solving DMF, ACN method in prior art, the present invention provides a kind of recovery system and the method for BEU tail gas, it is possible to the recycling of application solutions butadiene tail gas.
An object of the present invention is to provide a kind of BEU exhaust gas recovery system.
Including: absorption tower, I section of hydrogenation reactor and Analytic Tower.
Top, absorption tower is provided with absorbent entrance, and bottom, absorption tower is provided with butadiene gas inlet, and absorption tower outlet at bottom connects booster, allocates corresponding hydrogen into and be connected with bottom I section of hydrogenation reactor after pump；I section of hydrogenation reactor top exit connects in the middle part of Analytic Tower, connects the absorbent entrance on absorption tower bottom Analytic Tower, and Analytic Tower top connects out-of-bounds.
Described system also includes II section of hydrogenation reactor.
Described Analytic Tower top exit pipeline is connected bottom II section of hydrogenation reactor after merging with hydrogen gas lines, and II section of hydrogenation reactor top connects out-of-bounds.
Can be preferred:
Described II section of hydrogenation reactor is the beds being arranged on Analytic Tower internal upper part, namely resolves catalytic integration；It is provided with hydrogen inlet between described Analytic Tower upper catalyst bed layer and I section of hydrogenation reactor bottoms material entrance；Described Analytic Tower top connects return tank, two outlets bottom return tank, and an outlet connects the beds top resolving catalytic tower；Another outlet connects out-of-bounds.
The two of the purpose of the present invention are to provide a kind of BEU method for recovering tail gas.
Including: butadiene tail gas is through absorption, I section of hydrogenation reaction and parsing.
Specifically can comprise the following steps that
(1) absorb: butadiene tail gas is absorbed by absorbent in absorption tower, absorb tower top depletion of QI and discharge mutually；Described absorbent is that boiling point is higher than C-4-fraction and keeps the solvent of inertia in hydrogenation reaction；
(2) I section of hydrogenation: liquid phase boosting at the bottom of absorbing tower enters I section of hydrogenation reactor after allocating hydrogen into, carries out hydrogenation reaction；
(3) resolve: I section of hydrogenation reactor outlet material enters Analytic Tower, resolve outside tower top production streaming out-of-bounds, resolve tower reactor liquid phase material and recycle as absorbent return absorption tower.
Described recovery method also includes II section of hydrogenation reaction,
Specifically can comprise the following steps that
(1) absorb: butadiene tail gas is absorbed by absorbent in absorption tower, absorb tower top depletion of QI and discharge mutually；Described absorbent is that boiling point is higher than C-4-fraction and keeps the solvent of inertia in hydrogenation reaction；
(2) I section of hydrogenation: liquid phase boosting at the bottom of absorbing tower enters I section of hydrogenation reactor after allocating hydrogen into, carries out hydrogenation reaction；
(3) resolving: I section of hydrogenation reactor outlet material enters Analytic Tower, the C_4 hydrocarbon resolving overhead extraction enters II section of hydrogenation reactor；Resolve tower reactor liquid phase material and return absorption tower recycling as absorbent；
(4) II section of hydrogenation: the C_4 hydrocarbon after I section of hydrogenation and parsing proceeds hydrogenation reaction, the product after II section of hydrogenation reactor top extraction hydrogenation.
When II section of hydrogenation reactor is the beds being arranged on Analytic Tower internal upper part, following steps can be adopted:
(5) enter in the middle part of I section of hydrogenation reactor outlet material and hydrogen difference analytically tower, C_4 hydrocarbon and hydrogen are upwardly through catalytic bed, wherein carbon four alkynes and diolefin hydrogenation generation butylene or butane distillate from tower top, return tank is entered through supercooling, a part is back to catalytic bed top, all the other are as product extraction, and the raw material as downstream unit uses；Tower reactor extraction absorbent returns to absorption tower and recycles.
In practical operation, one-stage hydrogenation or secondary hydrogenation reaction can be carried out according to the different choice of final goal product.
The present invention specifically can be by the following technical solutions:
(1) absorb: butadiene height alkynes tail gas is absorbed by absorbent in absorption tower, absorb tower top depletion of QI and discharge mutually；
(2) I section of hydrogenation: the boosted pump boosting of liquid phase at the bottom of absorbing tower, enters I section of hydrogenation reactor after allocating the hydrogen of respective amount into, and as required, carbon four unsaturated hydrocarbons being dissolved in absorbent carries out selective hydrogenation reaction；
(3) resolve: I section of hydrogenation reactor outlet material enters Analytic Tower, resolve the C_4 hydrocarbon after overhead extraction hydrogenation and a small amount of fixed gas.The according to target requirement of product, the C_4 hydrocarbon after parsing enters II section of hydrogenation, it is also possible to directly extraction uses as the raw material of downstream unit.Tower bottoms phase materials returns as absorbent inhales tower recycling；
(4) II section of hydrogenation: the according to target requirement of product, the C_4 hydrocarbon after I section of hydrogenation and parsing proceeds hydrogenation reaction, is completely converted into butane to unsaturated hydrocarbons, and product returns pyrolysis furnace and makes the raw material of cracking of ethylene.
When adopting parsing hydrogenation integral process flow process,
Enter in the middle part of (5) I sections of hydrogenation reactor outlet materials and hydrogen difference analytically tower, C_4 hydrocarbon and hydrogen are upwardly through catalytic bed, wherein carbon four alkynes and diolefin hydrogenation generation butylene or butane distillate from tower top, return tank is entered through supercooling, a part is back to catalytic bed top, all the other are as product extraction, and the raw material as downstream unit uses；Solvent is downwardly into tower reactor, returns to absorption tower as absorbent and recycles.
BEU exhaust gas recovery system, the mode of hydrogenation, parsing, catalysis three-in-one integrated can also be adopted, collect I section of hydrogenation reactor, resolve and II section of hydrogenation catalyst is in a tower, I section of hydrogenation reactor under, resolving Duan Zhong, II section of hydrogenation catalyst section is in upper form.
The process flow diagram of the present invention is shown in Fig. 1 and Fig. 2.
Described step (1) in, the composition of butadiene tail gas includes: butane 0-5wt%, butylene 0-15wt%, butadiene 20-60wt%, allylene, ethyl acetylene and vinylacetylene 20-55wt%.
Described step (1) in, adopt absorbent absorb mode, the allylene in high unsaturated C_4 hydrocarbon, ethyl acetylene and vinylacetylene concentration are reduced in the margin of safety of below 20wt%, make C_4 hydrocarbon be dissolved in absorbent.
Described step (1) in, the boiling point of absorbent should be higher than that C-4-fraction, and under hydrogenation reaction temperature, pressure, catalyst, hydrogen existent condition, keep inertia, preferred solvent includes one or more mixture in C 5 alkane, benzene,toluene,xylene, N-Methyl pyrrolidone, DMF, acetonitrile, hexane, hexamethylene, hexahydrotoluene, Aromatic raffinate.More preferably benzene,toluene,xylene and N-Methyl pyrrolidone.One of effect of absorbent is the C-4-fraction of solution absorption height alkynes, it is ensured that it enters the safety in the operating process of reactor in boosting；Its two reaction heat released when being be hydrogenated with high unsaturated carbon four hydrocarbon, regulates the temperature rise of catalytic bed.
Described step (1) in, absorption tower tower top temperature is room temperature, pressure 0.1-0.2MPa(absolute pressure), number of theoretical plate is 2-10 block, the flow-rate ratio of absorbent and butadiene tail gas is 0.5-40, and concrete numerical value determines according to alkyne concentration in tail gas, to ensure that in absorption tower reactor liquid phase, alkynes content is less than 20wt%.
Described step (2) in, owing to high unsaturated C_4 hydrocarbon is dissolved in absorbent, within its alkyne concentration is reduced to margin of safety, it is possible to adopt conventional mode booster to boost, then enter reactor smoothly.
Described step (2) in, I section of hydrogenation reaction is selective hydrogenation process, it is possible to be vinylacetylene hydrogenation can be converted into butadiene, product through resolve return BEU make raw material；Can also be that vinylacetylene, ethyl acetylene and 1,3 butadiene hydrogenation are converted into butylene, as the raw material of downstream unit after product parsing.
Described step (2) in, selective hydrogenation catalyst can be selected for known in prior art in catalyst, such as CN1952061, CN101850250, CN101844081, CN1466486, CN101428228, selective hydrogenation catalyst disclosed in CN1321544 and CN102285859, selective hydrogenation catalyst disclosed in preferred CN1321544 and CN102285859, catalyst disclosed in preferred CN1321544 comprises the Cu of 1-30wt%, the Pd of 0.001-5wt%, the Bi of 0.001-6wt%, Zr, Pb, Ag, one or more metal promoters in Pt, load is selected from aluminium oxide, on at least one carrier in silicon oxide or titanium oxide.Catalyst disclosed in preferred CN102285859 can also be comprise alumina catalyst support containing palladium-silver bi-component or palladium-silver multicomponent catalyst.
Described step (2) in, the process conditions of I section of hydrogenation reaction can adopt common process conditions in prior art, in the present invention, it may be preferable to: reactor inlet temperature 20-50 DEG C, reaction pressure 1.0-3.0MPa, liquid volume air speed 2-30h-1, hydrogen alkynes compares 1.0-6.0mol.
Described step (3) in, the operation pressure of Analytic Tower lower than hydrogenation reaction pressure, will parse through the C_4 hydrocarbon of I section of hydrogenation in absorbent.Tower top adopts fractional distilling tube, and the C_4 hydrocarbon condensed out can enter II section of hydrogenation reactor, it is also possible to directly extraction, returns BEU or the direct extraction raw material as downstream unit.Tower top also can discharge the fixed gas that small part contains hydrogen, methane etc..The liquid phase of tower reactor extraction returns to absorption tower and recycles as absorbent.
In described step (3), Analytic Tower number of theoretical plate is 10-35 block, operates pressure 0.2-3.5MPa(absolute pressure), tower top temperature 35-55 DEG C, bottom temperature is 50-300 DEG C, reflux ratio 0.1-40.
Described step (4) in, through I section of hydrogenation and after parsing from absorbent, carbon four unsaturated hydrocarbons is further continued for hydrogenation further makes it be completely converted into butane, and product returns pyrolysis furnace and makes the raw material of cracking of ethylene；Can also being only hydrogenated with to butylene, the raw material as downstream unit uses.
Described step (4) in, II section of hydrogenation reactor used catalyst can be selected for catalyst commonly known in the art, such as, catalyst disclosed in CN1952061, CN101850250, CN101844081, CN1466486, CN101428228, CN1321544, CN102285859, CN101433853, CN101434508, CN1590513, CN1508103, it is preferable that the hydrogenation catalyst disclosed in CN1508103, CN1321544 and CN102285859.
Hydrogenation catalyst disclosed in preferred CN1508103, its main active component and help active component to be enriched in the surface of alumina catalyst support, comprise Pd or Pt of 0.01-1.0wt%, at least one in Cu, Ag, Au, Pb, Ni, Co, Mn of 0.001-1.0wt%, catalyst disclosed in preferred CN1321544 comprises the Cu of 1-30wt%, the Pd of 0.001-5wt%, one or more metal promoters in Bi, Zr, Pb, Ag, Pt of 0.001-6wt%, load is at least one carrier in aluminium oxide, silicon oxide or titanium oxide.Catalyst disclosed in preferred CN102285859 can also be comprise alumina catalyst support containing palladium-silver bi-component or palladium-silver multicomponent catalyst.
Described step (4) in, II section of hydrogenation reaction can adopt common process conditions in prior art, in the present invention preferably: react inlet temperature 20-60 DEG C, pressure 1.0-3.0MPa, liquid air speed 2-30h-1。
When adopting parsing catalytic integration technological process,
Mixed material after step (1) and (2) is directly entered step (5), in described step (5), resolves catalytic integration one tower of composition, and bottom is for resolving section, and top is catalytic section.In described step (5), resolve the operation pressure of catalytic tower lower than I section of hydrogenation reaction pressure, enter in the middle part of absorbent and the mixed material analytically section of C_4 hydrocarbon, hydrogen analytically section top enters, common upwardly through catalytic bed, reverse with catalytic bed upper return carbon four contact, carbon four alkynes and diolefin are hydrogenated with generation butylene in the process or butane distillates from tower top, return tank is entered through supercooling, a part returns to catalytic bed top as backflow, all the other are as product extraction, and the raw material as downstream unit uses.
In described step (5), the mixed material of absorbent and C_4 hydrocarbon isolates absorbent through resolving section, is downwardly into tower reactor, returns to absorption tower and recycle as absorbent after extraction.
In described step (5), Analytic Tower number of theoretical plate is 10-35 block, operates pressure 0.2-3.5MPa(absolute pressure), tower top temperature 35-55 DEG C, bottom temperature is 50-300 DEG C, reflux ratio 0.1-40.
In described step (5), the hydrogenation catalyst of catalytic section can be selected for catalyst commonly known in the art, such as, catalyst disclosed in CN1590353, CN1552816, CN101062483, CN102285859, it is preferable that the hydrogenation catalyst disclosed in CN102285859.Preferred catalyst mainly comprises one or more in palladium, rhodium, platinum, nickel, auxiliary agent one or more things mixed above in copper, silver, gold, zinc, stannum, bismuth, molybdenum, zirconium, rare earth element, also comprises the elements such as a small amount of potassium, sodium, calcium, magnesium, barium, fluorine.Preferred palladium-silver dual-component catalyst, or palladium-silver multicomponent catalyst, carrier is aluminium oxide.
In described step (5), the process conditions of II section of hydrogenation are preferably: react inlet temperature 30-80 DEG C, pressure 0.6-4.0MPa, liquid air speed 0.2-50h-1。
The mode of hydrogenation, parsing, catalysis three-in-one integrated can also be adopted, collect I section of hydrogenation reactor, resolve with II section of hydrogenation catalyst in a tower, I section of hydrogenation reactor under, parsing Duan Zhong, II section of hydrogenation catalyst section is upper.
Accompanying drawing explanation
Fig. 1 is the BEU exhaust gas recovery system schematic diagram of embodiment 1,2,3
Fig. 2 is the BEU exhaust gas recovery system schematic diagram of embodiment 4
1. butadiene tail gas, 2. absorbent, 3. blended liquid phase, 4. hydrogen, 5. I section of hydrogenated products, 6. II section of hydrogenated products (aforementioned serial no is also used for the logistics number in subordinate list).7. absorption tower, 8. pump, 9. I section of hydrogenation reactor, 10. Analytic Tower, 11. II sections of hydrogenation reactors, 12 return tanks
Detailed description of the invention
Below in conjunction with embodiment, further illustrate the present invention.But the present invention is not limited to embodiment, the authority of the present invention is with claim clause for foundation.
Embodiment 1:
A kind of BEU exhaust gas recovery system.Including: 7, I section of absorption tower hydrogenation reactor 9, Analytic Tower 10.
Top, absorption tower 7 is provided with absorbent entrance, and bottom, absorption tower is provided with butadiene gas inlet, and absorption tower outlet at bottom is connected after converging with hydrogen bottom I section of hydrogenation reactor after connecting pump 8；I section of hydrogenation reactor 9 top exit connects in the middle part of Analytic Tower 10, the absorbent entrance on absorption tower is connected bottom Analytic Tower 10, Analytic Tower 10 top is connected after converging with hydrogen gas lines bottom II section of hydrogenation reactor 11, and II section of cooled connection in hydrogenation reactor 11 top is out-of-bounds.
1. absorb: the butadiene tail gas 1(from BEU is mainly composed of: butylene 4.86wt%, butadiene 42.48wt%, alkynes 50.99wt%, flow 200kg/h, pressure 0.05MPa, butadiene tail gas enters from bottom, absorption tower 7, absorbent 2 is toluene, enter from top, absorption tower, flow 4000kg/h, pressure 0.5MPa, butadiene tail gas 1 contacts absorption with absorbent 2 in absorption tower, absorption tower number of theoretical plate 3 pieces, tower top temperature 42 DEG C, tower top pressure 0.1MPa.Tower top is without gas phase extraction, and in tower reactor liquid phase, ethyl acetylene and vinylacetylene content are 2.43%, as the charging of reactor 9 after the boosted pump boosting of tower reactor liquid；
2. I section of hydrogenation reaction: the boosted pump of liquid from absorption tower tower reactor boosts to 2.2MPa(logistics number 3), allocate the charging as I section of hydrogenation reactor 9 after hydrogen 4 into, I section of filled catalyst of hydrogenation reactor is prepared according to the method provided in CN1321544.Hydrogenation conditions is: reaction inlet temperature 40 DEG C, pressure 2.2MPa, liquid volume air speed 15h-1, hydrogen/alkynes mol ratio is 1.2, and vinylacetylene becomes butadiene by hydro-conversion, and I section of reactor outlet material part circulates to I section of reactor inlet place, and all the other are as the charging of Analytic Tower 10；
3. resolve: enter Analytic Tower 10, Analytic Tower number of theoretical plate 20 pieces, tower top temperature 36.5 DEG C, tower top pressure 1.5MPa, bottom temperature 255.5 DEG C from I section of reactor 9 outlet material.Tower top material (logistics number 5) contains the butadiene of 53.33wt%, it is possible to returning butadiene product equipment entrance and make the raw material of two stage extraction, tower bottoms cooled water-cooled but Posterior circle uses to absorption tower as absorbent.Main streams weight composition (wt%) is in Table 1.
Table 1
| 1 | 2 | 3 | 5 | |
| Hydrogen | 0 | 0 | 0 | 0.11 |
| Methane | 0 | 0 | 0 | 1.10 |
| Normal butane | 0.12 | 0 | 0.0057 | 0.23 |
| Iso-butane | 0.05 | 0 | 0.0024 | 0.05 |
| 1-butylene | 1.33 | 0 | 0.0633 | 25.33 |
| Isobutene. | 0.19 | 0 | 0.0091 | 0.19 |
| Cis-2-butene | 3.26 | 0 | 0.1550 | 7.15 |
| Trans-2-butene | 0.08 | 0 | 0.0038 | 7.88 |
| 1,3-butadiene | 41.12 | 0 | 1.9581 | 53.33 |
| 1,2-butadiene | 1.36 | 0 | 0.0648 | 1.35 |
| Allylene | 0.01 | 0 | 0.0005 | 0.00 |
| Ethyl acetylene | 9.76 | 0 | 0.4650 | 0.05 |
| Vinylacetylene | 41.22 | 0 | 1.9629 | 0.00 |
| Carbon five | 1.48 | 0 | 0.0705 | 1.34 |
| Toluene | 0 | 100 | 95.2381 | 1.89 |
Effect: through one-stage hydrogenation, as the butadiene containing 53.33wt% in the logistics number 5 of product extraction, it is possible to returning butadiene product equipment entrance and make raw material, improve the yield of butadiene, butadiene tail gas is thus utilized effectively.
Embodiment 2:
A kind of BEU exhaust gas recovery system.Including: 7, I section of absorption tower hydrogenation reactor 9, Analytic Tower 10.
Top, absorption tower 7 is provided with absorbent entrance, and bottom, absorption tower is provided with butadiene gas inlet, and absorption tower outlet at bottom is connected after converging with hydrogen bottom I section of hydrogenation reactor after connecting pump 8；I section of hydrogenation reactor 9 top exit connects in the middle part of Analytic Tower 10, the absorbent entrance on absorption tower is connected bottom Analytic Tower 10, Analytic Tower 10 top is connected after converging with hydrogen gas lines bottom II section of hydrogenation reactor 11, and II section of cooled connection in hydrogenation reactor 11 top is out-of-bounds.
1. absorb: the butadiene tail gas 1(from BEU is mainly composed of: butylene 4.86wt%, butadiene 42.48wt%, alkynes 50.99wt%, flow 200kg/h, pressure 0.05MPa, butadiene tail gas enters from bottom, absorption tower 7, absorbent 2 is toluene, enter from top, absorption tower, flow 4000kg/h, pressure 0.5MPa, butadiene tail gas 1 contacts absorption with absorbent 2 in absorption tower, absorption tower number of theoretical plate 3 pieces, tower top temperature 42 DEG C, tower top pressure 0.1MPa.Tower top is without gas phase extraction, and in tower reactor liquid phase, ethyl acetylene and vinylacetylene content are 2.43%, as the charging of reactor 9 after the boosted pump boosting of tower reactor liquid；
2. I section of hydrogenation reaction: the boosted pump of liquid from absorption tower tower reactor boosts to 2.2MPa(logistics number 3), allocate the charging as I section of hydrogenation reactor 9 after hydrogen 4 into, adopt the catalyst disclosed in CN1321544, hydrogenation conditions is: reaction inlet temperature 40 DEG C, pressure 2.2MPa, liquid volume air speed 10h-1, hydrogen/(alkynes+diolefin) mol ratio 1.5.I section of reactor outlet material part circulates to I section of reactor inlet place, and a part is as the charging of Analytic Tower 10；
3. resolve: enter Analytic Tower 10, Analytic Tower number of theoretical plate 20 pieces, tower top temperature 35 DEG C, tower top pressure 1.5MPa, bottom temperature 254 DEG C from I section of reactor 9 outlet material.Containing the butylene of 93.75wt% in tower top material (logistics number 5), direct extraction uses as the raw material of downstream unit, and tower bottoms cooled water-cooled but Posterior circle uses to absorption tower as absorbent.Main streams quality composition (wt%) is in Table 2.
Table 2
| 1 | 2 | 3 | 5 | |
| Hydrogen | 0 | 0 | 0 | 0.14 |
| Methane | 0 | 0 | 0 | 1.12 |
| Normal butane | 0.12 | 0 | 0.0057 | 1.69 |
| Iso-butane | 0.05 | 0 | 0.0024 | 0.07 |
| 1-butylene | 1.33 | 0 | 0.0633 | 60.20 |
| Isobutene. | 0.19 | 0 | 0.0091 | 0.16 |
| Cis-2-butene | 3.26 | 0 | 0.1550 | 9.48 |
| Trans-2-butene | 0.08 | 0 | 0.0038 | 23.91 |
| 1,3-butadiene | 41.12 | 0 | 1.9581 | 0 |
| 1,2-butadiene | 1.36 | 0 | 0.0648 | 0 |
| Allylene | 0.01 | 0 | 0.0005 | 0 |
| Ethyl acetylene | 9.76 | 0 | 0.4650 | 0 |
| Vinylacetylene | 41.22 | 0 | 1.9629 | 0 |
| Carbon five | 1.48 | 0 | 0.0705 | 1.34 |
| Toluene | 0 | 100 | 95.2381 | 1.89 |
Effect: through one-stage hydrogenation, as the butylene containing 93.75wt% in the logistics number 5 of product extraction, it is possible to directly extraction uses as the raw material of downstream unit, and butadiene tail gas is thus utilized effectively.
Embodiment 3
As it is shown in figure 1, a kind of BEU exhaust gas recovery system.Including: 7, I section of absorption tower hydrogenation reactor 9, Analytic Tower 10 and II section of hydrogenation reactor 11.
Top, absorption tower 7 is provided with absorbent entrance, and bottom, absorption tower is provided with butadiene gas inlet, and absorption tower outlet at bottom is connected after converging with hydrogen bottom I section of hydrogenation reactor after connecting pump 8；I section of hydrogenation reactor 9 top exit connects in the middle part of Analytic Tower 10, the absorbent entrance on absorption tower is connected bottom Analytic Tower 10, Analytic Tower 10 top is connected after converging with hydrogen gas lines bottom II section of hydrogenation reactor 11, and II section of cooled connection in hydrogenation reactor 11 top is out-of-bounds.
1. absorb: the butadiene tail gas 1(from BEU is mainly composed of: butylene 4.86wt%, butadiene 42.48wt%, alkynes 50.99wt%), flow 200kg/h, pressure 0.05MPa, butadiene tail gas enters from bottom, absorption tower 7, and absorbent 2 is toluene, enter from top, absorption tower, flow 4000kg/h, butadiene tail gas 1 contacts absorption, absorption tower number of theoretical plate 3 pieces with absorbent 2 in absorption tower, tower top temperature 42 DEG C, tower top pressure 0.1MPa.Tower top is without gas phase extraction, and in tower reactor liquid phase, ethyl acetylene and vinylacetylene content are 2.43%, as the charging of reactor 9 after the boosted pump boosting of tower reactor blended liquid phase；
2. allocating the charging as I section of hydrogenation reactor 9 after hydrogen 4 into, adopt the catalyst disclosed in CN1321544, hydrogenation conditions is: reaction inlet temperature 40 DEG C, pressure 2.2MPa, liquid volume air speed 10h-1, hydrogen/(alkynes+diolefin) mol ratio 1.5.I section of reactor outlet material part circulates to I section of reactor inlet place, and a part is as the charging of Analytic Tower 10；
3. resolve: enter Analytic Tower 10, Analytic Tower number of theoretical plate 20 pieces, tower top temperature 35 DEG C, tower top pressure 1.5MPa, bottom temperature 254 DEG C from I section of reactor 9 outlet material.As the charging of II section of hydrogenation reactor 11 after tower top material (logistics number 5) cooling, tower bottoms cooled water-cooled but Posterior circle uses to absorption tower as absorbent；
4. II section of hydrogenation reactor: be cooled to 35 DEG C from the material 5 resolving tower top, enters II section of reactor 11 after allocating hydrogen into, adopts the catalyst disclosed in CN1508103, reaction condition is: reaction inlet temperature 35 DEG C, pressure 1.5MPa, liquid volume air speed 20h-1, hydrogen/alkene mol ratio 1.5.A reactor 11 outlet material part circulates to reactor 11 porch, and a part (logistics number 6) is as output of products, and in product, total monoolefin concentration is less than 5wt%, and butane concentration, more than 90wt%, can return to pyrolysis furnace and makes the raw material of cracking of ethylene.Main streams quality composition (wt%) is in Table 3.
Table 3
| 1 | 2 | 3 | 5 | 6 | |
| Hydrogen | 0 | 0 | 0 | 0.14 | 0.01 |
| Methane | 0 | 0 | 0 | 1.12 | 1.23 |
| Normal butane | 0.12 | 0 | 0.0057 | 1.69 | 90.75 |
| Iso-butane | 0.05 | 0 | 0.0024 | 0.07 | 0.25 |
| 1-butylene | 1.33 | 0 | 0.0633 | 60.20 | 0.01 |
| Isobutene. | 0.19 | 0 | 0.0091 | 0.16 | 0.08 |
| Cis-2-butene | 3.26 | 0 | 0.1550 | 9.48 | 1.37 |
| Trans-2-butene | 0.08 | 0 | 0.0038 | 23.91 | 3.23 |
| 1,3-butadiene | 41.12 | 0 | 1.9581 | 0 | 0 |
| 1,2-butadiene | 1.36 | 0 | 0.0648 | 0 | 0 |
| Allylene | 0.01 | 0 | 0.0005 | 0 | 0 |
| Ethyl acetylene | 9.76 | 0 | 0.4650 | 0 | 0 |
| Vinylacetylene | 41.22 | 0 | 1.9629 | 0 | 0 8 --> |
| Carbon five | 1.48 | 0 | 0.0705 | 1.34 | 1.31 |
| Toluene | 0 | 100 | 95.2381 | 1.89 | 1.76 |
Effect: through secondary hydrogenation, as containing butane concentration in the logistics number 6 of product extraction more than 90wt%, can return to pyrolysis furnace and makes the raw material of cracking of ethylene, and butadiene tail gas is thus utilized effectively.
Embodiment 4
As in figure 2 it is shown, a kind of BEU exhaust gas recovery system.Including: absorption tower 7, booster 8, I section of hydrogenation reactor 9, Analytic Tower 10, II section of hydrogenation reactor 11, return tank 12.Described II section of hydrogenation reactor 11 is the beds being arranged on Analytic Tower 10 internal upper part；It is provided with hydrogen inlet between beds and I section of hydrogenation reactor top material entrance on described Analytic Tower 10 top.Described Analytic Tower 10 top connects return tank 12, two outlets bottom return tank 12, and an outlet connects the beds top of Analytic Tower；Another outlet connects out-of-bounds.
1. absorb: the butadiene tail gas 1(from BEU is mainly composed of: butylene 4.86wt%, butadiene 42.48wt%, alkynes 50.99wt%), flow 200kg/h, pressure 0.05MPa, butadiene tail gas enters from bottom, absorption tower 7, and absorbent 2 is toluene, enter from top, absorption tower, flow 4000kg/h, butadiene tail gas 1 contacts absorption, absorption tower number of theoretical plate 3 pieces with absorbent 2 in absorption tower, tower top temperature 42 DEG C, tower top pressure 0.1MPa.Tower top is without gas phase extraction, and in tower reactor liquid phase, ethyl acetylene and vinylacetylene content are 2.43%, as the charging of I section of reactor 9 after the boosted pump boosting of tower reactor blended liquid phase；
2. I section of hydrogenation reaction: the boosted pump of blended liquid phase from absorption tower tower reactor boosts to 2.2MPa(logistics number 3), allocate the charging as I section of hydrogenation reactor 9 after hydrogen 4 into.I section of filled catalyst of hydrogenation reactor is according to providing preparation method in CN1321544, (with total catalyst weight for 100%) Cu8.7wt%, Pd0.15wt%, Ag0.24wt%, carrier is Al2O3, specific surface is 198m2/ g.Hydrogenation conditions is: reaction inlet temperature 40 DEG C, pressure 2.2MPa, liquid volume air speed 10h-1, hydrogen/(alkynes+alkadienes) mol ratio is 1.2.I section of reactor outlet material part circulates to I section of reactor inlet place, and all the other are as the charging resolving catalytic tower.
3. resolve catalysis: entering from I section of reactor outlet material and resolve catalytic tower 10, the 10th piece of plate place of solvent+C_4 hydrocarbon analytically section enters, and the 1st piece of plate place of hydrogen analytically section enters.Solvent, by resolving section elimination, enters tower reactor cooled water-cooled but Posterior circle and uses as absorbent to absorption tower.Resolving section number of theoretical plate is 20 pieces, resolves section head temperature 35 DEG C, resolves section pressure 1.5MPa, resolves section bottom temperature 254 DEG C.C_4 hydrocarbon mixes with hydrogen after removing out from solvent by parsing section, ascends into catalytic section 11 and proceeds hydrogenation reaction.Catalyst disclosed in catalytic section filling CN102285859, (with total catalyst weight for 100%) palladium 0.42wt%, silver 0.14wt%, catalyst carrier is Al2O3.Catalytic hydrogenation process condition is: reaction inlet temperature 35 DEG C, pressure 1.5MPa, liquid volume air speed 10h-1, hydrogen/(alkynes+alkadienes) mol ratio is 2.21, reflux ratio 20.Entering return tank 12 after resolving the cooling of catalysis overhead stream, remove outside partial reflux, all the other, as the direct extraction of product (logistics number 6), wherein contain the butylene of more than 95wt%, it is possible to as the raw material of downstream unit.Main streams quality composition (wt%) is in Table 4.
Table 4
| 1 | 2 | 3 | 6 | |
| Hydrogen | 0 | 0 | 0 | 0.05 |
| Methane | 0 | 0 | 0 | 2.18 |
| Normal butane | 0.12 | 0 | 0.0057 | 0.44 |
| Iso-butane | 0.05 | 0 | 0.0024 | 0.06 9 --> |
| 1-butylene | 1.33 | 0 | 0.0633 | 54.98 |
| Isobutene. | 0.19 | 0 | 0.0091 | 0.17 |
| Cis-2-butene | 3.26 | 0 | 0.1550 | 12.84 |
| Trans-2-butene | 0.08 | 0 | 0.0038 | 27.97 |
| 1,3-butadiene | 41.12 | 0 | 0.0022 | 0 |
| 1,2-butadiene | 1.36 | 0 | 0.0005 | 0 |
| Allylene | 0.01 | 0 | 0.0005 | 0 |
Effect: after one-stage hydrogenation+parsing catalytic hydrogenation, as the butylene containing more than 95wt% in the logistics number 6 of product extraction, it is possible to as the raw material of downstream unit, butadiene tail gas is thus utilized effectively.
Claims (12)
1. a BEU exhaust gas recovery system, it is characterised in that described system includes:
Absorption tower, I section of hydrogenation reactor, Analytic Tower；
Top, absorption tower is provided with absorbent entrance, and bottom, absorption tower is provided with butadiene gas inlet, after absorption tower outlet at bottom connects pump, is connected bottom I section of hydrogenation reactor after merging with hydrogen gas lines；I section of hydrogenation reactor top exit connects in the middle part of Analytic Tower, connects the absorbent entrance on absorption tower bottom Analytic Tower, and Analytic Tower top connects out-of-bounds；Absorb tower top depletion of QI phase discharger.
2. BEU exhaust gas recovery system as claimed in claim 1, it is characterised in that:
Described system includes II section of hydrogenation reactor；
Described Analytic Tower top exit pipeline is connected bottom II section of hydrogenation reactor after merging with hydrogen gas lines, and II section of hydrogenation reactor top connects out-of-bounds.
3. BEU exhaust gas recovery system as claimed in claim 2, it is characterised in that:
Described II section of hydrogenation reactor is the beds being arranged on Analytic Tower internal upper part；
It is provided with hydrogen inlet between beds and I section of hydrogenation reactor top exit on described Analytic Tower top.
4. BEU exhaust gas recovery system as claimed in claim 3, it is characterised in that:
Described Analytic Tower top connects return tank, two outlets bottom return tank, and an outlet connects the beds top of Analytic Tower；Another outlet connects out-of-bounds.
5. the method for recovering tail gas adopting BEU exhaust gas recovery system as claimed in claim 1, it is characterised in that described method includes:
Butadiene tail gas is through absorption, I section of hydrogenation reaction and parsing.
6. method for recovering tail gas as claimed in claim 5, it is characterised in that described method includes:
Butadiene tail gas through absorbing, I section of hydrogenation reaction, parsing and II section of hydrogenation reaction.
7. method for recovering tail gas as claimed in claim 5, it is characterised in that described method includes:
(1) absorb: butadiene tail gas is absorbed by absorbent in absorption tower, absorb tower top depletion of QI and discharge mutually；Described absorbent is that boiling point is higher than C-4-fraction and keeps the solvent of inertia in hydrogenation reaction；
(2) I section of hydrogenation: liquid phase boosting at the bottom of absorbing tower enters I section of hydrogenation reactor after allocating hydrogen into, carries out hydrogenation reaction；
(3) resolve: I section of hydrogenation reactor outlet material enters Analytic Tower, resolve outside tower top production streaming out-of-bounds, resolve tower reactor liquid phase material and recycle as absorbent return absorption tower.
8. method for recovering tail gas as claimed in claim 6, it is characterised in that described method includes:
(1) absorb: butadiene tail gas is absorbed by absorbent in absorption tower, absorb tower top depletion of QI and discharge mutually；Described absorbent is that boiling point is higher than C-4-fraction and keeps the solvent of inertia in hydrogenation reaction；
(2) I section of hydrogenation: liquid phase boosting at the bottom of absorbing tower enters I section of hydrogenation reactor after allocating hydrogen into, carries out hydrogenation reaction；
(3) resolving: I section of hydrogenation reactor outlet material enters Analytic Tower, the C_4 hydrocarbon resolving overhead extraction enters II section of hydrogenation reactor；Resolve tower reactor liquid phase material and return absorption tower recycling as absorbent；
(4) II section of hydrogenation: the C_4 hydrocarbon after I section of hydrogenation and parsing proceeds hydrogenation reaction, the product after II section of hydrogenation reactor top extraction hydrogenation.
9. method for recovering tail gas as claimed in claim 6, it is characterised in that described method includes:
(1) absorb: butadiene tail gas is absorbed by absorbent in absorption tower, absorb tower top depletion of QI and discharge mutually；Described absorbent is that boiling point is higher than C-4-fraction and keeps the solvent of inertia in hydrogenation reaction；
(2) I section of hydrogenation: liquid phase boosting at the bottom of absorbing tower enters I section of hydrogenation reactor after allocating hydrogen into, carries out hydrogenation reaction；
Enter in the middle part of (3) I sections of hydrogenation reactor outlet materials and hydrogen difference analytically tower, C_4 hydrocarbon and hydrogen are upwardly through catalytic bed, wherein carbon four alkynes and diolefin hydrogenation generation butylene or butane distillate from tower top, return tank is entered through supercooling, a part is back to catalytic bed top, all the other are as product extraction, and tower reactor extraction absorbent returns to absorption tower and recycles.
10. the method for recovering tail gas as described in one of claim 7～9, it is characterised in that:
Absorption tower tower top temperature is room temperature, pressure 0.1-0.2MPa absolute pressure, and number of theoretical plate is 2-10 block, and the flow-rate ratio of absorbent and butadiene tail gas is 0.5-40；
Described absorbent is one or more in C 5 alkane, benzene,toluene,xylene, N-Methyl pyrrolidone, N,N-dimethylformamide, acetonitrile, hexane, hexamethylene, hexahydrotoluene, Aromatic raffinate；
Described Analytic Tower number of theoretical plate is 10-35 block, operates pressure 0.2-3.5MPa absolute pressure, and tower top temperature 35-55 DEG C, bottom temperature is 50-300 DEG C, and reflux ratio is 0.1-40.
11. method for recovering tail gas as claimed in claim 8, it is characterised in that:
In step (2), I section of hydrogenation reactor inlet temperature 20-50 DEG C, reaction pressure 1.0-3.0MPa, liquid volume air speed 2-30h-1, hydrogen alkynes compares 1.0-6.0mol；
Step (4) in, II section of hydrogenation reactor inlet temperature 20-60 DEG C, pressure 1.0-3.0MPa, liquid air speed 2-30h-1。
12. method for recovering tail gas as claimed in claim 9, it is characterised in that:
In step (2), I section of hydrogenation reactor inlet temperature 20-50 DEG C, reaction pressure 1.0-3.0MPa, liquid volume air speed 2-30h-1, hydrogen alkynes compares 1.0-6.0mol；
In step (3), the hydrogenation conditions of beds is: react inlet temperature 30-80 DEG C, pressure 0.6-4.0MPa, liquid air speed 0.2-30h-1。
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| JPS5662516A (en) * | 1979-10-26 | 1981-05-28 | Mitsubishi Kakoki Kaisha Ltd | Foaming preventing method of gas absorption process |
| CN101172929A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Extraction method for a segment of butadiene with NMP method |
| CN201505500U (en) * | 2009-03-23 | 2010-06-16 | 江苏工业学院 | Oil and gas recovery device by absorption and adsorption integration technology |
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| JPS5662516A (en) * | 1979-10-26 | 1981-05-28 | Mitsubishi Kakoki Kaisha Ltd | Foaming preventing method of gas absorption process |
| CN101172929A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Extraction method for a segment of butadiene with NMP method |
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