CN1348941A - Combined technological and comprehensive utilizing method in C5 prodn. splitting process - Google Patents
Combined technological and comprehensive utilizing method in C5 prodn. splitting process Download PDFInfo
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- 238000000034 method Methods 0.000 title abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000005336 cracking Methods 0.000 claims abstract description 29
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 28
- 238000005516 engineering process Methods 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 12
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 112
- 238000004821 distillation Methods 0.000 claims description 39
- 230000003197 catalytic effect Effects 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 30
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000006266 etherification reaction Methods 0.000 claims description 15
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 14
- 238000003808 methanol extraction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 241000282326 Felis catus Species 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- PMJHHCWVYXUKFD-UHFFFAOYSA-N pentadiene group Chemical group C=CC=CC PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 14
- -1 cyclic tert-amyl diene Chemical class 0.000 abstract description 12
- 239000005977 Ethylene Substances 0.000 abstract description 8
- 230000009466 transformation Effects 0.000 abstract description 6
- 238000007670 refining Methods 0.000 abstract description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 20
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 14
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 10
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 10
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 10
- 150000001941 cyclopentenes Chemical class 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 8
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 6
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004148 unit process Methods 0.000 description 2
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
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Abstract
This invention relates to a combined technology for cracking C5 fraction to produce methyl tert-amyl ether (TAME) by utilizing ethylene and use it for rich n-pentane-contained parafins of ethylene-cracked raw material. It features that decyclized pentadiene, selective hydrogenation, etherization reaction and saturated hydrogenation technique are organicly combined to decrease hydrogen consumption to the maximum extent, and an ideal harmonious ingredient without lead and containing oxygen and high octane number gasoline-TAME is obtained. Catalstic-distilled etherization reaction is used, tert-amy ethylene reaches deep transformation; the saturated-hydrogenated C5 paraffins contain rich n-pentane used as ethylene-cracked raw material or gasoline ingredient; crude cyclic tert-amyl diene can be produced in combination, and after further refining, it can be used as raw material for fine chemical industry.
Description
The present invention relates to the combination process of a kind of cracking c_5 comprehensive utilization, especially utilize cracking of ethylene C5 fraction production tert amyl methyl ether(TAME) (TAME) and be rich in the technology of the cracking of ethylene raw material of Skellysolve A.
As everyone knows, the a considerable amount of C5 fractions of by-product in the petroleum hydrocarbon thermo-cracking process of producing ethylene, main component is 3-methyl-1-butene, iso-pentane, 1,4-pentadiene, valerylene, 1-amylene, 2-methyl-1-butene alkene, Skellysolve A, isoprene, anti--the 2-amylene, suitable-the 2-amylene, 2-methyl-2-butene, anti--1,3-pentadiene, cyclopentadiene, suitable-1,3-pentadiene, cyclopentenes, pentamethylene and a spot of carbon four and carbon six cuts.At present, the utilization of cracking c_5 mainly contains following two aspects:
The one, the separation and purification of single component, promptly from cracking c_5, isolate diolefine such as isoprene, cyclopentadiene, m-pentadiene as industrial chemicals, because each component boiling point of cracking c_5 is close, be difficult to separate with conventional method, the general method that adopts chemistry or extractive distillation is separation and purification in addition, therefore, these method investments are big, cost is high.
The 2nd, the utilization of blending ingredients, hydrofining wherein is to adopt maximum technology (as CN1145891), C5 fraction behind the hydrogenation contains Skellysolve A, iso-pentane and pentamethylene, can be used as the blend component of gasoline or the raw material of cracking of ethylene, this method technology is simple but hydrogen consumption is big, and C5 fraction is owing to contain a large amount of iso-pentane, and the yield of ethene that therefore cracking obtains as cracking stock is lower; USP5352846 discloses a kind of technology of cracking c_5 comprehensive utilization, it is characterized in that earlier cracking c_5 being carried out hydrogenation and isomery handles, send into methyltertiarvbutyl ether reactor and methyl alcohol then and react generation tert amyl methyl ether(TAME) (TAME), then by distilling the cut that acquisition is rich in the cut of Skellysolve A and is rich in TAME, this method is not owing to adopt catalytic distillation technology, uncle's amylene does not obtain the degree of depth and transforms, thereby uncle's amylene content is higher in the C5 fraction that obtains, should not be as cracking stock, and the purity of TAME is about 80%.
The Technology that the purpose of this invention is to provide the comprehensive utilization of a kind of cracking c_5 promptly prepares highly purified alkyl tert amyl ether (particularly TAME) with cracked C 5 fraction and be rich in the C 5 alkane cut of Skellysolve A, and the latter can be used as the fine cracking stock.
To achieve these goals, the invention provides two kinds of COMBINED PROCESS routes, first kind of technological line is the combination process that adopts the decylization pentadiene, selects hydrogenation, etherificate and saturated hydrogenation; Second kind of technological line is to adopt the combination process of selecting hydrogenation, etherificate and saturated hydrogenation.
Accompanying drawing is a process flow diagram of the present invention.Now in conjunction with the accompanying drawings two kinds of technological lines, unit process and technical characterictics thereof of the present invention are described below:
The process prescription of first kind of technology path is:
Cracking c_5 (1) is introduced into decylization pentadiene unit, and this unit comprises cyclopentadiene polymer reactor (2) With carbon five knockout towers (4) two parts. Cyclopentadiene has two conjugated dienes, and is very active, and easily polymerization generates Dicyclopentadiene, utilize these characteristics to allow cracking c_5 enter reactor after, at reaction pressure 0.2～3.0MPa, 50～150 ℃ of reaction temperatures, air speed 0.1～1h-1Operating condition under, make the cyclopentadiene autohemagglutination become dicyclo penta Diene, reacting rear material (3) enters carbon five knockout towers (4) again, and the operating pressure of knockout tower (4) is 0.05～0.5MPa reflux ratio is 0.5: 1～10: 1, column bottom temperature is 70～150 ℃, and tower top temperature is 20～70 ℃, discharging is the dicyclopentadiene (7) of content more than 80% at the bottom of the tower, can be used as to produce glutaraldehyde, dicyclo penta 2 The raw material of the chemical products such as alkene Petropols; The cat head discharging is the C 5 fraction (5) that removes cyclopentadiene.
The C 5 fraction (5) that has removed cyclopentadiene mixes with hydrogen logistics (6), send into selective hydrogenation reaction device (9), under the effect of selecting hydrogenation catalyst, diolefine in the C5 fraction, alkynes are converted into corresponding monoolefine, and in this process, but the isoprene of the overwhelming majority generates uncle's amylene (2-methyl-1-butene alkene and 2-methyl-2-butene) of etherificate, 1,4-pentadiene, suitable-1,3-pentadiene, anti--1,3-pentadiene all are converted into straight chain mono-olefins or alkane.When selecting hydrogenation, some isomerization reactions also take place, and comprise that mainly the 3-methyl-1-butene isomery turns to that 2-methyl-1-butene alkene or 2-methyl-2-butene, 2-methyl-1-butene bisabolene isomer turn to the 2-methyl-2-butene, amylene-1 isomery turns to anti-amylene-2, turns to anti-amylene-2 etc. along amylene-2 isomery.Hydrogenation reaction is a strong exothermal reaction, for preventing the beds overtemperature, allows after reacted a part of material (10) cooling inlet of Returning reactor again.The operational condition of selective hydrogenation reaction device is mol ratio 1.0: 1～10: 1, the liquid phase air speed 0.2～5h of pressure 0.5～5MPa, 50～130 ℃ of temperature ins, hydrogen and diolefine
-1, recycle ratio 1: 1～50: 1 (v/v).In addition, the logistics of coming out from selective hydrogenation reaction device (9) can enter a distillation tower before entering the etherificate unit, and fractionation obtains being rich in the cut and the carbon six above cuts of carbon five, and the cut that will be rich in carbon five feeds the etherificate unit.Certainly the present invention also can adopt catalytic distillation tower to make the selective hydrogenation reaction device, at this moment in same catalytic distillation tower, can finish carbon five following cuts and carbon six above fraction separation simultaneously, and be rich in C5 fraction and contact with selection hydrogenation catalyst in the catalytic distillation tower, make wherein diolefine, alkynes and hydrogen reaction be converted into corresponding monoolefine.
The active ingredient of described selection hydrogenation catalyst is the metal of VIII family, and preferred active ingredient is a palladium, and active ingredient both can be used separately, also can be well known in the art with other, and especially the properties-correcting agent of VIB, IB family uses jointly; The carrier of catalyzer is aluminum oxide, silicon oxide or its mixture, preferred aluminum oxide; The content of palladium metal in catalyzer is 0.1～1% (weight), and the specific surface area of catalyzer is 5～200cm
2/ g; The selection hydrogenation catalyst that loads in described fixed bed can be column, spherical, trifolium shape etc., the selection hydrogenation catalyst that loads in described catalytic distillation tower can be column, spherical, trifolium shape, be preferably and itself have fractionation and the bifunctional filler shape of katalysis, Chinese patent CN1242410 discloses double-functional packing shape Preparation of catalysts method, reach with the catalytic distillation reactor and carry out the method that hydrogenation is selected in C5 fraction, the full text of this patent is quoted as the part of this patent.
Material behind the selective hydrogenation reaction (11) enters the etherificate unit, etherificate of the present invention unit comprises a catalytic distillation tower at least, and the operational condition of catalytic distillation tower is: pressure 0.2～0.6MPa, reflux ratio 0.2: 1～10: 1,40～100 ℃ of tower top temperatures, 120～180 ℃ of column bottom temperatures.
The preferred etherificate of the present invention unit comprises fixed bed etherification reactor (13), catalytic distillation tower (16), methanol extraction tower (19) and refining methanol tower (22) four parts.Catalyst for etherification preferably adopts ion-exchange resin catalyst, as by the macropore sulfonic acid ion exchange resin that obtains of sulfonation again after vinylbenzene homopolymerization or the copolymerization.For preventing that the etherification reaction liberated heat from causing that reaction bed temperature is too high, the fixed bed etherification reactor can adopt the outer circulation reactor, also can adopt shell and tube reactor.At first mix through the C5 fraction (11) after the selective hydrogenation reaction with methyl alcohol (12), enter fixed bed etherification reactor (13) and carry out pre-etherificate, if adopt the outer circulation operating method, then will react a part of material in back (14) cooling back and return the inlet of reactor with pump, if adopt shell and tube reactor, loading catalyst in the tube side feeds water coolant reaction heat is taken away in shell.Material (15) after the pre-etherificate directly enters catalytic distillation tower (16).The operational condition of fixed bed etherification reactor is pressure 0.3～2MPa, 30～90 ℃ of temperature ins, air speed 0.5～5h
-1, methyl alcohol and uncle's amylene mol ratio be 0.9: 1～1.5: 1, when adopting outer circulation mode, recycle ratio 0.5: 1～5: 1.
The characteristics of catalytic distillation technology are that reaction is combined in the equipment and finishes with separating two unit processes, have promptly both finished catalyzed reaction in a tower, finish separating of product and reaction residual again.Catalytic distillation tower (16) comprises rectifying section, conversion zone and stripping section, and its detailed structure is seen CN1022382C, US5523061.For the synthetic so typical reversible reaction of TAME,, destroyed the balance of reaction, thereby improved reactant uncle amylene and conversion of methanol because product is constantly told from reactant.Generate purity and discharge from the tower still greater than 97% TAME product (18), unreacted carbon five and methyl alcohol (17) are discharged from cat head and are entered methanol extraction tower (19).The preferred operations condition of catalytic distillation tower is: pressure 0.2～0.6MPa, reflux ratio 0.2: 1～10: 1,50～80 ℃ of tower top temperatures, 120～180 ℃ of column bottom temperatures.
In methanol extraction tower (19), use water as extraction agent, methyl alcohol is extracted from C5 fraction, extraction phase-methanol aqueous solution (21) is discharged by the tower still and is entered methanol rectifying tower (22), methyl alcohol (23) after refining is discharged by the cat head of tower (22), and water (24) is discharged and is back to methanol extraction tower (19) by the tower still and recycles; Extracting phase-C5 fraction (20) is discharged by the cat head of methanol extraction tower (19), and sends into saturated hydrogenation reactor (25) after hydrogen logistics (27) mixes.The operational condition of methanol extraction tower be 10～60 ℃ of temperature, tower top pressure 0.1～0.6MPa, hydrocarbon water than 1: 1～10: 1v/v; The operational condition of refining methanol tower is pressure 0.1～0.3MPa, 64～80 ℃ of tower top temperatures, reflux ratio 5: 1～20: 1.
In saturated hydrogenation reactor (25), under the effect of saturated hydrogenation catalyzer, the monoolefine in the C5 fraction (being mainly 1-amylene, suitable-the 2-amylene, anti--2-amylene and cyclopentenes etc.) generates the C5 fraction (26) of being rich in Skellysolve A with hydrogen reaction.The saturated hydrogenation reactor is fixed-bed reactor, and its operational condition is 200～400 ℃ of temperature of reaction, pressure 0.1～3MPa, hydrogen/hydrocarbon volume ratio 50: 1～200: 1, volume space velocity 0.5～5h
-1Except that containing a small amount of butane, mainly be iso-pentane, Skellysolve A and pentamethylene in the logistics that saturated hydrogenation obtains.
Described saturated hydrogenation activity of such catalysts component is preferably cobalt and molybdenum, and carrier is preferably aluminum oxide.
Second kind of technological line lacked decylization pentadiene unit than first kind of technological line, be that cracking c_5 raw material (1) is without the decylization pentadiene and with after hydrogen logistics (6) mixes, directly send into selective hydrogenation reaction device (9), cyclopentadiene wherein generates cyclopentenes, enter the etherificate unit with other material then, in catalytic distillation tower, come out from cat head with the unreacted C5 fraction again, send into the saturated hydrogenation reactor at last, hydrogenation is present in the C5 fraction discharging of being rich in Skellysolve A after generating pentamethylene.The operational condition of its key step is identical with the main operational condition of above-mentioned first kind of technological line.
The advantage that combination process provided by the present invention compared with prior art has mainly shows: the one, selection hydrogenation, etherification reaction and saturated hydrogenation technology are organically combined, reducing hydrogen gas consumption to greatest extent, when promptly reducing production costs significantly, obtained to produce unleaded, as to contain oxygen and stop bracket gasoline desirable blend component-TAME; The 2nd, adopted the etherification reaction technology of catalytic distillation, uncle's amylene to reach the degree of depth and transformed, be rich in Skellysolve A in the C 5 alkane behind the saturated hydrogenation, can be used as good cracking of ethylene raw material or gasoline component; The 3rd, but can be according to the thick cyclopentadiene of needs coproduction of market or producer, with the raw material of its further refining back as fine chemistry industry.
The present invention will be further described by means of embodiment below, but the present invention is not limited to embodiment.
Embodiment 1:
The classical group of petroleum hydrocarbon cracking ethylene preparation device by-product C5 fraction becomes to see Table 1.
The typical case of table 1 cracked C 5 fraction forms
Component content, % (m/m) component content, % (m/m)
Carbon 4 6.24 anti--2-amylenes 2.09
3-methyl-1-butene 0.39 suitable-2-amylene 1.30
Iso-pentane 4.66 2-methyl-2-butenes 2.62
1,4-pentadiene 1.95 anti--1,3-pentadienes 9.43
Valerylene 0.83 cyclopentadiene+suitable-1,3-pentadiene 23.23
1-amylene 2.96 cyclopentenes 3.40
2-methyl-1-butene alkene 4.69 pentamethylene 2.08
Skellysolve A 8.30 carbon 6 2.44
Isoprene 23.39
At first, cracked C 5 fraction enters polymerization reactor, and the control reaction pressure is 2MPa, 120 ℃ of temperature of reaction, air speed 0.3h
-1Cyclopentadiene (CPD) dimerization is a dicyclopentadiene with this understanding, and its autohemagglutination transformation efficiency can reach more than 95%.The boiling point of dicyclopentadiene is 166 ℃, apparently higher than other carbon five hydrocarbon, adopts conventional distillation tower, is 2: 1 in normal pressure, reflux ratio, and column bottom temperature is 125 ℃, and tower top temperature is under 35 ℃ the condition, dicyclopentadiene can be separated from C5 fraction.The content that obtains dicyclopentadiene is generally greater than more than 80%.The typical case who removes the C5 fraction after the dicyclopentadiene forms as shown in table 2.
The C5 fraction typical case that table 2 removes after the dicyclopentadiene forms
Component content, % (m/m) component content, % (m/m)
Carbon 4 8.02 anti--2-amylenes 2.70
3-methyl-1-butene 0.50 suitable-2-amylene 1.68
Iso-pentane 5.99 2-methyl-2-butenes 3.36
1,4-pentadiene 2.50 anti--1,3-pentadienes 12.13
Valerylene 1.07 cyclopentadiene+suitable-1,3-pentadiene 3.90
1-amylene 3.81 cyclopentenes 4.37
2-methyl-1-butene alkene 6.03 pentamethylene 2.68
Skellysolve A 10.67 carbon 6 0.51
Isoprene 30.08
The C5 fraction that removes dicyclopentadiene mixes with hydrogen, and the mol ratio of control hydrogen and diolefine is 4: 1, reaction pressure 1.5MPa, 80 ℃ of temperature ins, liquid phase air speed 1h
-1, recycle ratio 8: 1 (v/v).Under the effect of selecting hydrogenation catalyst, isoprene, m-pentadiene etc. changes into corresponding monoolefine with hydrogen generation addition reaction.Carbon five compositions behind the selection hydrogenation see Table 3.
Table 3 selects the carbon five behind the hydrogenation to form
Component title content, % (m/m) component title content, % (m/m)
Carbon 4 7.99 suitable-2-amylenes 5.66
3-methyl-1-butene 0.31 2-methyl-2-butene 33.09
Iso-pentane 5.97 cyclopentenes 4.35
1-amylene 7.46 pentamethylene 2.67
The 2-methyl-1-butene alkene 6.25 diene court of a feudal ruler≤300ppm
Skellysolve A 10.63 carbon 6 0.50
Instead-2-amylene 15.12
C5 fraction behind the hydrogenation and methanol mixed enter an outer circulation reactor, and under the effect of catalyst for etherification, part uncle's amylene in the carbon five and methyl alcohol reaction generate TAME.Catalyst for etherification adopts the macropore sulfonic acid ion exchange resin.The material that comes out from the outer circulation reactor enters catalytic distillation tower again, and the TAME of generation goes out device from the tower still, and unreacted carbon five and residue methyl alcohol are discharged from cat head and entered methanol recovery system.Table 4 has been listed the pilot-scale experiment of outer circulation reactor and catalytic distillation tower.
Table 4 outer circulation reactor and catalytic distillation tower synthesize the TAMEME test-results
Project result
The outer circulation reactor
Recycle ratio 1.5: 1
Air speed, h
-11.0
Alfin ratio, mol/mol 1.14
Temperature in, ℃ 48
Pressure, MPa 0.8
Transformation efficiency, % 62.29
Catalytic distillation
Reflux ratio 1.25: 1
Pressure, MPa 0.4
Cat head is formed, % (m/m)
Uncle's amylene 1.84
Methyl alcohol 5.85
Dme 0.65
Form % (m/m) at the bottom of the tower
C
5 0.18
Methyl alcohol 1.13
Tertiary amyl alcohol 1.08
TAME 97.02
Other is 0.59 years old
Uncle's amylene total conversion rate, % 95.64
The TAME overall selectivity, % 98.10
The residue carbon five that contains methyl alcohol is introduced into extraction tower, extracts methyl alcohol by water, the service temperature of methanol extraction tower be 40 ℃, tower top pressure 0.4MPa, hydrocarbon water than 3: 1v/v; Extracting phase-C 5 fraction is discharged by cat head, advances following saturated hydrogenation reactor.Extraction phase-first alcohol and water is discharged by the tower still and is entered methanol rectifying tower, and its pressure is normal pressure, 65 ℃ of tower top temperatures, reflux ratio 10: 1, and the methyl alcohol after making with extra care is discharged by cat head, can be back to etherification reaction and partly recycle; Water is discharged by the tower still, is back to the methanol extraction tower and recycles.
In saturated hydrogenation reactor (25), under the effect of catalyzer, the monoolefine in the C5 fraction (being mainly 1-amylene, suitable-the 2-amylene, anti--2-amylene and cyclopentenes etc.) generates the C5 fraction (26) of being rich in Skellysolve A with hydrogen reaction.The temperature of reaction of saturated hydrogenation is controlled at 300 ℃, pressure 1.5MPa, hydrogen/hydrocarbon volume ratio 100: 1, volume space velocity 1h
-1The transformation efficiency of monoolefine is greater than more than 99%.Table 5 has been listed carbon five compositions behind the saturated hydrogenation.
The cracking performance of material composition and each component behind table 5 saturated hydrogenation
Form content, % yield of ethene, % propene yield, %
Normal butane 12.0 42.2 14.6
Skellysolve A 62.0 46.0 23.9
Iso-pentane 14.0 13.0 20.0
Pentamethylene 12.0 31.6 15.6
Saturated carbon five ∑s 39.3 21.2
Lighter hydrocarbons cracked two alkene (ethene and propylene) yield with form relevantly, the listed saturated C5 fraction cracked ethene total recovery of table 5 is about 39%, the propylene total recovery is about 21%, is unusual fine cracking stock.
Embodiment 2:
Cracking c_5 raw material composition sees Table 1.C5 fraction mixes with hydrogen, 80 ℃ of mol ratio 4: 1, reaction pressure 1.5MPa, temperature ins, the liquid phase air speed 1h of control hydrogen and diolefine
-1, recycle ratio 10: 1 (v/v).Under the effect of selecting hydrogenation catalyst, isoprene, m-pentadiene etc. changes into corresponding monoolefine with hydrogen generation addition reaction.Carbon five compositions behind the selection hydrogenation see Table 6.
Table 6 selects the carbon five behind the hydrogenation to form
Component title content, % (m/m) component title content, % (m/m)
Carbon 4 6.66 suitable-2-amylenes 4.72
3-methyl-1-butene 0.26 2-methyl-2-butene 27.57
Iso-pentane 4.98 cyclopentenes 20.26
1-amylene 6.22 pentamethylene 2.22
The 2-methyl-1-butene alkene 5.21 diene court of a feudal ruler≤300ppm
Skellysolve A 8.86 carbon 6 0.41
Instead-2-amylene 12.60
C5 fraction behind the hydrogenation and methanol mixed enter a shell and tube reactor, and under the effect of catalyst for etherification, part uncle's amylene in the carbon five and methyl alcohol reaction generate TAME.Reacted material directly enters catalytic distillation tower again, and the TAME of generation goes out device from the tower still, and unreacted carbon five and residue methyl alcohol are discharged from cat head and entered methanol recovery system.Table 7 has been listed the pilot-scale experiment of shell and tube reactor and catalytic distillation tower.
Table 7 shell and tube reactor and catalytic distillation synthesize the TAME test-results
Project result
Shell and tube reactor
Air speed, h
-11.1
Alfin ratio, mol/mol 1.07
Temperature in, ℃ 55
Pressure, MPa 0.8
Transformation efficiency, % 62.28
Catalytic distillation
Reflux ratio 1.2: 1
Pressure, MPa 0.4
Cat head is formed, % (m/m)
Uncle's amylene 2.85
Methyl alcohol 6.41
Dme 0.43
Form % (m/m) at the bottom of the tower
C
5 0.48
Methyl alcohol 0.57
Tertiary amyl alcohol 1.29
TAME 97.20
Other is 0.46 years old
Uncle's amylene total conversion rate, % 93.45
The TAME overall selectivity, % 98.46
The residue carbon five that contains methyl alcohol is introduced into extraction tower, extracts methyl alcohol by water, the service temperature of methanol extraction tower be 40 ℃, tower top pressure 0.4MPa, hydrocarbon water than 4: 1v/v; Extracting phase-C 5 fraction is discharged by cat head, advances following saturated hydrogenation reactor.Extraction phase-first alcohol and water is discharged by the tower still and is entered methanol rectifying tower, and its pressure is normal pressure, 65 ℃ of tower top temperatures, reflux ratio 10: 1, and the methyl alcohol after making with extra care is discharged by cat head, can be back to etherification reaction and partly recycle; Water is discharged by the tower still, is back to the methanol extraction tower and recycles.
In saturated hydrogenation reactor (25), under the effect of catalyzer, the monoolefine in the C5 fraction (being mainly 1-amylene, suitable-the 2-amylene, anti--2-amylene and cyclopentenes etc.) generates the C5 fraction (26) of being rich in Skellysolve A with hydrogen reaction.The temperature of reaction of saturated hydrogenation is controlled at 280 ℃, pressure 1.5MPa, hydrogen/hydrocarbon volume ratio 150: 1, volume space velocity 1h
-1The transformation efficiency of monoolefine is greater than more than 99%.Table 8 has been listed carbon five compositions behind the saturated hydrogenation.
The cracking performance of material composition and each component behind table 8 saturated hydrogenation
Form content, % yield of ethene, % propene yield, %
Normal butane 10.0 42.2 14.6
Skellysolve A 51.60 46.0 23.9
Iso-pentane 11.74 13.0 20.0
Pentamethylene 26.66 31.6 15.6
Saturated carbon five ∑s 37.9 20.3
According to the composition of the listed saturated C5 fraction of table 8, the yield of ethene after its cracking is about 37.9%, and propene yield is about 20.3%, can be used as the fine cracking stock.
Claims (14)
1, a kind of with cracked C 5 fraction production tert amyl methyl ether(TAME) simultaneously be rich in the technology of the C5 fraction of Skellysolve A, may further comprise the steps:
(a) with cracked C 5 fraction and hydrogen logistics, send into the selective hydrogenation reaction device, under the effect of catalyzer, the diolefine in the C5 fraction, alkynes and hydrogen reaction generate corresponding monoolefine;
(b) material that at least a portion step (a) is come out is sent into the etherificate unit that comprises a catalytic distillation tower at least, under the effect of catalyst for etherification, uncle's amylene in the C5 fraction and methyl alcohol reaction generate tert amyl methyl ether(TAME), and finish the separation of residue C5 fraction, methyl alcohol and tert amyl methyl ether(TAME);
(c) the residue C5 fraction of coming out from step (b) enters the saturated hydrogenation reactor, and under the effect of saturated hydrogenation catalyzer, monoolefine and hydrogen reaction in the residue C5 fraction generate the C5 fraction of being rich in Skellysolve A.
2, according to the technology of claim 1, described cracked C 5 fraction raw material was introduced into decylization pentadiene unit before entering the selective hydrogenation reaction device, remove the cyclopentadiene in the C5 fraction.
3, according to the technology of claim 2, it is characterized in that: comprise a polymerization reactor and a distillation tower in the decylization pentadiene unit, after the cracking c_5 raw material enters polymerization reactor, make the cyclopentadiene autohemagglutination become dicyclopentadiene, reacting rear material enters distillation tower again, discharging is thick dicyclopentadiene at the bottom of the described distillation Tata, and the cat head discharging is the C 5 fraction that removes cyclopentadiene.
4, according to the technology of claim 3, it is characterized in that: the operational condition of described polymerization reactor is pressure 0.2～3.0MPa, 50～150 ℃ of temperature of reaction, air speed 0.1～1.0h
-1The operational condition of described distillation tower is pressure 0.05～0.5MPa, reflux ratio 0.5: 1～10: 1, and column bottom temperature is 70～150 ℃.
5, according to the technology of claim 1 or 2, it is characterized in that: described selective hydrogenation reaction device is fixed-bed reactor or catalytic distillation reactor.
6, according to the technology of claim 1 or 2, it is characterized in that: the catalyst activity component of using in the described selective hydrogenation reaction device is the metal of VIII family, and carrier is aluminum oxide, silicon oxide or its mixture.
7, according to the technology of claim 5, it is characterized in that: described selective hydrogenation reaction device is fixed-bed reactor, and operational condition is pressure 0.5～5Mpa, 50～130 ℃ of temperature ins, the mol ratio of hydrogen and diolefine 1.0: 1～10: 1, liquid phase air speed 0.2～5h
-1, circulation volume ratio 1: 1～50: 1.
8, according to the technology of claim 1 or 2, it is characterized in that: in the described etherificate unit that comprises a catalytic distillation tower at least, the operational condition of described catalytic distillation tower is pressure 0.2～0.6MPa, reflux ratio 0.2: 1～10: 1,40～100 ℃ of tower top temperatures, 120～180 ℃ of column bottom temperatures.
9, according to the technology of claim 1 or 2, it is characterized in that: the described etherificate unit that comprises a catalytic distillation tower at least comprises etherificate fixed-bed reactor, a catalytic distillation tower and a methanol extraction tower at least; C5 fraction after the selective hydrogenation reaction is introduced into the fixed bed etherification reactor that includes acidic ion exchange resin, make the reaction of a part of uncle's amylene and methyl alcohol generate tert amyl methyl ether(TAME), reacted material enters the catalytic distillation tower that includes acidic ion exchange resin, make the reaction of a part of uncle's amylene and methyl alcohol generate a part of tert amyl methyl ether(TAME) again, the product tert amyl methyl ether(TAME) is discharged from catalytic distillation Tata still, unreacted carbon five and residue methyl alcohol are discharged from the catalytic distillation cat head, enter the methanol extraction tower of making extraction agent with water, the residue C 5 fraction is flowed out by the methanol extraction column overhead, and methanol aqueous solution is flowed out by the tower still.
10, according to the described technology of claim 9, it is characterized in that: described etherificate fixed-bed reactor are an outer circulation reactor or a shell and tube reactor, and its operational condition is pressure 0.3～2MPa, 40～90 ℃ of temperature of reaction, air speed 0.5～5h
-1, methyl alcohol and uncle's amylene mol ratio be 0.9: 1～1.5: 1, if when adopting the outer circulation operation, recycle ratio is 0.5: 1～5: 1.
11, according to the described technology of claim 9, it is characterized in that: the operational condition of described catalytic distillation tower is pressure 0.2～0.6MPa, reflux ratio 0.2: 1～10: 1,50～80 ℃ of tower top temperatures, 120～180 ℃ of column bottom temperatures.
12, require described technology according to right 9, it is characterized in that: the operational condition of methanol extraction tower be 10～60 ℃ of temperature, tower top pressure 0.1～0.6MPa, hydrocarbon water than 1: 1～10: 1v/v.
13, according to claim 1 or 2 described technologies, it is characterized in that: the operational condition of described saturated hydrogenation reactor is 200～400 ℃ of temperature, pressure 0.1～3MPa, hydrogen/hydrocarbon volume ratio 50: 1～300: 1, liquid phase volume air speed 0.5～5h
-1
14, according to claim 1 or 2 described technologies, it is characterized in that: described saturated hydrogenation activity of such catalysts component is cobalt and molybdenum, and carrier is an aluminum oxide.
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