CN101219918B - Method for refining carbonization crude benzole - Google Patents
Method for refining carbonization crude benzole Download PDFInfo
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- CN101219918B CN101219918B CN2007100000444A CN200710000044A CN101219918B CN 101219918 B CN101219918 B CN 101219918B CN 2007100000444 A CN2007100000444 A CN 2007100000444A CN 200710000044 A CN200710000044 A CN 200710000044A CN 101219918 B CN101219918 B CN 101219918B
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 263
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000007670 refining Methods 0.000 title claims abstract description 29
- 238000003763 carbonization Methods 0.000 title claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 205
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 77
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 27
- 238000004821 distillation Methods 0.000 claims abstract description 15
- 238000004939 coking Methods 0.000 claims abstract description 8
- 239000008096 xylene Substances 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims description 68
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 229930192474 thiophene Natural products 0.000 claims description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims description 23
- 238000005516 engineering process Methods 0.000 claims description 20
- 241000282326 Felis catus Species 0.000 claims description 12
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 12
- 238000006396 nitration reaction Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010555 transalkylation reaction Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 238000004904 shortening Methods 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 238000005194 fractionation Methods 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 230000000153 supplemental effect Effects 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000000895 extractive distillation Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 23
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 alkane alkene Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
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- 150000003613 toluenes Chemical class 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention relates to a method for refining coking benzol, consisting of a process of benzol pretreatment and benzene extractive distillation, a hydrofining process of toluol, xylene distillation and a toluene disproportionation process. The method for refining coking benzol has the advantages that: high-purity and high-quality product of the benzene, toluol and/or thiophen can be obtained; device investment is reduced by times; processing cost is also greatly reduced without environmental pollution; product proportion can be regulated according to market requirement.
Description
The invention belongs to a kind of method for refining carbonization crude benzole, be specifically related to a kind of process for purification that obtains high quality benzene, toluene and/or dimethylbenzene and thiophene.
Background technology
Coking crude benzene (abbreviation crude benzol) purified commercial run has two kinds at present: the one, and acid wash, the 2nd, hydrogenation method.Acid wash is comparatively ripe, the degree of depth is not enough but it purifies, and the benzene rate of recovery is low, and its fatal shortcoming is that generation is many to extremely harmful and reluctant higher boiling sulfur compound of environment and acidic polymer in the process, and be difficult to the waste sulfate that utilizes in a large number, severe contamination environment; Hydrogenation method can obtain high-quality benzene or benzene-type products, and its shortcoming is that facility investment is big, the tooling cost height, and in hydrogenation process, some useful components in the crude benzol such as thiophene are decomposed generation hydrogen sulfide and can't recycle.Environment-friendly type method for refining carbonization crude benzole (CN1686977A) adopts the technology of extracting rectifying, can obtain high-quality benzene, also recyclable simultaneously thiophene, its shortcoming is that the toluene, the dimethylbenzene cut that account for crude benzol 15-18% do not obtain refining fully as yet, with regard to the triphen process that coked crude benzene refining reclaims most worthy, this method waits perfect.
Summary of the invention
The technical problem to be solved in the present invention is: toluene, the dimethylbenzene cut that will account for crude benzol 15-18% are fully refining, improve and finish the whole process that crude benzene refining reclaims triphen.
A kind of method for refining carbonization crude benzole is characterized in that being made up of following technological process:
1, crude benzol pre-treatment and benzene cut extracting rectifying process for refining
(1) crude benzol pretreatment technology
Coking crude benzene is through presorting tower, cat head is told light constituent, tower bottom distillate enters benzene blowing tower, at the bottom of this Tata, tell heavy constituent, overhead fraction enters narrow benzene tower, the benzene cut that obtains in this column overhead enters benzene cut extracting and refining technology, and toluene, dimethylbenzene cut enter toluene, dimethylbenzene cut fraction hydrogenation process for refining at the bottom of the tower.
(2) benzene cut extraction rectification technique
The benzene cut that a last technique unit obtains enters the benzene extraction tower, cat head tells boiling point and benzene is close or azeotropic alkane and olefin fraction, tower bottom distillate enters the benzene treating tower, and the extraction agent that this benzene extraction tower is used (mainly be the extraction agent that reclaims small amount of supplemental also arranged newly add extraction agent) is from mixing tank; In described benzene treating tower cat head get the product high pure benzene (purity＞99.9%, sulphur content＜10ppm), tower bottom distillate enters the extraction agent recovery tower; In the extraction agent recovery tower, extraction agent and thiophene cut are separated, extraction agent enters mixing tank and recycles, and the thiophene cut enters the thiophene extraction tower, obtains the thiophene product after entering the thiophene treating tower then, its purity is more than or equal to 99%, and extraction agent recycles successively.Described extraction agent is: tetramethylene sulfone, glycols, N-Methyl pyrrolidone, N-formyl morpholine or their mixture; solvent ratio 2-10; under vacuum or normal pressure, operate; 85-45 ℃ of benzene extraction tower tower top temperature; 85-45 ℃ of benzin system column overhead temperature, 86-45 ℃ of thiophene extraction tower tower top temperature.
2, toluene, dimethylbenzene cut fraction hydrogenation process for refining
From the toluene of a last technique unit, dimethylbenzene cut through pre-hydrogenator, remove styrenic, diene etc. and easily enter the shortening main reactor after the component of coking, after this finishes hydrogenation of unsaturated hydrocarbons and generates alkane and hydrogenation and remove heteroatomic compounds such as sulphur, nitrogen, oxygen, enter pre-distillation column, the pre-distillation column tower bottom distillate enters the xylene distillation tower, the benzenol hydrorefining cat head gets the dimethylbenzene product of 3 ℃ of boiling ranges, gets C at the bottom of the tower
9Cut; Enter the one-level extraction tower from pre-distillation column cat head distilled toluene fraction, tell non-aromatic component in this column overhead, toluene at the bottom of the tower and extraction agent enter the extraction agent recovery tower, and from then on the distilled extraction agent returns extraction tower and recycles at the bottom of the tower, and cat head gets nitration grade toluene; The nitration grade toluene of gained can be used as product and sells, and also can enter secondary extraction tower and toluene treating tower, can get the product high purity toluene at last.Described hydrorefined hydrogen source is a hydrogen, pre-hydrogenator Ni-Mo crude benzol catalyst for pre-hydrogenation, and hydrogenation temperature is 190～240 ℃; Described hydrogenation main reactor Co-Mo crude benzole hydrogenation catalyst for refining, hydrogenation temperature is 320～370 ℃, working pressure is 2.4～3.5MPa; The used extraction agent of described extracting rectifying is the N-formyl morpholine, and solvent ratio is 3～8, and I and II extraction tower top temperature is 92～110 ℃, and extraction tower is operated under normal pressure.
3, toluene disproportionation technology
The nitration grade toluene that is obtained by a last technique unit is as the raw material of disproportionation technology.Toluene and hydrogen are mixed into preheater, enter the disproportionation device after the preheating, resultant of reaction is through condenser condenses, and phlegma advances rectifying tower to carry out fractionation by distillation and obtain product high pure benzene and xylol, and unconverted toluene, the latter and remaining hydrogen all return preheater and recycle.Described toluene disproportionation technology can be general toluene disproportionation technology, also can be methylbenzene selective disproportionation technology, the catalyzer difference that the two is used, the ratio of three isomer is different in the products obtained therefrom xylol, contains the high p-Xylol of the huge market demand, added value of high density in latter's product.In addition, also can in raw material toluene, mix with C
9(come from xylene distillation bottom stream in the last technique unit, main component is C to cut
9, C
10Aromatic hydrocarbons), as the parallel feeding of disproportionation device, toluene disproportionation and transalkylation reaction then take place in alternative appropriate catalyst simultaneously in this reactor, and products therefrom still is high pure benzene and xylol.
Above-mentioned disproportionation catalyst system therefor and corresponding technological parameters are as follows:
A, toluene disproportionation reaction
Catalyzer TA-3, air speed～1.0, pressure 3.0MPa, temperature＜500 ℃
B, methylbenzene selective disproportionation
Catalyzer ZSM-5 molecular sieve, air speed 1.0～3.0, pressure 3.0MPa, temperature＜400 ℃
C, have the toluene disproportionation reaction of transalkylation
Catalyzer HAT-095, air speed～1.0, pressure 3.0MPa, temperature＜400 ℃
Technique effect of the present invention is as follows:
1, method of the present invention can obtain high quality, highly purified benzene,toluene,xylene and thiophene product from coking crude benzene, and can be according to turn of the market, by the ratio of disproportionation process adjustments product, optionally obtain the more huge market demand, p-Xylol that added value is high;
2, compare with crude benzol extracting rectifying process for refining, method of the present invention has been handled the toluene that accounts for crude benzol total amount 15-18% that waits to handle, the dimethylbenzene cut of its remainder, and technology is environmental protection more, and gained toluene, dimethylbenzene quality product reach hydrogenation level product quality;
3, compare with acid wash, it is serious that method of the present invention has solved the acid wash environmental pollution, a series of problems such as poor product quality, yield are low;
4, method of the present invention, the benzene of content about 70% has been finished refining extraction with reduced investment, extraction fractional distillation that tooling cost is low in the crude benzol, also reclaimed the thiophene of high added value simultaneously, just remaining toluene, dimethylbenzene cut carry out hydrofining, so compare with the direct hydrofining technology of crude benzol, facility investment reduces at double, and tooling cost also descends significantly; Adopt disproportionation technology also can change the ratio of the finished product according to turn of the market.
Above-mentioned these characteristic synthesis are that any up to now existing other crude benzene refining methods are incomparable, and its environmental benefit, economic benefit are conspicuous.
Description of drawings
Fig. 1 is the method for refining carbonization crude benzole schema
Fig. 2 is crude benzol pre-treatment and benzene cut extracting rectifying process for refining schema
Fig. 3 is toluene, dimethylbenzene cut fraction hydrogenation process for refining schema
Fig. 4 is the toluene disproportionation process schema
Embodiment
Embodiment 1
Byproduct crude benzol with coal tar factory is that raw material (wherein containing benzene 69.1%, toluene 14.6%, dimethylbenzene 3.6%, thiophene 0.577% etc.) is removed light constituent (hydrogen sulfide, dithiocarbonic anhydride, cyclopentadiene etc.) through presorting tower, enters benzene blowing tower then; Remove heavy constituent (naphthalene, coumarone, indenes etc.) at benzene blowing tower, this column overhead overhead product is the benzene,toluene,xylene cut, enters narrow benzene tower; Distillate the narrow benzene cut (wherein benzene content 98%) that contains thiophene in this column overhead, enter the unitary benzene extraction tower of benzene cut extracting and refining, and toluene, the dimethylbenzene cut of discharging at the bottom of the tower enter pre-hydrogenator as the raw material of hydrofining technology.Above-mentioned pretreatment unit operation is general distillation procedure.
Narrow benzene cut from narrow benzene tower enters the benzene extraction tower, at benzene extraction tower cat head, alkane alkene and the alkene removing or azeotropic close, be difficult to remove with common distillating method with the benzene boiling point, extraction tower pressure is 53KPa, 60 ℃ of tower top temperatures, used extraction agent is a N-Methyl pyrrolidone, solvent ratio 5: 1, and the bottomsstream advances the benzene treating tower; Benzin system column overhead gets the high quality benzaldehyde product, and the bottomsstream reclaims extraction agent through the extraction agent recovery tower and recycles, and extraction agent recovery tower overhead product makes high purity commercial grade thiophene through thiophene extraction tower and thiophene treating tower.More than the equal 53KPa of each pressure tower, tower top temperature is respectively: 60 ℃ of benzene treating towers, 64 ℃ of extraction agent recovery towers, 63 ℃ of thiophene extraction towers, 65 ℃ of thiophene treating towers.Wherein benzene extraction tower, benzene treating tower, thiophene extraction tower and thiophene treating tower adopt the high precision rectification tower respectively, products obtained therefrom benzene purity＞99.9%, thiophene content＜10ppm in the benzene, product thiophene purity＞99%.
Embodiment 2:
With toluene, the dimethylbenzene cut that obtains among the embodiment 1 is raw material (toluene 71.5%, dimethylbenzene 15%, trimethylbenzene 2%, unsaturatess such as vinylbenzene 5%, thiotolene sulfides 0.7%, pyridines nitrogenous compound 1.5%, oxygenatedchemicalss such as coumarone 1.1%), carry out hydrofining, processing condition are: the commercially available Ni-Mo catalyzer of filling in the pre-hydrogenator, 190 ℃ of reactor inlet temperatures, pressure 3.2MPa; The shortening main reactor loads commercially available Co-Mo catalyzer, 320 ℃ of reactor inlet temperatures, pressure 3.0MPa; The hydrogenated oil of hydrofining gained goes out dimethylbenzene, C through rectifying separation
9The gained toluene fraction enters toluene one-level extraction tower behind the cut; extraction agent is commercially available N-formyl morpholine; tower top temperature is 98 ℃; pressure is normal pressure; solvent ratio is 6; products obtained therefrom is nitration grade toluene and high-quality 3 ℃ of boiling range dimethylbenzene, also has a small amount of non-aromatics and C9 cut, and other are with embodiment 1.
Embodiment 3:
With embodiment 2 gained nitration grade toluenes is raw material; through secondary extraction tower and toluene treating tower; get the product high purity toluene; its processing parameter is: extraction agent is the N-formyl morpholine, 98 ℃ of secondary extraction tower top temperatures, and pressure is normal pressure; solvent ratio is 5; total sulfur content＜1ppm in the high purity toluene, non-aromatics content＜1.0%, no benzene and C
9, distillation range＜0.6 ℃ (comprising 110.6 ℃), other are with embodiment 2.
Embodiment 4:
The nitration grade toluene that obtains with embodiment 2 is a raw material, adopting commercially available TA-3 (H type mordenite) is catalyzer, 450 ℃ of temperature, pressure is under the hydro condition of 3.0MPa, carries out the toluene disproportionation reaction, obtains dimethylbenzene and benzene, its toluene per pass conversion is 44%, the selectivity that dimethylbenzene adds benzene is 95%, and p-Xylol content is 24% in the dimethylbenzene, and other are with embodiment 2.
Embodiment 5:
The nitration grade toluene that obtains with embodiment 2 is a raw material, adopt commercially available modification ZMS-5 sieve peg-raking catalyst, 390 ℃ of temperature, carry out the selectivity disproportionation under the hydro condition of pressure 2.8MPa, obtain dimethylbenzene and benzene, its toluene conversion 30%, dimethylbenzene adds the selectivity 88% of benzene, the p-Xylol content of the huge market demand is 95% in the dimethylbenzene, and other are with embodiment 2.
Embodiment 6:
The nitration grade toluene and the C9 cut that obtain with embodiment 2 are raw material, adopt commercially available HAT-095 (activity is mordenite mutually) to make catalyzer, 370 ℃ of temperature, have the toluene disproportionation reaction of transalkylation under the hydro condition of pressure 2.8MPa, obtain dimethylbenzene and benzene, its total conversion rate is 45%, and the selectivity that dimethylbenzene adds benzene is 96%, and the content of p-Xylol is 24% in the dimethylbenzene.
Claims (1)
1. method for refining carbonization crude benzole, form by following technological process:
(1) crude benzol pre-treatment and benzene cut extracting rectifying process for refining
A crude benzol pretreatment technology
Coking crude benzene is through presorting tower, cat head is told light constituent, tower bottom distillate enters benzene blowing tower, at the bottom of this Tata, tell heavy constituent, overhead fraction enters narrow benzene tower, the benzene cut that obtains in this column overhead enters benzene cut extracting and refining technology, and toluene, dimethylbenzene cut enter toluene, dimethylbenzene cut fraction hydrogenation process for refining at the bottom of the tower;
B benzene cut extraction rectification technique
The benzene cut that a last technique unit obtains enters the benzene extraction tower, cat head tells boiling point and benzene is close or azeotropic alkane and olefin fraction, tower bottom distillate enters the benzene treating tower, the extraction agent that this benzene extraction tower is used, mainly be the extraction agent that reclaims small amount of supplemental also arranged newly add extraction agent from mixing tank; Cat head gets product purity＞99.9% in described benzene treating tower, and the high pure benzene of sulphur content＜10ppm, tower bottom distillate enter the extraction agent recovery tower; In the extraction agent recovery tower, extraction agent and thiophene cut are separated, extraction agent enters mixing tank and recycles, and the thiophene cut enters the thiophene extraction tower, obtains the thiophene product after entering the thiophene treating tower then, its purity is more than or equal to 99%, and extraction agent recycles successively; Described extraction agent is: tetramethylene sulfone, glycols, N-Methyl pyrrolidone, N-formyl morpholine or their mixture, solvent ratio 2-10, under vacuum or normal pressure, operate, 85-45 ℃ of benzene extraction tower tower top temperature, 85-45 ℃ of benzin system column overhead temperature, 86-45 ℃ of thiophene extraction tower tower top temperature;
(2) toluene, dimethylbenzene cut fraction hydrogenation process for refining
From the toluene of a last technique unit, dimethylbenzene cut through pre-hydrogenator, remove styrenic, diene etc. and easily enter the shortening main reactor after the component of coking, after this finishes hydrogenation of unsaturated hydrocarbons and generates alkane and hydrogenation and remove heteroatomic compounds such as sulphur, nitrogen, oxygen, enter pre-distillation column, the pre-distillation column tower bottom distillate enters the xylene distillation tower, the benzenol hydrorefining cat head gets the dimethylbenzene product of 3 ℃ of boiling ranges, gets C at the bottom of the tower
9Cut; Enter the one-level extraction tower from pre-distillation column cat head distilled toluene fraction, tell non-aromatic component in this column overhead, toluene at the bottom of the tower and extraction agent enter the extraction agent recovery tower, and from then on the distilled extraction agent returns extraction tower and recycles at the bottom of the tower, and cat head gets nitration grade toluene; The nitration grade toluene of gained can be used as product and sells, and also can enter secondary extraction tower and toluene treating tower, can get the product high purity toluene at last; Described hydrorefined hydrogen source is a hydrogen, pre-hydrogenator Ni-Mo crude benzol catalyst for pre-hydrogenation, and hydrogenation temperature is 190～240 ℃; Described hydrogenation main reactor Co-Mo crude benzole hydrogenation catalyst for refining, hydrogenation temperature is 320～370 ℃, working pressure is 2.4～3.5MPa; The used extraction agent of described extracting rectifying is the N-formyl morpholine, and solvent ratio is 3～8, and I and II extraction tower top temperature is 92～110 ℃, and extraction tower is operated under normal pressure;
(3) toluene disproportionation technology
The nitration grade toluene that is obtained by a last technique unit is mixed into preheater as the raw material and the hydrogen of disproportionation technology, enter the disproportionation device after the preheating, resultant of reaction is through condenser condenses, phlegma advances rectifying tower to carry out fractionation by distillation and obtains product high pure benzene and xylol, and unconverted toluene, the latter and remaining hydrogen all return preheater and recycle; Described toluene disproportionation technology can be general toluene disproportionation technology, also can be methylbenzene selective disproportionation technology, the catalyzer difference that the two is used, the ratio of three isomer is different in the products obtained therefrom xylol, contains the high p-Xylol of the huge market demand, added value of high density in latter's product; In addition, also can mix in raw material toluene with xylene distillation bottom stream in the technique unit on coming from, main component is C
9, C
10The C of aromatic hydrocarbons
9Cut, as the parallel feeding of disproportionation device, toluene disproportionation and transalkylation reaction then take place in alternative appropriate catalyst simultaneously in this reactor, and products therefrom still is high pure benzene and xylol.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2773400C1 (en) * | 2021-04-23 | 2022-06-03 | Акционерное общество "Государственный Ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (АО "ГНИИХТЭОС") | Method for deep purification of benzene from thiophene |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519338B (en) * | 2009-02-25 | 2012-06-06 | 中国石油集团工程设计有限责任公司抚顺分公司 | Process for hydrofining coking crude benzene |
| CN101514136B (en) * | 2009-03-31 | 2013-03-20 | 山东元利科技股份有限公司 | Method for preparing high purity toluene from coking crude benzene |
| CN101913978B (en) * | 2010-07-23 | 2013-01-23 | 天津凯赛特科技有限公司 | Extraction and rectification system for coking benzene and sulfur-bearing benzene and refining method thereof |
| CN101962311B (en) * | 2010-09-13 | 2012-11-28 | 中冶焦耐(大连)工程技术有限公司 | Method and device for increasing service life of extractant in hydrofining process of crude benzene |
| CN102432422B (en) * | 2011-09-07 | 2016-06-08 | 太原理工大学 | A kind of technological process of halogen process crude benzene refining |
| CN102382099B (en) * | 2011-11-07 | 2013-04-03 | 山东元利科技股份有限公司 | Method for preparing thiophene through variable pressure azeotropic distillation |
| CN102964200B (en) * | 2012-11-26 | 2014-09-17 | 北京旭阳化工技术研究院有限公司 | Purifying method of coking toluene |
| CN103740170B (en) * | 2013-12-30 | 2016-05-18 | 惠州市立美特环保油墨有限公司 | The method of benzene and UV monomer, UV ink in expeling UV monomer |
| CN104926591B (en) * | 2015-03-30 | 2017-06-06 | 北京化工大学 | A kind of method of extracting rectifying and separating benzene and thiophene |
| CN106008139B (en) * | 2016-05-23 | 2019-04-02 | 临涣焦化股份有限公司 | A kind of coking crude benzene adds hydrogen recovery unit |
| CN109053356A (en) * | 2018-08-06 | 2018-12-21 | 宁夏宝丰能源集团股份有限公司 | A kind of extraction separating method and crude benzol processing technology of triphenyl fraction |
| CN111943796A (en) * | 2020-09-04 | 2020-11-17 | 中冶焦耐(大连)工程技术有限公司 | Process and system for hydrogenation and extractive distillation of crude benzene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686977A (en) * | 2005-05-09 | 2005-10-26 | 天津大学 | Method for refining environmental protection type carbonized benzene |
| CN1733746A (en) * | 2005-09-09 | 2006-02-15 | 太原市侨友化工有限公司 | Method for coke benzene oxydation to produce maleic anhydride |
-
2007
- 2007-01-08 CN CN2007100000444A patent/CN101219918B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686977A (en) * | 2005-05-09 | 2005-10-26 | 天津大学 | Method for refining environmental protection type carbonized benzene |
| CN1733746A (en) * | 2005-09-09 | 2006-02-15 | 太原市侨友化工有限公司 | Method for coke benzene oxydation to produce maleic anhydride |
Non-Patent Citations (3)
| Title |
|---|
| 曲义年.焦化粗苯加氢精制工艺的述评.《燃料与化工》.1997,第28卷(第1期),210-214. * |
| 林恒生 等.焦化粗苯催化加氢精制纯苯的研究与开发.《煤化工》.2004,(第1期),33-36. |
| 林恒生等.焦化粗苯催化加氢精制纯苯的研究与开发.《煤化工》.2004,(第1期),33-36. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2773400C1 (en) * | 2021-04-23 | 2022-06-03 | Акционерное общество "Государственный Ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (АО "ГНИИХТЭОС") | Method for deep purification of benzene from thiophene |
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