CN107365241A - A kind of crude benzole hydrogenation process for refining - Google Patents
A kind of crude benzole hydrogenation process for refining Download PDFInfo
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- CN107365241A CN107365241A CN201710509161.7A CN201710509161A CN107365241A CN 107365241 A CN107365241 A CN 107365241A CN 201710509161 A CN201710509161 A CN 201710509161A CN 107365241 A CN107365241 A CN 107365241A
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- hydrogenation
- refining
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000007670 refining Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- 239000012071 phase Substances 0.000 claims abstract description 16
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000000895 extractive distillation Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 abstract description 11
- 238000004939 coking Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003245 coal Substances 0.000 abstract description 2
- 239000002283 diesel fuel Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011282 acid tar Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- -1 nitrogenous organic compound Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
- C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to effective utilization of coking of coal byproduct crude benzol, and in particular to a kind of crude benzole hydrogenation process for refining, it is characterised in that：Including liquid-phase catalysis pre-hydrotreating reaction, gas phase catalysis pre-hydrotreating reaction, main catalytic hydrogenation reaction, the material obtained by the main hydrogenation reaction of extracting rectifying, raw material pre-separation unit, hydrofinishing unit, pre-distillation unit, extractive distillation unit, aromatic hydrocarbon refining unit, dimethylbenzene distillation unit.The invention has the advantages that：BTX aromatics the heavy benzene hydrogenation in crude benzol can be made in method, and the BTX aromatics can make the high-quality blend component of petrol and diesel oil, the material output value and added value lifting.
Description
Technical field
The present invention relates to effective utilization of coking of coal byproduct crude benzol, and in particular to a kind of crude benzole hydrogenation process for refining.
Background technology
In recent years, with the continuous development of national economy, the demand rapid growth of national STRENGTH ON COKE, coking crude benzene is caused
Yield Deng resource-type byproduct improves constantly, due to containing some unsaturated hydrocarbons and the nitrogenous organic compound of sulfur-bearing in coking crude benzene
Thing, such as linear paraffin mercaptan, aromatic radical mercaptan, thioether, thiophene, dibenzothiophenes, benzo-thiophene, pyridine, can not be directly as having
Machine uses into raw material, and only above-mentioned impurity removal rear can be used, and the traditional removing impurities method of coking crude benzene is acid wash, the party
Although sulfur-containing compound and some other impurity in the removing crude benzol of method energy part, aromatic compound damages in process
Lose larger, by-product waste acid tar oil and residue there is no effective governance approach, cause environmental pollution, end product quality and oil
Level product quality variance is larger, and use has larger limitation, and added value is low, and economic benefit is relatively poor, prior art
Show, there is many deficiencies in existing crude benzene refining technique, not only raw material is discarded more, and the easy coking and blocking of reaction system,
Higher is required to reaction temperature simultaneously.
The content of the invention
The shortcomings that in order to overcome above-mentioned prior art, it is an object of the invention to provide suitable for industrialized crude benzole hydrogenation essence
Technique processed, this method will not produce heavy benzol accessory substance, raw material adds without waste, product without carrying out pre-separation processing to crude benzol
Value improves, and simultaneity factor is not easy coking and blocking, and reaction condition more relaxes, process stabilization is easily-controllable.
In order to solve the above technical problems, technical scheme provided by the invention is：Including liquid-phase catalysis pre-hydrotreating reaction, gas phase
Pre-hydrotreating reaction is catalyzed, main catalytic hydrogenation reaction, the material obtained by the main hydrogenation reaction of extracting rectifying, raw material pre-separation unit, is added
Hydrogen refined unit, pre-distillation unit, extractive distillation unit, aromatic hydrocarbon refining unit, dimethylbenzene distillation unit.
Preferably, described crude benzole hydrogenation process for refining, it is characterised in that：The hydrogen oil volume of gas phase catalysis pre-hydrotreating reaction
Than for 400~500：1, reaction pressure is 2.0~2.8MPa, and volume space velocity is 0.5~5h-1.
Preferably, crude benzole hydrogenation process for refining according to claim 1, it is characterised in that：Main catalytic hydrogenation reaction
Hydrogen to oil volume ratio be 400~500：1, reaction pressure is 2.0~2.8MPa, and volume space velocity is 0.5~5h-1.
A kind of preparation method of described coking additire, it comprises the following steps：
(1), filter off except contained solid impurity in crude benzol, be then fed into hydrofinishing unit and carry out three sections of hydrogenation reactions,
The crude benzol temperature after filtering is increased to 130~140 DEG C particular by heater, is then fed into liquid phase pre-hydrogenator
Liquid-phase catalysis pre-hydrotreating reaction is carried out in (the reactor outlet temperature control is at 150~160 DEG C), after liquid phase pre-hydrotreating reaction
Material is vaporized into evaporator, and evaporator outlet temperature is controlled at 230~240 DEG C；Material after vaporization is hydrogenated with advance into gas phase
Gas phase catalysis pre-hydrotreating reaction is carried out in reactor, then enters back into main catalytic hydrogenation reactor and carries out main catalytic hydrogenation instead
Should；
(2), the H2S gases of hydrogenation gained are separated from tower top is stablized；
(3), in tower reactor BTXS (i.e. triphenyl fraction) passed sequentially through in rectification cell pre-rectifying tower, extraction tower, regenerator,
Benzene,toluene,xylene and a small amount of solvent naphtha is made in pure benzene tower, benzenol hydrorefining respectively.The operating method of rectification cell routinely skill
Art performs.In present invention process, material can obtain having more 8wt% or so compared with prior art after benzenol hydrorefining rectifying separation
BTX aromatics component.
The invention has the advantages that：A kind of crude benzole hydrogenation process for refining, it is that crude benzol is subjected to liquid-phase catalysis pre-add successively
Hydrogen reaction, gas phase catalysis pre-hydrotreating reaction and main catalytic hydrogenation reaction, the then material obtained by the main hydrogenation reaction of extracting rectifying, both
Obtain the cut of each boiling range；Compared with prior art, catalytic hydrogenation process is adjusted to three sections of hydrogen addition technologies, catalytic hydrogenation by the present invention
It is preceding without pre-separation heavy benzol, meanwhile, in the reformed pre-hydrogenated process of liquid-phase catalysis, realize 130~140 DEG C of relatively low reaction temperature
Saturated hydrocarbons is made in the unsaturated olefin hydrogenation in crude benzol under degree, avoids the easy unsaturated hydrocarbons in high temperature polymerization contained in crude benzol
The situation of high temperature polymerization coking and blocking system occurs in subsequent handling.
Embodiment
Raw material is coking crude benzene, and its contained component and mass fraction are as follows：
Benzene：75%th, toluene：13.9%th, dimethylbenzene：2.24%th, light component：0.86%th, heavy constituent：8%th, total sulfur content
6546.57ppm, total nitrogen content 899.3ppm.
In the present embodiment, the reaction temperature of liquid-phase catalysis pre-hydrotreating reaction is 140 DEG C, catalyst Co-Mo, hydrogen oil volume
Than for 500:1st, volume space velocity 3h-1, pressure 2.8MPa；
The reaction temperature of gas phase catalysis pre-hydrotreating reaction is 190 DEG C, and catalyst is Ni-Mo catalyst, hydrogen to oil volume ratio is
400:1st, volume space velocity 0.5h-1, pressure 2.0MPa；
The reaction temperature of main catalytic hydrogenation reaction is 270 DEG C, and catalyst is Cr-Mo catalyst, hydrogen to oil volume ratio 400:
1st, volume space velocity 0.5h-1, pressure 2.0MPa.
After hydrogenation reaction：Product total sulfur content is that 0.2ppm total nitrogen contents are less than 0.3ppm, liquid-phase catalysis pre-hydrotreating reaction
Aromatic hydrocarbons retention be that 99.669% gas phase catalysis pre-hydrotreating reaction aromatic hydrocarbons retention is that 99.673% main hydrogenation catalyst reacts
Aromatic hydrocarbons retention is 99.675%.
Hydrofinishing unit includes reactive moieties and steady component；Reactive moieties use three sections of hydrogenation reactions, one-stage hydrogenation
It is main hydrogenation reaction to react for pre-hydrotreating reaction, two, three sections of hydrogenation reactions.Three sections of hydrogenation reactions, extend hydrogenation process,
It ensure that sulfur-bearing organic compounds containing nitrogen at lower temperatures, can also be converted into inorganic sulfur, inorganic nitrogen compound, so as to reach
The purpose of purification.
Include extraction distillation column, stripping tower and Liquid liquid Separation groove in extractive distillation unit, extractant is from extractive distillation tower top
Portion enters, and hydrogenated oil enters in the middle part of extraction distillation column, and overhead product enters stripping tower, extractant and aromatic hydrocarbons in the form of gas phase
Aromatic hydrocarbon refining unit is drained into extraction distillation column tower reactor, extraction distillation column top gaseous phase product enters the progress rectifying of stripping tower and carried
It is pure, sent out in the non-aromatic hydrocarbon product of stripping column overhead, the heavy phase product of stripping tower bottom of towe is sent into Liquid liquid Separation groove by the effect of pump.
It is divided into heavy phase product and light phase product, heavy phase product extractant and aromatic hydrocarbons in Liquid liquid Separation groove, after fluid accumulation, returns to extraction
Destilling tower；Light phase product non-aromatics, return to stripping tower.
Claims (3)
- A kind of 1. crude benzole hydrogenation process for refining, it is characterised in that：Including liquid-phase catalysis pre-hydrotreating reaction, hydrogenation is anti-in advance for gas phase catalysis Should, main catalytic hydrogenation reaction, the material obtained by the main hydrogenation reaction of extracting rectifying, raw material pre-separation unit, hydrofinishing unit, in advance Distillation unit, extractive distillation unit, aromatic hydrocarbon refining unit, dimethylbenzene distillation unit.
- 2. crude benzole hydrogenation process for refining according to claim 1, it is characterised in that：The hydrogen oil of gas phase catalysis pre-hydrotreating reaction Volume ratio is 400~500：1, reaction pressure is 2.0~2.8MPa, and volume space velocity is 0.5~5h-1.
- 3. crude benzole hydrogenation process for refining according to claim 1, it is characterised in that：The hydrogen oil volume of main catalytic hydrogenation reaction Than for 400~500：1, reaction pressure is 2.0~2.8MPa, and volume space velocity is 0.5~5h-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710509161.7A CN107365241A (en) | 2017-06-28 | 2017-06-28 | A kind of crude benzole hydrogenation process for refining |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710509161.7A CN107365241A (en) | 2017-06-28 | 2017-06-28 | A kind of crude benzole hydrogenation process for refining |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107365241A true CN107365241A (en) | 2017-11-21 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710509161.7A Pending CN107365241A (en) | 2017-06-28 | 2017-06-28 | A kind of crude benzole hydrogenation process for refining |
Country Status (1)
| Country | Link |
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| CN (1) | CN107365241A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003929A (en) * | 2017-12-18 | 2018-05-08 | 金冬梅 | A kind of heavy benzene hydrogenation process for refining |
| CN108085059A (en) * | 2017-12-18 | 2018-05-29 | 金冬梅 | A kind of method that heavy benzene hydrogenation refines fuel oil |
| CN108441259A (en) * | 2018-04-13 | 2018-08-24 | 金冬梅 | A kind of heavy benzene hydrogenation process for purification |
| CN108485703A (en) * | 2018-04-11 | 2018-09-04 | 金冬梅 | A kind of heavy benzene hydrogenation process for purification |
| CN109651051A (en) * | 2019-01-14 | 2019-04-19 | 武汉聚川科技有限公司 | A kind of crude benzol catalytic hydrogenation process and equipment |
-
2017
- 2017-06-28 CN CN201710509161.7A patent/CN107365241A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003929A (en) * | 2017-12-18 | 2018-05-08 | 金冬梅 | A kind of heavy benzene hydrogenation process for refining |
| CN108085059A (en) * | 2017-12-18 | 2018-05-29 | 金冬梅 | A kind of method that heavy benzene hydrogenation refines fuel oil |
| CN108485703A (en) * | 2018-04-11 | 2018-09-04 | 金冬梅 | A kind of heavy benzene hydrogenation process for purification |
| CN108441259A (en) * | 2018-04-13 | 2018-08-24 | 金冬梅 | A kind of heavy benzene hydrogenation process for purification |
| CN109651051A (en) * | 2019-01-14 | 2019-04-19 | 武汉聚川科技有限公司 | A kind of crude benzol catalytic hydrogenation process and equipment |
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Application publication date: 20171121 |