CN103789032B - Method for hydrogenation of medium-low temperature coal tar to produce refrigerator oil base oil - Google Patents
Method for hydrogenation of medium-low temperature coal tar to produce refrigerator oil base oil Download PDFInfo
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- CN103789032B CN103789032B CN201210433553.7A CN201210433553A CN103789032B CN 103789032 B CN103789032 B CN 103789032B CN 201210433553 A CN201210433553 A CN 201210433553A CN 103789032 B CN103789032 B CN 103789032B
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000003921 oil Substances 0.000 title claims abstract description 56
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 40
- 239000002199 base oil Substances 0.000 title claims abstract description 27
- 239000011280 coal tar Substances 0.000 title abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010457 zeolite Substances 0.000 claims abstract description 12
- 238000005194 fractionation Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 239000002283 diesel fuel Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 3
- 238000004939 coking Methods 0.000 claims description 3
- 239000010763 heavy fuel oil Substances 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000003507 refrigerant Substances 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 abstract 1
- 239000011269 tar Substances 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000011161 development Methods 0.000 description 11
- 238000011160 research Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for hydrogenation of medium-low temperature coal tar to produce refrigerator oil base oil. The method includes: fractionating the medium-low temperature coal tar to obtain light fraction and heavy fraction, mixing the light fraction with hydrogen and leading the mixture into a hydrotreating reaction area to contact a hydrogenation protective catalyst and a hydrofining catalyst in order to undergo hydrogenation reaction; separating the hydrofining effluent, making the obtained liquid phase product enter a fractionating tower; bringing the 320-350DEG C diesel fraction obtained by fractionation into a hydro-upgrading reaction area where a hydro-upgrading catalyst containing amorphous aluminium silicon and modified Y zeolite is adopted, and performing hydro-upgrading reaction in the presence of hydrogen; subjecting the hydro-upgrading effluent into a hydrofinishing reaction area to undergo hydrofinishing reaction, and separating the hydrofinishing product to obtain the refrigerator oil base oil. The method provided by the invention adopts the medium-low temperature coal tar as the raw material to produce the refrigerator oil base oil with the characteristics of good low-temperature fluidity, corrosiveness, intersolubility with refrigerant and oxidation stability.
Description
Technical field
The present invention relates to a kind of production method of refrigerator oil base oil, specifically a kind ofly adopt in raw materials pretreatment, method that coalite tar adopts hydrotreatment-hydro-upgrading/hydrofinishing two-stage hydrogenation produces the method for refrigerator oil base oil.
Background technology
Refrigerator oil is specialized oil product, requires to have stronger oilness, low-temperature fluidity, oxidation stability and high flash point.Also require can dissolve each other between refrigerator oil and refrigerant, the chemical stability of product is fabulous, can the life-span same with compressor, and the requirement of these harshnesses, at present in mineral oil, only has naphthene base crude oil and synthetic oil to have the ability to reach.Thus naphthene base crude oil becomes the main raw material manufacturing refrigerator oil, at mineral oil origin refrigerator oil in the market, is substantially all cycloalkyl refrigerator oil.Although the mineral oil of other type also can produce very low pour point, the mutual solubility between they and refrigerant is poor, cannot in compressor assembly normal circulation and serious lubrication trouble may be caused.So one of naphthene base crude oil main application is just used to manufacture refrigerator oil.
The production technique of refrigerator oil base oil is along with the development of oil refining process.Be using naphthenic base crude as raw material the earliest, adopt sulfuric acid-clay-filtered explained hereafter refrigerator oil base oil, but the method cost be high, yield is low, treatment capacity is little, the most important thing is to produce a large amount of acid sludge contaminate environment.
CN201010218640.1 discloses a kind of refrigerator oil base oil with cycloalkyl distillate for raw material carries out hydrotreatment, and generation oil cuts 320 ~ 350 DEG C of cuts and carries out clay-filtered again, obtains the production method of refrigerator oil base oil.But the method poor continuity, and not through hydro-upgrading process, oxidation stability and low-temperature fluidity poor, also there is clay treated environmental problem simultaneously.
CN201010222066.7 discloses a kind of method adopting perhydro method to produce refrigerator oil base oil.With cycloalkyl distillate for raw material, the one-stage serial hydrogenation technique of hydrotreatment-hydrodewaxing-hydrofinishing is adopted to produce refrigerator oil base oil and other specialty oil products.The method energy consumption is low, good product quality, but there is the problem of cycloalkyl distillate resource-constrained.
At present, the naphthenic base crude resource of China mainly concentrates on the large block in Karamay, Xinjiang, Liaohe Huanxiling and Bohai Sea Gulf three, wherein, at home and abroad share of market is higher to utilize the cycloalkyl refrigerator oil base oil of Karamay, Xinjiang crude production, and effect is better.And Liaohe Huanxiling crude oil reduces and quality variation along with output, can not as the stable resources producing refrigerator oil.Along with the development of China's refrigeration industry, the domestic refrigerator oil market requirement constantly increases, and imbalance between supply and demand is more outstanding, therefore opens up the refrigerator oil raw materials for production that other is suitable, realizes refrigerator oil and significantly domesticize, be of great immediate significance.
China is the very abundant countries of coal resources, and a large amount of coal tar of Coal Chemical Industry process by-product, has certain natural crude oil characteristic, how to effectively utilize the important step that coal tar is the comprehensive utilization of coal.It is high that coal tar has aromaticity content, after hydrotreatment and hydro-upgrading, can be transformed into naphthenic hydrocarbon, can produce the refrigerator oil base oil that low-temperature fluidity is good, lubricity is outstanding, oxidation stability is good.
Summary of the invention
For the deficiencies in the prior art, the invention provides one with middle coalite tar for raw material, the method for employing hydrotreatment-hydro-upgrading-hydrofinishing Unionfining produces the method for refrigerator oil base oil.
Middle coalite tar hydrogenation of the present invention is produced refrigerator oil base oil method and is comprised following content:
(1) in, coalite tar obtains lighting end and last running through fractionation, and cut point is 480 ~ 510 DEG C;
(2) step (1) described lighting end enters hydrotreatment reaction zone after mixing with hydrogen, contacts successively carry out hydrogenation reaction with hydrogenation protecting catalyst with Hydrobon catalyst;
(3) step (2) gained hydrofining effluent carries out gas-liquid separation, and separating obtained liquid product enters separation column;
(4) step (3) fractionation gained 320 ~ 350 DEG C of diesel oil distillates enter hydro-upgrading reaction zone, and hydro-upgrading reaction zone uses the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite, in presence of hydrogen, carries out hydro-upgrading reaction;
(5) step (4) gained hydro-upgrading effluent enters hydrofinishing reaction zone, and in presence of hydrogen, with hydrofinishing catalyst exposure, carry out hydrofinishing reaction, hydrofinishing product is isolated to refrigerator oil base oil.
In the inventive method, the described middle coalite tar of step (1) carries out fractionation after first carrying out dewatering and remove mechanical impurity again.
In the inventive method, after the described middle coalite tar fractionation of step (1), gained last running can be used as modifying asphalt, heavy fuel oil (HFO), or is used as coking raw material.
In the inventive method, hydrotreatment reaction zone loads hydrogenation protecting catalyst and Hydrobon catalyst from top to bottom, and the admission space of hydrogenation protecting catalyst and Hydrobon catalyst is than being 10:25 ~ 75:90.
In the inventive method; hydrotreatment reaction zone uses conventional hydrogenation protecting catalyst; the FZC series protective material of Fushun Petrochemical Research Institute (FRIPP) development and production can be adopted; also can conventionally prepare; these catalyzer generally with porous refractory inorganic oxide if aluminum oxide is for carrier; group vib and/or group VIII metal such as the oxide compound of W, Mo, Co, Ni etc. are active ingredient, optionally add other various auxiliary agent as the catalyzer of the elements such as P, Si, F, B.
In the inventive method, the Hydrobon catalyst that hydrotreatment reaction zone uses, can select this field general goods catalyzer, also can prepare by this area general knowledge.The commercial catalysts that can select as Fushun Petrochemical Research Institute (FRIPP) development and production 3936,3996, the Hydrobon catalyst such as FF-16, FF-26.
In the inventive method, in order to play the performance of catalyst for hydro-upgrading better, at the better Hydrobon catalyst of a certain proportion of Hydrogenation of top grading loading of catalyst for hydro-upgrading, carry out desulfurization, denitrogenation, saturated condensed-nuclei aromatics, play the open-loop performance of catalyst for hydro-upgrading better, increase the running period of whole device.Hydro-upgrading reaction zone uses Hydrobon catalyst in the catalyst for hydro-upgrading top filling containing amorphous aluminum silicide and modified Y zeolite, and the admission space of Hydrobon catalyst and the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite is than being 25:75 ~ 60:40.
In the inventive method, the Hydrobon catalyst on top, hydro-upgrading district can select this field general goods catalyzer, also can prepare by this area general knowledge.The commercial catalysts that can select is as commodity Hydrobon catalysts such as the FTX of Fushun Petrochemical Research Institute (FRIPP) development and production.
In the inventive method, hydro-upgrading reaction zone uses the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite.Contain in described catalyst for hydro-upgrading: the group VIII metal (with oxide basis) of the modified Y zeolite of 20wt% ~ 60wt% amorphous aluminum silicide, 5wt% ~ 25wt%, the group VIB metal (with oxide basis) of 10wt% ~ 30wt% and 4wt% ~ 10wt%.The character of amorphous aluminum silicide wherein used is as follows: silicon oxide-containing 10wt% ~ 60wt%, and specific surface is 400 ~ 650m
2/ g, pore volume is 1.0 ~ 1.8mL/g, and infrared acidity is 0.34 ~ 0.50mmol/g, and the pore volume that the pore volume of bore dia 4 ~ 10nm accounts for 85% ~ 95%, >15nm of total pore volume accounts for less than 5% of total pore volume; Preferred property is as follows: silicon oxide-containing 10wt% ~ 35wt%, and specific surface is 530 ~ 650m
2/ g, pore volume is 1.2 ~ 1.5mL/g.The character of modified Y zeolite wherein used is as follows: SiO
2/ Al
2o
3mol ratio is 40 ~ 60, and lattice constant is 2.425 ~ 2.440nm, and relative crystallinity is 80% ~ 100%, infrared acidity 0.1 ~ 0.5mmol/g, and wherein the middle strong acid distribution of 250 ~ 550 DEG C is concentrated, and account for 60 ~ 70% of total acid, specific surface area is 600 ~ 900m
2/ g, pore volume 0.3 ~ 0.6mL/g, wherein the pore volume of the secondary mesopore of 4 ~ 15nm accounts for 40% ~ 50% of total pore volume.The components such as aluminum oxide, zirconium white, titanium oxide can also be contained in catalyst for hydro-upgrading.The specific surface area of catalyst for hydro-upgrading is 220 ~ 300m
2/ g, pore volume is 0.3 ~ 0.6mL/g, and the pore volume of bore dia 3 ~ 10nm accounts for 75% ~ 95% of total pore volume, and be preferably 85% ~ 95%, infrared acidity is at 0.3 ~ 0.5mmol/g.
In the inventive method, hydrofinishing reaction zone uses conventional hydrofinishing catalyzer, its active metal component is group vib and group VIII metal, uses procatalyst to carry out prevulcanized, ensures that hydrogenation active metals is in sulphided state in reaction process.Described group vib metal is selected from Mo and/or W, its content with oxide basis for 10 ~ 25%; Group VIII metal is selected from Co and/or Ni, its content with oxide basis for 3 ~ 7%.
In the inventive method, in step (3), the reaction conditions of hydrotreatment reaction zone is: reaction pressure 5.0 ~ 20.0MPa, preferably 12.0 ~ 15.0MPa; Temperature of reaction 250 ~ 420 DEG C, preferably 300 ~ 400 DEG C; Hydrogen to oil volume ratio 500:1 ~ 1500:1, preferred 1000:1 ~ 1200:1; Volume space velocity 0.1 ~ 1.0h
-1, preferably 0.5 ~ 0.7h
-1.
In the inventive method, in step (4), the reaction conditions of hydro-upgrading reaction zone is: reaction pressure 5.0 ~ 20.0MPa, preferably 12.0 ~ 15.0MPa; Temperature of reaction 250 ~ 370 DEG C, preferably 300 ~ 350 DEG C; Hydrogen to oil volume ratio 500:1 ~ 1500:1, preferred 800:1 ~ 1000:1; Volume space velocity 0.1 ~ 1.5h
-1, preferably 0.8 ~ 1.0h
-1.
In the inventive method, in step (5), the reaction conditions of hydrofinishing reaction zone is: reaction pressure 5.0 ~ 20.0MPa, preferably 12.0 ~ 15.0MPa; Temperature of reaction 200 ~ 350 DEG C, preferably 290 ~ 320 DEG C; Hydrogen to oil volume ratio 500:1 ~ 1500:1, preferred 1000:1 ~ 1200:1; Volume space velocity 0.1 ~ 1.5h
-1, preferably 0.8 ~ 1.0h
-1.
Compared with prior art, tool of the present invention has the following advantages:
(1) first the present invention will carry out hydrotreatment through pretreated middle coalite tar, because coal tar is different from distillate molecular structure, desulfurization during hydrotreatment, denitrogenation and aromatic moiety are saturated causes structure collapses, and then coal tar is done and is greatly moved forward (maximum move forward about 100 DEG C), structure redistributes, distillate characteristic increases greatly, and aromaticity content is higher than cycloalkyl straight-run diesel oil simultaneously.The present invention adopts suitable catalyst for hydro-upgrading, after hydro-upgrading open loop and hydrofinishing, generates the naphthenic hydrocarbon of the many side chains of a large amount of bands, can obtain oilness, with refrigerant mutual solubility and all good refrigerator oil base oil of oxidation stability.There is a small amount of straight-chain paraffin isomery of certain influence to become branched paraffin to condensation point simultaneously, ensure the low-temperature performance of product.
(2) the inventive method is that the middle coalite tar that added value is lower provides a kind of processing works improving its economy, and develops a kind of new raw material for refrigerator oil base oil.China is the country of a rich coal resources, there is a large amount of tar resources, utilize the inventive method can substitute rare naphthenic base crude resource, produce the refrigerator oil base oil that refrigeration industry is badly in need of, effectively can promote the Appropriate application of tar resource simultaneously.
(3) other cut after the inventive method hydrotreatment can as the blend component of gasoline and diesel oil, or the raw material of other specialty oil products.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
Below in conjunction with accompanying drawing, the inventive method is described in detail.
As shown in Figure 1, through dehydration with remove coalite tar 1 in mechanical impurity and enter vacuum still 2 and carry out fractionation, obtain lighting end 3 and last running 4, gained last running 4 can be used as modifying asphalt, heavy fuel oil (HFO), or as coking raw material.Lighting end 3 mixes back end hydrogenation treatment reactor 6 with hydrogen 5, contact with Hydrobon catalyst with hydrogenation protecting catalyst successively, carry out hydrogenation reaction, gained hydrofining effluent 7 is after separation system 8 is separated, described separation system 8 generally comprises high-pressure separator and light pressure separator, separating obtained gas phase 9 returns hydrotreating reactor 6 as recycle hydrogen, isolated liquid phase 10 removes after hydrogen sulfide and gas products 12 through stripping tower 11, stripping tower bottom liquid phase 13 removes separation column 14, obtain respectively being less than 160 DEG C of cuts 15, 160 ~ 320 DEG C of cuts 16, 320 ~ 350 DEG C of cuts 17 and be greater than 350 DEG C of cuts 18.Wherein, be less than 160 DEG C of cuts 15 and can do gasoline blending component, 160 ~ 320 DEG C of cuts 16 can do diesel oil blending component, are greater than 350 DEG C of cuts 18 and can cut further as rubber filling oil raw material or environment-friendly type aromatic hydrocarbon oil raw material.320 ~ 350 DEG C of cuts 17 enter hydro-upgrading reaction zone 19, in presence of hydrogen, contact with catalyst for hydro-upgrading, carry out saturated open loop to two rings and a small amount of thrcylic aromatic hydrocarbon, and on rear side of maintenance open loop simultaneously, chain is complete, becomes the monocycle or two Polycyclic aromatic hydrocarbons of being with many side chains.Hydro-upgrading reaction product 20 enters hydrofinishing reaction zone 21, under hydrogen and Hydrobon catalyst exist, carries out aromatic hydrocarbons degree of depth saturated reaction, reduces aromaticity content, ensure the oxidation stability index of product.Then hydrofinishing product 22 is isolated after gas 24 through separator 23, and liquid product 25 enters after separation column 26 isolates a small amount of byproduct 17, obtains refrigerator oil base oil product 28.
Below in conjunction with embodiment, the present invention will be further described.
The various catalyzer related in embodiment can select commercial catalyst by character, also can prepare by this area knowledge.The commercial catalysts that the hydrogenation protecting agent of hydroprocessing processes can be selected is as hydrogenation protecting agent such as FZC-100, FZC-102A, FZC-103 of Fushun Petrochemical Research Institute's development and production; The commercial catalysts that can select of Hydrobon catalyst as Fushun Petrochemical Research Institute's development and production 3936,3996, the Hydrobon catalyst such as FF-16, FF-26; The commercial catalysts that the Hydrobon catalyst on top, hydro-upgrading district can be selected is as commodity Hydrobon catalysts such as the FTX of Fushun Petrochemical Research Institute's development and production; The commercial catalysts that catalyst for hydro-upgrading can be selected is as commodity hydrotreating catalysts such as FC-14, FC-26 of Fushun Petrochemical Research Institute's development and production; The commercial catalysts that hydrofinishing process can be selected is as commodity Hydrobon catalysts such as FV-10, FV-20 of Fushun Petrochemical Research Institute's development and production.
Embodiment 1
With Datang coalite tar for raw material, cut point is 500 DEG C, and specific nature is in table 1.Hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936, the admission space of hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 is than being 1:4.Hydro-upgrading reaction zone filling FTX catalyzer and FC-28 catalyzer, admission space is than being 1:1, and hydrofinishing reaction zone filling Hydrobon catalyst FV-10, the processing condition of hydrogenation process and product property are in table 2.
Embodiment 2
With her eastern coal-tar middle oil for raw material, cut point is 500 DEG C, and specific nature is in table 1.Hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936, the admission space of hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 is than being 1:4.Hydro-upgrading reaction zone filling FTX catalyzer and FC-28 catalyzer, admission space is than being 1:1, and hydrofinishing reaction zone filling Hydrobon catalyst FV-10, the processing condition of hydrogenation process and product property are in table 2.
Comparative example 1
Adopt the raw material identical with embodiment 1, difference is that hydrotreatment products cuts out diesel oil distillate without hydro-upgrading, directly enters hydrofinishing reactor.Hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936, the admission space of hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 is than being 1:4.Hydrofinishing reaction zone filling Hydrobon catalyst FV-10, the processing condition of hydrogenation process and product property are in table 2.
Comparative example 2
With Datang coalite tar 320 ~ 350 DEG C of diesel oil distillates for raw material, specific nature is in table 1.Raw material Datang coalite tar 320 ~ 350 DEG C of diesel oil distillates carry out hydrofining reaction merely through hydrotreatment reaction zone; hydrotreatment reaction zone filling hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936, the admission space of hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 is than being 1:4.The processing condition of hydrogenation process and product property are in table 2.
Table 1 test feedstock property
| Material name | Datang coalite tar | Her eastern coal-tar middle oil | Datang coalite tar 320 ~ 350 DEG C of cuts |
| Density (20 DEG C), g.cm -3 | 1.0284 | 1.010 | 0.9547 |
| Boiling range (simulation distil), DEG C | |||
| IBP | 77 | 39 | 321 |
| 10%/30%/50% | 161/205/253 | 216/276/328 | 325/329/334 |
| 70%/90%/95% | 311/390/425 | 374/428/444 | 338/342/349 |
| EBP | 495 | 513 | 352 |
| Sulphur, μ g.g -1 | 8800 | 2300 | 7560 |
| Nitrogen, μ g.g -1 | 9500 | 6283 | 9400 |
| Viscosity (100 DEG C), mm.s -2 | 3.004 | ||
| Carbon residue, % | 0.45 | 1.14 | 0.14 |
| Condensation point, DEG C | 8 | 5 | -15 |
| Flash-point (opening), DEG C | 112 | 142 | 103(remains silent) |
| Acid number, mgKOH.g -1 | 0.81 | ||
| Mechanical impurity, wt% | 0.023 | 0 | |
| Mass spectrum forms, wt% | |||
| Colloid | 33.5 | 22.0 | 15.8 |
| Paraffinic hydrocarbons | 6.9 | 0 | 6.8 |
| Naphthenic hydrocarbon | 7.6 | 0 | 26.8 |
| Aromatic hydrocarbons | 52.0 | 78.0 | 50.4 |
| Monocycle/dicyclo/tri-ring | 13.1/24.4/8.5 | 21.3/31.7/13.5 | 15.3/26.6/8.3 |
| Fourth Ring/five rings/thiophene | 2.0/0.2/3.4 | 6.1/0.5/4.0 | 0.2/-/- |
| Do not identify aromatic hydrocarbons | 0.4 | 0.9 | 0.2 |
| Heavy metal, μ g.g -1 | <5 | <5 |
The processing condition of table 2 embodiment and comparative example and result
| Test number | Embodiment 1 | Comparative example 1 | Embodiment 2 | Comparative example 2 |
| Hydroprocessing technique condition | ||||
| Temperature of reaction, DEG C | 380 | 380 | 380 | 320 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 0.5 | 0.5 | 0.5 | 1.0 |
| 320 ~ 350 DEG C of cut yields, wt% | 15.21 | 15.21 | 13.76 | 37.23 |
| Hydro-upgrading reaction process condition | ||||
| Temperature of reaction, DEG C | 330 | 330 | ||
| Reaction pressure, MPa | 15.0 | 15.0 | ||
| Hydrogen to oil volume ratio | 800:1 | 800:1 | ||
| Volume space velocity, h -1 | 1.0 | 1.0 | ||
| Hydrofinishing reaction process condition | ||||
| Temperature of reaction, DEG C | 285 | 285 | 285 | |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 | |
| Hydrogen to oil volume ratio | 800:1 | 800:1 | 800:1 | |
| Volume space velocity, h -1 | 1.0 | 1.0 | 1.0 | |
| Object product yield, wt% | 75.3 | 91.6 | 73.2 | |
| Product property | ||||
| Density (20 DEG C), kg.m -3 | 0.8795 | 0.8883 | 0.8785 | 0.8983 |
| Viscosity (40 DEG C), mm 2.s -1 | 14.52 | 17.03 | 13.96 | 20.45 |
| Pour point, DEG C | -45 | -30 | -47 | -21 |
| Flash-point (opening), DEG C | 165 | 170 | 160 | 172 |
| Two-phase is dissolved each other temperature, DEG C | ||||
| Color (D1500), number | <0.5 | <0.5 | <0.5 | <0.5 |
| Acid number, mgKOH.g -1 | 0.01 | 0.01 | 0.01 | 0.01 |
| Carbon residue, wt% | 0.01 | 0.01 | 0.01 | 0.01 |
| Ash content, wt% | Vestige | Vestige | Vestige | Vestige |
| Corrosion test (copper sheet, 100 DEG C, 3h) level | 1b | 1b | 1b | 1c |
| Color/number (Sai Shi) | +30 | +30 | +30 | |
| Sulphur content, μ g.g -1 | 1 | 1 | 1 | 15 |
Can be found out by the product property of embodiment 1 and comparative example 1, only do not have hydrogenation modifying process process through hydrofining process, products obtained therefrom condensation point is high, and low-temperature fluidity is poor.And the product directly cutting 320 ~ 350 DEG C of cut fraction hydrogenation process in comparison example 2 is the poorest, oxidation stability, corrosive nature and low temperature flowability are all defective.
Can be found out by the product property of embodiment 1 and embodiment 2, in employing coalite tar by hydrotreatment-hydro-upgrading/hydrogenation post-refining process can produce low-temperature fluidity, corrodibility, with refrigerant mutual solubility and all good refrigerator oil base oil of oxidation stability, gained refrigerator oil performance can meet the performance perameter index of No. 15 L-DRB/A refrigerator oil base oils.Greatly can expand the raw material sources becoming refrigerator base oil, meet the needs of national refrigeration industry great development, also enrich the deep exploitation of tar resource simultaneously, there is very large economic benefit and social benefit.
Claims (14)
1. in, coalite tar hydrogenation produces a refrigerator oil base oil method, comprises following content:
(1) in, coalite tar obtains lighting end and last running through fractionation, and cut point is 480 ~ 510 DEG C;
(2) step (1) described lighting end enters hydrotreatment reaction zone after mixing with hydrogen, contacts successively carry out hydrogenation reaction with hydrogenation protecting catalyst with Hydrobon catalyst;
(3) step (2) gained hydrofining effluent carries out gas-liquid separation, and separating obtained liquid product enters separation column;
(4) step (3) fractionation gained 320 ~ 350 DEG C of diesel oil distillates enter hydro-upgrading reaction zone, and hydro-upgrading reaction zone uses the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite, in presence of hydrogen, carries out hydro-upgrading reaction;
(5) step (4) gained hydro-upgrading effluent enters hydrofinishing reaction zone, and in presence of hydrogen, with hydrofinishing catalyst exposure, carry out hydrofinishing reaction, hydrofinishing product is isolated to refrigerator oil base oil.
2. in accordance with the method for claim 1, it is characterized in that: the described middle coalite tar of step (1) carries out fractionation after first carrying out dewatering and remove mechanical impurity again.
3. in accordance with the method for claim 1, it is characterized in that: after the described middle coalite tar fractionation of step (1), gained last running is used as modifying asphalt, heavy fuel oil (HFO), or as coking raw material.
4. in accordance with the method for claim 1, it is characterized in that: hydrotreatment reaction zone loads hydrogenation protecting catalyst and Hydrobon catalyst from top to bottom, the admission space of hydrogenation protecting catalyst and Hydrobon catalyst is than being 10:25 ~ 75:90.
5. in accordance with the method for claim 1, it is characterized in that: hydro-upgrading reaction zone is at the catalyst for hydro-upgrading top filling Hydrobon catalyst containing amorphous aluminum silicide and modified Y zeolite, and the admission space of described Hydrobon catalyst and the catalyst for hydro-upgrading containing amorphous aluminum silicide and modified Y zeolite is than being 25:75 ~ 60:40.
6. in accordance with the method for claim 1, it is characterized in that: in step (2), the operational condition of hydrotreatment reaction zone is: reaction pressure 5.0 ~ 20.0MPa, temperature of reaction 250 ~ 420 DEG C, hydrogen to oil volume ratio 500:1 ~ 1500:1, volume space velocity 0.1 ~ 1.0h
-1.
7. the method for right as requested described in 1, is characterized in that: in step (4), the operational condition of hydro-upgrading reactor is: reaction pressure 5.0 ~ 20.0MPa, temperature of reaction 250 ~ 370 DEG C, hydrogen to oil volume ratio 500:1 ~ 1500:1, volume space velocity 0.1 ~ 1.5h
-1.
8. the method for right as requested described in 1, is characterized in that: in step (5), the operational condition of hydrofinishing reactor is: reaction pressure 5.0 ~ 20.0MPa, temperature of reaction 200 ~ 350 DEG C, hydrogen to oil volume ratio 500:1 ~ 1500:1, volume space velocity 0.1 ~ 1.5h
-1.
9. in accordance with the method for claim 1, it is characterized in that: the modified Y zeolite containing the amorphous aluminum silicide of 20wt% ~ 60wt%, 5wt% ~ 25wt% in described catalyst for hydro-upgrading, with the group VIB metal of oxide basis 10wt% ~ 30wt% with the group VIII metal of oxide basis 4wt% ~ 10wt%.
10. according to the method described in claim 1 or 9, it is characterized in that: in described catalyst for hydro-upgrading, the character of amorphous aluminum silicide is as follows: silicon oxide-containing 10wt% ~ 60wt%, specific surface is 400 ~ 650m
2/ g, pore volume is 1.0 ~ 1.8mL/g, and infrared acidity is 0.34 ~ 0.50mmol/g, and the pore volume that the pore volume of bore dia 4 ~ 10nm accounts for 85% ~ 95%, >15nm of total pore volume accounts for less than 5% of total pore volume.
11. in accordance with the method for claim 10, it is characterized in that: in described catalyst for hydro-upgrading, the character of amorphous aluminum silicide is as follows: silicon oxide-containing 10wt% ~ 35wt%, and specific surface is 530 ~ 650m
2/ g, pore volume is 1.2 ~ 1.5mL/g.
12. in accordance with the method for claim 1, it is characterized in that: the modified Y zeolite in described catalyst for hydro-upgrading has following character: SiO
2/ Al
2o
3mol ratio is 40 ~ 60, and lattice constant is 2.425 ~ 2.440nm, and relative crystallinity is 80% ~ 100%, infrared acidity 0.1 ~ 0.5mmol/g, and wherein the middle strong acid distribution of 250 ~ 550 DEG C is concentrated, and account for 60 ~ 70% of total acid, specific surface area is 600 ~ 900m
2/ g, pore volume 0.3 ~ 0.6mL/g, wherein the pore volume of the secondary mesopore of 4 ~ 15nm accounts for 40% ~ 50% of total pore volume.
13. in accordance with the method for claim 1, it is characterized in that: the specific surface area of described catalyst for hydro-upgrading is 220 ~ 300m
2/ g, pore volume is 0.3 ~ 0.6mL/g, and the pore volume of bore dia 3 ~ 10nm accounts for 75% ~ 95% of total pore volume, and infrared acidity is at 0.3 ~ 0.5mmol/g.
14. in accordance with the method for claim 1, it is characterized in that: the hydrofinishing catalyzer that hydrofinishing reaction zone uses, its active metal component is group vib and group VIII metal, and described group vib metal is selected from Mo and/or W, its content with oxide basis for 10 ~ 25%; Group VIII metal is selected from Co and/or Ni, its content with oxide basis for 3 ~ 7%.
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| CN104498090A (en) * | 2014-12-17 | 2015-04-08 | 王树宽 | System and method for preparing naphthenic base oil and low freezing point diesel oil through all-hydrogen coal tar |
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| CN109321273B (en) * | 2018-09-27 | 2020-11-13 | 国家能源投资集团有限责任公司 | Method and device for producing naphthenic base refrigerator oil base oil |
| CN109294621B (en) * | 2018-10-30 | 2020-09-29 | 东营奥星石油化工有限公司 | Hydrofining production method of lubricating oil base oil |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4387256A (en) * | 1980-09-02 | 1983-06-07 | Imperial Oil Limited | Traction fluid lubricants derived from coal tar |
| US5015404A (en) * | 1988-04-05 | 1991-05-14 | Nippon Oil Co., Ltd. | Oil composition containing hydrogenated oil |
| JPH07166167A (en) * | 1993-12-14 | 1995-06-27 | Nkk Corp | Process for improving coal tar |
| CN1952071A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Combined method for producing cleaning oil from coal-tar oil |
| CN101250432A (en) * | 2008-03-28 | 2008-08-27 | 湖南长岭石化科技开发有限公司 | Method for producing fuel oil by hydrogenation modification of coal tar |
| CN101307257A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | A two-stage coal tar hydrogenation upgrading method |
| CN101619229A (en) * | 2008-07-04 | 2010-01-06 | 汉能科技有限公司 | Method for preparing diesel oil components with coal tar oil light ends |
| CN101629103A (en) * | 2008-10-15 | 2010-01-20 | 何巨堂 | Hydro-conversion combination method for coal tar fraction with different boiling ranges |
| CN102465033A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Processing method of medium-low temperature coal tar |
-
2012
- 2012-11-05 CN CN201210433553.7A patent/CN103789032B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4387256A (en) * | 1980-09-02 | 1983-06-07 | Imperial Oil Limited | Traction fluid lubricants derived from coal tar |
| US5015404A (en) * | 1988-04-05 | 1991-05-14 | Nippon Oil Co., Ltd. | Oil composition containing hydrogenated oil |
| JPH07166167A (en) * | 1993-12-14 | 1995-06-27 | Nkk Corp | Process for improving coal tar |
| CN1952071A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Combined method for producing cleaning oil from coal-tar oil |
| CN101307257A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | A two-stage coal tar hydrogenation upgrading method |
| CN101250432A (en) * | 2008-03-28 | 2008-08-27 | 湖南长岭石化科技开发有限公司 | Method for producing fuel oil by hydrogenation modification of coal tar |
| CN101619229A (en) * | 2008-07-04 | 2010-01-06 | 汉能科技有限公司 | Method for preparing diesel oil components with coal tar oil light ends |
| CN101629103A (en) * | 2008-10-15 | 2010-01-20 | 何巨堂 | Hydro-conversion combination method for coal tar fraction with different boiling ranges |
| CN102465033A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Processing method of medium-low temperature coal tar |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498090A (en) * | 2014-12-17 | 2015-04-08 | 王树宽 | System and method for preparing naphthenic base oil and low freezing point diesel oil through all-hydrogen coal tar |
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