CN103436289B - Method for producing naphthenic base transformer oil base oil by using coal tar oil - Google Patents
Method for producing naphthenic base transformer oil base oil by using coal tar oil Download PDFInfo
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- 239000003921 oil Substances 0.000 title claims abstract description 153
- 239000011280 coal tar Substances 0.000 title claims abstract description 45
- 239000002199 base oil Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002283 diesel fuel Substances 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 60
- 238000000605 extraction Methods 0.000 claims description 35
- 230000003197 catalytic effect Effects 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 238000012546 transfer Methods 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 10
- 238000005194 fractionation Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000013557 residual solvent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000007670 refining Methods 0.000 abstract description 4
- 239000004927 clay Substances 0.000 abstract 1
- 238000004508 fractional distillation Methods 0.000 abstract 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000011269 tar Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for producing naphthenic base transformer oil base oil by using coal tar oil. The method is characterized in that high-additional value products such as naphtha oil, diesel oil and transformer oil base oil are obtained by adopting the steps of hydrotreating of the coal tar oil, the fractional distillation of hydrogenated products, solvent refining of transformer distillate oil and clay refining of the transformer distillate oil. The method has the advantages that the hydrogenation industrial chain of the coal tar oil is extended, the coal tar oil resource is reasonably utilized, the utilization value of the coal tar oil is increased, meanwhile, the density of the coal tar oil hydrogenated diesel oil can be reduced, the cycloparaffin distillate oil (300-360 DEG C) with high content can be obtained, the quality of the transformer oil base oil is ensured, and the obtained transformer oil base oil has high quality and high yield and is in line with the standards on the transformer oil No. 45 in national GB2536-1990 transformer oil.
Description
Technical field
The invention belongs to coal tar production technical field, particularly a kind of method of coal tar production cycloalkyl transformer oil base oil.
Background technology
The main application of transformer oil is by transformer insulated and cooling.Since transmitting transformer invention, people are just striving to find a kind of performance requriements such as insulation, cooling that can meet transformer always, again can long-term stable operation, low-cost medium.Through long-term actual use, naphthenic base oils is acknowledged as a kind of selection of the best, is also safe, the most most economical selection.At present, the transformer that the large multinational companies such as global transformer manufacturer, particularly ABB, Alstom produce, adopts the transformer oil produced with naphthenic base oils bar none.
Naphthenic base oils at high temperature viscosity is low, and the dissolving power under extremely low temperature is excellent, and has very high oxidation stability, fabulous electrical specification and good heat-transfer medium characteristic, thus becomes the best oil of transformer.But the reserves of naphthenic base crude only account for 2% ~ 3% of crude oil total reserves, due to the shortage of naphthenic base crude resource, still have a considerable amount of transformer oil by acyclic alkyl crude production in China.
Kinds of processes method is had to produce transformer oil at present both at home and abroad.
It is raw material with atmospheric distillate that the people such as Guo Huai disclose a kind of, adopt that alkali cleaning is refined, furfural treatment, hydrofining technology produce the method for ultrahigh voltage transformer oil (Guo Huai etc., face hydrogen explained hereafter No. 25 ultrahigh voltage transformer oils, refining of petroleum and chemical industry, 2nd phase in 1999,56-57).But the alkali washing process of the method can bring certain pollution, and the standard that product yield is low, condensation point does not reach No. 45 transformer oil.
US Patent No. 5167847 take paraffinic crude as raw material, produces transformer oil by hydrocracking, solvent dewaxing process; US Patent No. 4018666 for raw material, produces transformer oil by solvent treatment Arene removal and polar material with the cut of the 310-400 of paraffinic crude DEG C; CN1110709 discloses a kind of method of production of transformer oil with hydrocracking tail oil, the method is by adding aromatic hydrocarbon (alkylbenzene, refining heavy alkyl benzene or alkylnaphthalene) and naphthene base crude oil to improve its light stability in hydrocracking tail oil, all containing aliphatic hydrocarbon in raw material in these methods and product, so quality product does not have cycloalkyl transformer oil good.
Chinese patent CN100537722 discloses a kind of production method of ultrahigh voltage transformer oil, the method adopt the atmospheric distillate of naphthenic base crude and vacuum distillate one or more be raw material, hydrotreatment is carried out to it and hydrofining obtains ultrahigh voltage transformer oil.This method is raw materials used is fraction oil of petroleum, and the raw material of present method is more unmanageable coal tar, so processing method and correlation parameter also exist larger difference.
The raw material of the Technology of these reports is fraction oil of petroleum above, and the technique still not preparing whiteruss with coal tar or its derived product for raw material is reported.Contriver finds in further R&D process, has a large amount of naphthenic hydrocarbon and aromatic hydrocarbons in coal tar hydrogenating product, can as the raw material of preparation cycloalkyl transformer oil.
Summary of the invention
The object of the invention is to prepare as stock oil that naphthenic hydrocarbon distillate content is high, the measured cycloalkyl transformer oil of matter to realize coal tar, providing that a kind of technique is simple, cost is low and the method for the coal tar production cycloalkyl transformer oil base oil of Appropriate application tar resource.
The present invention realizes the technical scheme that above-mentioned purpose adopts and is made up of following steps:
(1) coal tar hydrogenating process
Coal tar is mixed with hydrogen, in hydrogenator Hydrobon catalyst and catalytic dewaxing catalyst katalysis under carry out hydrotreatment, temperature of reaction is 300 ~ 400 DEG C, pressure is 10 ~ 15MPa, hydrogen to oil volume ratio is 800 ~ 1500:1, is 0.3 ~ 0.6h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 0.6 ~ 1.0h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1, obtain hydrogenated oil;
(2) fractionation of hydrogenation products
Hydrogenated oil is sent into fractionation in separation column, obtain the residue fraction being less than the naphtha fraction of 180 DEG C, the diesel oil distillate of 180 ~ 300 DEG C, the transformer oil cut of 300 ~ 360 DEG C and being greater than 360 DEG C;
(3) solvent treatment of transformer distillate
With selective solvent to the countercurrent mass transfer heat transfer extraction in extraction tower of transformer oil cut, transformer oil after extraction carries out underpressure distillation and removes residual solvent in solvent recovery unit, the volume ratio of transformer oil cut and selective solvent is 1:1 ~ 2, extraction tower tower top temperature is 80 ~ 90 DEG C, column bottom temperature is 40 ~ 50 DEG C, completes solvent treatment;
Above-mentioned selectivity volume is phenol or N-first class pyrrolidone or furfural;
(4) transformer distillate is clay-filtered
Under nitrogen protection, mixed by the transformer oil cut after solvent treatment with carclazyte, carclazyte add-on is 7 ~ 10% of the transformer oil cut quality after solvent treatment, stirs, and 130 ~ 150 DEG C of reaction 40 ~ 50min, cooling, filters, obtain transformer oil base oil.
Above-mentioned Hydrobon catalyst take aluminium sesquioxide as the molybdenum-nickel type catalyzer of carrier, and in its catalytically-active metals, molybdic oxide content is at least 21wt%, and nickel oxide content is at least 6wt%, and total pore volume is at least 0.3mL/g, and specific surface area is at least 150m
2/ g;
Above-mentioned catalytic dewaxing catalyst is the ZSM-5 zeolite catalytic dewaxing catalyst of nickel-loaded, and in catalytically-active metals, nickel oxide content is 1 ~ 3wt%, and total pore volume is at least 0.1mL/g, and specific surface area is at least 200m
2/ g.
Coal tar mixes with hydrogen by above-mentioned steps (1), in hydrogenator Hydrobon catalyst and catalytic dewaxing catalyst katalysis under carry out hydrotreatment, temperature of reaction preferably 350 ~ 380 DEG C, be preferably 380 DEG C, pressure is 12 ~ 14MPa preferably, is preferably 14MPa, and hydrogen to oil volume ratio is 900 ~ 1200:1 preferably, be preferably 1000:1, relative to the liquid volume air speed preferably 0.4 ~ 0.5h of Hydrobon catalyst
-1, be preferably 0.4h
-1, relative to the liquid volume air speed preferably 0.8 ~ 0.9h of catalytic dewaxing catalyst
-1, be preferably 0.8h
-1, obtain hydrogenated oil.
Above-mentioned steps (3) in solvent recovery unit is carried out underpressure distillation after countercurrent mass transfer heat transfer extraction to transformer oil cut with selective solvent and is removed residual solvent in extraction tower, the volume ratio of transformer oil cut and selective solvent is preferably 1:1.2 ~ 1.8, be preferably 1:1.2, extraction tower tower top temperature is 85 ~ 90 DEG C, column bottom temperature is 45 DEG C, better tower top temperature is 90 DEG C, column bottom temperature is 45 DEG C, completes solvent treatment.
Under nitrogen protection, by the transformer oil cut after solvent treatment and carclazyte mixing, the better add-on of carclazyte is 8% of the transformer oil cut quality after solvent treatment to above-mentioned steps (4); stir, 140 DEG C of reaction 40min, cooling; filter, obtain transformer oil base oil.
The method of a kind of coal tar production cycloalkyl transformer oil base oil provided by the present invention, by coal tar hydrogenating and distillate solvent treatment, clay-filtered technique has carried out rational coupling, make full use of atlapulgite have adsorpting pigment and organic molecule ability its to the adsorptive power of impurity positively charged in transformer oil to remove residual solvent and colloid in oil product, the objectionable impuritiess such as basic nitrogen, improve the anti-oxidative stability of oil product and improve the color of oil product, and then obtain petroleum naphtha, the high value added product such as diesel oil and transformer oil base oil, extend coal tar hydrogenating industrial chain, Appropriate application tar resource, improve the utility value of coal tar, the density of coal tar hydrogenating diesel oil can be reduced simultaneously, obtain the naphthenic hydrocarbon distillate (300 ~ 360 DEG C) of high-content, ensure that the quality of transformer oil base oil, acquisition transformer oil base oil is of fine quality, yield is high and meet the standard of No. 45 transformer oil in national GB2536-1990 " transformer oil ".
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Now in conjunction with the accompanying drawings and embodiments technical scheme of the present invention is further described, but the present invention is not limited only to following enforcement situation.
Embodiment 1
With produce in coal pyrolysis process 500 ~ 700 DEG C of coalite tars for raw material, the method for production cycloalkyl transformer oil base oil is realized by following steps, see Fig. 1:
(1) coal tar hydrogenating process
Being mixed with hydrogen by coal tar sends in hydrogenator, successively with aluminium sesquioxide be carrier molybdenum-nickel type Hydrobon catalyst and with the katalysis of the ZSM-5 zeolite catalytic dewaxing catalyst of nickel-loaded under carry out hydrotreatment, temperature of reaction is 380 DEG C, pressure is 14MPa, hydrogen to oil volume ratio is 1000:1, is 0.4h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 0.8h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1, obtain hydrogenated oil;
Above-mentioned aluminium sesquioxide is the molybdenum-nickel type Hydrobon catalyst of carrier is the TK-561 type catalyzer (http://www.topsoe.com/products/CatalystPortfolio.aspx) adopting the exploitation of TOPSOE company, in its catalytically-active metals, molybdic oxide content is at least 21wt%, nickel oxide content is at least 6wt%, total pore volume is at least 0.3mL/g, and specific surface area is at least 150m
2/ g; The ZSM-5 zeolite catalytic dewaxing catalyst of above-mentioned nickel-loaded adopts the FDW-3 type catalyzer (http://sinopec-catalyst.com/product/detail/id/31.html) of catalyzer branch office of Sinopec Group, its catalyst activity Oxygen in Metals nickel content is 1 ~ 3wt%, total pore volume is at least 0.1mL/g, and specific surface area is at least 200m
2/ g.
(2) fractionation of hydrogenation products
Hydrogenated oil is sent into fractionation in separation column, obtain the residue fraction being less than the naphtha fraction of 180 DEG C, the diesel oil distillate of 180 ~ 300 DEG C, the transformer oil cut of 300 ~ 360 DEG C and being greater than 360 DEG C;
(3) solvent treatment of transformer distillate
With N-first class pyrrolidone to the countercurrent mass transfer heat transfer extraction in extraction tower of transformer oil cut, namely N-first class pyrrolidone is squeezed in extraction tower by pump from tower top after preheating, transformer oil cut is squeezed in extraction tower at the bottom of tower, carry out countercurrent mass transfer heat transfer, transformer oil after extraction enters in solvent recovery unit and carries out underpressure distillation and remove remaining N-first class pyrrolidone, the volume ratio of transformer oil cut and N-first class pyrrolidone is 1:1.2, extraction tower tower top temperature is 90 DEG C, column bottom temperature is 45 DEG C, complete solvent treatment, obtain the transformer oil cut after solvent treatment,
(4) transformer distillate is clay-filtered
Under nitrogen protection; transformer oil cut after solvent treatment is mixed with carclazyte; the mass percent that carclazyte accounts for transformer oil cut is 8%; stir; 140 DEG C of reaction 40min, cooling, filters; obtain transformer oil base oil, yield is 78.5wt%(in the transformer distillate of 300 ~ 360 after hydrotreatment DEG C for 100%).
The naphtha fraction of the present embodiment gained, diesel oil distillate and the yield of transformer oil cut and the character of product transformer oil base oil see the following form 1 ~ 4 respectively.
Table 1 embodiment 1 obtain the yield of various product
Note: calculate with feed coal tar 100%.
The naphtha fraction character that table 2 embodiment 1 obtains
As shown in Table 2, the sulphur of this naphtha fraction, nitrogen, olefin(e) centent are very low, and aromaticity content is less than 40%.Research octane number (RON) 72.1 is less than 90, all reaches motor spirit GB17930-2006 standard, can as premium blend component or solvent oil.
Table 3 embodiment 1 obtain the character of 180 ~ 300 DEG C of diesel oil distillates
As shown in Table 3, sulphur, the nitrogen content of this diesel oil distillate are very low, and condensation point reaches-20 DEG C, and each index all reaches the regulation of standard GB/T 252-2000, can be used as fine-quality diesel oil blending component.
Table 4 embodiment 1 obtains transformer foundation oil properties
As shown in Table 4, the transformer foundation oil indices obtained all meets the regulation of GB GB2536-1990.
Embodiment 2
In the present embodiment, coal tar mixes with hydrogen by step (1) to be sent in hydrogenator, successively with aluminium sesquioxide be carrier molybdenum-nickel type Hydrobon catalyst and with the katalysis of the ZSM-5 zeolite catalytic dewaxing catalyst of nickel-loaded under carry out hydrotreatment, temperature of reaction is 350 DEG C, pressure is 13MPa, hydrogen to oil volume ratio is 900:1, is 0.5h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 0.9h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1, obtain hydrogenated oil.Step (3) N-first class pyrrolidone extracts the countercurrent mass transfer heat transfer in extraction tower of transformer oil cut, transformer oil after extraction enters in solvent recovery unit and carries out underpressure distillation and remove remaining N-first class pyrrolidone, the volume ratio of transformer oil cut and N-first class pyrrolidone is 1:1.6, extraction tower tower top temperature is 88 DEG C, column bottom temperature is 45 DEG C, completes solvent treatment.Other step is identical with embodiment 1.
Embodiment 3
In the present embodiment, coal tar mixes with hydrogen by step (1) to be sent in hydrogenator, successively with aluminium sesquioxide be carrier molybdenum-nickel type Hydrobon catalyst and with the katalysis of the ZSM-5 zeolite catalytic dewaxing catalyst of nickel-loaded under carry out hydrotreatment, temperature of reaction is 360 DEG C, pressure is 12MPa, hydrogen to oil volume ratio is 1200:1, is 0.45h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 0.85h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1, obtain hydrogenated oil.The molybdenum-nickel type Hydrobon catalyst of what the present embodiment was used with aluminium sesquioxide is carrier is the FZC-41A type catalyzer (http://www.gqcat.com.cn/Chinese/ProductList.asp PID=25) adopting Gong Quan chemical inc, Shandong to produce, it is the MLDW-3 type catalyzer (http://www.exxonmobil.com/Apps/RefiningTechnologies/files/sells heet_mldw.pdf) adopting EXXON MOBIL company with the ZSM-5 zeolite catalytic dewaxing catalyst of nickel-loaded, step (3) N-first class pyrrolidone extracts the countercurrent mass transfer heat transfer in extraction tower of transformer oil cut, transformer oil after extraction enters in solvent recovery unit and carries out underpressure distillation and remove remaining N-first class pyrrolidone, the volume ratio of transformer oil cut and N-first class pyrrolidone is 1:1.8, extraction tower tower top temperature is 85 DEG C, column bottom temperature is 40 DEG C, complete solvent treatment.Other step is identical with embodiment 1.
Embodiment 4
In the present embodiment, coal tar mixes with hydrogen by step (1) to be sent in hydrogenator, successively with aluminium sesquioxide be carrier molybdenum-nickel type Hydrobon catalyst and with the katalysis of the ZSM-5 zeolite catalytic dewaxing catalyst of nickel-loaded under carry out hydrotreatment, temperature of reaction is 300 DEG C, pressure is 10MPa, hydrogen to oil volume ratio is 800:1, is 0.3h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 0.6h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1, obtain hydrogenated oil.Step (3) N-first class pyrrolidone extracts the countercurrent mass transfer heat transfer in extraction tower of transformer oil cut, transformer oil after extraction enters in solvent recovery unit and carries out underpressure distillation and remove remaining N-first class pyrrolidone, the volume ratio of transformer oil cut and N-first class pyrrolidone is 1:1, extraction tower tower top temperature is 80 DEG C, column bottom temperature is 40 DEG C, completes solvent treatment.Under nitrogen protection, by the transformer oil cut after solvent treatment and carclazyte mixing, carclazyte add-on is 7% of the transformer oil cut quality after solvent treatment to step (4), stirs, and 130 DEG C of reaction 50min, cooling, filters, obtain transformer oil base oil.Other step is identical with embodiment 1.
Embodiment 5
In the present embodiment, coal tar mixes with hydrogen by step (1) to be sent in hydrogenator, successively with aluminium sesquioxide be carrier molybdenum-nickel type Hydrobon catalyst and with the katalysis of the ZSM-5 zeolite catalytic dewaxing catalyst of nickel-loaded under carry out hydrotreatment, temperature of reaction is 400 DEG C, pressure is 15MPa, hydrogen to oil volume ratio is 1500:1, is 0.6h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 1.0h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1, obtain hydrogenated oil.Step (3) N-first class pyrrolidone extracts the countercurrent mass transfer heat transfer in extraction tower of transformer oil cut, transformer oil after extraction enters in solvent recovery unit and carries out underpressure distillation and remove remaining N-first class pyrrolidone, the volume ratio of transformer oil cut and N-first class pyrrolidone is 1:2, extraction tower tower top temperature is 90 DEG C, column bottom temperature is 50 DEG C, completes solvent treatment.Under nitrogen protection, by the transformer oil cut after solvent treatment and carclazyte mixing, carclazyte add-on is 10% of the transformer oil cut quality after solvent treatment to step (4), stirs, and 150 DEG C of reaction 40min, cooling, filters, obtain transformer oil base oil.Other step is identical with embodiment 1.
Embodiment 6
In above-described embodiment 1 ~ 5, furfural or the phenol of step (3) selective solvent N-used first class pyrrolidone equivalent are replaced, and other step is identical with corresponding embodiment.
Embodiment 7
In above-described embodiment 1 ~ 6, the coal-tar middle oil of the raw materials used coalite tar equivalent of step (1) is replaced, and is namely raw material production cycloalkyl transformer oil base oil with 700 ~ 900 DEG C of coal-tar middle oils produced in coal pyrolysis process.Other step is identical with corresponding embodiment.
In order to verify beneficial aspects of the present invention, contriver, through a large amount of Testing and research, is now described for following comparative example:
(1) hydrogenation conditions is changed
Hydrobon catalyst is identical with embodiment 1 with catalytic dewaxing catalyst, the reaction conditions of the hydrotreatment in this comparative example is as follows: temperature of reaction is 420 DEG C, reaction pressure is 16MPa, and hydrogen to oil volume ratio is 1800:1, is 0.4h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 0.8h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1.Under these processing condition, the liquid product that coal tar hydrogenating obtains is entered separation column and carry out fractionation, after fractionation, the yield of each component is in table 5.
The yield of the various products that table 5 comparative example 1 hydrotreatment obtains
Note: calculate with feed coal tar 100%.
Contrasted from table 5 and table 1, along with the severity of hydroconversion condition increases, the yield of the increase of the hydrogenation reaction degree of depth, light ends oil significantly increases, but the yield of transformer distillate significantly reduces, and is unfavorable for preparing transformer oil base oil.
(2) hydrogenation reaction air speed is changed
Hydrobon catalyst is identical with embodiment 1 with catalytic dewaxing catalyst, the reaction conditions of the hydrotreatment of this comparative example is as follows: temperature of reaction is 350 DEG C, reaction pressure is 14MPa, and hydrogen to oil volume ratio is 800:1, is 0.8h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 1.2h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1.Under these processing condition, the liquid product that coal tar hydrogenating obtains is entered separation column and carry out fractionation, after fractionation, the yield of each component is in table 6, adopted by the transformer distillate obtained the processing method of embodiment 1 to carry out solvent treatment and clay-filtered, obtain transformer oil base oil, character is in table 7.
The yield of the various products that table 6 comparative example 2 hydrotreatment obtains
Contrasted from table 6 and table 1, along with the increase of the reaction velocity of hydroconversion condition, the yield of all light ends oil all decreases, and residual oil ratio significantly increases, and illustrates that hydrogenation depth is inadequate, is unfavorable for preparing light-weight fuel oil and transformer oil base oil.
Table 7 comparative example 2 obtains transformer foundation oil properties
As shown in Table 7, the transformer foundation oil many index obtained can not reach the regulation of GB GB2536-1990.
Claims (6)
1. a method for coal tar production cycloalkyl transformer oil base oil, is characterized in that being made up of following steps:
(1) coal tar hydrogenating process
Coal tar is mixed with hydrogen, in hydrogenator Hydrobon catalyst and catalytic dewaxing catalyst katalysis under carry out hydrotreatment, temperature of reaction is 300 ~ 400 DEG C, pressure is 10 ~ 15MPa, hydrogen to oil volume ratio is 800 ~ 1500:1, is 0.3 ~ 0.6h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 0.6 ~ 1.0h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1, obtain hydrogenated oil;
(2) fractionation of hydrogenation products
Hydrogenated oil is sent into fractionation in separation column, obtain the residue fraction being less than the naphtha fraction of 180 DEG C, the diesel oil distillate of 180 ~ 300 DEG C, the transformer oil cut of 300 ~ 360 DEG C and being greater than 360 DEG C;
(3) solvent treatment of transformer distillate
With selective solvent to the countercurrent mass transfer heat transfer extraction in extraction tower of transformer oil cut, transformer oil after extraction carries out underpressure distillation and removes residual solvent in solvent recovery unit, the volume ratio of transformer oil cut and selective solvent is 1:1 ~ 2, extraction tower tower top temperature is 80 ~ 90 DEG C, column bottom temperature is 40 ~ 50 DEG C, completes solvent treatment;
It is phenol or N-Methyl pyrrolidone that above-mentioned selectivity holds agent;
(4) transformer distillate is clay-filtered
Under nitrogen protection, mixed by the transformer oil cut after solvent treatment with carclazyte, carclazyte add-on is 7 ~ 10% of the transformer oil cut quality after solvent treatment, stirs, 130 ~ 150 DEG C of reaction 40 ~ 50min, and cooling, filters, obtain transformer oil base oil;
Above-mentioned Hydrobon catalyst take aluminium sesquioxide as the molybdenum-nickel type catalyzer of carrier, and in its catalytically-active metals, molybdic oxide content is at least 21wt%, and nickel oxide content is at least 6wt%, and total pore volume is at least 0.3mL/g, and specific surface area is at least 150m
2/ g;
Above-mentioned catalytic dewaxing catalyst is the ZSM-5 zeolite catalytic dewaxing catalyst of nickel-loaded, and in catalytically-active metals, nickel oxide content is 1 ~ 3wt%, and total pore volume is at least 0.1mL/g, and specific surface area is at least 200m
2/ g.
2. the method for coal tar production cycloalkyl transformer oil base oil according to claim 1, it is characterized in that: coal tar mixes with hydrogen by described step (1), in hydrogenator Hydrobon catalyst and catalytic dewaxing catalyst katalysis under carry out hydrotreatment, temperature of reaction is 350 ~ 380 DEG C, pressure is 12 ~ 14MPa, hydrogen to oil volume ratio is 900 ~ 1200:1, is 0.4 ~ 0.5h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 0.8 ~ 0.9h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1, obtain hydrogenated oil.
3. the method for coal tar production cycloalkyl transformer oil base oil according to claim 1, it is characterized in that: coal tar mixes with hydrogen by described step (1), in hydrogenator Hydrobon catalyst and catalytic dewaxing catalyst katalysis under carry out hydrotreatment, temperature of reaction is 380 DEG C, pressure is 14MPa, hydrogen to oil volume ratio is 1000:1, is 0.4h relative to the liquid volume air speed of Hydrobon catalyst
-1, be 0.8h relative to the liquid volume air speed of catalytic dewaxing catalyst
-1, obtain hydrogenated oil.
4. the method for coal tar production cycloalkyl transformer oil base oil according to claim 1, it is characterized in that: described step (3) selective solvent in solvent recovery unit carries out underpressure distillation after countercurrent mass transfer heat transfer extraction to transformer oil cut and removes residual solvent in extraction tower, the volume ratio of transformer oil cut and selective solvent is 1:1.2 ~ 1.8, extraction tower tower top temperature is 85 ~ 90 DEG C, column bottom temperature is 45 DEG C, completes solvent treatment.
5. the method for coal tar production cycloalkyl transformer oil base oil according to claim 1, it is characterized in that: described step (3) selective solvent in solvent recovery unit carries out underpressure distillation after countercurrent mass transfer heat transfer extraction to transformer oil cut and removes residual solvent in extraction tower, the volume ratio of transformer oil cut and selective solvent is 1:1.2, extraction tower tower top temperature is 90 DEG C, column bottom temperature is 45 DEG C, completes solvent treatment.
6. the method for coal tar production cycloalkyl transformer oil base oil according to claim 1; it is characterized in that: described step (4) under nitrogen protection; by the transformer oil cut after solvent treatment and carclazyte mixing; carclazyte add-on is 8% of the transformer oil cut quality after solvent treatment; stir, 140 DEG C of reaction 40min, cooling; filter, obtain transformer oil base oil.
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Effective date of registration: 20200422 Address after: 719319 Jinyuan South Road, Jinjie Industrial Park, Shenmu City, Yulin City, Shaanxi Province Patentee after: SHENMUFUYOU ENERGY TECHNOLOGY Co.,Ltd. Address before: 719319 Shenmu oil rich energy technology Co., Ltd., Shenmu Industrial Zone, Shenmu, Shaanxi, Yulin Patentee before: Wang Shukuan |