CN103102920A - Two-stage hydrogenation method for producing high quality solvent oil - Google Patents
Two-stage hydrogenation method for producing high quality solvent oil Download PDFInfo
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- CN103102920A CN103102920A CN2011103537700A CN201110353770A CN103102920A CN 103102920 A CN103102920 A CN 103102920A CN 2011103537700 A CN2011103537700 A CN 2011103537700A CN 201110353770 A CN201110353770 A CN 201110353770A CN 103102920 A CN103102920 A CN 103102920A
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 41
- 239000002904 solvent Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 16
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000005194 fractionation Methods 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 75
- 239000012075 bio-oil Substances 0.000 claims description 16
- 238000005336 cracking Methods 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 239000004480 active ingredient Substances 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 235000013311 vegetables Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 241001465754 Metazoa Species 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 abstract 1
- 238000005987 sulfurization reaction Methods 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 64
- 239000003849 aromatic solvent Substances 0.000 description 9
- 239000002283 diesel fuel Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000009183 running Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 3
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 210000000582 semen Anatomy 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- -1 Oleum Cocois Substances 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002383 tung oil Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a two-stage hydrogenation method for producing a high quality solvent oil. The method is characterized in that a biological oil raw material and hydrogen pass through a first stage hydrogenation reaction zone containing at least two hydrogenation reactors, wherein the mixture passes through a low temperature operation reactor, and then passes through a high temperature operation reactor; the hydrogen-rich gas is recycled at the first stage; the liquid enters a second stage hydrocracking reaction zone; the sub-hydrogen gas after hydrocracking is recycled at the second stage; the liquid product is subjected to fractionation to obtain various solvent oil products; and under a reaction state, active components of the hydrogenation catalyst used at the first stage are one or a plurality of materials selected from sulfurization state W, Mo, Ni and Co, and active components of the hydrogenation catalyst used at the second stage are reduction state Pt and/or Pd. Compared to the method in the prior art, the method of the present invention has the following advantages that: low aromatic hydrocarbon solvent oil production methods are increased, activity stability of the catalyst can be ensured, and stable and long period device operation can be ensured.
Description
Technical field
The present invention relates to a kind of method of hydrotreating, particularly a kind of take bio-oil as stock oil, the two-stage method method of hydrotreating of direct production high-quality solvent oil.
Background technology
The world economy sustainable development, at present in global range, the main source of Chemicals is fossil energy, wherein most importantly oil and coal.These two kinds of fossil energies all belong to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality aggravation, difficulty of processing and tooling cost increase gradually, except being improved, existing oil Refining Technologies seeks new oil substitutes, produce satisfactory product with minimum cost, especially the development and utilization of renewable resources obtains paying attention to more and more widely.
Bio-oil is as renewable resources, and chief component is carbon, hydrogen and oxygen, and very similar to the composition of alkane, alcohol, ether etc., each research unit and enterprise are all making great efforts to carry out it as the research of clean energy.Utilizing the method production biofuel (being generally fatty acid methyl ester) of transesterify has been proven technique, but because the fatty acid methyl ester oxygen level is high, although many countries and regions have been put into effect the standard of biofuel successively, and be not suitable for all oil engines.Bio-oil is produced automotive fuel by the method for hydrogenation, and soon oxygen is all removed or partly removed and produce the product that meets the automotive fuel standard, and this method can directly satisfy the requirement of existing market.
existing animal-plant oil hydrogenation method is produced the processing technology of automotive fuel, US20060186020, EP1693432, CN101321847A, CN200710012090.6, CN200680045053.9, CN200710065393.4, CN200780035038.0, CN200710012208.5, CN200780028314.0 and CN101029245A etc. disclose the vegetables oil hydroconversion process, adopt the coker gasoline cut, diesel oil distillate (straight-run diesel oil, LCO and coker gas oil), the petroleum hydrocarbon cuts such as wax oil cut and bio-oil are mixed into the hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.US5705722 discloses vegetables oil such as containing unsaturated fatty acids, fat and animal oil mixing back end hydrogenation is produced the diesel oil blending component of diesel oil distillate scope.EP1741767 and EP1741768 disclose a kind of method of producing the low freezing point diesel fuel cut with animal-plant oil.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter that runs into is that the bed carbon distribution causes shortening running period, the more catalyst changeout of need to often stopping work, and also the main purpose product of these technology is automotive fuel.
Solvent oil is important petroleum products, and its added value is higher than fuel product, and particularly the added value of high-grade low aromatic solvent naphtha is higher.High-grade low aromatic solvent naphtha raw materials for production are limited at present (generally only limits to gasoline fraction or the kerosene(oil)fraction of paraffinic crude, perhaps reforming raffinate oil etc.), owing to requiring aromaticity content lower (some solvent oil index request aromaticity content is lower than 0.1%), therefore need to adopt complicated processing route, condition is harsh, production cost is high, has limited the production of high-grade low aromatic solvent naphtha.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of two-stage method method of hydrotreating of producing the high-quality solvent oil, take bio-oil as stock oil, under the condition of hydrogenation, at first by using sulfide type catalyst first paragraph reaction zone, then by using the second segment reaction zone of Nobel metal hydrogen cracking catalyst, direct production solvent oil, has hydrogenation process stable, the characteristics such as running period is long.
The two-stage method method of hydrotreating of production high-quality solvent oil of the present invention comprises following content:
(a) one or more in bio-oil are stock oil;
(b) under the hydroprocessing condition, stock oil and hydrogen are by the first paragraph reaction zone of at least two hydrogenators, load hydrogenation catalyst in hydrogenator, stock oil and hydrogen is the hydrogenator by cold operation at first, then the hydrogenator by high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and the Co of sulphided state;
(c) first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration recycles at the first paragraph reaction zone after processing, liquid phase with enter the second segment reaction zone that uses hydrocracking catalyst after second segment reaction zone circulation gas mixes, under response behaviour, the active metal component of hydrocracking catalyst is Pt and/or the Pd of reduction-state;
(d) gas phase that obtains of second segment reaction zone reaction effluent gas-liquid separation recycles at the second segment reaction zone, and liquid phase fractionation in separation column that the gas-liquid separation of second segment reaction zone reaction effluent obtains obtains all kinds of SOLVENTS oil distillate;
(e) replenish S-contained substance in the first paragraph reaction mass, to keep hydrogen sulfide content in first paragraph reaction zone circulation gas.
In the inventive method step (a), the bio-oil that uses can comprise vegetables oil or animal grease, vegetables oil comprises one or more in soybean oil, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, sesame oil, Oleum Gossypii semen, sunflower seed oil and rice bran wet goods, and animal grease comprises one or more in butter, lard, sheep oil and fish oil etc.
In the inventive method step (b), the hydroprocessing condition of the hydrotreating reactor of cold operation is generally reaction pressure 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, 120 ℃ ~ 280 ℃ of average reaction temperature; The operational condition of the hydrotreating reactor of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.3h
-1~ 6.0h
-1, average reaction temperature than the hydrotreating reactor of cold operation high 50 ℃ ~ 300 ℃, preferred high 80 ~ 220 ℃.Between the hydrotreating reactor of cold operation and the hydrotreating reactor of high-temperature operation, process furnace or interchanger are set, with the temperature of reaction of the hydrotreating reactor of adjusting high-temperature operation.
In the inventive method step (b), reaction mass is at first by in the hydrogenator of cold operation, and the active ingredient of the hydrogenation catalyst of use is take the weight content of oxide compound as 3%～20%.Reaction mass continues the hydrogenator by high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses in the hydrogenator of high-temperature operation counts 15%～40% with oxide weight.In the hydrogenator of preferred high-temperature operation, the active component content of catalyzer is higher than 3～25 percentage points of catalyzer in the cold operation hydrogenator.Reactor generally can arrange 2 ~ 5, is preferably 2.A kind of catalyzer can be loaded in each hydrogenator, also multiple catalysts can be loaded.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent simultaneously, as P, Si, B, Ti, Zr etc.Can adopt the commercial catalyst, also can be by the existing method preparation in this area.The hydrogenation activity component is the catalyzer of oxidation state, carries out conventional sulfidizing before using, and makes the hydrogenation activity component be converted into sulphided state.the business hydrogenation catalyst mainly contains, as 3926 of Fushun Petrochemical Research Institute (FRIPP) development, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FH-98, FH-UDS, the hydrogenation catalysts such as FZC-41, the HR-416 of Inst Francais Du Petrole, the hydrogenation catalysts such as HR-448, the ICR174 of CLG company, ICR178, the hydrogenation catalysts such as ICR179, Uop Inc. is newly developed HC-P, HC-K UF-210/220, the TK-525 of Topsor company, TK-555, the hydrogenation catalysts such as TK-557, the KF-752 of AKZO company, KF-840, KF-848, KF-901, the hydrogenation catalysts such as KF-907.First paragraph reaction zone hydrogenation effluent separates can comprise fractionating system, also can not comprise fractionating system (only comprising Separate System of Water-jet).When comprising fractionating system, the middle runnings (being diesel oil distillate) that the fractionating system fractionation is obtained enters the second segment reaction zone.
In the inventive method step (b), first paragraph reaction zone hydrogenation activity component is the catalyzer of oxidation state, carries out conventional sulfidizing before using, and makes the hydrogenation activity component be converted into sulphided state, perhaps uses the outer good catalyzer of prevulcanized of device.
In the inventive method step (c), the hydroprocessing condition of second segment reaction zone is generally reaction pressure 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, 180 ℃ ~ 465 ℃ of average reaction temperature; Preferred operational condition is reaction pressure 3.0MPa ~ 18.0MPa, hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h
-1~ 4.0h
-1, 200 ℃ ~ 445 ℃ of average reaction temperature.The working pressure of second segment reaction zone can be identical with the first paragraph reaction zone, also can be different.The liquid phase that enters the second segment reaction zone can be the liquid phase material after the gas-liquid separation of first paragraph reaction zone, can be also the liquid phase material intermediate oil that fractionation obtains through separation column after the gas-liquid separation of first paragraph reaction zone.The working pressure of second segment reaction zone can be identical with first paragraph, also can be different.
In the inventive method step (c), the hydrocracking catalyst of second segment reaction zone has the cracking function, as contains the components such as Y zeolite and/or ZSM-5 molecular sieve.Hydrocracking catalyst is in the element of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01%～1.50%.In hydrocracking catalyst, the massfraction of molecular sieve is generally 5%～40%.Other component in catalyst for hydro-upgrading is generally the porous refractory oxides such as aluminum oxide, silicon oxide, amorphous aluminum silicide.
In the inventive method step (c), catalyzer uses hydrogen 200 ℃～500 ℃ temperature before use, reduces under preferred 220 ℃～450 ℃ conditions.Whenever forbid to inject sulfur-bearing, nitrogenous medium in the second segment system, avoid poisoning of catalyst.
In the inventive method step (d), the low aromatic solvent naphtha that obtains is the mixed solvent oil distillate, can continue according to the actual requirements fractionation and obtain vegetable oil extraction solvent, No. 90 solvent oils, No. 120 solvent oils, No. 200 solvent oils, D30, D40 etc. trade mark low aromatic solvent naphtha.Specifically can specifically determine according to the boiling range of mixed solvent oil.If there is unconverted oil, unconverted oil can go out system, also capable of circulation time reactive system.
The sulfur-containing medium that replenishes in first paragraph reaction mass (optimum is dosed in the liquid phase feeding of first paragraph reaction zone) in the inventive method step (e) can be the compound of sulfur-bearing, as DMDS, and CS
2Deng, can be also the oil light-end products of sulfur-bearing, as the petroleum naphtha of sulfur-bearing, boat coal etc.By replenishing of sulphur, can guarantee that the hydrogen sulfide content in first paragraph reaction zone circulation gas is not less than 0.005v%, preferred 0.01v%～2.0v%.
In prior art bio-oil usually by separately or with the method for the method production automotive fuel of other petroleum products mixings back end hydrogenations.The present invention uses grating technology and operational condition by optimization, first paragraph hydrotreatment (sulfurized hydrogenation catalyst of grating), and second segment hydrocracking (noble metal catalyst) can be directly take bio-oil as the raw material production low aromatic solvent naphtha.The present invention has expanded the raw material sources of high added value low aromatic solvent naphtha, and production cost is low, can further improve added value of product.
Description of drawings
Fig. 1 is the two-stage method method of hydrotreating principle flow chart of production high-quality solvent oil of the present invention.
Fig. 2 is the another one principle flow chart of the two-stage method method of hydrotreating of production high-quality solvent oil of the present invention.
Embodiment
method of the present invention is specific as follows: the mixing oil of one or more in the bio-oil is as stock oil, under the hydroprocessing condition, stock oil and hydrogen are by low temperature and the high temperature hydrogenation reactor of filling sulphided state catalyzer, the hydrogenated oil that obtains separates in high-pressure separator (abbreviation high score) gas that obtains and recycles at the first paragraph reaction zone after processed, the liquid fractionation that obtains and hydrogen are mixed into and comprise the second segment reaction zone with cracking performance Nobel metal hydrogen cracking catalyst, obtaining the hydrocracking logistics recycles at the second segment reaction zone at the gas that high-pressure separator (abbreviation high score) separation obtains, the liquid fractionation that obtains obtains all kinds of SOLVENTS oil production, also consider at first paragraph, a part of last running and unconverted oil to be looped back the first paragraph reaction zone.The bio-oil that embodiment uses is the commercially available prod, filtering solid impurity before using.
Further illustrate particular case of the present invention below by embodiment.
The chief component of table 1 hydrogenation catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 | Cracking catalyst |
| Catalyzer forms | ? | ? | ? | ? |
| MoO 3，wt% | 6.0 | 13.4 | 26.3 | ? |
| NiO，wt% | 1.8 | ? | 4.7 | ? |
| CoO，wt% | ? | 2.6 | ? | ? |
| Pt，wt% | ? | ? | ? | 1.05 |
| Pd，wt% | ? | ? | ? | 0.03 |
| Y molecular sieve, wt% | ? | ? | ? | 25.6 |
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus |
| The main character of catalyzer | ? | ? | ? | ? |
| Specific surface, m 2/g | >160 | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | >0.30 | >0.30 | >0.34 |
Table 2 embodiment processing condition and test-results.
| Processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Tung oil | Cocounut oil | Peanut oil | Oleum Gossypii semen+5% turning oil |
| First paragraph reaction zone operational condition | ? | ? | ? | ? |
| The cold operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 1 | Catalyzer 1/ catalyzer 2 | Catalyzer 1/ catalyzer 2 | Catalyzer 1 |
| The catalyst volume ratio | 100 | 30:70 | 50:50 | 100 |
| Reaction pressure, MPa | 15.0 | 8.0 | 4.0 | 12.0 |
| The entrance hydrogen to oil volume ratio | 1000:1 | 600:1 | 1500:1 | 300:1 |
| Volume space velocity, h -1 | 1.2 | 0.4 | 0.9 | 3.0 |
| Average reaction temperature, ℃ | 190 | 240 | 280 | 300 |
| The high-temperature operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 2/ catalyzer 3 |
| The catalyst volume ratio | 100 | 100 | 100 | 50:50 |
| Reaction pressure, MPa | 15.0 | 8.0 | 4.0 | 12.0 |
| The entrance hydrogen to oil volume ratio | 1000:1 | 800:1 | 2000:1 | 1000:1 |
| Volume space velocity, h -1 | 1.0 | 1.5 | 3.0 | 0.8 |
| Average reaction temperature, ℃ | 260 | 280 | 340 | 360 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 | CS 2 |
| Hydrogen sulfide content in circulation gas, μ L/L | 10000 | 2000 | 100 | 900 |
| Second segment reaction zone operational condition | ? | ? | ? | ? |
| Catalyzer | Cracking catalyst | Cracking catalyst | Cracking catalyst | Cracking catalyst |
| Reaction pressure, MPa | 15.0 | 16.0 | 4.0 | 6.0 |
| The entrance hydrogen to oil volume ratio | 1000 | 500 | 800 | 2000 |
| Volume space velocity, h -1 | 3.0 | 2.5 | 2.0 | 1.5 |
| Average reaction temperature, ℃ | 310 | 270 | 260 | 280 |
| The solvent oil cut | ? | ? | ? | ? |
| Yield, quality % | 82 | 86 | 87 | 85 |
| Aromaticity content | Do not detect | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | Do not detect | Do not detect | Do not detect | Do not detect |
| The boiling range scope, ℃ | 61～160 | 63～175 | 61～145 | 61～145 |
Table 3 embodiment processing condition and test-results.
| Processing condition | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Stock oil | Oleum lini | Oleum lini | Oleum lini | Oleum lini |
| The cold operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 1 | ? | ? | ? |
| Reaction pressure, MPa | 8.0 | ? | ? | ? |
| The entrance hydrogen to oil volume ratio | 1000:1 | ? | ? | ? |
| Volume space velocity, h -1 | 3.0 | ? | ? | ? |
| Average reaction temperature, ℃ | 220 | ? | ? | ? |
| The high-temperature operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 |
| Reaction pressure, MPa | 8.0 | 8.0 | 8.0 | 8.0 |
| The entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 1.0 | 0.75 | 0.75 | 0.75 |
| Average reaction temperature, ℃ | 320 | 320 | 320 | 330 |
| Sulfur-containing medium | CS 2 | CS 2 | CS 2 | CS 2 |
| Hydrogen sulfide content in circulation gas, μ L/L | 300 | 300 | 300 | 300 |
| The two step process condition | ? | ? | ? | ? |
| Catalyzer | Cracking catalyst | Cracking catalyst | Cracking catalyst | Cracking catalyst |
| Reaction pressure, MPa | 8.0 | 8.0 | 8.0 | 8.0 |
| The entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| The cumulative volume air speed, h -1 | 3.5 | 3.5 | 3.5 | 3.5 |
| Average reaction temperature, ℃ | 330 | 330 | 330 | 330 |
| Runtime, h | 1000 | 200 | 400 | 800 |
| The solvent oil cut | ? | ? | ? | ? |
| Yield, quality % | 85 | 85 | 58 | 20 |
| Aromaticity content | Do not detect | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | Do not detect | Do not detect | Do not detect | Do not detect |
| The boiling range scope, ℃ | 61～170 | 61～170 | 61～170 | 61～170 |
Yield is take the second segment reaction zone feeds as benchmark.
Can be found out by embodiment, the method for hydrotreating of bio-oil by present technique can the various high-quality low aromatic solvent of direct production oil production, by selecting different bio-oils, can production high-quality low aromatic solvent naphtha, and running is stable.
Claims (10)
1. two-stage method method of hydrotreating of producing the high-quality solvent oil is characterized in that comprising following content:
(a) one or more in bio-oil are stock oil;
(b) under the hydroprocessing condition, stock oil and hydrogen are by the first paragraph reaction zone of at least two hydrogenators, load hydrogenation catalyst in hydrogenator, stock oil and hydrogen is the hydrogenator by cold operation at first, then the hydrogenator by high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and the Co of sulphided state;
(c) first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration recycles at the first paragraph reaction zone after processing, liquid phase with enter the second segment reaction zone that uses hydrocracking catalyst after second segment reaction zone circulation gas mixes, under response behaviour, the active metal component of hydrocracking catalyst is Pt and/or the Pd of reduction-state;
(d) gas phase that obtains of second segment reaction zone reaction effluent gas-liquid separation recycles at the second segment reaction zone, and liquid phase fractionation in separation column that the gas-liquid separation of second segment reaction zone reaction effluent obtains obtains the solvent oil cut;
(e) replenish S-contained substance in the first paragraph reaction mass, to keep hydrogen sulfide content in first paragraph reaction zone circulation gas.
2. in accordance with the method for claim 1, it is characterized in that: in step (a), the bio-oil of use comprises vegetables oil or animal grease.
3. in accordance with the method for claim 1, it is characterized in that: in step (b), the reaction pressure 3.0MPa of the hydrotreating reactor of cold operation ~ 20.0MPa, hydrogen to oil volume ratio are 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, 120 ℃ ~ 280 ℃ of average reaction temperature; The operational condition of the hydrotreating reactor of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.3h
-1~ 6.0h
-1, average reaction temperature than the hydrotreating reactor of cold operation high 50 ℃ ~ 300 ℃.
4. according to the described method of claim 1 or 3, it is characterized in that: in step (b), the average reaction temperature of the hydrotreating reactor of high-temperature operation is higher 80 ~ 220 ℃ than the hydrotreating reactor of cold operation.
5. according to the described method of claim 1 or 3, it is characterized in that: step (b) reaction mass is at first by in the hydrogenator of cold operation, and the active ingredient of the hydrogenation catalyst of use is take the weight content of oxide compound as 3%～20%; Reaction mass continues the hydrogenator by high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses in the hydrogenator of high-temperature operation counts 15%～40% with oxide weight.
6. it is characterized in that in accordance with the method for claim 5: in the hydrogenator of high-temperature operation, the active component content of catalyzer is higher than 3～25 percentage points of the catalyzer in the cold operation hydrogenator.
7. according to the described method of claim 1 or 3, it is characterized in that: the first paragraph reaction zone in step (b) arranges 2～5 reactors.
8. in accordance with the method for claim 1, it is characterized in that: in step (c), the reaction pressure of second segment reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, 180 ℃ ~ 465 ℃ of average reaction temperature; Preferred reaction pressure is 3.0MPa ~ 18.0MPa, and hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.4h
-1~ 4.0h
-1, average reaction temperature is 200 ℃ ~ 445 ℃.
9. according to the described method of claim 1 or 8, it is characterized in that: in step (c), the hydrocracking catalyst of second segment reaction zone has the cracking function, hydrocracking catalyst contains Y zeolite and/or ZSM-5 molecular sieve component, catalyst for hydro-upgrading is in the element quality of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01%～1.50%.
10. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium that replenishes in the first paragraph reaction mass is the compound of sulfur-bearing, or the oil light-end products of sulfur-bearing, and in first paragraph reaction zone circulation gas, hydrogen sulfide content is not less than 0.005v%.
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| CN105733821A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Production method of special oil by rosin hydrogenation |
| CN116948672A (en) * | 2022-04-20 | 2023-10-27 | 中国石油化工股份有限公司 | A device and method for hydrogenating bio-oil to produce low-aromatic solvent oil |
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| CN101321847A (en) * | 2005-11-30 | 2008-12-10 | 新日本石油株式会社 | Hydrofining process and hydrofined oil |
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| CN101321847A (en) * | 2005-11-30 | 2008-12-10 | 新日本石油株式会社 | Hydrofining process and hydrofined oil |
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| CN116948672A (en) * | 2022-04-20 | 2023-10-27 | 中国石油化工股份有限公司 | A device and method for hydrogenating bio-oil to produce low-aromatic solvent oil |
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