CN103102919B - 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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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 59
- 239000002904 solvent Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- 239000003921 oil Substances 0.000 claims abstract description 76
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 18
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000005194 fractionation Methods 0.000 claims abstract description 7
- 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
- 239000012075 bio-oil Substances 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 238000005336 cracking Methods 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
- 239000012071 phase Substances 0.000 claims description 7
- 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
- 238000002156 mixing Methods 0.000 claims description 6
- 235000013311 vegetables Nutrition 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 241001465754 Metazoa Species 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 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 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 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
- 239000013589 supplement Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 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 58
- 239000003849 aromatic solvent Substances 0.000 description 9
- 239000002283 diesel fuel Substances 0.000 description 7
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 7
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003549 soybean oil Substances 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- 230000009183 running Effects 0.000 description 5
- 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
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 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 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [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
- 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
- 230000001186 cumulative effect Effects 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000012046 mixed solvent 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
- 239000003208 petroleum Substances 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 210000000582 semen Anatomy 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 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
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 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
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011066 ex-situ storage 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
- 238000001914 filtration Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000003502 gasoline Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000312 peanut oil 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 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
- 230000001502 supplementing effect Effects 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
- 239000002383 tung oil Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 is adopted as a raw material oil; under a hydrogenation condition, the raw material oil and hydrogen are mixed, and pass through a first stage hydrogenation reaction zone; the stream generated from hydrogenation is separated to obtain hydrogen-rich gas; the hydrogen-rich gas is recycled at the first stage; the separated liquid enters a second stage hydrocracking reaction zone; the sub-hydrogen gas separated from the oil generated through second stage hydrogenation is recycled at the second stage; and the separated liquid product is subjected to fractionation to obtain various solvent oils, wherein hydrogenation activity 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 hydrogenation activity components of the hydrogenation catalyst used at the second stage are reduction state Pt and/or Pd under a reaction state. Compared to the method in the prior art, the two-stage hydrogenation method of the present invention has the following characteristics 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 is stock oil with bio-oil, the two-stage method method of hydrotreating of direct production high-quality solvent oil.
Background technology
World economy sustainable development, in current 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, new oil substitutes is found except carrying out existing oil Refining Technologies improving, 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 main composition is carbon, hydrogen and oxygen, very similar to the composition of alkane, alcohol, ether etc., and each research unit and enterprise are all making great efforts to carry out its research as clean energy.The method production biofuel (being generally fatty acid methyl ester) utilizing transesterify has been proven technique, but because fatty acid methyl ester oxygen level is high, although many countries and regions have put into effect the standard of biofuel successively, and are not suitable for all oil engines.Bio-oil produces automotive fuel by the method for hydrogenation, and all remove by oxygen or partly remove the product produced and meet automotive fuel standard, this method directly can meet the requirement of existing market.
Existing animal-plant oil hydrogenation method produces 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 vegetables oil hydroconversion process, adopt coker naphtha, 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 hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.US5705722 discloses the diesel oil blending component producing diesel oil distillate scope containing the vegetables oil such as unsaturated fatty acids, fat and animal oil mixing back end hydrogenation.EP1741767 and EP1741768 discloses a kind of method of producing low freezing point diesel fuel cut with animal-plant oil.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter run into is that bed carbon distribution causes shorten running period, needs more catalyst changeout of often stopping work, and 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.The low aromatic solvent naphtha raw materials for production of current top grade are limited (is generally only limitted to gasoline fraction or the kerosene(oil)fraction of paraffinic crude, or 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, limits the production of high-grade low aromatic solvent naphtha.
In prior art, bio-oil usually passes through separately or produces the method for automotive fuel with the method for other petroleum products mixing back end hydrogenations.The present invention uses grating technology and operational condition by optimizing, and first paragraph hydrotreatment (sulfurized hydrogenation catalyst of grating), second segment hydrocracking (noble metal catalyst) can be directly raw material production low aromatic solvent naphtha with bio-oil.The present invention extends the raw material sources of high added value low aromatic solvent naphtha, and production cost is low, can improve added value of product further.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of two-stage method method of hydrotreating producing high-quality solvent oil, independent is stock oil with bio-oil, first paragraph uses the sulphided state hydrogenation catalyst of grating, second segment uses Nobel metal hydrogen cracking catalyst, the method of direct production solvent oil under the condition of hydrogenation, has hydrogenation process and stablizes, the features such as running period is long.
A kind of two-stage method method of hydrotreating producing high-quality solvent oil of the present invention comprises following content:
A one or more in () bio-oil are stock oil;
B () is under Hydroprocessing conditions, stock oil and hydrogen are by first paragraph reaction zone, first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation active component content raise successively, first stock oil and hydrogen pass through the low beds of hydrogenation active component content, then the high beds of hydrogenation active component content is passed through, under response behaviour, hydrogenation active component is one or more in W, Mo, Ni and Co of sulphided state;
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, recycle in first paragraph reaction zone after gas-phase dehydration process, liquid phase enters the second segment reaction zone using hydrocracking catalyst after mixing with second segment reaction zone circulation gas, under response behaviour, the active metal component of hydrocracking catalyst is Pt and/or Pd of reduction-state;
D the gas phase of () second segment reaction zone resultant stream gas-liquid separation recycles at second segment, liquid phase fractionation in separation column of second segment reaction zone resultant stream gas-liquid separation obtains petroleum naphtha and low freezing point diesel fuel;
E () supplements S-contained substance in first paragraph reaction mass, to maintain hydrogen sulfide content in the circulation gas of first paragraph reaction zone.
In the inventive method step (a), the bio-oil used 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 conditions of first paragraph 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 0.1h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C; Preferred operational condition is reaction pressure 3.0MPa ~ 18.0MPa, hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.2h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.
In the inventive method step (b), first paragraph reaction zone beds generally can arrange 2 ~ 5, in the beds that first reaction mass passes through, hydrogenation active component with the weight content of oxide basis for 3% ~ 10%, the hydrogenation catalyst that first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes in first paragraph reaction zone, preferably 20% ~ 70%, best 30% ~ 60%.In first paragraph reaction zone, the hydrogenation active component content of the downstream catalyst that reaction mass passes through increases by 3 ~ 25 percentage points in oxide weight than adjacent upstream catalyzer, preferably increases by 5 ~ 20 percentage points.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent, as P, Si, B, Ti, Zr etc. simultaneously.Can commercial catalyst be adopted, also can by the existing method preparation in this area.The business hydrogenation catalyst that first paragraph reaction zone uses mainly contains, as Fushun Petrochemical Research Institute (FRIPP) develop 3926, 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, hydrogenation catalyst such as ICR 179 grade, 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 is separated can comprise fractionating system, also can not comprise fractionating system (only comprising Separate System of Water-jet).When comprising fractionating system, the middle runnings (i.e. diesel oil distillate) fractionating system fractionation obtained enters second segment reaction zone.
In the inventive method step (b), first paragraph reaction zone hydrogenation active component is the catalyzer of oxidation state, carries out conventional sulfidizing before the use, makes hydrogenation active component be converted into sulphided state, or use the catalyzer that ex situ presulfiding is good.
In the inventive method step (c), the Hydroprocessing conditions 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, average reaction temperature 180 DEG C ~ 465 DEG C; 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, average reaction temperature 200 DEG C ~ 445 DEG C.First paragraph reaction zone hydrogenation effluent does not need cooling to carry out gas-liquid separation, and the water that reaction generates enters in gas phase.The liquid phase entering second segment reaction zone can be the liquid phase material after the gas-liquid separation of first paragraph reaction zone, also can be the intermediate oil that the liquid phase material after the gas-liquid separation of first paragraph reaction zone obtains through separation column fractionation.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 cracking function, as containing the component such as Y zeolite and/or ZSM-5 molecular sieve.Hydrocracking catalyst is in the element quality of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01% ~ 1.5%.The massfraction of hydrocracking catalyst Middle molecule sieve is generally 5% ~ 60%.Other component in hydrocracking catalyst is generally the porous refractory oxide such as aluminum oxide, silicon oxide, amorphous aluminum silicide.
In the inventive method step (c), catalyzer uses hydrogen 200 DEG C ~ 500 DEG C temperature before use, reduces under preferably 220 DEG C ~ 450 DEG C conditions.Whenever forbid in second segment reactive system, inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.
In the inventive method step (d), the low aromatic solvent naphtha obtained is mixed solvent oil distillate, can continue fractionation according to the actual requirements 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 naphthas.Specifically specifically can determine according to the boiling range of mixed solvent oil distillate.If there is unconverted oil, unconverted oil can go out system, also capable of circulation time reactive system.
The sulfur-containing medium supplemented in 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, CS
2deng, also can be the oil light-end products of sulfur-bearing, as the petroleum naphtha, boat coal etc. of sulfur-bearing.Supplementing by sulphur, can ensure that the hydrogen sulfide content in the circulation gas of first paragraph reaction zone is not less than 0.005v%, preferred 0.01v% ~ 2.0v%.
Accompanying drawing explanation
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: with the mixing oil of one or more in bio-oil for stock oil, under Hydroprocessing conditions, stock oil and hydrogen are by comprising the first paragraph hydroconversion reaction zone of at least two kinds of hydrogenation catalysts, the hydrogenated oil obtained is separated in high-pressure separator (abbreviation high score) gas obtained and recycles in first paragraph reaction zone, the liquid distillate obtained and hydrogen are mixed into the second segment reaction zone comprising and have cracking performance Nobel metal hydrogen cracking catalyst, obtain hydrocracking logistics to be separated in high-pressure separator (abbreviation high score) gas obtained and to recycle at second segment, the liquid fractionation obtained obtains all kinds of SOLVENTS oil production, also consider, at first paragraph, a part of middle runnings and unconverted oil are looped back first paragraph reaction zone.The bio-oil that embodiment uses is commercially available prod, uses front filtering solid impurity.
Particular case of the present invention is further illustrated below by embodiment.
The main composition of table 1 hydrogenation catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 | Catalyzer 4 | Cracking catalyst |
| Catalyzer forms | |||||
| MoO 3，wt% | 4.2 | 7.5 | 15.4 | 26.0 | |
| NiO，wt% | 2.4 | 2.6 | 3.6 | ||
| CoO，wt% | 1.4 | ||||
| Pt，wt% | 1.10 | ||||
| Pd，wt% | 0.12 | ||||
| Y molecular sieve, wt% | 12.6 | ||||
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus | Surplus |
| The main character of catalyzer | |||||
| Specific surface, m 2/g | >160 | >160 | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | >0.30 | >0.30 | >0.30 | >0.34 |
Table 2 embodiment processing condition and test-results.
| First paragraph reaction zone processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Catalyzer | Catalyzer 1/ catalyzer 3 | Catalyzer 1/ catalyzer 4 | Catalyzer 1/ catalyzer 2/ catalyzer 3 |
| Catalyst volume ratio | 15:85 | 40:60 | 12:28:60 |
| Stock oil | Soybean oil | Plam oil | Viscotrol C |
| Reaction pressure, MPa | 16.0 | 8.0 | 4.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 |
| Cumulative volume air speed, h -1 | 2.5 | 0.6 | 1.0 |
| Average reaction temperature, DEG C | 340 | 290 | 310 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 |
| Hydrogen sulfide content in first paragraph circulation gas, μ L/L | 600 | 12000 | 2000 |
| Second segment reaction zone processing condition | |||
| Catalyzer | Cracking catalyst | Cracking catalyst | Cracking catalyst |
| Reaction pressure, MPa | 16.0 | 8.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1500:1 | 700:1 |
| Volume space velocity, h -1 | 4.0 | 2.6 | 1.5 |
| Average reaction temperature, DEG C | 240 | 320 | 290 |
| Spirit fraction | |||
| Yield, quality % | 85 | 86 | 75 |
| Aromaticity content | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | Do not detect | Do not detect | Do not detect |
| Boiling range scope, DEG C | 61～175 | 63～160 | 61～145 |
Table 3 embodiment processing condition and test-results.
| First paragraph reaction zone processing condition | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Catalyzer | Catalyzer 1/ catalyzer 4 | Catalyzer 4 | Catalyzer 4 | Catalyzer 4 |
| Catalyst volume ratio | 40:60 | |||
| Stock oil | Soybean oil | Soybean oil | Soybean oil | Soybean oil |
| Reaction pressure, MPa | 10.0 | 10.0 | 10.0 | 10.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Cumulative volume air speed, h -1 | 0.5 | 0.5 | 0.5 | 0.5 |
| Average reaction temperature, DEG C | 330 | 330 | 330 | 330 |
| Sulfur-containing medium | DMDS | DMDS | DMDS | DMDS |
| Hydrogen sulfide content in first paragraph circulation gas, μ L/L | 500 | 500 | 500 | 500 |
| Second segment reaction zone processing condition | ||||
| Catalyzer | Cracking catalyst | Cracking catalyst | Cracking catalyst | Cracking catalyst |
| Reaction pressure, MPa | 10.0 | 10.0 | 10.0 | 10.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 2.0 | 2.0 | 2.0 | 2.0 |
| Average reaction temperature, DEG C | 300 | 300 | 300 | 300 |
| Runtime, h | 1000 | 100 | 300 | 600 |
| Pressure Drop, MPa | 0 | 0.1 | 0.3 | 0.6 |
| Spirit fraction | ||||
| Yield, quality % | 86 | 86 | 60 | 38 |
| 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 |
| Boiling range scope, DEG C | 61～175 | 61～175 | 61～175 | 61～175 |
Yield with second segment reaction zone feeds for benchmark.
As can be seen from embodiment, bio-oil can direct production various high-quality low aromatic solvent oil production by the method for hydrotreating of this technology, by selecting different bio-oils, can production high-quality low aromatic solvent naphtha, and running is stable.
Claims (9)
1. produce a two-stage method method of hydrotreating for solvent oil, it is characterized in that comprising following content:
A one or more in () bio-oil are stock oil;
B () is under Hydroprocessing conditions, stock oil and hydrogen are by first paragraph reaction zone, first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation active component content raise successively, first stock oil and hydrogen pass through the low beds of hydrogenation active component content, then the high beds of hydrogenation active component content is passed through, under response behaviour, hydrogenation active component is one or more in W, Mo, Ni and Co of sulphided state;
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, recycle in first paragraph reaction zone after gas-phase dehydration process, liquid phase enters the second segment reaction zone using hydrocracking catalyst after mixing with second segment reaction zone circulation gas, under response behaviour, the active metal component of hydrocracking catalyst is Pt and/or Pd of reduction-state;
D the gas phase of () second segment reaction zone resultant stream gas-liquid separation recycles at second segment, liquid phase fractionation in separation column of second segment reaction zone resultant stream gas-liquid separation obtains solvent oil;
E () supplements S-contained substance in first paragraph reaction mass, to maintain hydrogen sulfide content in the circulation gas of first paragraph reaction zone;
Wherein in step (b), the reaction pressure of first paragraph reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.1h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C;
Wherein 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, average reaction temperature 180 DEG C ~ 465 DEG C.
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 ~ 18.0MPa of first paragraph reaction zone, hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.2h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: in step (b), first paragraph reaction zone beds arranges 2 ~ 5, in the beds that first reaction mass passes through, hydrogenation active component is with the weight content of oxide basis for 3% ~ 10%, and the hydrogenation catalyst bed that first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes in first paragraph reaction zone; The hydrogenation active component content of the downstream catalyst that reaction mass passes through increases by 3 ~ 25 percentage points in oxide weight than adjacent upstream catalyzer.
5. in accordance with the method for claim 4, it is characterized in that: in step (b) first paragraph reaction zone, the hydrogenation catalyst that first reaction mass passes through accounts for 20% ~ 70% of all hydrogenation catalyst volumes in first paragraph reaction zone, and the hydrogenation active component content of the downstream catalyst that reaction mass passes through increases by 5 ~ 20 percentage points in oxide weight than adjacent upstream catalyzer.
6. 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 ~ 18.0MPa 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 DEG C ~ 445 DEG C.
7. in accordance with the method for claim 1, it is characterized in that: in step (c), the hydrocracking catalyst of second segment reaction zone has cracking function, hydrocracking catalyst contains Y zeolite and/or ZSM-5 molecular sieve component, hydrocracking catalyst is in the element quality of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01% ~ 1.5%.
8. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium supplemented in the reaction mass of first paragraph reaction zone is the compound of sulfur-bearing, or the oil light-end products of sulfur-bearing.
9. according to the method described in claim 1 or 8, it is characterized in that: in the circulation gas of first paragraph reaction zone, hydrogen sulfide content is not less than 0.005v%.
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| EP1741767A1 (en) * | 2005-07-04 | 2007-01-10 | Neste Oil OYJ | Process for the manufacture of diesel range hydrocarbons |
| CN101029245A (en) * | 2007-04-13 | 2007-09-05 | 清华大学 | Production of biological diesel oil by integrated hydrogenation |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Process for producing paraffins |
| CN102027098A (en) * | 2008-03-17 | 2011-04-20 | 环球油品公司 | Production of transportation fuel from renewable feedstocks |
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|---|---|---|---|---|
| EP1741767A1 (en) * | 2005-07-04 | 2007-01-10 | Neste Oil OYJ | Process for the manufacture of diesel range hydrocarbons |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Process for producing paraffins |
| CN101029245A (en) * | 2007-04-13 | 2007-09-05 | 清华大学 | Production of biological diesel oil by integrated hydrogenation |
| CN102027098A (en) * | 2008-03-17 | 2011-04-20 | 环球油品公司 | Production of transportation fuel from renewable feedstocks |
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