Background technology
The energy in current global range is mainly derived from fossil energy, and its PetroChina Company Limited. is the main source of automotive fuel.Oil belongs to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality trend aggravation, and world economy sustainable development, environmental regulation increasingly stringent need to produce a large amount of light clean fuel, these increase new oil substitutes while all requiring to improve existing oil Refining Technologies, produce satisfactory product with minimum cost.Conversion for residual oil mainly contains residual hydrogenation and coking two kinds of approach, and wherein residual hydrogenation is the important technology producing clean fuel, and hydrogenated residue provides high-quality charging for catalytic cracking, can reduce SO in catalytic cracking unit operating process flue gasxand NOxdischarge, and the sulphur content increasing light oil yield and effectively reduce in catalytic gasoline.
Bio-oil, as renewable resources, obtains the extensive attention in the world, 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 diesel oil distillate with animal-plant oil, be mainly animal-plant oil first through hydrotreatment, then by isomerization catalyst bed layer, obtain low freezing point diesel fuel component, but owing to generating water in hydroprocessing processes, cause very adverse influence to isomerization catalyst, device can not long-period stable operation.
For residual hydrogenation technology, mainly for the feature of residual oil, select the catalyst loading technology of grating and the operational condition of optimization, for catalytic cracking unit provides the raw material after hydrogenation.CN200810246649.6 discloses a kind of method of hydrotreating of residual oil, CN200610007532.3 discloses a kind of method of hydrotreating producing catalytically cracked material, CN02133138.3 discloses a kind of heavy hydrocarbon hydroprocessing method, CN01114166.2 discloses a kind of process for hydrogenating residual oil, US20050311134 discloses a kind of hydrogenating conversion process of heavy resid, EP19930201257 discloses a kind of hydroprocessing process, the i.e. hydroprocessing process of residue oil fraction, the density 0845 ~ 0.870g/cm of the diesel product of these method by-products3, cetane value 40 ~ 48, sulphur content 100 ~ 600 μ g/g, can not meet the requirement of the Europe IV standard or higher standard.In addition, the method that diesel oil for residual hydrogenation by-product carries out upgrading is mainly CN01123761.9 and discloses a kind of method reducing aromatic content of diesel oil in residual hydrogenation equipment, the method is only carry out hydrogenation aromatics-removing to the diesel oil of by-product, there is no the introducing of renewable raw materials, add process cost.
CN200910187930.1 discloses a kind of method of mixing refining bio-oil improvement residual hydrogenation, mainly bio-oil is directly mixed refining to residual hydrogenation equipment, the working method of the character that then improved by fractionation.But the H generated in production process2o has adverse influence to residual oil hydrocatalyst, and reaction generates CO and CO2have an impact to catalyst performance, and methanation reaction can occur, the methane of generation is difficult to discharge system, thus greatly reduces the hydrogen dividing potential drop of reactive system, or discharges methane by the method for discharge, has increased considerably the hydrogen consumption of device like this.
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, need more catalyst changeout of often stopping work, particularly independent with bio-oil be raw material or bio-oil blending ratio higher time, the running period of hydrogenation catalyst is more subject to obvious impact.And for mixing the hydrogenation unit of refining bio-oil, the H that reaction process generates2o, CO and CO2and CH4very adverse influence can be produced Deng to existing hydrogenation catalyst system.
In prior art, bio-oil hydrogenation produces the method for automotive fuel, petroleum fractions (gasoline, diesel oil, wax oil or the residual oil) hybrid process of general needs and larger proportion, or directly by hydrofining-catalyst for hydro-upgrading bed, the H that reaction process generates2o, CO and CO2and CH4very adverse influence can be produced Deng to existing hydrogenation catalyst system, affect the life-span of plant running cycle or catalyzer.The present invention is by optimizing the grating technology and operational condition that use catalyzer, first paragraph hydrofining (the bio-oil raw material DNA vaccine that the reduction-state hydrogenation catalyst of grating and control are suitable for), second segment first paragraph hydrogenated oil and the process of residual oil mixed hydrogenation, can directly with by-product fine-quality diesel oil while production hydrogenated residue, have residual oil hydrocatalyst impact little, the advantages such as the plant running cycle is long.Control the DNA vaccine be suitable in bio-oil hydrogenation process, be conducive to the stability of bio-oil hydrogenation process and the stability of residual hydrocracking process simultaneously.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of hydrotreating being stock oil by-product diesel oil with bio-oil and residual oil, first bio-oil and new hydrogen are by loading hydrogenation catalyst first paragraph reaction zone, then liquid and residual oil are mixed into the second segment reaction zone of loading residual hydrogenation catalyst series, can direct production fine-quality diesel oil and hydrogenated residue, have hydrogenation process to stablize, running period is long, affects the features such as little to residual hydrogenation reaction zone.
The residual hydrogenation method of by-product fine-quality diesel oil of the present invention comprises following content:
A () take residual oil as stock oil, with one or more in bio-oil for auxiliary material;
B () is under Hydroprocessing conditions, bio-oil and hydrogen pass through the first paragraph reaction zone of at least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, bio-oil and hydrogen are first by the hydrogenator of cold operation, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and Co of sulphided state;
C () first paragraph reaction zone hydrogenation effluent is separated the gas phase obtained and recycles, liquid phase generates oily entering with residual oil raw material and uses the second segment reaction zone of catalyst for hydrotreatment of residual oil to carry out hydrotreatment reaction;
D the gas phase of () second segment reaction zone resultant stream gas-liquid separation recycles, liquid phase fractionation in separation column of second segment reaction zone resultant stream gas-liquid separation obtains petroleum naphtha, diesel oil and hydrogenated residue.
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.Residual oil can be long residuum or vacuum residuum, also can mix other cuts of other cut close range.In the inventive method, first paragraph reaction zone liquid phase generates oil and accounts for 5% ~ 40% of second segment reaction zone liquid phase feeding weight, is preferably 10% ~ 30%.
In the inventive method step (b), the Hydroprocessing conditions 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 0.5h-1~ 6.0h-1, average reaction temperature 120 DEG C ~ 280 DEG C; 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 0.5h-1~ 6.0h-1, average reaction temperature is higher than the hydrotreating reactor of cold operation 50 DEG C ~ 300 DEG C, preferably high 80 ~ 220 DEG C.Process furnace or interchanger are set between the hydrotreating reactor of cold operation and the hydrotreating reactor of high-temperature operation, to adjust the temperature of reaction of the hydrotreating reactor of high-temperature operation.
Bio-oil first by the hydrogenator of cold operation, hydrogenation active component with the weight content of oxide basis for 3% ~ 10%.Multiple catalysts grating can be used in the hydrogenator of cold operation to use.In the hydrogenator of high-temperature operation, the active component content of catalyzer is in element quality, higher than the catalyzer in cold operation hydrogenator 3 ~ 25 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 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, 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.
In the inventive method step (b), reaction system hydrogen sulfide in gas phase concentration controls higher than 0.005v%, preferred 0.01v% ~ 2.0v%, to maintain the sulfided state of catalyst stabilization, keeps catalytic activity.Specifically can be realized by the method for adding S-contained substance in reaction mass, also the circulation gas containing hydrogen sulfide in step (c) can be circulated in step (b) and use.Containing water in the hydrogenation effluent of first paragraph reaction zone, suitable method can be adopted to remove, as cooled rear separation removal.First paragraph reaction zone hydrogenation effluent is separated the gas phase obtained and can uses at first paragraph reaction zone internal recycle, also can as the hydrogen make-up of second segment reaction zone.The gas phase of second segment reaction zone resultant stream gas-liquid separation recycles in second reaction zone, also can be circulated to the first reaction zone on a small quantity.
In the inventive method step (c), the Hydroprocessing conditions of second segment reaction zone is generally reaction pressure 8.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.1h-1~ 4.0h-1, average reaction temperature 280 DEG C ~ 465 DEG C; Preferred operational condition is reaction pressure 10.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 500:1 ~ 2500:1, volume space velocity 0.1h-1~ 2.0h-1, average reaction temperature 300 DEG C ~ 460 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 working pressure of second segment reaction zone can be identical with first paragraph, also can be different.
In the inventive method step (c), the residual hydrogenation catalyst series of second segment reaction zone can use the hydrogenation catalyst of this area routine, specifically can comprise protective material, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrification (de-carbon residue) catalyzer etc., mainly contain ICR series protective material and the ICR catalyst series of the exploitation of CHEVRON company, the RM series of CRITERION company exploitation and RN catalyst series, the RF series protective material of Uop Inc.'s exploitation, RF catalyst series and RCD catalyst series, the KG series protective material of AKZO company exploitation and KFR catalyst series, the TK series protective material of Haldor Topsoe company exploitation and TK catalyst series, the RG series protective material of RIPP exploitation and RDM, RMS, RSN catalyst series, the FZC series protective material of FRIPP exploitation and FZC catalyst series, as: FZC-100, FZC-101, FZC102, FZC-103, FZC104, FZC-105, FZC106, FZC10, FZC-11, FZC12, FZC13, FZC-14, the protective materials such as FZC15, FZC-201, FZC202, FZC-203, FZC-204, FZC-21, FZC22, FZC-23, the Hydrodemetalation catalysts such as FZC-24, FZC301, FZC-302, FZC-303, FZC31, FZC-32, FZC-33, the Hydrobon catalysts such as FZC-34, FZC-40, FZC-41, the hydrodenitrifications such as FZC-41A (de-carbon residue) catalyzer etc.
In the inventive method step (c), first paragraph reaction zone and second segment reaction zone hydrogenation active component are the catalyzer of oxidation state, carry out conventional sulfidizing before the use, make hydrogenation active component be converted into sulphided state, or use the catalyzer that ex situ presulfiding is good.