CN102234538B - Method for hydrotreating ethylene tar - Google Patents
Method for hydrotreating ethylene tar Download PDFInfo
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Abstract
The invention discloses a method for hydrotreating ethylene tar, which comprises the following steps of: performing fractional distillation on the ethylene tar by selecting a proper cutting point to obtain light and heavy fractions; making the light fraction contact a hydrogenation protective agent, a hydrogenation refining catalyst, a hydrogenation carbon residue catalyst and a hydrocracking catalyst in turn, reacting to obtain products, and separating the products to obtain gasoline and diesel fractions; and making the heavy fraction contact a hydrogenation protecting catalyst, a hydrogenation carbon residue removing catalyst and a hydro-conversion catalyst in turn to obtain hydro-conversion generated oil, wherein partial hydro-conversion generated oil is circulated to enter a hydrogenation reaction area, and the rest hydro-conversion generated oil is separated to form gasoline and diesel fractions. In the method, according to composition characteristics of the light and heavy fractions of the ethylene tar, different hydrotreating schemes are selected, so that the ethylene tar is converted into fuel oil to the greatest extent, the problem of high temperature rise of a hydrogenation reactor bed can be effectively solved, the running period of the device is prolonged, full fractions of the ethylene tar are fully utilized and the added value of the ethylene tar is improved.
Description
Technical field
The present invention relates to a kind of hydroprocessing process of ethylene bottom oil.
Background technology
The scarcity day by day of world petroleum resource and price thereof day by day raised, makes refinery reduce discharging synergy and necessitates, and ethylene bottom oil is sold mainly as heavy fuel oil (HFO) or carbon black raw material at present, and added value is lower.
Ethylene bottom oil be ethylene cracking material at steam cracking process Raw and product pyrocondensation product, its initial boiling point is at 170～260 ℃, 600 ℃ of final boiling point >, are generally 600～700 ℃, belong to last running scope.Ethylene bottom oil is mainly the mixture of the above condensed-nuclei aromatics of dicyclo, and aromaticity content reaches more than 90%, and density (20 ℃) is greater than 1.0g/cm
3, the foreign matter contents such as sulphur and nitrogen are low, substantially metal impurities not.
In order to increase economic efficiency, each refinery is developed multiple method of comprehensive utilization, such as extracting naphthalene and series product thereof, light constituent (300 ℃ of <) synthesizing petroleum resin, tar heavy oil is produced carbon fibre asphalt and carbon fiber, (seeing the comprehensive utilization > > of < < Jilin Chemical science and technology > > second phase P47-P50:< < ethylene bottom oil in 1997) such as gacs produced in 540 ℃ of last running of >.In aforesaid method, still have some intermediate oils not to be fully used, overall economic efficiency needs to be further improved, and procedure of processing is complicated.
The disclosed method of CN1970688A is that ethylene bottom oil is cut out to the lighting end that boiling point is less than 260～280 ℃, by hydrorefined method, remove the unsaturated hydro carbons in this lighting end again, and then therefrom extract naphthalene and methylnaphthalene product, a small amount of solvent oil product of by-product simultaneously.The method has only been utilized proportion lighting end seldom in ethylene bottom oil, and the ethylene bottom oil cut of still having an appointment more than 80% is not effectively addressed; Simultaneously its hydrofining condition providing cannot be processed boiling point higher than the ethylene bottom oil cut of 280 ℃.
Summary of the invention
In order to overcome deficiency of the prior art, the invention provides the hydroprocessing process that a kind of maximum is produced the ethylene bottom oil of light-weight fuel oil.
The method of hydrotreating of ethylene bottom oil provided by the invention, comprise: ethylene bottom oil is fractionated into lighting end and last running, cut point is 400～450 ℃, be preferably 400～430 ℃, described lighting end is successively by lighting end hydrogenation protecting catalyst, Hydrobon catalyst, lighting end removal of ccr by hydrotreating catalyzer and hydrocracking catalyst, gained isocrackate enters separation system, obtains gasoline and diesel oil distillate; Described last running is successively by heavy fractioning hydrogenation guard catalyst, the de-carbon residue catalyzer of heavy fractioning hydrogenation, hydrogenation conversion catalyst; the hydrocracking of reaction gained generates the circulation of oil part and mixes duplicate removal cut fraction hydrogenation reaction zone with ethylene bottom oil last running; remainder, through further separated, obtains gasoline and diesel oil distillate.
In the inventive method, it can be the liquid product obtaining in hydroconverted products sepn process that the hydrocracking that loops back heavy fractioning hydrogenation reaction zone generates oil, one or more in low minute oil of as oily in the hot high score obtaining through high pressure hot separator separation, the heat that obtains through thermal low-pressure separators separation, the stripping tower oil that obtains after stripping tower stripping.
The weight ratio that the described hydrocracking that loops back heavy fractioning hydrogenation reaction zone generates oily weight and described ethylene bottom oil last running is 1.0～4.0.
In the inventive method, lighting end can partly circulate through the hydrocracking generation oil of hydrogenation gained, Recycle design at least adopts following a kind of: (1) mixes lighting end hydroconversion reaction zone with ethylene bottom oil lighting end, and (2) mix duplicate removal cut fraction hydrogenation reaction zone with ethylene bottom oil last running.The weight ratio that the hydrocracking of described circulation generates oily weight and described ethylene bottom oil fresh feed is 1.0～4.0.Wherein, lighting end enters separation system sepn process through the isocrackate of hydrogenation gained and comprises: isocrackate passes through high pressure hot separator successively, thermal low-pressure separators carries out gas-liquid separation, through stripping tower, separate gaseous product again, the stripping tower oil obtaining is through separation column fractionation, obtain gasoline fraction and diesel oil distillate, wherein for the hydrocracking that circulates, generate the liquid product that oil can obtain in separation system sepn process for isocrackate, as the hot high score oil obtaining through high pressure hot separator separation, the low minute oil of heat obtaining through thermal low-pressure separators separation, one or more in the stripping tower oil obtaining after stripping tower stripping.
Hydrogenation of the present invention is to adopt fixed bed hydrogenation technique.
Hydrobon catalyst, lighting end removal of ccr by hydrotreating catalyzer and hydrocracking catalyst used in described lighting end hydrogenation can be seated in same reactor in layering, also can, respectively in different reactors, preferably removal of ccr by hydrotreating catalyzer and hydrocracking catalyst be seated in same reactor.Hydrogenation protecting catalyst can be seated in same reactor with Hydrobon catalyst, also can adopt separately a reactor.Lighting end hydrogenation of the present invention adopts tandem process, and diesel oil distillate yield is higher, invests less.
In described lighting end hydrogenation; it is benchmark that the admission space of lighting end hydrogenation protecting catalyst, Hydrobon catalyst, lighting end removal of ccr by hydrotreating catalyzer and hydrocracking catalyst be take lighting end hydrogenation used catalyst cumulative volume, as follows respectively: 2%～20%, 5%～40%, 5%～40% and 30%～50%.
In the inventive method, described Hydrobon catalyst is conventional Hydrobon catalyst or pretreating catalyst by hydrocracking, general YiⅥ B family and/or group VIII metal are active ingredient, the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus of take is carrier, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.The weight of catalyzer of take is benchmark, and group VIB metal content is counted 10wt%～35wt% with oxide compound, and group VIII metal content is counted 3wt%～15wt% with oxide compound, and the character of this catalyzer is as follows: specific surface is 100～350m
2/ g, pore volume is 0.15～0.60ml/g.Main catalyzer have that China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops 3936,3996, FF-16, FF-26 etc.
Described lighting end removal of ccr by hydrotreating catalyzer is that to take VI B HeⅧ family metal be hydrogenation activity component, as two or three in W, Mo, Ni and Co, is preferably W, Mo and Ni, and this catalyzer preferably contains auxiliary agent Si and Ti, take aluminum oxide as carrier.The weight of catalyzer of take is benchmark, WO
3content be 16%～23%, MoO
3content be 6%～13%, NiO content is 3%～8%, silicone content is with SiO
2count 4%～12%, be preferably 5%～9%, titanium oxide content is 0.5%～4.0%, is preferably 1%～2%, and surplus is aluminum oxide.The character of this catalyzer is as follows: pore volume is 0.30～0.55cm
3/ g, specific surface area is 120～300m
2/ g, average pore diameter is 5～10nm, is preferably 5～8nm.
In the inventive method, at hydrocracking catalyst, can adopt conventional hydrocracking catalyst.The inventive method is produced low-coagulation diesel oil for maximum, described hydrocracking catalyst preferably adopts two kinds of hydrocracking catalysts, the first hydrocracking catalyst is that to take Y molecular sieve and amorphous aluminum silicide be main acidic components, and the second hydrocracking catalyst bed is that to take beta-molecular sieve and amorphous aluminum silicide be main acidic components.The first described hydrocracking catalyst composed as follows, the weight of catalyzer of take is benchmark: the content of Y molecular sieve is 8%～20%, the content of amorphous aluminum silicide is 38%～60%, it is 15%～40% that group VIB hydrogenation activity component be take the content of oxide compound, it is l%～l0% that Ⅷ family hydrogenation activity component be take the content of oxide compound, and surplus is little porous aluminum oxide; The character of the first hydrocracking catalyst is as follows: specific surface is 180～300m
2/ g, pore volume is 0.25～0.45ml/g.The character of described Y molecular sieve is as follows: SiO
2/ Al
2o
3mol ratio is 5～40, lattice constant 2.425～2.440nm, specific surface 500～750m
2/ g, infrared acidity 0.25～0.50mmol/g, Na
2o content < 0.2wt%; The character of described amorphous aluminum silicide is as follows: pore volume 0.8～1.5ml/g, specific surface 350～600m
2/ g, silica weight content 20%～60%.The second hydrocracking catalyst composed as follows, the weight of catalyzer of take is benchmark: the content of beta-molecular sieve is l0%～28%, the content of amorphous aluminum silicide is 20%～40%, it is 15%～40% that group VIB hydrogenation activity component be take the content of oxide compound, it is 1%～10% that Ⅷ family hydrogenation activity component be take the content of oxide compound, and surplus is little porous aluminum oxide; Wherein the character of beta-molecular sieve is as follows: SiO
2/ Al
2o
3mol ratio is 20～150, specific surface 500～750m
2/ g, infrared acidity 0.05～0.50mmol/g, Na
2o content < 0.2wt%.The first hydrocracking catalyst is 1～5: 1 with the admission space ratio of the second hydrocracking catalyst, is preferably 1～3: 1.The first hydrocracking catalyst is positioned at the upstream of the second hydrocracking catalyst, and reactant flow first contacts with the first hydrocracking catalyst, and then contacts with the second hydrocracking catalyst.Two kinds of hydrocracking catalysts can be seated in a reactor in layering, also can be divided in two reactors.
Said hydrorefined operational condition is: 340～390 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～18.0MPa, hydrogen to oil volume ratio 800: 1～2500: volume space velocity 0.1～2.6h when l and liquid
-1; Preferred operations condition is: volume space velocity 0.2～2.5h when 340～380 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1.The operational condition of said removal of ccr by hydrotreating and hydrocracking is: volume space velocity 0.1～2.2h when 370～420 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～18.0MPa, hydrogen to oil volume ratio are 800: 1～2500: 1 and liquid
-1; Preferred operations condition is: volume space velocity 0.2～2.0h when 370～410 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1.
Ethylene bottom oil lighting end described in the present invention first contacts with hydrogenation protecting catalyst respectively with last running, mainly removes impurity and part carbon residue wherein, to avoid downstream hydrogenation catalyst coking, the running period of extension fixture.In the present invention, hydrogenation protecting catalyst used can adopt conventional residual hydrogenation protective material or residuum hydrogenating and metal-eliminating catalyst; general YiⅥ B family and/or group VIII metal are active ingredient; take aluminum oxide or silicon-containing alumina as carrier; group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.The weight of catalyzer of take is benchmark, active metallic content is counted 0.5wt%～18wt% with oxide compound, preferably composed as follows: group VIB metal content is counted 0.5wt%～15wt% with oxide compound, group VIII metal content is counted 0.5wt%～8wt% with oxide compound, and shape can be hollow cylinder, trifolium shape, Herba Galii Bungei or spherical etc.For example: FZC-103, FZC-200, FZC-100 and the FZC-102B residual oil hydrocatalyst of Fushun Petrochemical Research Institute's research and development.
Ethylene bottom oil last running of the present invention is successively by heavy fractioning hydrogenation guard catalyst, the de-carbon residue catalyzer of heavy fractioning hydrogenation, hydrogenation conversion catalyst; above-mentioned catalyst loading is according to along reactant flow flow direction; aperture reduces successively, the active order increasing is successively carried out, and its admission space accounts for respectively 5%～20%, 20%～60%, 20%～60% of heavy fractioning hydrogenation catalyzer total fill able volume.Above-mentioned three kinds of catalyzer can be seated in a reactor; also can be seated in respectively in different reactors; also can be by hydrogenation protecting catalyst and removal of ccr by hydrotreating catalyst loading in a reactor, hydrogenation conversion catalyst is seated in another reactor.The de-carbon residue catalyzer of described heavy fractioning hydrogenation, can adopt heavy, the de-carbon residue catalyzer of residual hydrogenation of the prior art, preferably adopt two removal of ccr by hydrotreating beds, the volume ratio of upstream removal of ccr by hydrotreating catalyzer and downstream removal of ccr by hydrotreating catalyzer is 3～7: 7～3.In upstream catalyst bed, the active metal oxide content of removal of ccr by hydrotreating catalyzer used is 25wt%～40wt%, average pore diameter is 15～25nm, the active metal oxide content of the removal of ccr by hydrotreating catalyzer used in lower catalyst bed layer is 28wt%～45wt%, and average pore diameter is 10～20nm.The de-residual catalyzer of described hydrogenation is generally that to take VI B HeⅧ family metal be hydrogenation activity component, as two or three in W, Mo, Ni or Co, is preferably W, Mo and Ni, and this catalyzer preferably contains auxiliary agent Si and Ti, take aluminum oxide as carrier.The weight of catalyzer of take is benchmark, WO
3content be 16%～23%, MoO
3content be 6%～13%, NiO content is 3%～8%, silicone content is with SiO
2count 4%～12%, be preferably 5%～9%, titanium oxide content is 0.5～4.0%, is preferably 1%～2%, and surplus is aluminum oxide.The character of this catalyzer is as follows: pore volume is 0.40～0.55cm
3/ g, specific surface area is 120～180m
2/ g.
Last running, through hydrogenation conversion catalyst, is mainly to carry out hydroconversion reactions, removes sulphur and nitrogen simultaneously, can adopt hydrotransforming catalyst for residual oil.This catalyzer is to take aluminum oxide as carrier, Yi VIII family and VI B metallic element are active ingredient, Ⅷ family active metal component is nickel or cobalt, VI B active metal component is molybdenum or tungsten, YiⅣ A Zu HeⅣ B family element is auxiliary agent, described IV A family element is silicon, and described IV B family element is titanium and/or zirconium.Such as the hydrotransforming catalyst for residual oil that can adopt in CN02109422.5, the weight of catalyzer of take is benchmark, this catalyzer composed as follows: Ⅷ family active ingredient counts 5%～10% with oxide compound, and group VIB active ingredient is counted 20%～30%, SiO with oxide compound
2content at catalyzer is 2.0%～10.0%, TiO by weight
2content at catalyzer is 0～4.0% by weight, is preferably 1.0～4.0%, ZrO
2be 0～8.0%, be preferably 2.0%～8.0%, surplus is aluminum oxide.The character of this catalyzer is as follows: pore volume is 0.3ml/g～0.6ml/g, and specific surface area is 150m
2/ g～270m
2/ g, average pore diameter is 6.0nm～10.0nm, it is 80%～90% that the pore volume integration rate of bore dia within the scope of 4nm～15nm accounts for the pore volume integration rate of bore dia within the scope of 0nm～100nm, and the pore volume integration rate of its median pore diameter within the scope of 5nm～10nm is 65%～75%.
The operational condition of described heavy fractioning hydrogenation is as follows: reaction pressure is 14～18MPa, and temperature of reaction is 360～410 ℃, and during liquid, volume space velocity is 1.0～2.1h
-1, hydrogen to oil volume ratio is 500～1500.
In sum, adopting method of the present invention to process ethylene bottom oil tool has the following advantages:
1, the inventive method is selected the suitable full cut of cut point fractionation ethylene bottom oil, for the compositing characteristic of lighting end and last running, select to adopt different hydrogenating conversion process, lighting end is produced diesel oil blending component through hydrocracking, last running can be produced gasoline and diesel oil distillate through removal of ccr by hydrotreating and hydrocracking, make the production oil fuel of ethylene bottom oil maximum, improve the added value of ethylene bottom oil.
2, the inventive method considers composition and the character of ethylene bottom oil lighting end, select the hydrocracking catalyst of two types to carry out grading loading, can make full use of the not feature of isomorphism type molecular sieve, and match with amorphous aluminum silicide, aromatic hydrocarbons open loop after making hydrogenation in ethylene bottom oil saturated, appropriate cracking and/or isomerization again, can high yield obtains condensation point and is less than the diesel oil distillate of-40 ℃, simultaneously by-product stop bracket gasoline cut.
3, the present invention is directed in ethylene bottom oil last running aromaticity content high, cause the higher problem of beds temperature rise, adopt hydrocracking to generate oil circulation go back to hydroconversion reaction zone, effectively reduce on the one hand the aromaticity content in the charging of hydroconversion reaction zone, device temperature rise is obviously reduced, so just avoided due to temperature rise, and many reactors or more beds must be set; On the other hand, due to temperature rise, between reactor or bed, cold hydrogen amount increases, and will cause circulating hydrogen compressor load to increase, and facility investment all can be saved greatly in this two aspect.
4, the present invention adopts hydrocracking generation oil to mix the method as hydroconversion reaction zone charging with ethylene bottom oil last running, can avoid owing to needing liquid hydrogen injection reference mark many, cause misoperation probability to increase, thereby cause temperature runaway, cause catalyzer coking, cause the industrial accidents such as permanent inactivation, favourable to the safety and steady operation of device.
5, the present invention adopts hydrocracking to generate oil circulation time hydrogenation unit, mix the method as hydroconversion reaction zone charging with ethylene bottom oil last running, can effectively reduce the concentration of colloid, bituminous matter and carbon residue in hydrogenating materials oil, permanent performance to hydrogenation conversion catalyst activity is favourable, long period safety in production that can implement device.
6, lighting end hydrogenation of the present invention increases removal of ccr by hydrotreating beds between Hydrobon catalyst and hydrocracking catalyst; be conducive to remove the carbon residue in ethylene bottom oil; protected the hydrocracking catalyst in downstream; extended the running period of device; simultaneously; also can make a part of aromatic hydrogenation saturated, be conducive to further cracking, useful to improving yield of light oil.In addition, raw material through catalyst for refining, de-carbon residue catalyzer and cracking catalyst, can make exothermic heat of reaction even successively, avoids the temperature rise of hydrocracking bed too high, favourable to the safety and steady operation of device.
7, process program of the present invention is flexible, can be according to different product demands, and Choice and process scheme.
8, the present invention provides a kind of processing means that improves its economy for the lower ethylene bottom oil of added value; Under the crude supply present situation of growing tension, refinery is reduced discharging to synergy useful.
9,, in the inventive method, last running employing, first through the method for de-carbon residue repeated hydrogenation conversion, has realized the object of ethylene bottom oil heavy fractioning hydrogenation conversion light-weight fuel oil, favourable to prolong operating period, has expanded the raw material sources of producing light-weight fuel oil simultaneously.
Accompanying drawing explanation
Fig. 1 is the block diagram of the inventive method.
Embodiment
In conjunction with Fig. 1 take low minute of heat oil circulation be example, the invention will be further described.Ethylene bottom oil last running 1 enters hydrogenating materials surge tank 2, mix as hydrogenator raw material with low minute oil 10 of the heat liquid product of low minute heat, this raw material is with new hydrogen 4 and come the recycle hydrogen 9 of self cooling high score 7 to be mixed into hydrogenator 3, successively by heavy fractioning hydrogenation guard catalyst, heavy fractioning hydrogenation takes off carbon residue catalyzer, hydrogenation conversion catalyst, gained hydrogenation products enters high pressure hot separator 5, carry out gas-liquid separation, liquid product enters thermal low-pressure separators 6, further carry out gas-liquid separation and obtain low minute oil 10 of heat, heat oil 10 part circulations in low minute are as hydrogenation reaction raw material, being mixed into hydrogenator 3 with ethylene bottom oil last running 1 reacts, remainder enters cold high pressure separator 7 successively, cold low separator 8 carries out gas-liquid separation, through stripping tower 11 and separation column 12, obtain gasoline fraction 13 and diesel oil distillate 14.
The following examples will be further described present method, but be not limited in this.
Embodiment of the present invention hydrocracking catalyst used is prepared as follows:
1, contain the preparation of the hydrocracking catalyst of amorphous aluminum silicide and Y zeolite: A1, A2.
(1) hydrocracking catalyst A1:
By amorphous aluminum silicide (specific surface 520m
2/ g, SiO
235wt%, pore volume 1.2ml/g) and Y molecular sieve (SiO
2/ Al
2o
3mol ratio is 9, lattice constant 2.432, specific surface 650m
2/ g, infrared acidity 0.45mmol/g), after mixing, add (added by the little porous aluminum oxide of pore volume 0.42ml/g prepared by rare nitric acid peptization) tackiness agent roll agglomerating after, put into after banded extruder extruded moulding, at 110 ℃, be dried 10 hours, 500 ℃ of activation make carrier for 4 hours, then steep by Mo-Ni total immersion stain immersion, then at 110 ℃, be dried 12 hours, and 500 ℃ activate 3 hours.Catalyzer finally consists of: amorphous aluminum silicide 48wt%, Y molecular sieve 15wt%, aluminum oxide 12wt%, nickel oxide 5wt%, molybdenum oxide 20wt%.Catalyst specific surface 220m
2/ g, pore volume 0.35ml/g.
(2) hydrocracking catalyst A2:
By amorphous aluminum silicide (specific surface 490m
2/ g, SiO
245wt%, pore volume 1.0ml/g) and Y molecular sieve (SiO
2/ Al
2o
3mol ratio is 12, lattice constant 2.436, specific surface 680m
2/ g, infrared acidity 0.41mmol/g), after mixing, add the tackiness agent of (being added the preparation of rare nitric acid peptization by the little porous aluminum oxide of pore volume 0.42ml/g) roll agglomerating after, put into after banded extruder extruded moulding, at 110 ℃, be dried 10 hours, 500 ℃ of activation make after carrier for 4 hours, then steep by W-Ni total immersion stain immersion, then at 110 ℃, be dried 12 hours, and 500 ℃ activate 3 hours.Catalyzer finally consists of: amorphous aluminum silicide 45wt%, Y molecular sieve 13wt%, aluminum oxide 12wt%, nickel oxide 6.5wt%, Tungsten oxide 99.999 22.5wt%.Catalyst specific surface 210m
2/ g, pore volume 0.31ml/g.
2, contain the preparation of the hydrocracking catalyst of amorphous aluminum silicide and beta-molecular sieve: B1, B2.
(1) hydrocracking catalyst B1:
By beta-molecular sieve (SiO
2/ Al
2o
3mol ratio is 40, specific surface 580m
2/ g, infrared acidity 0.21mmol/g), amorphous aluminum silicide (specific surface 450m
2/ g, SiO
255wt%, pore volume 0.9ml/g) mix, add little porous aluminum oxide (the specific surface area 240m of dilute nitric acid solution peptization by concentration 3.3wt%
2/ g, pore volume is 0.42ml/g) tackiness agent that obtains, continue kneading until become paste, extruded moulding, institute's moulding bar that obtains is dried 12 hours at 110 ℃, and 500 ℃ of activation make after activated carrier for 4 hours.With W-Ni co-impregnated solution, flood again the carrier of above-mentioned preparation, then be dried 8 hours at 110 ℃, and 500 ℃ activate 3 hours.Catalyzer finally consists of: β zeolite 25wt%, amorphous aluminum silicide 25wt%, aluminum oxide 20wt%, nickel oxide 7.5wt%, Tungsten oxide 99.999 22.5wt%.Catalyst specific surface 235m
2/ g, pore volume 0.32ml/g.
(2) hydrocracking catalyst B2:
By beta-molecular sieve (SiO
2/ Al
2o
3mol ratio is 60, specific surface 550m
2/ g, infrared acidity 0.19mmol/g), amorphous aluminum silicide (specific surface 490m
2/ g, SiO
245wt%, pore volume 1.0ml/g) mix, in the situation that continuing to roll, slowly add little porous aluminum oxide (the specific surface area 240m of dilute nitric acid solution peptization by concentration 3.3%
2/ g, pore volume is 0.42ml/g) tackiness agent that obtains, continue kneading until become paste, extruded moulding, institute's moulding bar that obtains is dried 12 hours at 110 ℃, and 500 ℃ of activation make after activated carrier for 4 hours.Again with W-Ni co-impregnated solution dipping, then at 110 ℃, be dried 8 hours, and 500 ℃ activate 3 hours.Catalyzer finally consists of: beta-molecular sieve 10wt%, amorphous aluminum silicide 30wt%, aluminum oxide 30wt%, nickel oxide 7.5wt%, Tungsten oxide 99.999 22.5wt%.Catalyst specific surface 260m
2/ g, pore volume 0.33ml/g.
Embodiment of the present invention removal of ccr by hydrotreating catalyzer used is prepared as follows:
Take 298g Si-Al
2o
3(butt 67wt%, dioxide-containing silica is 13wt%) powder, powdered active carbon 20.5g, sesbania powder 5g, mixed, and adds by 208g water, 22.0g containing 17wt%TiCl
3tiCl
3the acidic solution that solution and 22g acetic acid mix, kneading 1.5 hours, gained plastic, extrusion mechanism is extruded into the special-shaped strip of Φ 2.58～2.64mm, and this strip is dried 4 hours at 108 ℃, and at 480 ℃, roasting is 4 hours.By ordinary method, flood active metal, molybdenum, tungsten and nickel are then dried 3 hours at 80 ℃, and at 500 ℃, roasting is 3 hours, makes catalyzer HDC-1.The composition of this catalyzer and physico-chemical property see the following form 1.
Take 298g Si-Al
2o
3(butt 67wt%, dioxide-containing silica is 19wt%) powder, sesbania powder 5g, is mixed, and adds by 188g water, 43.0g containing 17wt%TCl
3tiCl
3the acidic solution that solution and 22g acetic acid mix, kneading 1.5 hours, gained plastic, extrusion mechanism is extruded into the special-shaped strip of Φ 1.10～1.35mm, and this strip is dried 4 hours at 108 ℃, and at 960 ℃, roasting is 4 hours.By ordinary method, flood active metal, molybdenum, tungsten and nickel are then dried 2 hours at 120 ℃, and at 550 ℃, roasting is 3 hours, makes catalyzer HDC-2.The composition of this catalyzer and physico-chemical property see the following form 1.
Take 298g Si-Al
2o
3(butt 67wt%, dioxide-containing silica is 19wt%) powder, sesbania powder 5g, is mixed, and adds by 188g water, 43.0g containing 17wt%TiCl
3tiCl
3the acidic solution that solution and 22g acetic acid mix, kneading 1.5 hours, gained plastic, extruded moulding, this strip is dried 4 hours at 108 ℃, and at 550 ℃, roasting is 4 hours.By ordinary method, flood active metal, molybdenum, tungsten and nickel are then dried 2 hours at 120 ℃, and at 550 ℃, roasting is 3 hours, makes catalyzer HDC-3.The composition of this catalyzer and physico-chemical property see the following form 1.
Composition and the character of table 1 removal of ccr by hydrotreating catalyzer
| Catalyzer | HDC-1 | HDC-2 | HDC-3 |
| Form % (massfraction) | |||
| WO 3 | 18 | 20 | 22 |
| MoO 3 | 8 | 11 | 11 |
| NiO | 5 | 5 | 5 |
| SiO 2 | 6 | 9 | 9 |
| TiO 2 | 1 | 2 | 2 |
| Al 2O 3 | Surplus | Surplus | Surplus |
| Character | |||
| Specific surface area, m 2/g | 138 | 175 | 220 |
| Mean pore size, nm | 18.4 | 11.8 | 6.8 |
Embodiment 1～3
Ethylene bottom oil lighting end used and last running character are in Table 2 and table 4.Embodiment adopts serial flow to process ethylene bottom oil lighting end; adopt two reactors; the first reactor in-built hydrogenation protecting agent FZC-103 and Hydrobon catalyst 3936; second adds reactor top filling removal of ccr by hydrotreating catalyzer HDC-3; the first hydrocracking catalyst of middle part filling is the hydrocracking catalyst containing amorphous aluminum silicide and Y molecular sieve, and the second hydrocracking catalyst of bottom filling is the hydrocracking catalyst containing amorphous aluminum silicide and beta-molecular sieve.In embodiment, FZC-103:3936:HDC-3: the first hydrocracking catalyst: the volume ratio of the second hydrocracking catalyst is as follows: 12: 19: 19: 25: 25.That reacts gained the results are shown in Table 3.In addition, this device has carried out the service test of 5000 hours, product distributes and each narrow fraction product property is substantially constant or it is very little to change, and illustrates that present method can solve the high problem of ethylene bottom oil lighting end carbon residue, realizes the object that obtains light-weight fuel oil through hydrotreatment.Wherein FC-18 is produced by oil three factories of Fushun petrochemical industry branch office of CNPC.
Table 2 ethylene bottom oil lighting end character
| Crude title | Ethylene bottom oil lighting end (430 ℃ of <) |
| Boiling range/℃ | |
| IBP/10％ | 170/214 |
| 30％/50％ | 260/320 |
| 70％/90％ | 367/392 |
| 95％/EBP | 410/441 |
| Density (20 ℃)/gcm -3 | 1.01 |
| S/μg·g -1 | 300 |
| N/μg·g -1 | 120 |
| Stable hydrocarbon, % (massfraction) | 0.57 |
| Aromatic hydrocarbons, % (massfraction) | 78.39 |
| Colloid, % (massfraction) | 20.56 |
| Bituminous matter, % (massfraction) | 1.08 |
Table 3 one-stage serial hydrogenation technique condition and diesel oil distillate product property
| Scheme | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Hydrogenation protecting agent | FZC-103 | FZC-103 | FZC-103 |
| Hydrobon catalyst | 3936 | 3936 | 3936 |
| Removal of ccr by hydrotreating catalyzer | HDC-3 | HDC-3 | HDC-3 |
| Hydrocracking catalyst | A2/B1 | A1/FC-18 | A1/B2 |
| Processing condition | |||
| Hydrogen dividing potential drop/MPa | 12.0 | 13.5 | 15.0 |
| One anti-/ bis-anti-temperature/℃ | 365/395 | 375/385 | 355/405 |
| One anti-/ bis-anti-air speed/h -1 | 0.5/0.8 | 0.4/0.5 | 0.6/0.6 |
| Hydrogen to oil volume ratio | 1400 | 1200 | 1500 |
| Diesel product character | |||
| Yield, % (massfraction) | 84.2 | 90.4 | 81.6 |
| Density (20 ℃)/gcm -3 | 0.9063 | 0.9108 | 0.9030 |
| Sulphur content, μ g/g | 17 | 16 | 15 |
| Nitrogen content, μ g/g | 1 | 2 | 1 |
| Condensation point/℃ | -50 | ＜-50 | ＜-50 |
| Cold filter clogging temperature/℃ | -27 | -26 | -30 |
| Boiling range/℃ 50% recovery 90% is reclaimed 95% and is reclaimed | 199 276 310 | 216 281 312 | 197 274 300 |
| Cetane value | 29.1 | 32.0 | 28.3 |
| Gasoline fraction character | |||
| Yield, % (massfraction) | 14.8 | 9.1 | 17.4 |
| Octane value | 82 | 80 | 85 |
Table 4 ethylene bottom oil last running character
| Crude title | Ethylene bottom oil last running (430 ℃ of >) |
| Density (20 ℃), g/cm 3 | 1.06 |
| S, % (massfraction) | 0.06 |
| N, % (massfraction) | 0.02 |
| CCR, % (massfraction) | 14.3 |
| Ni+V, % (massfraction) | 4.0 |
Embodiment 4
Adopt the flow process shown in Fig. 1; ethylene bottom oil last running (character is in Table 4) is successively through hydrogenation protecting catalyst, the de-residual catalyzer of hydrogenation and hydrogenation conversion catalyst; its volume ratio is 10: 40: 50; wherein hydrogenation protecting catalyst used is FZC-100 and FZC-102B; its volume ratio is 1: 2; hydrogenation conversion catalyst is designated as ZH1 as the catalyzer of CN02109422.5 embodiment 1 gained, and its character is in Table 5.
The composition of table 5 hydrogenation conversion catalyst and character
| Character | MoO 3/ % (massfraction) | NiO/% (massfraction) | TiO 2/ % (massfraction) | SiO 2/ % (massfraction) | Pore volume/cm 3·g -1 | Specific surface area/m 2·g -1 | Average pore diameter/nm | 4～15nm pore volume integration rate/% |
| ZH1 | 25.3 | 9.0 | 2.0 | 5.0 | 0.40 | 240 | 7.0 | 80 |
Removal of ccr by hydrotreating catalyzer HDC-1 used is 4: 6 with the admission space ratio of HDC-2.The packing sequence of ethylene bottom oil heavy fractioning hydrogenation catalyzer is as follows: FZC-100, FZC-102B, HDC-1, HDC-2, ZH1.In the present embodiment, described in loop back hydroconversion reaction zone the weight of low minute of heat oil and the weight ratio of described ethylene bottom oil last running be 2.0.The processing condition of heavy fractioning hydrogenation are as follows: reaction pressure is 16MPa, and temperature of reaction is 390 ℃, and during liquid, volume space velocity is 1.8h
-1, hydrogen to oil volume ratio is 1000, the reaction result turning round after 500 hours and 7000 hours is in Table 6.
Embodiment 5
Compare with embodiment 4, adopt hot high score oil circulation, the weight of hot high score oil and the weight ratio of described ethylene bottom oil last running that loop back hydroconversion reaction zone are 2.0, and removal of ccr by hydrotreating catalyzer HDC-1 used is become to 5: 5 with the admission space ratio of HDC-2, and all the other are identical with embodiment 4.
Embodiment 6
Compare with embodiment 4, adopt stripping tower oil circulation, the weight of stripping tower oil and the weight ratio of described ethylene bottom oil last running that loop back hydroconversion reaction zone are 2.0, and all the other are identical with embodiment 4.
Table 6 heavy fractioning hydrogenation result
Claims (15)
1. the method for hydrotreating of an ethylene bottom oil, comprise: ethylene bottom oil is fractionated into lighting end and last running, cut point is 400～450 ℃, described lighting end is successively by lighting end hydrogenation protecting catalyst, Hydrobon catalyst, lighting end removal of ccr by hydrotreating catalyzer and hydrocracking catalyst, the isocrackate of reaction gained enters separation system, obtains gasoline and diesel oil distillate; Described last running is successively by heavy fractioning hydrogenation guard catalyst, the de-carbon residue catalyzer of heavy fractioning hydrogenation, hydrogenation conversion catalyst, the hydrocracking of reaction gained generates the circulation of oil part and mixes duplicate removal cut fraction hydrogenation reaction zone with ethylene bottom oil last running, remainder, through further separated, obtains gasoline and diesel oil distillate;
In described lighting end hydrogenation, it is benchmark that the admission space of lighting end hydrogenation protecting catalyst, Hydrobon catalyst, lighting end removal of ccr by hydrotreating catalyzer and hydrocracking catalyst be take lighting end hydrogenation used catalyst cumulative volume, as follows respectively: 2%～20%, 5%～40%, 5%～40% and 30%～50%; Described hydrocracking catalyst adopts two kinds of hydrocracking catalysts, the first hydrocracking catalyst bed is that to take Y molecular sieve and amorphous aluminum silicide be main acidic components, the second hydrocracking catalyst bed is that to take beta-molecular sieve and amorphous aluminum silicide be main acidic components, reactant flow first contacts with the first hydrocracking catalyst, and then contacts with the second hydrocracking catalyst; The first hydrocracking catalyst is 1～5: 1 with the admission space ratio of the second hydrocracking catalyst; Hydrorefined operational condition is: volume space velocity 0.1～2.6h when 340～390 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～18.0MPa, hydrogen to oil volume ratio 800: 1～2500: 1 and liquid
-1; The operational condition of removal of ccr by hydrotreating and hydrocracking is: volume space velocity 0.1～2.2h when 370～420 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～18.0MPa, hydrogen to oil volume ratio are 800: 1～2500: 1 and liquid
-1;
Described ethylene bottom oil last running is successively by heavy fractioning hydrogenation guard catalyst, the de-carbon residue catalyzer of heavy fractioning hydrogenation and hydrogenation conversion catalyst, above-mentioned catalyst loading is according to along reactant flow flow direction, aperture reduces successively, the active order increasing is successively carried out, and its admission space accounts for respectively 5%～20%, 20%～60%, 20%～60% of heavy fractioning hydrogenation catalyzer total fill able volume; The operational condition of heavy fractioning hydrogenation is as follows: reaction pressure is 14～18MPa, and temperature of reaction is 360～410 ℃, and during liquid, volume space velocity is 1.0～2.1h
-1, hydrogen to oil volume ratio is 500～1500; The weight ratio that the hydrocracking that loops back heavy fractioning hydrogenation reaction zone generates oily weight and described ethylene bottom oil last running is 1.0～4.0.
2. method according to claim 1, it is characterized in that, for the hydrocracking that circulates generate that the hot high score that oil obtains through high pressure hot separator separation for hydroconverted products is oily, low minute oil of the heat that obtains through thermal low-pressure separators separation, the stripping tower oil that obtains after stripping tower stripping one or more.
3. method according to claim 1 and 2, it is characterized in that described lighting end generates the circulation of oil part through the hydrocracking of hydrogenation gained, Recycle design at least adopts following a kind of: (1) mixes lighting end hydroconversion reaction zone with ethylene bottom oil lighting end, and (2) mix duplicate removal cut fraction hydrogenation reaction zone with ethylene bottom oil last running; The weight ratio that the hydrocracking of circulation generates oily weight and described ethylene bottom oil fresh feed is 1.0～4.0.
4. method according to claim 3, it is characterized in that, for the hydrocracking that circulates generate that the hot high score that oil obtains through high pressure hot separator separation for isocrackate is oily, low minute oil of the heat that obtains through thermal low-pressure separators separation, the stripping tower oil that obtains after stripping tower stripping one or more.
5. method according to claim 1 and 2, is characterized in that described ethylene bottom oil lighting end and the cut point of last running are 400～430 ℃.
6. method according to claim 1 and 2, it is characterized in that described Hydrobon catalyst is as follows: take aluminum oxide or silicon-containing alumina as carrier, the weight of catalyzer of take is benchmark, group vib active metallic content is counted 10wt%～35wt% with oxide compound, group VIII active metallic content is counted 3wt%～15wt% with oxide compound, and the character of this catalyzer is as follows: specific surface area is 100～350m
2/ g, pore volume is 0.15～0.60ml/g.
7. method according to claim 1 and 2, is characterized in that described lighting end removal of ccr by hydrotreating catalyzer contains auxiliary agent Si and Ti, take aluminum oxide as carrier, take catalyst weight as benchmark, composed as follows: WO
3content be 16%～23%, MoO
3content be 6%～13%, NiO content is 3%～8%, SiO
2content is 4%～12%, and titanium oxide content is 0.5%～4.0%, and surplus is aluminum oxide; The character of this catalyzer is as follows: pore volume is 0.30～0.55cm
3/ g, specific surface area is 120～300m
2/ g, average pore diameter is 5～10nm.
8. method according to claim 1, is characterized in that the character of Y molecular sieve described in the first described hydrocracking catalyst is as follows: SiO
2/ Al
2o
3mol ratio is 5～40, lattice constant 2.425～2.440nm, specific surface area 500～750m
2/ g, infrared acidity 0.25～0.50mmol/g, Na
2o content < 0.2wt%; The character of described amorphous aluminum silicide is as follows: pore volume 0.8～1.5ml/g, specific surface area 350～600m
2/ g, silica weight content 20%～60%.
9. method according to claim 1, it is characterized in that the composed as follows of the first described hydrocracking catalyst: the weight of catalyzer of take is benchmark, the content of Y molecular sieve is 8%～20%, the content of amorphous aluminum silicide is 38%～60%, it is 15%～40% that group vib hydrogenation activity component be take the content of oxide compound, it is 1%～10% that group VIII hydrogenation activity component be take the content of oxide compound, and surplus is little porous aluminum oxide; The character of the first hydrocracking catalyst is as follows: specific surface area is 180～300m
2/ g, pore volume is 0.25～0.45ml/g.
10. method according to claim 1, is characterized in that the character of beta-molecular sieve in the second hydrocracking catalyst is as follows: SiO
2/ Al
2o
3mol ratio is 20～150, specific surface area 500～750m
2/ g, infrared acidity 0.05～0.50mmol/g, Na
2o content < 0.2wt%; The character of described amorphous aluminum silicide is as follows: pore volume 0.8～1.5ml/g, specific surface area 350～600m
2/ g, silica weight content 20%～60%.
11. according to the method described in claim 1 or 10, it is characterized in that the composed as follows of the second hydrocracking catalyst, the weight of catalyzer of take is benchmark: the content of beta-molecular sieve is 10%～28%, the content of amorphous aluminum silicide is 20%～40%, it is 15%～40% that group vib hydrogenation activity component be take the content of oxide compound, it is 1%～10% that group VIII hydrogenation activity component be take the content of oxide compound, and surplus is little porous aluminum oxide.
12. methods according to claim 1, is characterized in that the de-carbon residue catalyzer of described heavy fractioning hydrogenation adopts two removal of ccr by hydrotreating beds, and the volume ratio of upstream removal of ccr by hydrotreating catalyzer and downstream removal of ccr by hydrotreating catalyzer is 3～7: 7～3; In upstream catalyst bed, the active metal oxide content of removal of ccr by hydrotreating catalyzer used is 25wt%～40wt%, average pore diameter is 15～25nm, the active metal oxide content of the removal of ccr by hydrotreating catalyzer used in downstream catalyst bed is 28wt%～45wt%, and average pore diameter is 10～20nm.
13. according to the method described in claim 1 or 12, it is characterized in that the de-carbon residue catalyzer of described heavy fractioning hydrogenation contains auxiliary agent Si and Ti, take aluminum oxide as carrier, take catalyzer weight as benchmark composed as follows: WO
3content be 16%～23%, MoO
3content be 6%～13%, NiO content is 3%～8%, silicone content is with SiO
2count 4%～12%, titanium oxide content is 0.5%～4%, and surplus is aluminum oxide; The character of this catalyzer is as follows: pore volume is 0.40～0.55cm
3/ g, specific surface area is 120～180m
2/ g.
14. methods according to claim 1 and 2, is characterized in that described hydrogenation conversion catalyst adopts hydrotransforming catalyst for residual oil.
15. methods according to claim 14, hydrogenation conversion catalyst described in it is characterized in that be take aluminum oxide as carrier, the weight of catalyzer of take is benchmark, this catalyzer is composed as follows: group VIII active ingredient counts 5%～10% with oxide compound, group vib active ingredient counts 20%～30% with oxide compound, SiO
2content is 2.0%～10.0%, TiO
2content is 0～4.0%, ZrO
2content is 0～8.0%, and surplus is aluminum oxide; The character of this catalyzer is as follows: pore volume is 0.3ml/g～0.6ml/g, and specific surface area is 150m
2/ g～270m
2/ g, average pore diameter is 6.0nm～10.0nm, it is 80%～90% that the pore volume integration rate of bore dia within the scope of 4nm～15nm accounts for the pore volume integration rate of bore dia within the scope of 0nm～100nm, and the pore volume integration rate of its median pore diameter within the scope of 5nm～10nm is 65%～75%.
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| US6280606B1 (en) * | 1999-03-22 | 2001-08-28 | Institut Francais Du Petrole | Process for converting heavy petroleum fractions that comprise a distillation stage, ebullated-bed hydroconversion stages of the vacuum distillate, and a vacuum residue and a catalytic cracking stage |
| CN1100122C (en) * | 2000-03-10 | 2003-01-29 | 中国石油化工集团公司 | Process for hydrogenating poor-quality raw material for catalytic cracking |
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| CN1100122C (en) * | 2000-03-10 | 2003-01-29 | 中国石油化工集团公司 | Process for hydrogenating poor-quality raw material for catalytic cracking |
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