CN102234537A - Hydrogenation method for ethylene tar - Google Patents
Hydrogenation method for ethylene tar Download PDFInfo
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- CN102234537A CN102234537A CN2010102273804A CN201010227380A CN102234537A CN 102234537 A CN102234537 A CN 102234537A CN 2010102273804 A CN2010102273804 A CN 2010102273804A CN 201010227380 A CN201010227380 A CN 201010227380A CN 102234537 A CN102234537 A CN 102234537A
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Abstract
The invention discloses a hydrogenation method for 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 protecting catalyst, a hydrogenation refining catalyst, a hydrogenation carbon residue removing catalyst and a hydrocracking catalyst in turn, and reacting to obtain hydrocracking generated oil, wherein partial hydrocracking generated oil is circulated and mixed with the light fraction of the ethylene tar to enter a hydrogenation reaction area, and the rest hydrocracking generated oil is separated to form 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 preferably in turn, and separating to obtain 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 method of hydrotreating of ethylene bottom oil.
Background technology
The scarcity day by day of world petroleum resource and price thereof high day by day makes the refinery reduce discharging synergy and necessitates that 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 is cracking of ethylene raw material raw material and product pyrocondensation product in the steam cracking process, and its initial boiling point is at 170～260 ℃, and final boiling point＞600 ℃ are generally 600～700 ℃, belong to the last running scope.Ethylene bottom oil mainly is 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, foreign matter contents such as sulphur and nitrogen are low, substantially containing metal impurity not.
In order to increase economic efficiency, each refinery is developed multiple method of comprehensive utilization, such as extract naphthalene and series product thereof, light constituent (＜300 ℃) synthesizing petroleum resin, tar heavy oil produce carbon fibre asphalt and carbon fiber,＞540 ℃ of last running produces gac etc. (see " Jiization science and technology " second phase P47-P50 in 1997: " comprehensive utilization of ethylene bottom oil ").Still have some intermediate oils not to be fully used in the aforesaid method, overall economic efficiency remains further to be promoted, and the procedure of processing complexity.
The CN1970688A disclosed method is that ethylene bottom oil is cut out boiling point less than 260～280 ℃ lighting end, remove unsaturated hydro carbons in this lighting end with hydrorefined method again, and then therefrom extract naphthalene and methylnaphthalene product, by-product a small amount of solvent oil production simultaneously.This method has only been utilized proportion lighting end seldom in the ethylene bottom oil, and the ethylene bottom oil cut of still having an appointment more than 80% is not effectively addressed; The hydrofining condition that it provided simultaneously can't be handled the ethylene bottom oil cut that boiling point is higher than 280 ℃.
Summary of the invention
In order to overcome deficiency of the prior art, the invention provides a kind of method of hydrotreating that effectively utilizes ethylene bottom oil, produces 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; the gained hydrocracking generates the circulation of oil part and mixes hydroconversion reaction zone with the ethylene bottom oil lighting end, and remainder obtains gasoline and diesel oil distillate through further separating.
Last running described in the inventive method also can be produced light-weight fuel oil through hydrotreatment as the common carbon fiber asphalt stock.Described last running is preferably taken off carbon residue catalyzer, hydrogenation conversion catalyst by heavy fractioning hydrogenation guard catalyst, heavy fractioning hydrogenation successively, and the hydroconverted products of reaction gained enters separation system, obtains gasoline and diesel oil distillate.
In the inventive method, the hydrocracking that loops back the lighting end hydroconversion reaction zone generates oil and can be the liquid product that obtains in the isocrackate sepn process, as separating the hot high score oil that obtains through high pressure hot separator, separating in the low stripping tower oil that divides oil, obtains of the heat that obtains one or more through thermal low-pressure separators behind the stripping tower stripping.
The weight ratio that olefiant weight and described ethylene bottom oil lighting end are given birth in the described hydrocracking that loops back the lighting end hydroconversion reaction zone is 1.0～4.0.
Hydrogenation of the present invention is to adopt fixed bed hydrogenation technology.
Hydrobon catalyst, lighting end removal of ccr by hydrotreating catalyzer and hydrocracking catalyst used in the described lighting end hydrogenation can be seated in the same reactor in layering, also can respectively in different reactors, preferably removal of ccr by hydrotreating catalyzer and hydrocracking catalyst be seated in the same reactor.Hydrogenation protecting catalyst can be seated in the same reactor with Hydrobon catalyst, also can adopt a reactor separately.Lighting end hydrogenation of the present invention adopts tandem process, and the diesel oil distillate yield is higher, invests less.
In the described lighting end hydrogenation; the admission space of lighting end hydrogenation protecting catalyst, Hydrobon catalyst, lighting end removal of ccr by hydrotreating catalyzer and hydrocracking catalyst is a benchmark with lighting end hydrogenation catalyst system therefor cumulative volume, and is as follows respectively: 2%～18%, 5%～35%, 5%～35% and 30%～45%.
In the inventive method, described Hydrobon catalyst is conventional Hydrobon catalyst or hydrocracking pretreatment catalyst, be active ingredient generally with VI B family and/or group VIII metal, aluminum oxide with aluminum oxide, siliceous aluminum oxide or siliceous and phosphorus is a carrier, the group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.Weight with catalyzer is benchmark, and the 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 are 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 to be the hydrogenation activity component with VI B and VIII family metal, as two or three among W, Mo, Ni and the Co, is preferably W, Mo and Ni, and this catalyzer preferably contains auxiliary agent Si and Ti, is carrier with the aluminum oxide.Weight with catalyzer is benchmark, WO
3Content be 16%～23%, MoO
3Content be 6%～13%, the content of NiO 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 an aluminum oxide.The character of this catalyzer is as follows: the pore volume of catalyzer 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, can adopt conventional hydrocracking catalyst at hydrocracking catalyst.The inventive method is produced low-coagulation diesel oil for maximum, described hydrocracking catalyst preferably adopts two kinds of hydrocracking catalysts, first hydrocracking catalyst is to be main acidic components with Y molecular sieve and amorphous aluminum silicide, and the second hydrocracking catalyst bed is to be main acidic components with beta-molecular sieve and amorphous aluminum silicide.Described first hydrocracking catalyst composed as follows, weight with catalyzer is benchmark: the content of Y molecular sieve is 8%～20%, the content of amorphous aluminum silicide is 38%～60%, group vib hydrogenation activity component is 15%～40% in the content of oxide compound, VIII family hydrogenation activity component is 1%～10% in the content of oxide compound, and surplus is little porous aluminum oxide; The character of first hydrocracking catalyst is as follows: specific surface is 180～300m
2/ g, pore volume are 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%.Second hydrocracking catalyst composed as follows, weight with catalyzer is benchmark: the content of beta-molecular sieve is 10%～28%, the content of amorphous aluminum silicide is 20%～40%, group VIB hydrogenation activity component is 15%～40% in the content of oxide compound, VIII family hydrogenation activity component is 1%～10% in 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%.First hydrocracking catalyst is 1～5: 1 with the admission space ratio of second hydrocracking catalyst, is preferably 1～3: 1.First hydrocracking catalyst is positioned at the upstream of second hydrocracking catalyst, and promptly reactant flow contacts with first hydrocracking catalyst earlier, and then contacts with second hydrocracking catalyst.But two kinds of hydrocracking catalyst layerings are seated in the reactor, also can be divided in two reactors.
Said hydrorefined operational condition is: volume space velocity 0.8～2.6h when 340～370 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～15.0MPa, hydrogen to oil volume ratio 800: 1～1400: 1 and liquid
-1The preferred operations condition is: volume space velocity 1.6～2.5h when 340～360 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～14.0MPa, hydrogen to oil volume ratio 900: 1～1400: 1 and liquid
-1The operational condition of said removal of ccr by hydrotreating and hydrocracking is: volume space velocity 1.0～2.2h when 370～400 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～15.0MPa, hydrogen to oil volume ratio are 800: 1～1400: 1 and liquid
-1The preferred operations condition is: volume space velocity 1.5～2.0h when 370～390 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～14.0MPa, hydrogen to oil volume ratio 900: 1～1400: 1 and liquid
-1
Ethylene bottom oil lighting end described in the present invention contacts with hydrogenation protecting catalyst earlier respectively with last running, mainly removes wherein impurity and part carbon residue, to avoid downstream hydrogenation catalyst coking, the running period of extension fixture.Used hydrogenation protecting catalyst can adopt conventional residual hydrogenation protective material or residuum hydrogenating and metal-eliminating catalyst among the present invention; be active ingredient generally with VI B family and/or group VIII metal; with aluminum oxide or siliceous aluminum oxide is carrier; the group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.Weight with catalyzer is benchmark, active metallic content is counted 0.5wt%～18wt% with oxide compound, preferably composed as follows: the 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 taken off carbon residue catalyzer, hydrogenation conversion catalyst by heavy fractioning hydrogenation guard catalyst, heavy fractioning hydrogenation successively; above-mentioned catalyst loading is according to along the reactant flow flow direction; the aperture reduces successively, the active order that increases is successively carried out, and its admission space accounts for 5%～15%, 30%～70%, 20%～60% of heavy fractioning hydrogenation catalyzer total fill able volume respectively.Above-mentioned three kinds of catalyzer can be seated in the reactor; also can be seated in the different reactors respectively; also can be in a reactor with hydrogenation protecting catalyst and removal of ccr by hydrotreating catalyst loading, hydrogenation conversion catalyst is seated in another reactor.Described heavy fractioning hydrogenation takes off the carbon residue catalyzer, can adopt heavy, residual hydrogenation of the prior art to take off the carbon residue catalyzer, two removal of ccr by hydrotreating beds of preferred employing, the volume ratio of upstream removal of ccr by hydrotreating catalyzer and downstream removal of ccr by hydrotreating catalyzer is 3～7: 7～3.Removal of ccr by hydrotreating activity of such catalysts metal oxide content used in the upstream catalyst bed is 25wt%～40wt%, average pore diameter is 15～25nm, used removal of ccr by hydrotreating activity of such catalysts metal oxide content in the lower catalyst bed layer is 28wt%～45wt%, and average pore diameter is 10～20nm.It generally is to be the hydrogenation activity component with VI B and VIII family metal that described hydrogenation takes off residual catalyzer, as two or three among W, Mo, Ni or the Co, is preferably W, Mo and Ni, and this catalyzer preferably contains auxiliary agent Si and Ti, is carrier with the aluminum oxide.Weight with catalyzer is benchmark, WO
316%～23%, MoO
36%～13%, NiO 3%～8%, and 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 an aluminum oxide.The character of this catalyzer is as follows: the pore volume of catalyzer is 0.40～0.55cm
3/ g, specific surface area is 120～180m
2/ g.
Last running mainly is to carry out hydroconversion reactions through hydrogenation conversion catalyst, removes sulphur and nitrogen simultaneously, can adopt hydrotransforming catalyst for residual oil.This catalyzer is to be carrier with the aluminum oxide, with VIII family and VI B metallic element is active ingredient, VIII family active metal component is nickel or cobalt, VI B active metal component is molybdenum or tungsten, with IV A family and IV B family element is auxiliary agent, described IV A family element is a silicon, and described IV B family element is titanium and/or zirconium.Such as the hydrotransforming catalyst for residual oil that can adopt among the CN02109422.5, weight with catalyzer is benchmark, this catalyzer composed as follows: VIII family active ingredient counts 5%～10% with oxide compound, and the group VIB active ingredient counts 20%～30% with oxide compound, SiO
2Content at catalyzer is 2.0%～10.0% by weight, TiO
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 an 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 in 4nm～15nm scope accounts for the pore volume integration rate of bore dia in 0nm～100nm scope, and the pore volume integration rate of its median pore diameter in 5nm～10nm scope is 65%～75%.
The operational condition of described heavy fractioning hydrogenation is as follows: reaction pressure is 14～20MPa, and temperature of reaction is 360～420 ℃, and volume space velocity is 0.1～0.6h during liquid
-1, hydrogen to oil volume ratio is 500～1500.
In sum, adopt method of the present invention to handle ethylene bottom oil and have following advantage:
1, selects the suitable full cut of cut point fractionation ethylene bottom oil, select to adopt different treatment processs at the compositing characteristic of lighting end and last running, 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, also can be used as the common carbon fiber asphalt stock.
2, the inventive method is taken all factors into consideration the composition and the character of ethylene bottom oil lighting end, select two types hydrocracking catalyst to carry out grading loading, can make full use of the not characteristics of isomorphism type molecular sieve, and match with amorphous aluminum silicide, aromatic hydrocarbons open loop after making hydrogenation in the ethylene bottom oil saturated, appropriate again cracking and/or isomerization can high yield obtain condensation point less than-40 ℃ diesel oil distillate, by-product stop bracket gasoline cut simultaneously.
3, the present invention is directed to aromaticity content height in the ethylene bottom oil lighting end, cause the higher problem of beds temperature rise, adopt hydrocracking to generate oil circulation time hydroconversion reaction zone, effectively reduce the aromaticity content in the hydroconversion reaction zone charging on the one hand, the device temperature rise is obviously reduced, so just avoided owing to temperature rise, and many reactors or more beds must be set; On the other hand, because temperature rise, cold hydrogen amount increases between reactor or bed, will cause the circulating hydrogen compressor load to increase, and facility investment all can be saved greatly in this two aspect.
4, the present invention adopts hydrocracking to generate oily method of mixing with the ethylene bottom oil lighting end as the hydroconversion reaction zone charging, can avoid owing to need the liquid hydrogen injection reference mark many, cause the misoperation probability to increase, thereby cause temperature runaway, cause the catalyzer coking, cause 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 method as the hydroconversion reaction zone charging with the ethylene bottom oil lighting end, can effectively reduce the concentration of colloid, bituminous matter and carbon residue in the hydrogenating materials oil, favourable to hydrofining and the active permanent performance of hydrocracking catalyst, but the safety in production of the long period of implement device.
6, lighting end hydrogenation of the present invention increases the removal of ccr by hydrotreating beds between Hydrobon catalyst and hydrocracking catalyst; help removing the carbon residue in the ethylene bottom oil; protected the hydrocracking catalyst in downstream; prolonged the running period of device; simultaneously; also can make a part of aromatic hydrogenation saturated, help further cracking, useful to improving yield of light oil.In addition, raw material successively through catalyst for refining, take off carbon residue catalyzer and cracking catalyst, can make exothermic heat of reaction even, avoid 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 select processing scheme according to different product demands.
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, it is useful that the refinery is reduced discharging synergy.
9, in the inventive method, last running is preferably adopted earlier through taking off the method that the carbon residue repeated hydrogenation transforms, realized that the ethylene bottom oil heavy fractioning hydrogenation transforms the purpose of light-weight fuel oil, favourable to prolong operating period, expanded the raw material sources of producing light-weight fuel oil simultaneously.
10, in the inventive method, the last running that is fractionated out by ethylene bottom oil is during as the carbon fibre asphalt raw material, compare with ethylene bottom oil, lighting end has not only been removed in the last running of ethylene bottom oil fractionation gained, and aromaticity content increases, and C/H increases, and softening temperature generally can be increased to 220 ℃～240 ℃, solved because the full cut softening temperature of ethylene bottom oil is low excessively, needed a large amount of high softening-point components of modulation could be used as the problem of carbon fibre asphalt; Though quinoline insolubles slightly increases, but still in the scope that carbon fibre asphalt requires, therefore, ethylene bottom oil last running is fine carbon fibre asphalt raw material.Described last running can be by the known prior art of these those skilled in the art, promptly obtain asphalt base carbon fiber through modulation treatment, melt-spinning, non-melt processed and carburising step, its intensity is at 650MPa～860MPa, Young's modulus is at 45GPa～65GPa, elongation at break is 0.9%～1.7%, and attribute can universal preferably asphalt base carbon fiber.
Description of drawings
Fig. 1 is the block diagram of the inventive method.
Embodiment
Hanging down branch oil circulation in conjunction with Fig. 1 with heat is example, and the invention will be further described.Ethylene bottom oil 1 obtains lighting end 3 and last running 4 through separation column 2.Lighting end 3 enters hydrogenating materials surge tank 5, mix as the hydrogenator raw material with the low oil 11 that divides of the low liquid product heat of dividing of heat, this raw material is with new hydrogen 7 and come the recycle hydrogen 8 of self cooling high score 12 to be mixed into hydrogenator 6, carry out hydrofining/cracking reaction, product enters high pressure hot separator 9, carry out gas-liquid separation, liquid product enters thermal low-pressure separators 10, further carry out gas-liquid separation and obtain the low oil 11 that divides of heat, heat is low divides oil 11 part circulations as the hydrogenation reaction raw material, being mixed into hydrogenator 6 with lighting end 3 reacts, remainder enters cold high pressure separator 12 successively, cold low separator 13 carries out gas-liquid separation, obtains gasoline fraction 16 and diesel oil distillate 17 through stripping tower 14 and separation column 15.Last running 4 is the hydroprocessing technique flow processing routinely; promptly enter hydrotreating reactor; take off carbon residue catalyzer, hydrogenation conversion catalyst by heavy fractioning hydrogenation guard catalyst, heavy fractioning hydrogenation successively, the hydrogenation products of gained enters separation system, obtains gasoline and diesel oil distillate.Last running 4 also can be used as the common carbon fiber asphalt stock.
The following examples will be further specified present method, but be not limited in this.
The used hydrocracking catalyst of the embodiment of the invention is prepared as follows:
1, contains the preparation of the hydrocracking catalyst of amorphous aluminum silicide and Y zeolite: A1, A2.
(1) hydrocracking catalyst A1:
With 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), add behind the mixing (adding rare nitric acid peptization preparation) tackiness agent by the little porous aluminum oxide of pore volume 0.42ml/g roll agglomerating after, after putting into the banded extruder extruded moulding, 110 ℃ of dryings 10 hours, 500 ℃ of activation made carrier in 4 hours, again with Mo-Ni steeping fluid dipping altogether, then 110 ℃ of dryings 12 hours, and 500 ℃ of activation 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:
With 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), the tackiness agent that adds (adding the preparation of rare nitric acid peptization by the little porous aluminum oxide of pore volume 0.42ml/g) behind the mixing roll agglomerating after, after putting into the banded extruder extruded moulding, 110 ℃ of dryings 10 hours, after 500 ℃ of activation made carrier in 4 hours, again with W-Ni steeping fluid dipping altogether, then 110 ℃ of dryings 12 hours, and 500 ℃ of activation 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:
With 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 are 0.42ml/g) tackiness agent that obtains, continue to mix and pinch up to becoming paste, extruded moulding, institute's moulding bar that obtains be 110 ℃ of dryings 12 hours down, 500 ℃ activate 4 hours and make activated carrier after.Flood the carrier of above-mentioned preparation again with the W-Ni co-impregnated solution, again 110 ℃ of dryings 8 hours, and 500 ℃ of activation 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:
With 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, under the situation that continues 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 are 0.42ml/g) tackiness agent that obtains, continue to mix and pinch up to becoming paste, extruded moulding, institute's moulding bar that obtains be 110 ℃ of dryings 12 hours down, 500 ℃ activate 4 hours and make activated carrier after.Again with W-Ni co-impregnated solution dipping, again 110 ℃ of dryings 8 hours, and 500 ℃ of activation 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.
The used removal of ccr by hydrotreating Preparation of Catalyst of the embodiment of the invention is as follows:
Take by weighing 298g Si-Al
2O
3(butt 67wt%, dioxide-containing silica are 13wt%) powder, powdered active carbon 20.5g, sesbania powder 5g mix it, add and contain 17wt%TiCl by 208g water, 22.0g
3TiCl
3The acidic solution that solution and 22g acetate mix mixes and pinched 1.5 hours, the gained plastic, and extrusion mechanism is extruded into the special-shaped strip of Φ 2.58～2.64mm, and this strip was descended dry 4 hours at 108 ℃, 480 ℃ of following roastings 4 hours.Flood reactive metal with ordinary method, molybdenum, tungsten and nickel descended dry 3 hours at 80 ℃ then, 500 ℃ of following roastings 3 hours, promptly made catalyzer HDC-1.The composition of this catalyzer and physico-chemical property see the following form 1.
Take by weighing 298g Si-Al
2O
3(butt 67wt%, dioxide-containing silica are 19wt%) powder, sesbania powder 5g mixes it, adds and contains 17wt%TCl by 188g water, 43.0g
3TiCl
3The acidic solution that solution and 22g acetate mix mixes and pinched 1.5 hours, the gained plastic, and extrusion mechanism is extruded into the special-shaped strip of Φ 1.10～1.35mm, and this strip was descended dry 4 hours at 108 ℃, 960 ℃ of following roastings 4 hours.Flood reactive metal with ordinary method, molybdenum, tungsten and nickel descended dry 2 hours at 120 ℃ then, 550 ℃ of following roastings 3 hours, promptly made catalyzer HDC-2.The composition of this catalyzer and physico-chemical property see the following form 1.
Take by weighing 298g Si-Al
2O
3(butt 67wt%, dioxide-containing silica are 19wt%) powder, sesbania powder 5g mixes it, adds and contains 17wt%TiCl by 188g water, 43.0g
3TiCl
3The acidic solution that solution and 22g acetate mix mixes and pinched 1.5 hours, the gained plastic, and extruded moulding, this strip was descended dry 4 hours at 108 ℃, 550 ℃ of following roastings 4 hours.Flood reactive metal with ordinary method, molybdenum, tungsten and nickel descended dry 2 hours at 120 ℃ then, 550 ℃ of following roastings 3 hours, promptly made catalyzer HDC-3.The composition of this catalyzer and physico-chemical property see the following form 1.
The 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 |
| |
8 | 11 | 11 |
| NiO | 5 | 5 | 5 |
| |
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
Used ethylene bottom oil lighting end and last running character see Table 2 and table 4.Embodiment adopts serial flow to handle the ethylene bottom oil lighting end; adopt two reactors; dress hydrogenation protecting agent FZC-103 and Hydrobon catalyst 3936 in first reactor; second adds reactor top filling removal of ccr by hydrotreating catalyzer HDC-3; first hydrocracking catalyst of middle part filling is the hydrocracking catalyst that contains amorphous aluminum silicide and Y molecular sieve, and second hydrocracking catalyst of bottom filling is the hydrocracking catalyst that contains amorphous aluminum silicide and beta-molecular sieve.Among the embodiment, FZC-103:3936:HDC-3: first hydrocracking catalyst: the volume ratio of second hydrocracking catalyst is as follows: 12: 23: 23: 21: 21.That reacts gained the results are shown in Table 3.In addition, this device has carried out 5000 hours service test, and presentation of results present method can solve the high problem of ethylene bottom oil lighting end carbon residue, realizes obtaining through hydrotreatment the purpose of light-weight fuel oil.Wherein FC-18 is produced by oil three factories of Fushun petrochemical industry branch office of CNPC.Embodiment 1 adopts hot low branch oil circulation, and wherein the weight of the low branch oil of round-robin heat and the weight ratio of described ethylene bottom oil lighting end are 2.0.Embodiment 2 adopts hot high score oil circulation, and wherein the heavy oil of the hot high score oil of round-robin is 2.0 with weight ratio with described ethylene bottom oil lighting end.Embodiment 3 adopts stripping tower oil circulation, and wherein round-robin stripping tower weight ratio oily and with described ethylene bottom oil lighting end is 2.0.
Table 2 ethylene bottom oil lighting end character
| Crude title | Ethylene bottom oil lighting end (＜430 ℃) |
| 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 | |
|
| The hydrogenation protecting agent | FZC-103 | FZC-103 | FZC-103 |
| Hydrobon catalyst | 3936 | 3936 | 3936 |
| The removal of ccr by hydrotreating catalyzer | HDC-3 | HDC-3 | HDC-3 |
| Hydrocracking catalyst | A2/B1 | A2/FC-18 | A1/B2 |
| Processing condition | |||
| Hydrogen dividing potential drop/MPa | 11.0 | 11.5 | 11.0 |
| One anti-/ two anti-temperature/℃ | 360/370 | 360/390 | 360/390 |
| One anti-/ two anti-air speed/h -1 | 2.4/1.5 | 2.0/1.5 | 1.9/1.8 |
| Hydrogen to oil volume ratio | 1400 | 1200 | 1400 |
| Diesel product character | |||
| Yield, % (massfraction) | 82.4 | 90.5 | 81.7 |
| Density (20 ℃)/gcm -3 | 0.9046 | 0.9140 | 0.9040 |
| Sulphur content, μ g/ |
17 | 16 | 17 |
| Nitrogen content, μ g/g | 1 | 2 | 1 |
| Condensation point/℃ | -50 | ＜-50 | ＜-50 |
| Cold filter clogging temperature/℃ | -28 | -26 | -30 |
| Boiling range/℃ 50% recovery 90% is reclaimed 95% and is reclaimed | 199 275 310 | 216 280 312 | 200 273 310 |
| Cetane value | 29.0 | 33.0 | 28.6 |
| Gasoline fraction character | |||
| Yield, % (massfraction) | 17.0 | 9.4 | 17.6 |
| Octane value | 84 | 80 | 82 |
Table 4 ethylene bottom oil last running character
| Crude title | Ethylene bottom oil last running (＞430 ℃) |
| 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
Ethylene bottom oil last running (character sees Table 4) is taken off residual catalyzer and hydrogenation conversion catalyst through hydrogenation protecting catalyst, hydrogenation successively; its volume ratio is 8: 55: 37; wherein used hydrogenation protecting catalyst is FZC-100 and FZC-102B; its volume ratio is 1: 2; the catalyzer of hydrogenation conversion catalyst such as CN02109422.5 embodiment 1 gained is designated as ZH1, and its character sees 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 |
Used removal of ccr by hydrotreating catalyzer HDC-1 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, the processing condition of heavy fractioning hydrogenation are as follows: reaction pressure is 16MPa, and temperature of reaction is 390～400 ℃, and volume space velocity is 0.4h during liquid
-1, hydrogen to oil volume ratio is 1000, the reaction result that turns round after 500 hours and 5000 hours sees Table 6.
Embodiment 5
Compare with embodiment 4, the admission space ratio of used removal of ccr by hydrotreating catalyzer HDC-1 and HDC-2 is become 5: 5, all the other are identical with embodiment 4.
Table 6 heavy fractioning hydrogenation result
Ethylene bottom oil last running (character sees Table 4) obtains mesophase pitch normal pressure, 350 ℃ of following thermal treatment 40 minutes; This mesophase pitch air pressure type spinning-drawing machine melt-spinning, spun pitch fibers changes into fusion-free fibre through atmospheric oxygen under 330 ℃～380 ℃, and charing becomes carbon fiber under 1000 ℃ of nitrogen again, and the asphalt base carbon fiber character of gained sees Table 7.
Table 7 asphalt base carbon fiber character
| Project | Last running gained carbon fiber |
| Average intensity/MPa | 910 |
| Average modulus/GPa | 61 |
| Extension at break/% | 1.75 |
Claims (24)
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 hydrocracking of reaction gained generates the circulation of oil part and mixes hydroconversion reaction zone with the ethylene bottom oil lighting end, and remainder obtains gasoline and diesel oil distillate through further separating.
2. method according to claim 1, it is characterized in that the hydrocracking that loops back the lighting end hydroconversion reaction zone generates oil for separating the hot high score oil that obtains through high pressure hot separator, separating in the low stripping tower oil that divides oil, obtains of the heat that obtains one or more through thermal low-pressure separators behind the stripping tower stripping.
3. method according to claim 1 and 2; it is characterized in that described last running takes off carbon residue catalyzer, hydrogenation conversion catalyst by heavy fractioning hydrogenation guard catalyst, heavy fractioning hydrogenation successively; the hydroconverted products of reaction gained enters separation system, obtains gasoline and diesel oil distillate.
4. method according to claim 1 and 2 is characterized in that described last running is as the common carbon fiber asphalt stock.
5. method according to claim 1 and 2 is characterized in that the weight ratio that olefiant weight and described ethylene bottom oil lighting end are given birth in the described hydrocracking that loops back the lighting end hydroconversion reaction zone is 1.0～4.0.
6. method according to claim 1 and 2, the cut point that it is characterized in that described ethylene bottom oil lighting end and last running is 400～430 ℃.
7. method according to claim 1 and 2; it is characterized in that in the described lighting end hydrogenation; the admission space of lighting end hydrogenation protecting catalyst, Hydrobon catalyst, lighting end removal of ccr by hydrotreating catalyzer and hydrocracking catalyst is a benchmark with lighting end hydrogenation catalyst system therefor cumulative volume, and is as follows respectively: 2%～18%, 5%～35%, 5%～35% and 30%～45%.
8. method according to claim 1 and 2, it is characterized in that described Hydrobon catalyst is as follows: the aluminum oxide with aluminum oxide, siliceous aluminum oxide or siliceous and phosphorus is a carrier, weight with catalyzer is benchmark, the group VIB active metallic content is counted 10wt%～35wt% with oxide compound, VIII family active metallic 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 are 0.15～0.60ml/g.
9. method according to claim 1 and 2 is characterized in that described lighting end removal of ccr by hydrotreating catalyzer, is carrier with the aluminum oxide, is benchmark with the catalyst weight, and is composed as follows: WO
3Content be 16%～23%, MoO
3Content be 6%～13%, the content of NiO is 3%～8%, contains auxiliary agent Si and Ti, SiO
2Content is 4%～12%, and titanium oxide content is 0.5%～4.0%, and surplus is an 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.
10. method according to claim 1 and 2, it is characterized in that described hydrocracking catalyst adopts two kinds of hydrocracking catalysts, the first hydrocracking catalyst bed is to be main acidic components with Y molecular sieve and amorphous aluminum silicide, the second hydrocracking catalyst bed is to be main acidic components with beta-molecular sieve and amorphous aluminum silicide, reactant flow contacts with first hydrocracking catalyst earlier, and then contacts with second hydrocracking catalyst.
11. method according to claim 10 is characterized in that the character of Y molecular sieve described in described first hydrocracking catalyst 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%.
12. method according to claim 10, it is characterized in that the composed as follows of described first hydrocracking catalyst: the weight with catalyzer is benchmark, the content of Y molecular sieve is 8%～20%, the content of amorphous aluminum silicide is 38%～60%, group VIB hydrogenation activity component is 15%～40% in the content of oxide compound, VIII family hydrogenation activity component is 1%～10% in the content of oxide compound, and surplus is little porous aluminum oxide; The character of first hydrocracking catalyst is as follows: specific surface is 180～300m
2/ g, pore volume are 0.25～0.45ml/g.
13. method according to claim 10 is characterized in that the character of beta-molecular sieve in second hydrocracking catalyst 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 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%.
14. according to claim 10 or 13 described methods, it is characterized in that the composed as follows of second hydrocracking catalyst, weight with catalyzer is benchmark: the content of beta-molecular sieve is 10%～28%, the content of amorphous aluminum silicide is 20%～40%, group VIB hydrogenation activity component is 15%～40% in the content of oxide compound, VIII family hydrogenation activity component is 1%～10% in the content of oxide compound, and surplus is little porous aluminum oxide.
15. method according to claim 10 is characterized in that first hydrocracking catalyst and the admission space ratio of second hydrocracking catalyst are 1～5: 1.
16. method according to claim 1 and 2 is characterized in that said hydrorefined operational condition is: volume space velocity 0.8～2.6h when 340～370 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～15.0MPa, hydrogen to oil volume ratio 800: 1～1400: 1 and liquid
-1
17. method according to claim 1 and 2 is characterized in that the operational condition of said removal of ccr by hydrotreating and hydrocracking is: volume space velocity 1.0～2.2h when 370～400 ℃ of temperature of reaction, hydrogen dividing potential drop 11.0～15.0MPa, hydrogen to oil volume ratio are 800: 1～1400: 1 and liquid
-1
18., it is characterized in that described hydrogenation protecting catalyst is residual hydrogenation protective material or residuum hydrogenating and metal-eliminating catalyst according to claim 1 or 3 described methods.
19. method according to claim 3; it is characterized in that described ethylene bottom oil last running takes off carbon residue catalyzer and hydrogenation conversion catalyst by heavy fractioning hydrogenation guard catalyst, heavy fractioning hydrogenation successively; above-mentioned catalyst loading is according to along the reactant flow flow direction; the aperture reduces successively, the active order that increases is successively carried out, and its admission space accounts for 5%～15%, 30%～70%, 20%～60% of heavy fractioning hydrogenation catalyzer total fill able volume respectively.
20. method according to claim 19 is characterized in that described heavy fractioning hydrogenation takes off the carbon residue catalyzer and adopts 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; Removal of ccr by hydrotreating activity of such catalysts metal oxide content used in the upstream catalyst bed is 25wt%～40wt%, average pore diameter is 15～25nm, used removal of ccr by hydrotreating activity of such catalysts metal oxide content in the lower catalyst bed layer is 28wt%～45wt%, and average pore diameter is 10～20nm.
21., it is characterized in that it is carrier with the aluminum oxide that described heavy fractioning hydrogenation takes off residual catalyzer, be that benchmark is composed as follows with the weight of catalyzer: WO according to claim 19 or 20 described methods
3Content be 16～23wt%, MoO
3Content be 6～13wt%, the content of NiO is 3～8wt%; Contain auxiliary agent Si and Ti, silicone content is with SiO
2Count 4～12%, titanium oxide content is 0.5～4%, and surplus is an 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.
22. method according to claim 3 is characterized in that described hydrogenation conversion catalyst adopts hydrotransforming catalyst for residual oil.
23. method according to claim 22, it is characterized in that described hydrogenation conversion catalyst is carrier with the aluminum oxide, weight with catalyzer is benchmark, this catalyzer is composed as follows: VIII family active ingredient counts 5%～10% with oxide compound, the group VIB active ingredient counts 20%～30% with oxide compound, SiO
2Content is 2.0%～10.0%, TiO
2Content is 1.0～4.0% or ZrO
2Content is 2.0%～8.0%, and surplus is an 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 in 4nm～15nm scope accounts for the pore volume integration rate of bore dia in 0nm～100nm scope, and the pore volume integration rate of its median pore diameter in 5nm～10nm scope is 65%～75%.
24. method according to claim 3 is characterized in that the operational condition of described heavy fractioning hydrogenation is as follows: reaction pressure is 14～20MPa, and temperature of reaction is 360～420 ℃, volume space velocity is 0.1～0.6h during liquid
-1, hydrogen to oil volume ratio is 500～1500.
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| CN112391201A (en) * | 2020-10-22 | 2021-02-23 | 中国科学院大连化学物理研究所 | Method for mixing ethylene cracking tar with naphthenic base heavy oil or residual oil thereof |
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| JP2000336375A (en) * | 1999-05-05 | 2000-12-05 | Bar Co Processes Joint Venture | Improved fluidized catalytic cracking method for residual oil with high conversion |
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| CN112391201A (en) * | 2020-10-22 | 2021-02-23 | 中国科学院大连化学物理研究所 | Method for mixing ethylene cracking tar with naphthenic base heavy oil or residual oil thereof |
| CN112391201B (en) * | 2020-10-22 | 2022-01-07 | 中国科学院大连化学物理研究所 | Method for mixing ethylene cracking tar with naphthenic base heavy oil or residual oil thereof |
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