CN102041077B - Method for hydrogenating deeply-drawing carbolineum - Google Patents
Method for hydrogenating deeply-drawing carbolineum Download PDFInfo
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Abstract
The invention discloses a method for hydrogenating deeply-drawing carbolineum. The two-section hydrocracking process is applied to the method. The deeply-drawing carbolineum passes through a hydrorefining reaction area firstly to obtain a hydrorefining product; the obtained hydrorefining product is separated to obtain a liquid phase product which enters a hydrocracking reaction area, is sequentially contacted with a hydrorefining catalyst, a hydrogenating residual carbon removing catalyst and a hydrocracking catalyst for reaction to obtain a hydrocracking product; and the hydrocracking product is separated to obtain gasoline and diesel oil fractions. By using the method, the deeply-drawing carbolineum is processed, the range of raw materials is widened, the deeply-drawing carbolineum can be converted to maximum extent, the yield of lightweight fuel oil can be improved and the added value of carbolineum is improved; meanwhile, the activity of the hydrocracking catalyst can be effectively protected, so that the device can operate for a long period.
Description
Technical field
The present invention relates to the method for hydrotreating of a kind of method of hydrotreating of carbolineum, particularly deep drawing anthracene oil.
Background technology
The scarcity day by day of world petroleum resource, the technology that makes various non-conventional oil resources processings produce light-weight fuel oils becomes focus, and one of technology wherein is with coal-based producing clean fuel.
Coal tar is the byproduct of coking technology, and carbolineum is one of its product of distillation, and usually 300～360 ℃ of cuts are called I carbolineum, and 360～500 ℃ of cuts are called II carbolineum, is greater than 500 ℃ of cuts and belongs to asphalt component.In recent years, coal tar hydrogenating receives much concern in the Coal Chemical Industry industry, hydrogenating materials is done and generally all is less than 500～550 ℃, asphalt component processes raw material as the added value that has much room for improvement, at present only as electrode and carbon raw materials, but economy slightly poor (seeing " exploitation of coal-tar pitch and prospect thereof ", " the entrepreneur world " the 8th phase in 2007).At present the coal tar hydrogenating raw material forms and take aromatic hydrocarbons as main, and the foreign matter contents such as sulphur, nitrogen, oxygen are higher, and producing light-weight fuel oil with it also needs further processing.
With the method for hydrogenation process coal tar or wherein the part cut produce light-weight fuel oil and have been reported.As CN1351130A has introduced a kind of method that coal tar hydrogenating is produced diesel oil, the method is that the coal tar full distillate oil is distilled, the lighting end that is less than 370 ℃ is carried out to hydrogenation, last running is not as hydrogenating materials, its used catalyst is Hydrobon catalyst and dearomatization catalyst, is mainly to carry out refining and edulcoration matter and aromatic saturation reaction.This method only is suitable for processes the following cut of diesel oil in coal tar, the last running more than the diesel oil in coal tar can not be converted into to light-weight fuel oil.
CN1464031A discloses a kind of coal tar hydrotreating process and catalyzer, and this technique is to adopt hydrofining and hydro-upgrading one-stage serial, by coal tar production high-quality petroleum naphtha and fine-quality diesel oil.Although this technique is according to nitrogen in coal tar, characteristics that iron level is high, selected specially the Hydrobon catalyst of titaniferous, catalyst for hydro-upgrading containing titanium oxide and molecular sieve, but the water generated due to coal tar hydrogenating can saboteur's sieve catalyst structure, make the deactivation rate of catalyst for hydro-upgrading fast, running period is short.
CN101024780A be take conventional carbolineum as raw material, produce fine-quality diesel oil, to adopt hydrofining-hydrocracking one-stage serial flow process, the ammonia generated in unifining process and water produce adverse influence to follow-up hydrogenation catalyst activity stability, affect the running period of device, can not process deep drawing anthracene oil.
CN101033409A still be take conventional carbolineum as raw material, though adopted two-stage hydrogenation technique, hydrofining generates oil content and heats up in a steamer, and will be greater than 200 ℃ of cuts as hydrocracking raw material.Nitrogen content in the refining generation oil of the method gained<400 μ g/g, then contact with hydrocracking catalyst and carry out hydrocracking reaction.Middle coal-tar heavy oil hydrocracking production premium, diesel oil and the lubricating oil technique of CN1676583A, this process is to adopt coal tar after hydrofining, carry out fractionation, the gasoline of gained, diesel oil and lubricating oil go out device, tail oil enters hydrocracking reactor, after gas-liquid separation, the gained liquid phase generates oil and enters separation column with hydrofining generation oil.At present hydrocracking catalyst used requires the content of sulphur and nitrogen impurity in charging usually, especially the requirement of nitrogen is preferably in below 100 μ g/g, otherwise will affects activity and the stability of hydrocracking catalyst.The refining oily nitrogen content<400 μ g/g that generate of CN101033409A, the CN1676583A tail oil directly enters hydrocracking reactor, there is same problem in these two kinds of methods: the more difficult nitrogenous compound removed concentrates in the last running as the hydrocracking charging, under conventional Hydrobon catalyst and hydroconversion condition, be difficult to make nitrogen content in last running to meet the charging requirement of hydrocracking.These two kinds of methods can not be processed deep drawing anthracene oil.
Summary of the invention
In order to overcome deficiency of the prior art, the invention provides a kind of method of hydrotreating of deep drawing anthracene oil.This method is light-weight fuel oil by the deep drawing anthracene oil hydrocracking, for coal tar provides the application approach that a kind of added value is higher, and, in hydrogenation process, has effectively protected the hydrocracking catalyst activity, has extended device running period.
The method of hydrotreating of deep drawing anthracene oil provided by the invention; comprise: deep drawing anthracene oil and hydrogen are mixed into the hydrofining reaction district; with hydrogenation protecting catalyst, with Hydrobon catalyst, contact successively; mainly remove sulphur, nitrogen, oxygen impurities wherein; hydrotreated product is after gas-liquid separation; the liquid phase of gained enters the hydrocracking reaction district; contact and reacted with hydrocracking catalyst with Hydrobon catalyst, removal of ccr by hydrotreating catalyzer successively; the isocrackate of gained, after separation system, obtains gasoline fraction and diesel oil distillate.
Hydrogenation of the present invention is to adopt fixed bed hydrogenation technique.Described hydrofining reaction district and hydrocracking reaction district adopt two-stage process.
Described deep drawing anthracene oil comes from coal tar, and its character is as follows: density (20 ℃) is greater than 1.0g/m
3, be generally 1.0～1.2g/m
3, within saturated minute, content is below 1.0wt%, fragrance divides and gum level is more than 90wt%, be generally 90wt%～98wt%, initial boiling point, for being greater than 220 ℃, is generally 220～260 ℃, doing is 560～650 ℃, and weight nitroxide content is 1.0%～1.4%, and the oxygen weight content is 1.3%～2.0%.It is 25%～30% (massfraction) that coal-tar heavy oil can obtain this deep drawing anthracene oil yield through distillation.
Hydrogenation protecting catalyst described in the present invention can adopt conventional residual hydrogenation protective material or residuum hydrogenating and metal-eliminating catalyst; generally take group vib and/or group VIII metal is active ingredient; take aluminum oxide or silicon-containing alumina as carrier; the group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni.Weighing scale with catalyzer, active metallic content counts 0.5%～18% with oxide compound, preferably composed as follows: the group vib metal content counts 0.5%～15% with oxide compound, the group VIII metal content counts 0.5%～8% 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.
In described hydrofining reaction district, described hydrogenation protecting catalyst and Hydrobon catalyst admission space account for 2%～40% and 40%～98% of hydrofining reaction district catalyzer total fill able volume.Above-mentioned catalyzer can be seated in a reactor, also can be seated in respectively in different reactors.
In the inventive method, described Hydrobon catalyst and aftertreatment Hydrobon catalyst are conventional Hydrobon catalyst or pretreating catalyst by hydrocracking, generally take group vib and/or group VIII metal is active ingredient, the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus of take is carrier, the group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni.With the weighing scale of catalyzer, the group vib metal content is counted 10wt%～35wt% with oxide compound, and the group VIII metal content is counted 3wt%～15wt% with oxide compound, and its character is as follows: specific surface is 100～350m
2/ g, pore volume is 0.15～0.60ml/g.Main catalyzer have China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute to develop 3936,3996, FF-16, FF-26 etc.
Said hydrofining operational condition is: volume space velocity 0.1～0.8h when 360～400 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1; The preferred operations condition is: 380～400 ℃ of temperature of reaction, pressure 12.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and air speed 0.3～0.6h
-1.
The liquid product that hydrotreated product described in the inventive method is isolated to enters the hydrocracking reaction district, through Hydrobon catalyst, removal of ccr by hydrotreating catalyzer, with hydrocracking catalyst, contact successively, its admission space accounts for respectively 20%～60%, 10%～30%, 20%～60% of hydrocracking reaction district catalyzer total fill able volume.In the inventive method, in the hydrocracking catalyst reaction zone, in order to remove in isocrackate mercaptan and to make the part unreacted, the further hydrogenation of aromatic hydrocarbons is saturated completely, preferably, at hydrocracking catalyst downstream filling aftertreatment Hydrobon catalyst, its admission space accounts for 5%～15% of hydrocracking reaction district catalyzer total fill able volume.
Hydrocracking catalyst described in the inventive method can adopt one or more conventional hydrocracking catalysts, generally take group vib and/or group VIII metal is active ingredient, the group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni.The carrier of this catalyzer is two or more in aluminum oxide, silicon-containing alumina and molecular sieve, preferably adopts the hydrocracking catalyst containing molecular sieve and amorphous aluminum silicide.That the present invention recommends is composed as follows the weight of catalyzer (take be benchmark): Y molecular sieve or beta-molecular sieve 10%～40%, amorphous aluminum silicide 20%～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 hydrocracking catalyst is as follows: specific surface is 180～300m
2/ g, pore volume is 0.25～0.45ml/g.
The present invention preferably adopts two kinds of filling hydrocracking catalyst at different stages, wherein the first hydrocracking catalyst is the hydrocracking catalyst that is main acidic components containing Y molecular sieve and amorphous aluminum silicide, wherein the weight content of Y molecular sieve is 10%～30%, the weight content of amorphous aluminum silicide is 35%～60%, and wherein the character of 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 hydrocracking catalyst that the second hydrocracking catalyst is is main acidic components containing beta-molecular sieve and amorphous aluminum silicide, wherein the weight content of beta-molecular sieve is 10%～30%, the weight content of amorphous aluminum silicide is 20%～40%, and 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 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 first hydrocracking catalyst is 1～5: 1 with the admission space ratio of the second hydrocracking catalyst.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.But two kinds of hydrocracking catalyst layerings are seated in a reactor, also can be divided in two reactors.
Removal of ccr by hydrotreating catalyzer described in hydrocracking reaction of the present invention district, can adopt heavy, the de-carbon residue catalyzer of residual hydrogenation of the prior art, the de-residual catalyzer of described hydrogenation is generally that to take group vib and group VIII metal be the hydrogenation activity component, as two or three in W, Mo, Ni or Co, be preferably W, Mo and Ni, this catalyzer preferably contains auxiliary agent Si and Ti, take aluminum oxide as carrier.The weight of catalyzer of take 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%, is preferably 1～2%, and surplus is 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, average pore diameter is 8～20nm.The inventive method preferably adopts two or more removal of ccr by hydrotreating beds, and along the liquid phase stream direction, active metal oxide content increases, and average pore diameter reduces.
The operational condition in said hydrocracking reaction district is: volume space velocity 0.1～0.6h when 350～410 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1; The preferred operations condition is: volume space velocity 0.2～0.5h when 360～400 ℃ of temperature of reaction, pressure 12.0～16.0MPa, hydrogen to oil volume ratio are 900: 1～1500: 1 and liquid
-1.
In the inventive method, separating of the gas-liquid separation of hydrotreated product and isocrackate can adopt conventional separation method and tripping device, be that hydrotreated product is when gas-liquid separation, tripping device generally comprises high-pressure separator and light pressure separator and stripping tower, mainly remove hydrogen sulfide, ammonia G&W in hydrotreated product, then enter the hydrocracking reaction district.When isocrackate is separated through separation system, the separation system adopted generally comprises high-pressure separator, light pressure separator, stripping tower and separation column, finally obtains gasoline fraction and diesel oil distillate.
In sum, adopt method of the present invention to process deep drawing anthracene oil and there is following advantage:
1, carbolineum is done and brought up to 560 ℃～650 ℃ by 500～550 ℃, make the deep drawing anthracene oil yield improve approximately 2%～7%, expanded the material quantity of coal tar hydrogenating, can make more coal tar be converted into the lightweight transport fuel, improve the added value of coal tar.
2,, in the hydrofining reaction district of the inventive method before Hydrobon catalyst, the filling hydrogenation protecting catalyst, remove impurity and part carbon residue in deep drawing anthracene oil, can protect the activity of follow-up hydrogenation catalyzer, prolong operating period.
3, the inventive method is for the characteristics of deep drawing anthracene oil, select suitable catalyst grade formula formula in the hydrocracking reaction district: Hydrobon catalyst, removal of ccr by hydrotreating catalyzer and hydrocracking catalyst, can further reduce the content that hydrofining generates colloid, bituminous matter and carbon residue in oil so on the one hand, also can reduce the content of nitrogen and aromatic hydrocarbons simultaneously, protection hydrocracking catalyst activity is favourable to prolong operating period; On the other hand, can make more heavy component be converted into the light Fuel oil ingredient, improve the light-weight fuel oil yield.
4, the inventive method is for the characteristics of deep drawing anthracene oil, preferably the hydrocracking catalyst of two types carries out grading loading, can take full advantage of the not characteristics of isomorphism type molecular sieve, and match with amorphous aluminum silicide, aromatic hydrocarbons open loop after making hydrogenation in deep drawing anthracene oil saturated, appropriate cracking and/or isomerization again, can high yield obtain condensation point and be less than the diesel oil distillate of-50 ℃, simultaneously by-product clean gasoline cut.
5, hydrocracking reaction of the present invention district adds a small amount of post-refining catalyzer after hydrocracking catalyst, this method can reduce the mercaptan generated in product on the one hand, can make on the other hand the minute quantity alkene that generates and unreacted aromatic saturation completely, favourable to improving the diesel oil distillate cetane value.
6, adopt two-stage hydrocracking technique in the inventive method, after hydrofining is generated to moisture in oil and goes out, be re-used as hydrocracking reaction district raw material, avoided due to the existence of the water disadvantageous effect to hydrocracking catalyst, to giving full play to, hydrocracking catalyst is active and to extend its work-ing life favourable.
7, the inventive method, by adopting suitable technical process and catalyst grade formula formula, can be processed heavier deep drawing anthracene oil cut, to greatest extent inferior raw material is converted into to the clean fuel oil ingredient.
Embodiment
The following examples will be further described present method, but be not limited in this.
Deep drawing anthracene oil feedstock property used is in Table 1.
Table 1 stock oil character
| Crude title | Deep drawing anthracene oil |
| Boiling range/℃ | |
| IBP/10％ | 203/324 |
| 30％/50％ | 345/380 |
| 70％/90％ | 407/492 |
| 95％/EBP | 550/648 |
| Density (20 ℃)/gcm -3 | 1.15 |
| S/μg·g -1 | 5500 |
| N/μg·g -1 | 13200 |
| Four components *, % (massfraction) | |
| Saturated minute | 0.1 |
| Fragrance minute | 72.09 |
| Colloid | 23.31 |
| Bituminous matter | 4.5 |
*four components are to adopt SH/T 0509-1992 standard method to measure.
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, after putting into the banded extruder extruded moulding, 110 ℃ of dryings 10 hours, 500 ℃ of activation made carrier in 4 hours, then steeped by Mo-Ni total immersion stain immersion, 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:
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, after putting into the banded extruder extruded moulding, 110 ℃ of dryings 10 hours, after 500 ℃ of activation make carrier in 4 hours, then steep by W-Ni total immersion stain immersion, 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:
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 drying 12 hours under 110 ℃, 500 ℃ activate and make activated carrier in 4 hours after.Flood again the carrier of above-mentioned preparation with the W-Ni co-impregnated solution, then 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:
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 continue to roll little porous aluminum oxide (the specific surface area 240m of dilute nitric acid solution peptization slowly added 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 drying 12 hours under 110 ℃, 500 ℃ activate and make activated carrier in 4 hours after.Again with W-Ni co-impregnated solution dipping, then 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.
Embodiment of the present invention removal of ccr by hydrotreating catalyzer used is prepared as follows:
Take 298g Si-Al
2o
3(butt 67w%, dioxide-containing silica is 13w%) powder, powdered active carbon 20.5g, sesbania powder 5g, mix it, adds by 208g water, 22.0g containing 17wt%TiCl
3tiCl
3the acidic solution that solution and 22g acetic acid mix, kneading 1.5 hours, the gained plastic, extrusion mechanism is extruded into the special-shaped strip of Φ 2.58～2.64mm, and this strip under 108 ℃ dry 4 hours, 480 ℃ of lower roastings 4 hours.Flood reactive metal by ordinary method, molybdenum, tungsten and nickel, then under 80 ℃ dry 3 hours, 500 ℃ of lower roastings 3 hours, make catalyzer HDC-1.The composition of this catalyzer and physico-chemical property see the following form 1.
Take 298g Si-Al
2o
3(butt 67w%, dioxide-containing silica is 19w%) powder, sesbania powder 5g, mix it, adds by 188g water, 43.0g containing 17wt%TCl
3tiCl
3the acidic solution that solution and 22g acetic acid mix, kneading 1.5 hours, the gained plastic, extrusion mechanism is extruded into the special-shaped strip of Φ 1.10～1.35mm, and this strip under 108 ℃ dry 4 hours, 960 ℃ of lower roastings 4 hours.Flood reactive metal by ordinary method, molybdenum, tungsten and nickel, then under 120 ℃ dry 2 hours, 550 ℃ of lower roastings 3 hours, make catalyzer HDC-2.The composition of this catalyzer and physico-chemical property see the following form 2.
Composition and the character of table 2 removal of ccr by hydrotreating catalyzer
| Catalyzer | HDC-1 | HDC-2 |
| Form % (massfraction) | ||
| WO 3 | 18 | 20 |
| MoO 3 | 8 | 11 |
| NiO | 5 | 5 |
| SiO 2 | 6 | 9 |
| TiO 2 | 1 | 2 |
| Al 2O 3 | Surplus | Surplus |
| Character | ||
| Specific surface area, m 2/g | 138 | 175 |
| Average pore diameter, nm | 18.4 | 11.8 |
Embodiment 1～3
In embodiment, the hydrofining reaction district adopts two reactors, and the first reactor loads hydrogenation protecting agent FZC-100, FZC-102B, FZC-103 from top to bottom successively, the second reactor charge Hydrobon catalyst 3936.In embodiment, FZC-100: FZC-102B: FZC-103: 3936 volume ratios are as follows: 6: 15: 19: 60.That reacts gained the results are shown in Table 3.
Table 3 hydrofining reaction district's processing condition and hydrofining generate oil nature
| Scheme | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| The hydrogenation protecting agent | FZC-100/ FZC-102B/ FZC-103 | FZC-100/ FZC-102B/ FZC-103 | FZC-100/ FZC-102B/ FZC-103 |
| Hydrobon catalyst | 3936 | 3936 | 3936 |
| Processing condition | |||
| Hydrogen dividing potential drop/MPa | 16.0 | 13.0 | 14.5 |
| Temperature of reaction/℃ | 385 | 395 | 390 |
| Volume space velocity/h during liquid -1 | 0.35 | 0.45 | 0.55 |
| Hydrogen to oil volume ratio | 1400 | 1200 | 1500 |
| Hydrofining generates oil nature | |||
| Density (20 ℃)/gcm -3 | 0.9704 | 0.9795 | 0.9786 |
| Sulphur content/μ gg -1 | 186 | 190 | 194 |
| Nitrogen content/μ gg -1 | 158 | 164 | 162 |
| Free-water/μ gg -1 | ＜300 | ＜300 | ＜300 |
Embodiment 4
Embodiment 1 gained hydrofining is generated to oil after separation system is carried out gas-liquid separation, the liquid product of gained enters the hydrocracking reaction district, pass through successively Hydrobon catalyst 3936, the removal of ccr by hydrotreating catalyzer, hydrocracking catalyst and aftertreatment Hydrobon catalyst FF-26, its volume ratio is 40: 15: 40: 5, wherein the first hydrocracking catalyst is loaded for the hydrocracking catalyst containing amorphous aluminum silicide and Y molecular sieve in hydrocracking catalyst top, the second hydrocracking catalyst of bottom filling is the hydrocracking catalyst containing amorphous aluminum silicide and beta-molecular sieve, both volume ratios are 2: 1.
Embodiment 5
The hydrofining of embodiment 1 gained is generated to the hydrofining generation oil that oil changes embodiment 2 gained into, and all the other are with embodiment 4.
Embodiment 6
Embodiment 3 gained hydrofinings are generated to oil after separation system is carried out gas-liquid separation, the liquid product of gained enters the hydrocracking reaction district, pass through successively Hydrobon catalyst FF-26, the removal of ccr by hydrotreating catalyzer, hydrocracking catalyst and aftertreatment Hydrobon catalyst 3936, its volume ratio is 20: 7: 20: 3, wherein the first hydrocracking catalyst is loaded for the hydrocracking catalyst containing amorphous aluminum silicide and Y molecular sieve in hydrocracking catalyst top, the second hydrocracking catalyst of bottom filling is the hydrocracking catalyst containing amorphous aluminum silicide and beta-molecular sieve, both volume ratios are 4: 1.
Embodiment 4～6 processing condition and the results are shown in table 4.Wherein FC-18 is produced by Fushun petrochemical industry branch office of CNPC oil three factories.
Table 4 hydrocracking process condition and result
| Scheme | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Hydrobon catalyst | 3936 | 3936 | FF-26 |
| The removal of ccr by hydrotreating catalyzer | HDC-1 | HDC-2 | HDC-2 |
| Hydrocracking catalyst | A1/B1 | A2/FC-18 | A2/B2 |
| The aftertreatment Hydrobon catalyst | FF-26 | FF-26 | 3936 |
| Processing condition | |||
| Hydrogen dividing potential drop/MPa | 14.5 | 13.0 | 16.0 |
| Temperature of reaction/℃ | 405 | 395 | 385 |
| Volume space velocity/h during liquid -1 | 0.3 | 0.5 | 0.4 |
| Hydrogen to oil volume ratio | 1500 | 1200 | 1400 |
| Diesel product character | |||
| Yield, % (massfraction) | 81.0 | 90.6 | 81.3 |
| Density (20 ℃)/gcm -3 | 0.9070 | 0.9145 | 0.9010 |
| Sulphur content/μ gg -1 | 38 | 36 | 35 |
| Nitrogen content/μ gg -1 | 1 | 2 | 1 |
| Condensation point/℃ | -54 | -52 | -58 |
| Cold filter clogging temperature/℃ | -28 | -26 | -30 |
| Boiling range/℃ 50% recovery 90% is reclaimed 95% and is reclaimed | 247 293 309 | 253 295 312 | 245 290 306 |
| Cetane value | 28.1 | 33.0 | 29.0 |
| Gasoline fraction character | |||
| Yield, % (massfraction) | 18.5 | 9.3 | 18.3 |
| Octane value (RON) | 82 | 79 | 81 |
Embodiment 7
By embodiment 6 in following hydrocracking process condition: reaction pressure is 16MPa, and temperature of reaction is 385～395 ℃, and during liquid, volume space velocity is 0.5h
-1, hydrogen to oil volume ratio is 1200, when the reaction result of running 500 hours and 5000 hours in Table 5.
Table 5 different runtime of result
Claims (13)
1. the method for hydrotreating of a deep drawing anthracene oil, comprise: deep drawing anthracene oil and hydrogen are mixed into the hydrofining reaction district, with hydrogenation protecting catalyst, with Hydrobon catalyst, contact successively, mainly remove sulphur, nitrogen, oxygen impurities wherein, hydrotreated product is after gas-liquid separation, the liquid phase of gained enters the hydrocracking reaction district, contact and reacted with hydrocracking catalyst with Hydrobon catalyst, removal of ccr by hydrotreating catalyzer successively, the isocrackate of gained, after separation system, obtains gasoline fraction and diesel oil distillate; In described hydrocracking reaction district, the admission space of Hydrobon catalyst, removal of ccr by hydrotreating catalyzer and hydrocracking catalyst accounts for respectively 20%～60%, 10%～30%, 20%～60% of hydrocracking reaction district catalyzer total fill able volume; Described hydrocracking catalyst is composed as follows, the weight of catalyzer of take is benchmark: Y molecular sieve or beta-molecular sieve 10%～40%, amorphous aluminum silicide 20%～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 hydrocracking catalyst is as follows: specific surface is 180～300m
2/ g, pore volume is 0.25～0.45ml/g; The operational condition in said hydrofining reaction district is: volume space velocity 0.1～0.8h when 360～400 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1; The operational condition in said hydrocracking reaction district is: volume space velocity 0.1～0.6h when 350～410 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1.
2. in accordance with the method for claim 1, it is characterized in that described deep drawing anthracene oil comes from coal tar, its character is as follows: 20 ℃ of density are greater than 1.0g/m
3, within saturated minute, content is below 1.0wt%, and it is more than 90wt% that fragrance divides with the colloid total amount, and initial boiling point is 220～260 ℃, and doing is 560～650 ℃, and weight nitroxide content is 1.0%～1.4%, and the oxygen weight content is 1.3%～2.0%.
3. in accordance with the method for claim 1, it is characterized in that in described hydrofining reaction district, described hydrogenation protecting catalyst and Hydrobon catalyst admission space account for 2%～40% and 40%～98% of hydrofining reaction district catalyzer total fill able volume.
4. in accordance with the method for claim 1, it is characterized in that in the hydrocracking catalyst reaction zone, at described hydrocracking catalyst downstream filling aftertreatment Hydrobon catalyst, its admission space accounts for 5%～15% of hydrocracking reaction district catalyzer total fill able volume.
5. in accordance with the method for claim 1, it is characterized in that said hydrofining operational condition is: 380～400 ℃ of temperature of reaction, pressure 12.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and air speed 0.3～0.6h
-1; Said hydrocracking operational condition is: volume space velocity 0.2～0.5h when 360～400 ℃ of temperature of reaction, pressure 12.0～16.0MPa, hydrogen to oil volume ratio are 900: 1～1500: 1 and liquid
-1.
6. in accordance with the method for claim 1, it is characterized in that described hydrogenation protecting catalyst adopts residual hydrogenation protective material or residuum hydrogenating and metal-eliminating catalyst.
7. in accordance with the method for claim 1; it is characterized in that described hydrogenation protecting catalyst; take group vib and/or group VIII metal is active ingredient; take aluminum oxide or silicon-containing alumina as carrier; the weight of catalyzer of take is benchmark; the group vib metal content counts 0.5%～15% with oxide compound, and the group VIII metal content counts 0.5%～8% with oxide compound.
8. in accordance with the method for claim 1, it is characterized in that it is active ingredient that described Hydrobon catalyst and aftertreatment Hydrobon catalyst be take group vib and/or group VIII metal, the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus of take is carrier, weighing scale with catalyzer, the group vib metal content is counted 10wt%～35wt% with oxide compound, the group VIII metal content is counted 3wt%～15wt% with oxide compound, and its character is as follows: specific surface is 100～350m
2/ g, pore volume is 0.15～0.60ml/g.
9. in accordance with the method for claim 1, it is characterized in that described hydrocracking reaction district adopts two kinds of filling hydrocracking catalyst at different stages, wherein the first hydrocracking catalyst is the hydrocracking catalyst that is main acidic components containing Y molecular sieve and amorphous aluminum silicide, the hydrocracking catalyst that the second hydrocracking catalyst is is main acidic components containing beta-molecular sieve and amorphous aluminum silicide; The first hydrocracking catalyst is 1～5: 1 with the admission space ratio of the second hydrocracking catalyst; The first hydrocracking catalyst is positioned at the upstream of the second hydrocracking catalyst.
10. in accordance with the method for claim 9, the weight content that it is characterized in that Y molecular sieve in the first hydrocracking catalyst is 10%～30%, and the weight content of amorphous aluminum silicide is 35%～60%, and wherein the character of 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%.
11. in accordance with the method for claim 9, it is characterized in that the composed as follows of described the second hydrocracking catalyst, the weight of catalyzer of take is benchmark: beta-molecular sieve 10%～28%, amorphous aluminum silicide 20%～40%; 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 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. in accordance with the method for claim 1, it is characterized in that described removal of ccr by hydrotreating catalyzer, adopt heavy, the de-carbon residue catalyzer of residual hydrogenation.
13., according to the described method of claim 1 or 12, it is characterized in that it is benchmark that the de-residual catalyzer of described hydrogenation be take the weight of catalyzer, WO
316%～23%, MoO
36%～13%, NiO3%～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: the pore volume of catalyzer is 0.40～0.55cm
3/ g, specific surface area is 120～180m
2/ g, average pore diameter is 8～20nm.
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| WO2000034416A1 (en) * | 1998-12-08 | 2000-06-15 | Exxon Research And Engineering Company | Production of low sulfur/low aromatics distillates |
| CN101024780A (en) * | 2006-02-26 | 2007-08-29 | 何巨堂 | Method for hydrogenation cracking anthracent |
| CN101033409A (en) * | 2006-03-06 | 2007-09-12 | 何巨堂 | Method of hydrogenation conversion for anthracene oil |
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| WO2000034416A1 (en) * | 1998-12-08 | 2000-06-15 | Exxon Research And Engineering Company | Production of low sulfur/low aromatics distillates |
| CN101024780A (en) * | 2006-02-26 | 2007-08-29 | 何巨堂 | Method for hydrogenation cracking anthracent |
| CN101033409A (en) * | 2006-03-06 | 2007-09-12 | 何巨堂 | Method of hydrogenation conversion for anthracene oil |
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