CN102041077A - 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 a kind of method of hydrotreating of carbolineum, particularly the method for hydrotreating of deep drawing carbolineum.
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, belongs to asphalt component greater than 500 ℃ of cuts.In recent years, coal tar hydrogenating receives much concern in the Coal Chemical Industry industry, hydrogenating materials is done general all 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 poor slightly (seeing " development and use of coal-tar pitch and prospect thereof ", " the entrepreneur world " the 8th phase in 2007).At present the coal tar hydrogenating raw material is formed based on aromatic hydrocarbons, and 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 handle coal tar or wherein the part cut produce the existing report of light-weight fuel oil.Introduced the method that a kind of coal tar hydrogenating is produced diesel oil as CN1351130A, this method is that the coal tar full distillate oil is distilled, to carry out hydrogenation less than 370 ℃ lighting end, last running is not as hydrogenating materials, its catalyst system therefor is Hydrobon catalyst and dearomatization catalyst, mainly is to carry out refining and edulcoration matter and aromatic hydrocarbons saturated reaction.This method only is suitable for handles the following cut of diesel oil in the coal tar, the last running more than the diesel oil in the coal tar can not be converted into light-weight fuel oil.
CN1464031A discloses a kind of coal tar hydrotreating process and catalyzer, and this technology is to adopt hydrofining and hydro-upgrading one-stage serial, by coal tar production high-quality petroleum naphtha and fine-quality diesel oil.Though this technology is according to nitrogen in the coal tar, characteristics that iron level is high, selected titaniferous Hydrobon catalyst specially, the catalyst for hydro-upgrading that contains titanium oxide and molecular sieve, but because the structure of the water that coal tar hydrogenating generates meeting saboteur sieve catalyst, make the deactivation rate of catalyst for hydro-upgrading fast, running period is short.
CN101024780A is a raw material with conventional carbolineum, produce fine-quality diesel oil, be to adopt hydrofining-hydrocracking one-stage serial flow process, ammonia that generates in the unifining process and water produce adverse influence to follow-up hydrogenation catalyst activity stability, influence the running period of device, can not process deep drawing carbolineum.
CN101033409A is a raw material with conventional carbolineum still, though adopted two-stage hydrogenation technology, hydrofining generates oil content and heats up in a steamer, will be greater than 200 ℃ of cuts as hydrocracking raw material.Nitrogen content in the refining generation oil of this method gained＜400 μ g/g contacts with hydrocracking catalyst then and carries out hydrocracking reaction.Middle coal-tar heavy oil hydrocracking production premium, diesel oil and the lubricating oil technology 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 used hydrocracking catalyst requires the content of sulphur and nitrogen impurity in the charging usually, and especially the requirement to nitrogen is preferably in below the 100 μ g/g, otherwise will influence the active and stable 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 difficult nitrogenous compound that removes concentrates in the last running as the hydrocracking charging, under the Hydrobon catalyst and hydroconversion condition of routine, be difficult to make nitrogen content in the last running to meet the charging requirement of hydrocracking.These two kinds of methods can not be processed deep drawing carbolineum.
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 carbolineum.This method is a light-weight fuel oil with the hydrocracking of deep drawing carbolineum, for coal tar provides a kind of added value higher application approach, and in hydrogenation process, has effectively protected the hydrocracking catalyst activity, has prolonged device running period.
The method of hydrotreating of deep drawing carbolineum provided by the invention; comprise: deep drawing carbolineum and hydrogen are mixed into the hydrofining reaction district; contact with Hydrobon catalyst with hydrogenation protecting catalyst successively; mainly remove wherein sulphur, nitrogen, oxygen impurities; hydrotreated product is after gas-liquid separation; the liquid phase of gained enters the hydrocracking reaction district; contact with hydrocracking catalyst with Hydrobon catalyst, removal of ccr by hydrotreating catalyzer successively and react; the isocrackate of gained obtains gasoline fraction and diesel oil distillate after separation system.
Hydrogenation of the present invention is to adopt fixed bed hydrogenation technology.Described hydrofining reaction district and hydrocracking reaction district adopt two-stage process.
Described deep drawing carbolineum 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, content was below the 1.0wt% in saturated minute, fragrance divides and gum level is more than the 90wt%, be generally 90wt%～98wt%, initial boiling point is 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 get this deep drawing carbolineum 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; be active ingredient generally with group vib 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 the group VIII metal is generally Co and/or Ni.Weight in 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 the 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 the reactor, also can be seated in respectively in the different reactors.
In the inventive method, described Hydrobon catalyst and aftertreatment Hydrobon catalyst are conventional Hydrobon catalyst or hydrocracking pretreatment catalyst, be active ingredient generally with group vib 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 the group VIII metal is generally Co and/or Ni.In the weight 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 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.
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
-1The 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 obtains through separation enters the hydrocracking reaction district, contact with hydrocracking catalyst through Hydrobon catalyst, removal of ccr by hydrotreating catalyzer successively, its admission space accounts for 20%～60%, 10%～30%, 20%～60% of hydrocracking reaction district catalyzer total fill able volume respectively.In the inventive method, in the hydrocracking catalyst reaction zone, the further hydrogenation of aromatic hydrocarbons is saturated completely in order to remove in the isocrackate mercaptan and to make the part unreacted, 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, be active ingredient generally with group vib and/or group VIII metal, 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, siliceous aluminum oxide and the molecular sieve, the preferred hydrocracking catalyst that contains molecular sieve and amorphous aluminum silicide that adopts.The present invention recommends (weight with catalyzer is benchmark) composed as follows: Y molecular sieve or beta-molecular sieve 10%～40%, amorphous aluminum silicide 20%～60%, group vib hydrogenation activity component is 15%～40% in the content of oxide compound, group VIII hydrogenation activity component is 1%～10% in 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 are 0.25～0.45ml/g.
The present invention preferably adopts two kinds of filling hydrocracking catalyst at different stages, wherein first hydrocracking catalyst is to contain Y molecular sieve and amorphous aluminum silicide is the hydrocracking catalyst of main acidic components, 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%; Second hydrocracking catalyst is to contain beta-molecular sieve and amorphous aluminum silicide is the hydrocracking catalyst of main acidic components, 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%.First hydrocracking catalyst is 1～5: 1 with the admission space ratio of second hydrocracking catalyst.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.
Removal of ccr by hydrotreating catalyzer described in the hydrocracking reaction of the present invention district, can adopt heavy, residual hydrogenation of the prior art to take off the carbon residue catalyzer, it generally is to be the hydrogenation activity component with group vib and group VIII metal that described hydrogenation takes off residual catalyzer, as two or three among W, Mo, Ni or the Co, be preferably W, Mo and Ni, 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%, 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, 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
-1The 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 be adopted 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 the hydrotreated product, enter the hydrocracking reaction district then.When isocrackate separated through separation system, the separation system that is adopted generally comprised high-pressure separator, light pressure separator, stripping tower and separation column, finally obtained gasoline fraction and diesel oil distillate.
In sum, adopt method of the present invention to handle deep drawing carbolineum and have following advantage:
1, carbolineum is done by 500～550 ℃ and brought up to 560 ℃～650 ℃, it is about 2%～7% that deep drawing carbolineum yield has been improved, and expanded the material quantity of coal tar hydrogenating, can make more coal tar be converted into the lightweight transport fuel, improves the added value of coal tar.
2, in the hydrofining reaction district of the inventive method before the Hydrobon catalyst, the filling hydrogenation protecting catalyst removes impurity and part carbon residue in the deep drawing carbolineum, can protect the follow-up hydrogenation activity of such catalysts, prolong operating period.
3, the inventive method is at the characteristics of deep drawing carbolineum, select suitable catalyst grade prescription 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 the oil so on the one hand, also can reduce simultaneously the content of nitrogen and aromatic hydrocarbons, 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 at the characteristics of deep drawing carbolineum, preferred two types hydrocracking catalyst carries 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 deep drawing carbolineum saturated, appropriate again cracking and/or isomerization can high yield obtain condensation point less than-50 ℃ diesel oil distillate, by-product clean gasoline cut simultaneously.
5, hydrocracking reaction of the present invention district adds a spot of post-refining catalyzer behind hydrocracking catalyst, this method can reduce the mercaptan that generates in the product on the one hand, aromatic hydrocarbons is saturated completely can to make the minute quantity alkene of generation and unreacted on the other hand, and is favourable to improving the diesel oil distillate cetane value.
6, adopt two-stage hydrocracking technology in the inventive method, after hydrofining generated moisture in the oil and go out, be re-used as hydrocracking reaction district raw material, avoided since the existence of water to the disadvantageous effect of hydrocracking catalyst, active and to prolong its favourable in work-ing life to giving full play to hydrocracking catalyst.
7, the inventive method can be handled heavier deep drawing carbolineum cut by adopting suitable technical process and catalyst grade prescription formula, to greatest extent inferior raw material is converted into the clean fuel oil ingredient.
Embodiment
The following examples will be further specified present method, but be not limited in this.
Used deep drawing carbolineum feedstock property sees Table 1.
Table 1 stock oil character
| Crude title | Deep drawing carbolineum |
| 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 component *, % (massfraction) | |
| Saturated branch | 0.1 |
| Fragrance divides | 72.09 |
| Colloid | 23.31 |
| Bituminous matter | 4.5 |
* four components are to adopt SH/T 0509-1992 standard method to measure.
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 67w%, dioxide-containing silica are 13w%) 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 67w%, dioxide-containing silica are 19w%) 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 2.
The 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
The hydrofining reaction district adopts two reactors among the embodiment, and first reactor loads hydrogenation protecting agent FZC-100, FZC-102B, FZC-103 from top to bottom successively, the second reactor charge Hydrobon catalyst 3936.Among the 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
Embodiment 4
Embodiment 1 gained hydrofining is generated oil after separation system is carried out gas-liquid separation, the liquid product of gained enters the hydrocracking reaction district, pass through Hydrobon catalyst 3936 successively, the removal of ccr by hydrotreating catalyzer, hydrocracking catalyst and aftertreatment Hydrobon catalyst FF-26, its volume ratio is 40: 15: 40: 5, wherein to load first hydrocracking catalyst be the hydrocracking catalyst that contains amorphous aluminum silicide and Y molecular sieve on hydrocracking catalyst top, second hydrocracking catalyst of bottom filling is the hydrocracking catalyst that contains amorphous aluminum silicide and beta-molecular sieve, and both volume ratios are 2: 1.
Embodiment 5
The hydrofining of embodiment 1 gained is generated 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 oil after separation system is carried out gas-liquid separation, the liquid product of gained enters the hydrocracking reaction district, pass through Hydrobon catalyst FF-26 successively, the removal of ccr by hydrotreating catalyzer, hydrocracking catalyst and aftertreatment Hydrobon catalyst 3936, its volume ratio is 20: 7: 20: 3, wherein to load first hydrocracking catalyst be the hydrocracking catalyst that contains amorphous aluminum silicide and Y molecular sieve on hydrocracking catalyst top, second hydrocracking catalyst of bottom filling is the hydrocracking catalyst that contains amorphous aluminum silicide and beta-molecular sieve, and 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 oil three factories of Fushun petrochemical industry branch office of CNPC.
Table 4 hydrocracking process condition and result
Embodiment 7
With embodiment 6 in following hydrocracking process condition: reaction pressure is 16MPa, and temperature of reaction is 385～395 ℃, and volume space velocity is 0.5h during liquid
-1, hydrogen to oil volume ratio is 1200, the reaction result when running 500 hours and 5000 hours sees Table 5.
Table 5 different runtime of result
Claims (16)
1. the method for hydrotreating of a deep drawing carbolineum; comprise: deep drawing carbolineum and hydrogen are mixed into the hydrofining reaction district; contact with Hydrobon catalyst with hydrogenation protecting catalyst successively; mainly remove wherein sulphur, nitrogen, oxygen impurities; hydrotreated product is after gas-liquid separation; the liquid phase of gained enters the hydrocracking reaction district; contact with hydrocracking catalyst with Hydrobon catalyst, removal of ccr by hydrotreating catalyzer successively and react; the isocrackate of gained obtains gasoline fraction and diesel oil distillate after separation system.
2. in accordance with the method for claim 1, it is characterized in that described deep drawing carbolineum comes from coal tar, its character is as follows: 20 ℃ of density are greater than 1.0g/m
3, content was below the 1.0wt% in saturated minute, and fragrance divides and the colloid total amount is more than the 90wt%, 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 the described hydrofining reaction district that 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 described hydrocracking reaction district that the admission space of Hydrobon catalyst, removal of ccr by hydrotreating catalyzer and hydrocracking catalyst accounts for 20%～60%, 10%～30%, 20%～60% of hydrocracking reaction district catalyzer total fill able volume respectively.
5. according to claim 1 or 4 described methods, 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.
6. in accordance with the method for claim 1, it is characterized in that 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
-1Said hydrocracking operational condition 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
7. 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
-1Said 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
8. 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.
9. in accordance with the method for claim 1; it is characterized in that described hydrogenation protecting catalyst; with group vib and/or group VIII metal is active ingredient; with aluminum oxide or siliceous aluminum oxide is carrier; weight with catalyzer 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.
10. in accordance with the method for claim 1, it is characterized in that described Hydrobon catalyst and aftertreatment Hydrobon catalyst are active ingredient with group vib and/or group VIII metal, aluminum oxide with aluminum oxide, siliceous aluminum oxide or siliceous and phosphorus is a carrier, weight in 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 are 0.15～0.60ml/g.
11. in accordance with the method for claim 1, it is characterized in that described hydrocracking catalyst is composed as follows, weight with catalyzer is benchmark: Y molecular sieve or beta-molecular sieve 10%～40%, amorphous aluminum silicide 20%～60%, group vib hydrogenation activity component is 15%～40% in the content of oxide compound, group VIII hydrogenation activity component is 1%～10% in 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 are 0.25～0.45ml/g.
12. according to claim 1 or 11 described methods, it is characterized in that described hydrocracking reaction district adopts two kinds of filling hydrocracking catalyst at different stages, wherein first hydrocracking catalyst is to contain Y molecular sieve and amorphous aluminum silicide is the hydrocracking catalyst of main acidic components, and second hydrocracking catalyst is to contain beta-molecular sieve and amorphous aluminum silicide is the hydrocracking catalyst of main acidic components; First hydrocracking catalyst is 1～5: 1 with the admission space ratio of second hydrocracking catalyst; First hydrocracking catalyst is positioned at the upstream of second hydrocracking catalyst.
13. in accordance with the method for claim 12, the weight content that it is characterized in that Y molecular sieve in 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%.
14. in accordance with the method for claim 12, it is characterized in that the composed as follows of described second hydrocracking catalyst, is benchmark with the weight of catalyzer: 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%
15. in accordance with the method for claim 1, it is characterized in that described removal of ccr by hydrotreating catalyzer, employing is heavy, residual hydrogenation takes off the carbon residue catalyzer.
16., it is characterized in that it is benchmark with the weight of catalyzer that described hydrogenation takes off residual catalyzer, WO according to claim 1 or 15 described methods
316%～23%, MoO
36%～13%, NiO 3%～8%, and 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: 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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| CN106675646A (en) * | 2016-12-07 | 2017-05-17 | 北京神雾环境能源科技集团股份有限公司 | Weight lightening system and method for whole fraction of coal tar |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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| CN106675646A (en) * | 2016-12-07 | 2017-05-17 | 北京神雾环境能源科技集团股份有限公司 | Weight lightening system and method for whole fraction of coal tar |
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