CN102041073A - Hydrocracking method for anthracene oil - Google Patents
Hydrocracking method for anthracene oil Download PDFInfo
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Abstract
The invention discloses a hydrocracking method for anthracene oil, which is implemented in the following steps: performing hydrofining on anthracene oil; performing solid-liquid separation on the anthracene oil after hydrofining by a hot high-pressure separator; partially circulating the obtained hot high-pressure separator oil in a hydrofining area to mix with anthracene oil, and feeding the residual hot high-pressure separator oil in a hydrocracking reaction area by adopting differential pressure; and feeding the hydrocracking product and the gas separated from a hot high-pressure separator in a cold high-pressure separator, charging the separated liquid in a cold low-pressure separator, and introducing the separated liquid to a product fractionating tower after steam stripping to obtain gasoline and diesel fractions. The method in the intention can reduce temperature rise of equipment, lower equipment investment, lessen energy consumption, simplify equipment operation, improve the stationarity of equipment operation, and prolong the equipment operation period due to the concentrations of colloid and asphaltene in raw materials are reduced.
Description
Technical field
The present invention relates to a kind of method for hydrogen cracking of carbolineum, specifically relate to the method that light-weight fuel oil is produced in a kind of carbolineum hydrocracking.
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 to be producing clean fuel with the coal.
Carbolineum is one of cut of coal-tar heavy oil distillation gained, and its initial boiling point is at 220～260 ℃, and final boiling point is at 500～550 ℃, and boiling range is heavier, belongs to the last running scope.The mixture that carbolineum mainly is made up of compounds such as anthracene, phenanthrene, carbazole, acenaphthenes mostly is the above aromatic hydrocarbons of three rings and Fourth Ring greatly, and density (20 ℃) is greater than 1.0g/m
3, and foreign matter content height, especially nitrogen content be about 1wt%, in addition higher, oxygen level is higher, is generally 0.9～1.3wt%, and carbolineum is a kind of special material that is different from petroleum fractions.
At present the purposes of carbolineum is as carbon black raw material or is used for wood preserving oil, or separates and obtain products such as anthracene, acenaphthene, phenanthrene, carbazole, but the added value of aforesaid method is all lower.
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 make with extra care to remove impurity and aromatic hydrocarbons saturated reaction.This method only is suitable for the following cut of handling in the coal tar of diesel oil, 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 to be raw material with carbolineum, adopts hydrofining-hydrocracking one-stage serial flow process, obtains vapour, diesel component product.This method adopts the one-stage serial flow process, and 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.In order to overcome this shortcoming, CN101033409A adopts two-stage hydrogenation technology, after the carbolineum hydrofining, with the refined products fractionation, obtains greater than 200 ℃ of cuts as hydrocracking raw material.But above-mentioned two kinds of methods are to be raw material with carbolineum, can emit a large amount of heat in unifining process, exist the device temperature rise big, operate jiggly problem, and cause the catalyzer coking easily, influence the work-ing life of catalyzer.And gained is refining to generate nitrogen content＜400 μ g/g in the oil, and this just requires to select the strong hydrocracking catalyst of anti-nitrogen ability, not only to the requirement height of hydrocracking catalyst, but also has limited the application of carbolineum hydrocracking process.
Summary of the invention
In order to overcome deficiency of the prior art, the invention provides that the temperature rise of a kind of hydrofining section is little, smooth operation, the carbolineum method for hydrogen cracking that is easy to use.This method not only can make carbolineum hydrogenation production lightweight vapour, diesel product, and makes device running safety and steady, simplifies the operation prolong operating period.
Carbolineum method for hydrogen cracking provided by the invention comprises:
(1) in the presence of hydrogen, carbolineum enters the hydrofining reaction district, contacts with Hydrobon catalyst to carry out hydrofining reaction;
(2) the generation oil of step (1) hydrofining gained carries out gas-liquid separation through high pressure hot separator;
(3) the hot high score oil of liquid product told of step (2) high pressure hot separator is partly recirculated to the hydrofining reaction district;
(4) the hot high score oil of step (3) remainder enters the hydrocracking reaction district, in the presence of hydrogen, successively through Hydrobon catalyst contact with hydrocracking catalyst react after, obtain isocrackate; Wherein the pressure in hydrofining reaction district is higher than the pressure in hydrocracking reaction district;
(5) isocrackate of step (4) gained with enter cold high pressure separator from the isolated gas of high pressure hot separator;
(6) liquid told of step (5) cold high pressure separator enters the cold low separator;
(7) the isolated liquid of step (6) cold low separator is behind product stripping tower stripping, and liquid removes the product separation column at the bottom of the stripping tower, obtains gasoline and diesel oil distillate.
The pressure in the described hydrofining reaction of step of the present invention (4) district is higher than more than the pressure 0.1MPa in hydrocracking reaction district, is preferably 0.2～1.0MPa.
In the inventive method, the hydrogen-rich gas that cold high pressure separator is told, after separatory and compressor boost, a part is mixed the dereaction system as recycle hydrogen with new hydrogen, use hydrogen as reaction, also can be used as cold hydrogen and be used to control hydrofining and the temperature rise of hydrocracking reactor beds.
In the inventive method, the weight in oil circulation time hydrofining reaction district of the described hot high score of step (3) and the weight ratio of raw material carbolineum, the weight ratio that promptly circulates is 2.0～6.0.
In the inventive method, Hydrobon catalyst, hydrocracking catalyst can be divided in two reactors in the hydrocracking reaction district, also can be contained in the reactor, and Hydrobon catalyst is 1: 1～1: 3 with the admission space ratio of hydrocracking catalyst.
Described carbolineum is the product that coal-tar heavy oil obtains through distillation, and its character is as follows: density (20 ℃) is greater than 1.0g/cm
3, be generally 1.0～1.2g/cm
3, aromatic hydrocarbons and colloid total amount are generally more than the 90wt%, and initial boiling point is greater than 220 ℃, is generally 220～260 ℃, do greater than 500 ℃, be generally 500～550 ℃, nitrogen content is greater than 1.0wt%, be generally 1.0～1.2wt%, oxygen level is greater than 0.9wt%, is generally 0.9～1.3wt%.
In the inventive method, adopt mass spectrometric determination aromatic hydrocarbons and gelationus content.
The present invention can adopt conventional hydrocracking catalyst in the hydrocracking reaction district, preferred employing contains amorphous aluminum silicide and molecular sieve is the hydrocracking catalyst of main acidic components, recommend (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.
Fixed bed hydrogenation technology is all adopted in hydrofining of the present invention and hydrocracking.
Hydrobon catalyst in the inventive method is conventional 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 0.15～0.6ml/g.Main catalyzer have that China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops 3936,3996, FF-16, FF-26 etc.
Said hydrofining reaction district and hydrocracking reaction district adopt two-stage process.The operational condition (to fresh feed) in said hydrofining reaction district: volume space velocity 0.1～0.8h when 370～400 ℃ 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: 380～390 ℃ of temperature of reaction, pressure 12.0～15.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and air speed 0.3～0.6h
-1The operational condition in said hydrocracking reaction district is: volume space velocity 0.1～0.6h when 350～400 ℃ of temperature of reaction, pressure 9.0～15.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1The preferred operations condition is: volume space velocity 0.3～0.4h when 350～390 ℃ of temperature of reaction, pressure 11.0～14.0MPa, hydrogen to oil volume ratio are 900: 1～1500: 1 and liquid
-1
In sum, adopt method of the present invention to handle carbolineum and have following advantage:
1, the present invention is directed to aromaticity content height in the carbolineum, cause the higher problem of Hydrobon catalyst bed temperature rise, adopt oil circulation go back to hydrofining reaction district of hot high score, with the charging of carbolineum as the hydrofining reaction district, like this, effectively reduce the aromaticity content in the charging of hydrofining reaction district on the one hand, the device temperature rise is obviously reduced, can avoid 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, causes the circulating hydrogen compressor load to increase, and facility investment all can be saved greatly in this two aspect.
2, the inventive method is optimized flow process, compare with conventional two-stage hydrocracking technology, can be less with a cover separation system, instant heating high score, cold high score, cold low branch and stripping tower are respectively with one, hydrofining simultaneously and cold high pressure separator of hydrocracking units shared, go out the hydrogen-rich gas of self cooling high score, only need just can obtain returning the recycle hydrogen of two reaction zones, reduce by a circulating hydrogen compressor so again with a circulating hydrogen compressor.Facility investment all can be saved to a great extent in this two aspect.
3, the present invention adopts hot high score oil directly to loop back refined unit, saved a thermal low-pressure separators like this, because hot high score oil utilizes pressure difference to enter hydrocracking reactor, can save two conveying pumps again, on the basis of further reducing investment outlay, also has the advantage that cuts down the consumption of energy and simplify the operation like this.
4, to adopt hot high score oil be that hydrofining generates oil and mixes method as the hydrofining unit feed with carbolineum in the present invention, 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 oil circulation go back to hydrofining unit of hot high score, can effectively reduce the concentration of colloid and carbon residue in the carbolineum raw material, and is favourable to hydrofining and the active permanent performance of hydrocracking catalyst, but the safety in production of the long period of implement device.
6, the present invention adopts oil circulation go back to hydrofining unit of hot high score, utilize the similar principle that mixes, making the high melting compound in the carbolineum---the concentration of anthracene, phenanthrene, carbazole, firefly anthracene and pyrene reduces, reduced harsh degree, made device be similar to smooth and easy charging under the paraffin device holding temperature feed system insulation uniformity requirement.
7, the present invention also can obtain clean gasoline blend component and fuel gas product except obtaining the clean diesel blend component, has realized that carbolineum is converted into light Fuel fully.
8, the present invention provides a kind of processing means that improves its economy for the lower carbolineum of added value; Under the crude supply present situation of growing tension, for clean fuel oil production provides new raw material sources.
Description of drawings
Fig. 1 is the block diagram of carbolineum method of hydrotreating of the present invention.
Embodiment
In conjunction with Fig. 1 the inventive method is described further.Carbolineum is behind hydrofining reactor 2, gained hydrofining generates oil and carries out gas-liquid separation through high pressure hot separator 3, the hot high score oil of the liquid product of telling 4 parts loop back the hydrofining reaction district and mix with carbolineum, the hot high score oil 4 of remainder directly goes to hydrocracking reaction district 17 to make raw material, successively behind Hydrobon catalyst and hydrocracking catalyst, obtain isocrackate 7, isocrackate 7 with mix from high pressure hot separator 3 isolated hot high score gases 16, enter cold high pressure separator 8.The hydrogen-rich gas that comes from cold high pressure separator is through separatory, again through circulating hydrogen compressor 15 superchargings, a part as recycle hydrogen 6 with can the dereaction system after newly hydrogen 1 mixes, as carbolineum hydrofining unit and hydrocracking unitary reactor inlet hydrogen, also can be used as cold hydrogen and be used to control hydrofining and the temperature rise of hydrocracking reactor beds.Cold high pressure separator 8 isolated liquid enter cold low separator 9.Cold low separator 9 isolated liquid products remove hydrogen sulfide and gas products 11 through product stripping tower 10 strippings, and liquid removes product separation column 12 at the bottom of the stripping tower, produce gasoline fraction 13 and diesel oil distillate 14 through distillation.
To be further specified the inventive method below in conjunction with embodiment, but be not limited in this.
Embodiment 1～3
Used carbolineum feedstock property sees Table 1.
Adopt two-stage hydrocracking technology, the concrete operations flow process is seen Fig. 1.
Contain the preparation of the hydrocracking catalyst of amorphous aluminum silicide and Y zeolite: A1, A2.
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
3Be 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.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
3Be 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.
Contain the preparation of the hydrocracking catalyst of amorphous aluminum silicide and beta-molecular sieve: B1, B2.
Hydrocracking catalyst B1:
With beta-molecular sieve (SiO
2/ Al
2O
3Be 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 30wt%, 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.
Hydrocracking catalyst B2:
With beta-molecular sieve (SiO
2/ Al
2O
3Be 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.
Filling scheme is to adorn 3936 Hydrobon catalysts in the hydrofining reactor 1, hydrocracking reactor 6 tops adorn 3936, bottom filling hydrocracking catalyst, specific as follows: embodiment 1 bottom dress contains the hydrocracking catalyst of amorphous aluminum silicide and Y molecular sieve, and the admission space ratio of the two kinds of catalyzer in hydrocracking reaction district is 50: 50; Embodiment 2 bottoms dress contains the hydrocracking catalyst of amorphous aluminum silicide and Y molecular sieve, and the admission space ratio of the two kinds of catalyzer in hydrocracking reaction district is 50: 50; Embodiment 3 bottoms dress contains the hydrocracking catalyst B1 and the B2 of amorphous aluminum silicide and beta-molecular sieve, and the admission space ratio of the three kinds of catalyzer in hydrocracking reaction district is 30: 35: 35.
Embodiment 1～3 hydrofining generation oil liquid product of gained after separation system loops back the hydrofining reaction district to be mixed with carbolineum, and the circulation weight ratio of embodiment 1 and embodiment 2 is 3.0, and the circulation weight ratio of embodiment 3 is 5.0.
Table 1 stock oil character
| Crude title | Carbolineum |
| Boiling range/℃ | |
| IBP/10％ | 222/300 |
| 30％/50％ | 335/365 |
| 70％/90％ | 410/470 |
| 95％/EBP | 490/510 |
| Density (20 ℃)/gcm -3 | 1.1512 |
| S/μg·g -1 | 4950 |
| N/μg·g -1 | 10145 |
| Mass spectrum is formed, wt% | |
| Aromatic hydrocarbons | 93.1 |
| Colloid | 6.9 |
Table 2 hydrogenation technique condition and diesel oil distillate product property
| Scheme | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| The hydrofining reaction district | |||
| Catalyzer | 3936 | 3936 | 3936 |
| Processing condition | |||
| Hydrogen dividing potential drop/MPa | 15.0 | 13.5 | 12.0 |
| Temperature of reaction/℃ | 380 | 390 | 390 |
| Air speed/h -1 | 0.50 | 0.35 | 0.25 |
| Hydrogen to oil volume ratio | 1000 | 1200 | 1400 |
| Hydrofining generates oily nitrogen content/μ gg -1 | 150 | 155 | 140 |
| The hydrocracking reaction district | |||
| Catalyzer | 3936/A2 | 3936/A1 | 3936/B1/B2 |
| Processing condition | |||
| Hydrogen dividing potential drop/MPa | 14.0 | 13.0 | 11.0 |
| Temperature of reaction/℃ | 365 | 375 | 385 |
| Air speed/h -1 | 0.4 | 0.35 | 0.3 |
| Hydrogen to oil volume ratio | 1000 | 1200 | 1400 |
| The hydrofining reaction district is higher than the pressure/MPa in hydrocracking reaction district | 1.0 | 0.5 | 1.0 |
| Diesel product character | |||
| Yield, wt% | 81.2 | 81.7 | 82.4 |
| Density (20 ℃)/kgm -3 | 899.0 | 896.5 | 905.0 |
| Sulphur content/μ gg -1 | 25 | 27 | 29 |
| Nitrogen content/μ gg -1 | 1 | 1 | 2 |
| Condensation point/℃ | -54 | -52 | -50 |
| Cold filter clogging temperature/℃ | -28 | -28 | -26 |
| Boiling range/℃ | |||
| 50% reclaims | 212 | 214 | 215 |
| 90% reclaims | 276 | 275 | 277 |
| 95% reclaims | 310 | 310 | 312 |
| Cetane value | 29.5 | 29.6 | 29.1 |
| Gasoline fraction character | |||
| Yield, % (massfraction) | 18.6 | 18.2 | 18.1 |
| Octane value (RON) | 76.0 | 76.1 | 76.3 |
Claims (14)
1. carbolineum method of hydrotreating comprises:
(1) in the presence of hydrogen, carbolineum enters the hydrofining reaction district, contacts with Hydrobon catalyst to carry out hydrofining reaction;
(2) the generation oil of step (1) hydrofining gained carries out gas-liquid separation through high pressure hot separator;
(3) the hot high score oil of liquid product told of step (2) high pressure hot separator is partly recirculated to the hydrofining reaction district;
(4) the hot high score oil of step (3) remainder enters the hydrocracking reaction district, in the presence of hydrogen, successively through Hydrobon catalyst contact with hydrocracking catalyst react after, obtain isocrackate; Wherein the pressure in hydrofining reaction district is higher than the pressure in hydrocracking reaction district;
(5) isocrackate of step (4) gained with enter cold high pressure separator from the isolated gas of high pressure hot separator;
(6) liquid told of step (5) cold high pressure separator enters the cold low separator;
(7) the isolated liquid of step (6) cold low separator is behind product stripping tower stripping, and liquid removes the product separation column at the bottom of the stripping tower, obtains gasoline and diesel oil distillate.
2. in accordance with the method for claim 1, the pressure that it is characterized in that described hydrofining reaction district is higher than more than the pressure 0.1MPa in hydrocracking reaction district.
3. in accordance with the method for claim 1, it is characterized in that the pressure in described hydrofining reaction district is higher than the pressure 0.2～1.0MPa in hydrocracking reaction district.
4. in accordance with the method for claim 1, it is characterized in that hydrogen-rich gas that described cold high pressure separator tells after separatory and compressor boost, uses as recycle hydrogen, perhaps as cold hydrogen.
5. in accordance with the method for claim 1, it is characterized in that the weight in oil circulation time hydrofining reaction district of the described hot high score of step (3) and the weight ratio of raw material carbolineum, the weight ratio that promptly circulates is 2.0～6.0.
6. in accordance with the method for claim 1, it is characterized in that the admission space ratio of Hydrobon catalyst and hydrocracking catalyst is 1: 1～1: 3 in the described hydrocracking reaction district.
7. in accordance with the method for claim 1, it is characterized in that described carbolineum is the product that coal-tar heavy oil obtains through distillation, its character is as follows: 20 ℃ of density are greater than 1.0g/cm
3, aromatic hydrocarbons and colloid total amount are more than the 90wt%, and initial boiling point is 220～260 ℃, does 500～550 ℃, and nitrogen content is greater than 1.0wt%, and oxygen level is greater than 0.9wt%.
8. in accordance with the method for claim 1, it is characterized in that described hydrofining operational condition, to fresh feed: volume space velocity 0.1～0.8h when 370～400 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1
9. in accordance with the method for claim 1, it is characterized in that described hydrofining operational condition, to fresh feed: 380～390 ℃ of temperature of reaction, pressure 12.0～15.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and air speed 0.3～0.6h
-1
10. in accordance with the method for claim 1, it is characterized in that described hydrocracking operational condition is: volume space velocity 0.1～0.6h when 350～400 ℃ of temperature of reaction, pressure 9.0～15.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1
11. in accordance with the method for claim 1, it is characterized in that described hydrocracking operational condition is: volume space velocity 0.3～0.4h when 350～390 ℃ of temperature of reaction, pressure 11.0～14.0MPa, hydrogen to oil volume ratio are 900: 1～1500: 1 and liquid
-1
12. in accordance with the method for claim 1, it is characterized in that described hydrocracking catalyst is that employing contains amorphous aluminum silicide and molecular sieve is the hydrocracking catalyst of main acidic components.
13. according to claim 1 or 12 described methods, 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.
14. in accordance with the method for claim 1, it is characterized in that described Hydrobon catalyst is the hydrocracking pretreatment catalyst, with group vib and/or group VIII metal is active ingredient, is carrier with the aluminum oxide of aluminum oxide, siliceous aluminum oxide or siliceous and phosphorus; 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 0.15～0.6ml/g.
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| CN102703118A (en) * | 2012-06-04 | 2012-10-03 | 神华集团有限责任公司 | Preparation method of diesel |
| CN102703117A (en) * | 2012-06-04 | 2012-10-03 | 神华集团有限责任公司 | Preparation method for diesel oil |
| CN103102957A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Two-stage hydrocracking method for high-nitrogen raw material |
| CN103695030A (en) * | 2013-12-18 | 2014-04-02 | 宁波金远东工业科技有限公司 | Method for preparing diesel by hydrogenating anthracene oil of coal tar |
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| JP4785250B2 (en) * | 1998-12-08 | 2011-10-05 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Production of low sulfur / low aromatic distillate |
| 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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