CN102041074B - Hydrogenation method of deep drawing anthracene oil - Google Patents
Hydrogenation method of deep drawing anthracene oil Download PDFInfo
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Abstract
The invention discloses a hydrogenation method of deep drawing anthracene oil, comprising the following steps of: hydrorefining the deep drawing anthracene oil, separating gas and liquid through a hot high-pressure separator, mixing the obtained hot high-fraction oil part with the deep drawing anthracene oil when the obtained hot high-fractionoil part is circulated to a hydrorefeining reaction zone, introducing the remaining hot high-fraction oil part into a hydrocracking reaction zone by utilizing differential pressure for sequentially passing by a hydrorefining catalyst, a hydrogenation decarbonation catalyst and a hydrocrakcing catalyst to obtain a hydrocracking product, introducing the obtained hydrocracking product and the gas separated from the hot high-pressure separator into a cold high-pressure separator, introducing the separated liquid into a cold low-pressure separator, introducing the liquid separated from the cold low-pressure separator into a product fractionating tower after the liquid is subjected to steam stripping to obtain gasoline and diesel distillate. The method not only can be used for processing the deep drawing anthracene oil and broadening the rang of raw materials, but also benefits the transformation of the deep drawing oil to the greatest extent, thereby improving the yield of light fuel oil and enhancing the additional value of the anthracene oil, and in addition, the method is favorable for lowering the temperature rise of a device, reducing equipment investment and energy consumption, simplifying the operation of the device and prolonging the running period of the device.
Description
Technical field
The present invention relates to a kind of deep drawing anthracene oil method of hydrotreating, specifically relate to a kind of method of hydrocracking production clean fuel oil of deep drawing anthracene oil.
Background technology
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 Coal Chemical Industry industry, hydrogenating materials is done and is generally 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 slightly poor (seeing " exploitation of coal-tar pitch and prospect thereof ", < < entrepreneur world > > the 8th phase in 2007).At present coal tar hydrogenating raw material forms and take aromatic hydrocarbons as main, and the foreign matter content such as sulphur, nitrogen, oxygen is higher, and with it, producing light-weight fuel oil also needs further processing.
With the method for hydrogenation process coal tar or wherein 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 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 is only suitable for processes the cut below diesel oil in coal tar, the last running more than diesel oil in coal tar can not be converted into 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, feature 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 generating 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 generating 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.In the refining generation oil of the method gained, nitrogen content < 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, 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 conventionally, especially the requirement of nitrogen is preferably in below 100 μ g/g, otherwise will affects activity and the stability of hydrocracking catalyst.The oily nitrogen content < 400 μ g/g of the refining generation of CN101033409A, CN1676583A tail oil directly enters hydrocracking reactor, there is same problem in these two kinds of methods: the more difficult nitrogenous compound removing concentrates in the last running as 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 effective control hydrofining reaction district temperature rise, improve the method for hydrotreating of the deep drawing anthracene oil of device smooth operation, simplification device operation.The method not only can be processed deep drawing anthracene oil; widened raw material range; and can transform to greatest extent deep drawing anthracene oil; improved the yield of light-weight fuel oil; improved the added value of carbolineum, capable of reducing energy consumption, reduce investment outlay; the activity of effectively having protected hydrocracking catalyst, makes device long-term operation simultaneously.
Deep drawing anthracene oil method for hydrogen cracking provided by the invention, comprising:
(1) under hydrogen exists, deep drawing anthracene oil enters hydrofining reaction district, contacts and carries out hydrofining reaction successively with hydrogenation protecting catalyst with Hydrobon catalyst;
(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 that step (2) high pressure hot separator separates is partly recirculated to hydrofining reaction district;
(4) the hot high score oil of step (3) remainder enters hydrocracking reaction district, under hydrogen exists, after Hydrobon catalyst, removal of ccr by hydrotreating catalyzer contact with hydrocracking catalyst and react, obtains isocrackate successively; Wherein the pressure in hydrofining reaction district is higher than the pressure in hydrocracking reaction district;
(5) isocrackate of step (4) gained with from the isolated gas of high pressure hot separator, enter cold high pressure separator;
(6) liquid that step (5) cold high pressure separator separates enters cold low separator;
(7) the isolated liquid of step (6) cold low separator is after product stripping tower stripping, and stripping tower bottom liquid removes product separation column, obtains gasoline and diesel oil distillate.
More than the pressure 0.1MPa of the pressure in the hydrofining reaction district that step of the present invention (4) is described higher than the hydrogenation reaction zone of cracking, be preferably 0.3～1.0MPa.
In the inventive method, the hydrogen-rich gas that cold high pressure separator separates, after separatory and compressor boost, a part is mixed dereaction system as recycle hydrogen with new hydrogen, as reaction hydrogen, also can be used as cold hydrogen for controlling hydrofining and the temperature rise of hydrocracking reactor beds.This method, to reducing device temperature rise, reduces facility investment, reduces energy consumption, simplification device smooth operation.Owing to having reduced the concentration of resin and asphalt in raw material, can make device extend running period simultaneously.
In the inventive method, the weight in oil circulation time hydrofining reaction district of hot high score and the weight ratio of raw material deep drawing anthracene oil that step (3) is described, the weight ratio that circulates is 2.0～6.0.
Hydrogenation of the present invention is to adopt fixed bed hydrogenation technique.Described hydrofining reaction district and hydrocracking reaction interval selection 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 nitrogen content is 1.0wt%～1.4wt%, and oxygen level is 1.3wt%～2.0wt%.It is 25%～30% 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; group vib metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.Weighing scale with catalyzer, active metallic content is counted 0.5wt%～18wt% with oxide compound, preferably composed as follows: group vib metal content is counted 0.5wt%～15wt% with oxide compound, group VIII metal content is counted 0.5wt%～8wt% with oxide compound, and shape can be hollow cylinder, trifolium shape, Herba Galii Bungei or spherical etc.For example: FZC-103, FZC-200, FZC-100 and the FZC-102B residual oil hydrocatalyst of Fushun Petrochemical Research Institute's research and development.
In described hydrofining reaction district, described hydrogenation protecting catalyst and Hydrobon catalyst admission space account for 2%～40% and 60%～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, group vib metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.With the weighing scale of catalyzer, group vib metal content is counted 10wt%～35wt% with oxide compound, and 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 that China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops 3936,3996, FF-16, FF-26 etc.
In said hydrofining reaction district, hydrofining operational condition, to fresh feed: volume space velocity 0.1～0.8h when 370～400 ℃ of temperature of reaction, pressure 12.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1; Preferred operations condition, to fresh feed: 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.
In the inventive method, in 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.In the inventive method, in hydrocracking catalyst reaction zone, saturated in order to remove the further hydrogenation of aromatic hydrocarbons that mercaptan in isocrackate and part are completely unsaturated, preferably, at hydrocracking catalyst downstream filling aftertreatment Hydrobon catalyst, its admission space accounts for 2%～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, group vib metal is generally Mo and/or W, and 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.
Removal of ccr by hydrotreating catalyzer used 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 YiVIBHe VIII family metal is hydrogenation activity component, as two or three in W, Mo, Ni or Co, is preferably W, Mo and Ni, and this catalyzer preferably contains auxiliary agent Si and Ti, take aluminum oxide as carrier.The weight of catalyzer of take is benchmark, WO
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 operational condition in said hydrocracking reaction district is: volume space velocity 0.1～0.6h when 350～410 ℃ of temperature of reaction, pressure 11.0～15.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1; Preferred operations condition is: volume space velocity 0.2～0.5h when 360～410 ℃ of temperature of reaction, pressure 11.0～15.0MPa, hydrogen to oil volume ratio are 900: 1～1500: 1 and liquid
-1.
In sum, adopting method of the present invention to process deep drawing anthracene oil tool has the following advantages:
1, the present invention is directed in deep drawing anthracene oil aromaticity content high, cause the higher problem of beds temperature rise, adopt oil circulation go back to hydrofining reaction district of hot high score, effectively reduce on the one hand the aromaticity content in the charging of hydrofining reaction district, device temperature rise is obviously reduced, so just avoided due to temperature rise, and many reactors or more beds must be set; On the other hand, due to temperature rise, between reactor or bed, cold hydrogen amount increases, and causes circulating hydrogen compressor load to increase, and facility investment all can be saved greatly in this two aspect.
2, the inventive method Optimizing Flow, compares with conventional two-stage hydrocracking technique, can use less a set of separation system, instant heating high score, cold high score, cold low minute and stripping tower each with one, reduced the equipment of separation system; Simultaneously hydrofining and cold high pressure separator of hydrocracking units shared, go out the rich gas gas of self cooling high score, only need just can obtain returning the recycle hydrogen of two reaction zones with a circulating hydrogen compressor, reduces so again by 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 direct circulation to return refined unit, saved like this thermal low-pressure separators, because hot high score oil utilizes pressure difference to enter hydrocracking reactor, can save again two conveying pumps, further reducing investment outlay on basis like this, also thering is the energy consumption of reduction and simplify the operation.
4, the present invention adopts hot high score oil to mix the method as the charging of hydrofining reaction district with deep drawing anthracene oil, can avoid owing to needing liquid hydrogen injection reference mark many, cause misoperation probability to increase, thereby cause temperature runaway, cause catalyzer coking, cause the industrial accidents such as permanent inactivation, favourable to the safety and steady operation of device.
5, the present invention adopts oil circulation go back to hydrofining unit of hot high score, mix the method as the charging of hydrofining reaction district with deep drawing anthracene oil, can effectively reduce the concentration of colloid in deep drawing anthracene oil, bituminous matter and carbon residue, permanent performance to hydrofining and hydrocracking catalyst activity is favourable, long period safety in production that can implement device.
6, carbolineum is done and brought up to 560 ℃～650 ℃ by 500～550 ℃, make 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 lightweight transport fuel, improve the added value of coal tar.
7,, in the hydrofining reaction district of the inventive method before Hydrobon catalyst, filling hydrogenation protecting catalyst, removes impurity and part carbon residue in deep drawing anthracene oil, can protect the activity of follow-up hydrogenation catalyzer, prolong operating period.
8, the inventive method is for the feature of deep drawing anthracene oil, select suitable hydrocracking unit catalyzer grating or matching way: hot high score oil passes through Hydrobon catalyst, removal of ccr by hydrotreating catalyzer, hydrocracking catalyst successively, can further reduce so on the one hand hydrofining and generate colloid, bituminous matter and the carbon residue in oil, reduce nitrogen and aromaticity content simultaneously, protection hydrocracking catalyst is active, favourable running period to growing apparatus; On the other hand, can make more heavy component be converted into hydrocarbon matter oil fuel component, improve light-weight fuel oil yield.
9, in hydrocracking reaction of the present invention district, after hydrocracking catalyst, add a small amount of post-refining catalyzer, this method reduces the mercaptan generating in can product on the one hand, can make on the other hand the minute quantity alkene generating with partly the complete unsaturated further hydrogenation of aromatic hydrocarbons is saturated, favourable to improving diesel oil distillate cetane value.
10, the inventive method, by adopting suitable technical process and catalyzer grating, matching way, can be processed heavier coal tar fraction, to greatest extent inferior raw material is converted into clean fuel oil ingredient.
Accompanying drawing explanation
Fig. 1 is the block diagram of the inventive method.
Embodiment
In conjunction with Fig. 1, the inventive method is described further.Deep drawing anthracene oil is after 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 liquid product 4 parts that separate loop back hydrofining reaction district and mix with deep drawing anthracene oil, the hot high score oil 4 of remainder directly goes to hydrocracking reaction district 17 to make raw material, successively after Hydrobon catalyst, removal of ccr by hydrotreating agent and hydrocracking catalyst, obtain isocrackate 7, isocrackate 7 with from the isolated hot high score gas 16 of high pressure hot separator 3, mix, enter cold high pressure separator 8.Come from the hydrogen-rich gas of cold high pressure separator through separatory, again through circulating hydrogen compressor 15 superchargings, a part as recycle hydrogen 6 with can dereaction system after new hydrogen 1 mixes, as deep drawing anthracene oil hydrofining unit and hydrocracking unitary reactor entrance hydrogen, also can be used as cold hydrogen for controlling hydrofining and the temperature rise of hydrocracking reactor beds.The isolated liquid of cold high pressure separator 8 enters cold low separator 9.The isolated liquid product of cold low separator 9 removes hydrogen sulfide and gas products 11 through product stripping tower 10 strippings, and stripping tower bottom liquid removes product separation column 12, through distillation, produces gasoline fraction 13 and diesel oil distillate 14.
The following examples will be further described present method, but be not limited in this.
Embodiment of the present invention hydrocracking catalyst used is prepared as follows:
1, contain the preparation of the hydrocracking catalyst of amorphous aluminum silicide and Y zeolite: A1, A2.
(1) hydrocracking catalyst A1:
By amorphous aluminum silicide (specific surface 520m
2/ g, SiO
235wt%, pore volume 1.2ml/g) and Y molecular sieve (SiO
2/ Al
2o
3mol ratio is 9, lattice constant 2.432, specific surface 650m
2/ g, infrared acidity 0.45mmol/g), after mixing, add (added by the little porous aluminum oxide of pore volume 0.42ml/g prepared by rare nitric acid peptization) tackiness agent roll agglomerating after, put into after banded extruder extruded moulding, at 110 ℃, be dried 10 hours, 500 ℃ of activation make carrier for 4 hours, then steep by Mo-Ni total immersion stain immersion, then at 110 ℃, be dried 12 hours, and 500 ℃ activate 3 hours.Catalyzer finally consists of: amorphous aluminum silicide 48wt%, Y molecular sieve 15wt%, aluminum oxide 12wt%, nickel oxide 5wt%, molybdenum oxide 20wt%.Catalyst specific surface 220m
2/ g, pore volume 0.35ml/g.
(2) hydrocracking catalyst A2:
By amorphous aluminum silicide (specific surface 490m
2/ g, SiO
245wt%, pore volume 1.0ml/g) and Y molecular sieve (SiO
2/ Al
2o
3mol ratio is 12, lattice constant 2.436, specific surface 680m
2/ g, infrared acidity 0.41mmol/g), after mixing, add the tackiness agent of (being added the preparation of rare nitric acid peptization by the little porous aluminum oxide of pore volume 0.42ml/g) roll agglomerating after, put into after banded extruder extruded moulding, at 110 ℃, be dried 10 hours, 500 ℃ of activation make after carrier for 4 hours, then steep by W-Ni total immersion stain immersion, then at 110 ℃, be dried 12 hours, and 500 ℃ activate 3 hours.Catalyzer finally consists of: amorphous aluminum silicide 45wt%, Y molecular sieve 13wt%, aluminum oxide 12wt%, nickel oxide 6.5wt%, Tungsten oxide 99.999 22.5wt%.Catalyst specific surface 210m
2/ g, pore volume 0.31ml/g.
2, contain the preparation of the hydrocracking catalyst of amorphous aluminum silicide and beta-molecular sieve: B1, B2.
(1) hydrocracking catalyst B1:
By beta-molecular sieve (SiO
2/ Al
2o
3mol ratio is 40, specific surface 580m
2/ g, infrared acidity 0.21mmol/g), amorphous aluminum silicide (specific surface 450m
2/ g, SiO
255wt%, pore volume 0.9ml/g) mix, add little porous aluminum oxide (the specific surface area 240m of dilute nitric acid solution peptization by concentration 3.3wt%
2/ g, pore volume is 0.42ml/g) tackiness agent that obtains, continue kneading until become paste, extruded moulding, institute's moulding bar that obtains is dried 12 hours at 110 ℃, and 500 ℃ of activation make after activated carrier for 4 hours.With W-Ni co-impregnated solution, flood again the carrier of above-mentioned preparation, then be dried 8 hours at 110 ℃, and 500 ℃ activate 3 hours.Catalyzer finally consists of: β zeolite 25wt%, amorphous aluminum silicide 25wt%, aluminum oxide 20wt%, nickel oxide 7.5wt%, Tungsten oxide 99.999 22.5wt%.Catalyst specific surface 235m
2/ g, pore volume 0.32ml/g.
(2) hydrocracking catalyst B2:
By beta-molecular sieve (SiO
2/ Al
2o
3mol ratio is 60, specific surface 550m
2/ g, infrared acidity 0.19mmol/g), amorphous aluminum silicide (specific surface 490m
2/ g, SiO
245wt%, pore volume 1.0ml/g) mix, in the situation that continuing to roll, slowly add little porous aluminum oxide (the specific surface area 240m of dilute nitric acid solution peptization by concentration 3.3%
2/ g, pore volume is 0.42ml/g) tackiness agent that obtains, continue kneading until become paste, extruded moulding, institute's moulding bar that obtains is dried 12 hours at 110 ℃, and 500 ℃ of activation make after activated carrier for 4 hours.Again with W-Ni co-impregnated solution dipping, then at 110 ℃, be dried 8 hours, and 500 ℃ activate 3 hours.Catalyzer finally consists of: beta-molecular sieve 10wt%, amorphous aluminum silicide 30wt%, aluminum oxide 30wt%, nickel oxide 7.5wt%, Tungsten oxide 99.999 22.5wt%.Catalyst specific surface 260m
2/ g, pore volume 0.33ml/g.
Embodiment of the present invention removal of ccr by hydrotreating catalyzer used is prepared as follows:
Take 298g Si-Al
2o
3(butt 67w%, dioxide-containing silica is 13w%) powder, powdered active carbon 20.5g, sesbania powder 5g, mixed, and adds by 208g water, 22.0g containing 17wt%TiCl
3tiCl
3the acidic solution that solution and 22g acetic acid mix, kneading 1.5 hours, gained plastic, extrusion mechanism is extruded into the special-shaped strip of Φ 2.58～2.64mm, and this strip is dried 4 hours at 108 ℃, and at 480 ℃, roasting is 4 hours.By ordinary method, flood active metal, molybdenum, tungsten and nickel are then dried 3 hours at 80 ℃, and at 500 ℃, roasting is 3 hours, makes catalyzer HDC-1.The composition of this catalyzer and physico-chemical property see the following form 1.
Take 298g Si-Al
2o
3(butt 67w%, dioxide-containing silica is 19w%) powder, sesbania powder 5g, is mixed, and adds by 188g water, 43.0g containing 17wt%TCl
3tiCl
3the acidic solution that solution and 22g acetic acid mix, kneading 1.5 hours, gained plastic, extrusion mechanism is extruded into the special-shaped strip of Φ 1.10～1.35mm, and this strip is dried 4 hours at 108 ℃, and at 960 ℃, roasting is 4 hours.By ordinary method, flood active metal, molybdenum, tungsten and nickel are then dried 2 hours at 120 ℃, and at 550 ℃, roasting is 3 hours, makes catalyzer HDC-2.The composition of this catalyzer and physico-chemical property see the following form 1.
Composition and the character of table 1 removal of ccr by hydrotreating catalyzer
| Catalyzer | HDC-1 | HDC-2 |
| Form % (massfraction) | ||
| WO 3 | 18 | 20 |
| |
8 | 11 |
| NiO | 5 | 5 |
| |
6 | 9 |
| |
1 | 2 |
| Al 2O 3 | Surplus | Surplus |
| Character | ||
| Specific surface area, m 2/g | 138 | 175 |
| Mean pore size, nm | 18.4 | 11.8 |
Deep drawing anthracene oil feedstock property used is in Table 2.Embodiment flow process is shown in Fig. 1.
Table 2 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.
In embodiment, 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, and second adds 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.
The hot high score oil of embodiment 1 gained be take to circulation weight ratio and loop back hydrofining reaction district as 3.0, remainder enters hydrocracking reaction district, pass through successively Hydrobon catalyst 3936, removal of ccr by hydrotreating catalyzer HDC-1, hydrocracking catalyst A1 and aftertreatment Hydrobon catalyst FF-26, its volume ratio is 40: 15: 40: 5.
The hot high score oil of embodiment 3 gained be take to circulation weight ratio and loop back hydrofining reaction district as 3.0, remainder enters hydrocracking reaction district, pass through successively Hydrobon catalyst FF-26, removal of ccr by hydrotreating catalyzer HDC-2, hydrocracking catalyst B1, hydrocracking catalyst B2 and aftertreatment Hydrobon catalyst 3936, its volume ratio is 20: 9: 10: 10: 1.
Table 3 hydrofining cell process condition and hydrofining generate oil nature
| | Embodiment | 1 | |
|
| 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 | 14.5 | 13.0 | |
| Temperature of reaction/℃ | 385 | 390 | 395 | |
| Air speed/h -1 | 0.55 | 0.45 | 0.35 | |
| Hydrogen to oil volume ratio | 1500 | 1400 | 1200 | |
| Hot high score oil nature | ||||
| Density (20 ℃)/gcm -3 | 0.9840 | 0.9833 | 0.9815 | |
| Sulphur content/μ gg -1 | 201 | 202 | 200 | |
| Nitrogen content/μ gg -1 | 182 | 180 | 180 | |
| Free-water/μ gg -1 | ＜300 | ＜300 | ＜300 |
Table 4 hydrocracking process condition and result
| | Embodiment | 4 | |
|
| Hydrobon catalyst | 3936 | 3936 | FF-26 | |
| Removal of ccr by hydrotreating catalyzer | HDC-1 | HDC-1 | HDC-2 | |
| Hydrocracking catalyst | A1 | A2 | B1/B2 | |
| Aftertreatment Hydrobon catalyst | FF-26 | FF-26 | 3936 | |
| Processing condition | ||||
| Hydrogen dividing potential drop/MPa | 15.0 | 14.0 | 12.0 | |
| Temperature of reaction/℃ | 390 | 400 | 410 | |
| Air speed/h -1 | 0.4 | 0.5 | 0.3 | |
| Hydrogen to oil volume ratio | 1400 | 1200 | 1500 | |
| Hydrofining reaction district is higher than the pressure in hydrocracking reaction district, MPa | 1.0 | 0.5 | 1.0 | |
| Diesel product character | ||||
| Yield, % (massfraction) | 81.4 | 81.7 | 80.7 | |
| Density (20 ℃)/gcm -3 | 0.9090 | 0.9175 | 0.9050 | |
| Sulphur content/μ gg -1 | 41 | 42 | 38 | |
| Nitrogen content/μ gg -1 | 1.5 | 1.5 | 1.5 | |
| Condensation point/℃ | -52 | -51 | -54 | |
| Cold filter clogging temperature/℃ | -29 | -28 | -32 | |
| Boiling range/℃ | ||||
| 50% reclaims | 243 | 250 | 241 | |
| 90% reclaims | 296 | 298 | 293 | |
| 95% reclaims | 312 | 315 | 312 | |
| Cetane value | 29.0 | 32.5 | 28.1 | |
| Gasoline fraction character | ||||
| Yield, % (massfraction) | 19.1 | 19.1 | 19.7 | |
| Octane value (RON) | 78.1 | 80.2 | 79.5 |
Table 5 different runtime of result
Claims (14)
1. a method for hydrogen cracking for deep drawing anthracene oil, comprising:
(1) under hydrogen exists, deep drawing anthracene oil enters hydrofining reaction district, contacts and carries out hydrofining reaction successively with hydrogenation protecting catalyst with Hydrobon catalyst;
(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 that step (2) high pressure hot separator separates is partly recirculated to hydrofining reaction district; The described weight in oil circulation time hydrofining reaction district of hot high score and the weight ratio of raw material deep drawing anthracene oil, the weight ratio that circulates is 2.0～6.0;
(4) the hot high score oil of step (3) remainder enters hydrocracking reaction district, under hydrogen exists, after Hydrobon catalyst, removal of ccr by hydrotreating catalyzer contact with hydrocracking catalyst and react, obtains isocrackate successively; Wherein the pressure in hydrofining reaction district is higher than the pressure in hydrocracking reaction district; In 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;
(5) isocrackate of step (4) gained with from the isolated gas of high pressure hot separator, enter cold high pressure separator;
(6) liquid that step (5) cold high pressure separator separates enters cold low separator;
(7) the isolated liquid of step (6) cold low separator is after product stripping tower stripping, and stripping tower bottom liquid removes product separation column, obtains gasoline and diesel oil distillate;
In said hydrofining reaction district, hydrofining operational condition, to fresh feed: volume space velocity 0.1～0.8h when 370～400 ℃ of temperature of reaction, pressure 12.0～16.0MPa, 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 11.0～15.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1.
2. more than the pressure 0.1MPa of the pressure that in accordance with the method for claim 1, it is characterized in that described hydrofining reaction district higher than 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 0.3～1.0MPa in hydrocracking reaction district.
4. in accordance with the method for claim 1, the hydrogen-rich gas that the cold high pressure separator described in it is characterized in that separates, after separatory and compressor boost, is used as recycle hydrogen, or as cold hydrogen.
5. in accordance with the method for claim 1, it is characterized in that described hydrogenation is to adopt fixed bed hydrogenation technique.
6. 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/cm
3, within saturated minute, content is below 1.0wt%, and it is more than 90wt% that fragrance divides with colloid total amount, and initial boiling point is 220～260 ℃, and doing is 560～650 ℃, and nitrogen content is 1.0wt%～1.4wt%, and oxygen level is 1.3wt%～2.0wt%.
7. 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 60%～98% of hydrofining reaction district catalyzer total fill able volume.
8. in accordance with the method for claim 1, it is characterized in that in hydrocracking catalyst reaction zone, at hydrocracking catalyst downstream filling aftertreatment Hydrobon catalyst, its admission space accounts for 2%～15% of hydrocracking reaction district catalyzer total fill able volume.
9. in accordance with the method for claim 1, it is characterized in that in said hydrofining reaction district, hydrofining operational condition, to fresh feed: volume space velocity 0.3～0.6h when 380～400 ℃ of temperature of reaction, pressure 12.0～16.0MPa, hydrogen to oil volume ratio 900: 1～1500: 1 and liquid
-1; The operational condition in said hydrocracking reaction district is: volume space velocity 0.2～0.5h when 360～410 ℃ of temperature of reaction, pressure 11.0～15.0MPa, hydrogen to oil volume ratio are 900: 1～1500: 1 and liquid
-1.
10. 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.
11. in accordance with the method for claim 1; it is characterized in that it is active ingredient that described hydrogenation protecting catalyst be take group vib and/or group VIII metal; take aluminum oxide or silicon-containing alumina as carrier; weighing scale with catalyzer; composed as follows: group vib metal content is counted 0.5wt%～15wt% with oxide compound, group VIII metal content is counted 0.5wt%～8wt% with oxide compound.
12. 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 group VIII metal, the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus of take is carrier, weighing scale with catalyzer, group vib metal content is counted 10wt%～35wt% with oxide compound, 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.
13. in accordance with the method for claim 1, it is characterized in that described removal of ccr by hydrotreating catalyzer adopts heavy, the de-carbon residue catalyzer of residual hydrogenation.
14. according to the method described in claim 1 or 13, it is characterized in that the de-residual catalyzer of described hydrogenation, and the weight of catalyzer of take is benchmark, 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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