CN1171430A - Middle-pressure hydrocracking process for heavy fractional oil - Google Patents
Middle-pressure hydrocracking process for heavy fractional oil Download PDFInfo
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Abstract
A medium pressure hydrocracking process for heavy fractional oil to prepare reforming raw material, jet fuel, low-sulphur diesel oil for vehicles, catalytic cracking raw material and ethylene raw material features that a hydrorefining catalyst and a hydrocracking catalyst are used in one-run flow route to obtain high transform rate up to 80 vol.%. The intermediate fractional oil has an output rate up to 40 wt% or more and a selectivity not lower than 50 wt%. Said process is suitable for the heavy oil with nitrogen content up to 1500 ppm, sulfur content up to 3.5 wt%, and a fractional dry point higher than 500 deg. C.
Description
The invention relates to the catalysis conversion method of petroleum hydrocarbon.Specifically, be about heavy fraction of oil is carried out the method that middle distillate oil is produced in catalytic cracking in the presence of hydrogen.
Along with the dieselization of development, transport by road sharp increase and the vehicle of air system, variation has taken place world's oil product market demand structure: heavy oil product reduces, and motor spirit slightly descends, and middle distillate such as rocket engine fuel and derv fuel oil increase.And the trend of crude oil heaviness and poor qualityization makes various countries must take the policy of deep processing could obtain enough middle distillate.Though catalytic cracking and coking all belong to deep process technology, because of it is a decarbonization process, so the middle distillate product quality is relatively poor.
Hydrocracking process not only can be produced fine rocket engine fuel and derv fuel oil from heavy, inferior raw material, can also produce the demand that ethylene raw satisfies petrochemical industry, thereby become one of important process of deep processing, more and more is subject to people's attention.Owing to conventional hydrocracking process working pressure height, plant investment and process cost make its industrial application be subjected to certain restriction greatly, therefore some oil companies and research unit all are devoted to the middle pressure hydrocracking technology of Development and Production middle distillate oil and suitable catalyzer thereof both at home and abroad.
Though the mild hydrocracking technology that is used for production middle distillate oil disclosed in the prior art is under the condition of pressure heavy raw oil to be converted into the purpose product, its transformation efficiency generally all is lower than 50 body %.For example: EP93, disclosed single hop two doses (hydrotreatment and hydrocracking catalysts) the one-pass flow process of connecting in 552, its processing condition are: 5.25～7MPa, 360～440 ℃, LHSV 0.1～10 o'clock
-1The transformation efficiency of the product below 345 ℃ is 30～40 body %, raw materials used oil is the heavy gas oil more than 340 ℃, hydrotreating catalyst is VIA or the VIII family metal that loads on unformed aluminum oxide or the silica-alumina supports, and hydrocracking catalyst is VIA or the VIII family metal that loads on X or y-type zeolite or the mordenite.
And for example, USP4, disclosing in 686,030 a kind of is the process of 500～1100F fraction oil mild hydrocracking with boiling range, and its temperature of reaction is 500～900F, and the hydrogen dividing potential drop is 200～1500psig, LHSV 0.05～3.0 o'clock
-1, transformation efficiency is 15～35 body %, gained product liquid mid-boiling point＜700F accounts at least 85 body %.Used catalyzer is the Mo-Ni-P that loads on the unformed porous refractory oxide, and the diameter at least 75% hole is 50～130A in this catalyzer, the pore volume of diameter＞110A＜10%.
Though also there is transformation efficiency to be higher than 50% hydrocracking technology in the prior art, they require harsh to the nitrogen content in the hydrocracking charging.For example, USP4 discloses a kind of method by hydrocracking and isomerization production middle distillate oil in 859,312, this method be with do＞to account at least 90% hydrocarbon be raw material for the fraction of 600F, at 260～482 ℃, LHSV0.1～20 o'clock
-1, 200～3000psig condition under, contact with the catalyzer that contains SAPO-11 or SAPO-41 zeolite, transformation efficiency＞50%, the product yield of gained 300～725F fraction is higher than 40 body %.This method requires the nitrogen content＜50ppmw in the raw materials used oil, and is best＜10ppmw.
And for example, EP19, disclose in 959 that a kind of (fraction accounts for more than the 50 body % more than 350 ℃ with heavy hydrocarbon feedstocks, fraction accounts for more than the 10 body % more than 450 ℃) under the condition of the hydrogen dividing potential drops, 250～450 ℃, LHSV0.2～5.0 of＜100 crust o'clock-1, carry out the process of hydrocracking system lighter hydrocarbons fraction, wherein used catalyzer is the Ni-W that loads on faujusite and the inertia aluminum oxide.This method requires the nitrogen content＜100ppmw in the raw materials used oil equally, and is best＜10ppmw, therefore all needs through pre-hydrodenitrification for the stock oil of nitrogen content above 100ppmw.
Purpose of the present invention is exactly to provide a kind of new for the method for heavy fraction of oil hydrocracking with production middle distillate oil on the basis of existing technology, this method can be in demulcent under the press strip spare operation and can obtain can be up to 80 body % once pass through transformation efficiency, and can directly process the inferior feedstock oil of nitrogen content up to 1500ppm, the organonitrogen content of hydrocracking catalyst charging allows up to 150ppm.
The mink cell focus middle pressure hydrocracking method of production middle distillate oil provided by the invention is:
Is that 6.0～10.0MPa, temperature are that 340～440 ℃, hydrogen/oil volume ratio are 400～1200, liquid hourly space velocity is 0.1～3.0 o'clock with heavy oil feed in the hydrogen dividing potential drop
-1Condition under contact with a kind of hydrocracking catalyst with a kind of Hydrobon catalyst successively and without intermediate section from, reacted effluent through cooling, separate, hydrogen-containing gas recycles, product liquid enters fractionating system.
Used Hydrobon catalyst consists of: 1～5 heavy %NiO, 12～35 heavy %WO
3, 1～9 heavy %F and surplus Al
2O
3, this Al
2O
3Be by one or more apertures Al
2O
3With one or more macropores Al
2O
3Be composited this aperture Al according to 75: 25～50: 50 weight ratios
2O
3The pore volume of median pore diameter＜80A accounts for total pore volume more than 95%, this macropore Al
2O
3The pore volume of median pore diameter 60～600A accounts for total pore volume more than 70%, and described pore volume is measured with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature.
Used hydrocracking catalyst consists of: 2.5～6.0 heavy %NiO, 10～38 heavy %WO
3, 0.5～5.0 heavy %F and balance carriers, this carrier is that the acidity value by 20～90 heavy % is the Al of 0.5～0.8 mmole/gram
2O
3With the acidity value of 10～80 heavy % be that the mesopore or the large pore zeolite of 1.0～2.0 mmole/grams formed, described acidity value is to use NH
3-TPD method records.
Specifically, the present invention thes contents are as follows.
(1) catalyzer of the present invention's use
Used a kind of Hydrobon catalyst and a kind of hydrocracking catalyst among the present invention, be respectively described below:
The Hydrobon catalyst that uses among the present invention be 97112397.7 at application number, denomination of invention is the catalyzer disclosed in the application of " a kind of fraction oil Hydrobon catalyst and preparation thereof ".This catalyzer is by 1～5 heavy %NiO, 12～35 heavy %WO
3, 1～9 heavy %F and surplus Al
2O
3Form this Al
2O
3Be by one or more apertures Al
2O
3With one or more macropores Al
2O
3Be composited according to 75: 25～50: 50 weight ratios.This Al generally
2O
3Be by a kind of aperture Al
2O
3With a kind of macropore Al
2O
3Be composited.This aperture Al
2O
3The volume in median pore diameter＜80A hole should account for total pore volume more than 95%, this macropore Al
2O
3The volume in median pore diameter 60～600A hole should account for total pore volume more than 70%, these two kinds of Al
2O
3The Al of compound back gained
2O
3The carrier median pore diameter is that the pore volume of 40～100A accounts for more than 75% of total pore volume.Described pore volume records with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature.This aperture Al
2O
3With macropore Al
2O
3Precursor be respectively a diaspore content greater than 60% with greater than 50% hydrated aluminum oxide.
The preparation method of this Hydrobon catalyst is as follows: the precursor of little porous aluminum oxide and macroporous aluminium oxide is pressed the even aftershaping of required mixed, in 550～650 ℃ of roastings 3～5 hours; With fluorine-containing inorganic compound aqueous solution dipping, dry back was in 400～600 ℃ of roastings 3～5 hours then; With the aqueous solution dipping of nickeliferous and tungsten, dry back was in 400～600 ℃ of roastings 3～5 hours at last.
The hydrocracking catalyst that uses among the present invention be 97112396.9 at application number, denomination of invention is the catalyzer disclosed in the application of " a kind of fraction oil hydrocracking catalyst and preparation thereof ".This catalyzer is by 2.5～6.0 heavy %, best 2.0～5.0 heavy %NiO, 10～38 heavy %, best 19～25 heavy %WO
3, 0.5～5.0 heavy %, the carriers of best 1.0～4.0 heavy %F and surplus are formed.This carrier is that the acidity value of best 50～80 heavy % is the Al of 0.5～0.8 mmole/gram by 20～90 heavy %
2O
3With 10～80 heavy %, the acidity value of best 20～50 heavy % is that the mesopore or the large pore zeolite of 1.0～2.0 mmole/grams formed.Described acidity value is to use NH
3-TPD method is measured.This mesopore or large pore zeolite are selected from the y-type zeolite and/or the mordenite of H type or RE type.This Al
2O
3Get through the roasting dehydration by one or more hydrated aluminum oxides that are selected from sodium metaaluminate-carbon dioxide process, sodium metaaluminate-Tai-Ace S 150 method, aluminum alkyls or the preparation of aluminum alkoxide hydrolysis method, diaspore content＞60%.
The preparation method of this hydrocracking catalyst is as follows: hydrated aluminum oxide and zeolite are mixed aftershaping by predetermined proportion, in 550～650 ℃ of roastings 3～5 hours; With fluorine-containing inorganic compound aqueous solution dipping, dry back was in 400～500 ℃ of roastings 3～5 hours then; With the aqueous solution dipping of nickeliferous and tungsten, dry back was in 400～500 ℃ of roastings 3～5 hours at last.
Above-mentioned Hydrobon catalyst and hydrocracking catalyst should carry out prevulcanized before use.Prevulcanized can be carried out according to the method for common Hydrobon catalyst and hydrocracking catalyst prevulcanized.The general gas phase sulfuration method that adopts among the present invention, vulcanizing agent can be selected dithiocarbonic anhydride or dimethyl disulfide for use, and sulfide stress is generally 3.0～8.0MPa, and the volume ratio of vulcanizing agent gas and catalyzer is generally 300～600 during sulfuration: 1.Sulfuration is that the segmentation alternating temperature carries out, and generally vulcanizes 2～6 hours down at 200～240 ℃, vulcanizes 8～12 hours down at 320～360 ℃ again.The injection rate of vulcanizing agent should be with H in sulfurized different steps and the circulation gas
2The concentration of S is regulated: the injection rate of cryogenic vulcanization vulcanizing agent during the stage should be controlled at and make H in the circulation gas
2The concentration of S remains in 0.1～0.5% scope; Along with the rising of curing temperature, the injection rate of vulcanizing agent can be controlled in the H that makes in the circulation gas
2S concentration is increased to 1.0% gradually; During high temperature vulcanized stage, the injection rate of vulcanizing agent then should make H
2The concentration of S is controlled in 1.0～2.0% scopes.
(2) hydrocarbon feed that is suitable for of the present invention
Used hydrocarbon feed can be the various raw materials that common hydrocracking is suitable among the present invention.Because the Hydrobon catalyst that the present invention uses has the saturated performance of good desulfurization, nitrogen and aromatic hydrocarbons, simultaneously again because the hydrocracking catalyst that the present invention uses has good anti-nitrogen ability (nitrogen content in the hydrocracking charging allows up to 150ppmw), thereby the present invention more is applicable to sulphur, the heavy raw oil that nitrogen content is high, for example boiling range do＞500 ℃, be generally 500～580 ℃, density is 0.8～0.93 gram per centimeter
3, nitrogen content can be up to the poor quality oil raw material of the heavy % in 1500ppmw, sulphur content ≯ 3.5, as normal pressure or vacuum gas oil, coker gas oil, mix slag catalytic cracking circulation wet goods.
In order to prolong the running period of catalyzer, the nitrogen content in the stock oil preferably is controlled at ≯ 1300ppmw, and sulphur content preferably is controlled at ≯ 3.0 heavy %, can guarantee that like this catalyzer is no less than 1 year the running period before regeneration.
(3) processing method provided by the invention and operational condition
The one-pass flow process of process using single hop provided by the invention is being loaded Hydrobon catalyst and hydrocracking catalyst with series system in the bed.
Specifically, this processing method is such: is 340～440 ℃ with hydrogen in hydrogen dividing potential drop 6.0～10.0MPa, best 6.5～9.5MPa, average reaction temperature with the heavy feed stock of sulfur-bearing, nitrogen and polycyclic aromatic hydrocarbons, best 350～420 ℃, stock liquid hourly space velocity LHSV0.1～3.0 o'clock
-1, best 0.2～1.0 o'clock
-1, hydrogen/oil volume is than 400～1200, contact with Hydrobon catalyst under best 600～1000 the condition.Hydrogen dividing potential drop wherein should account for 85% of stagnation pressure at least, and the raw material after refining need not isolated H
2S and NH
3, directly contact with hydrocracking catalyst according to above-mentioned reaction conditions with hydrogen.Reaction effluent enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and rich hydrogenous gas circulation is returned conversion zone.
The temperature of hydrofining and hydrocracking reaction can adopt cold hydrogen to control.
Hydrobon catalyst and hydrocracking catalyst can be seated in the same reactor, also can be seated in two placed in-line reactors, and its loadings separately can be adjusted its relative proportion according to the employing raw material properties.Raw materials quality is poor more, and the ratio that Hydrobon catalyst accounts for is also just big more.The admission space ratio of this two catalyzer can be adjusted in 25: 75～75: 25 scope.
If carbon residue, bituminous matter or metal content are higher in the raw material; for falling, the pressure that prevents beds reaches limit value too quickly; can before the hydrofining agent, add a certain amount of protective material with the running of assurance device long period ground; protectant add-on is generally 1～20% of Hydrobon catalyst volume, decides according to feedstock property.
Above-mentioned all processing condition are used in the ordinary course of things, it is not definitely immutable, according to raw materials used kind, different in kind, hope for the distribution difference of purpose product, different with the combination of technologies such as coking, catalytic cracking, catalytic reforming, steam cracking, it can be adjusted the demand that product is distributed to satisfy.
Processing method provided by the invention can be in a particular design, implement on the form device similar to existing middle pressure hydrocracking device, also can on existing medium-pressure hydrocracking refining plant, do the change of a little necessity, can implement as enlarging or increase reactor, increase fractionation plant etc.
Method provided by the invention has following characteristics and advantage:
1. having selected two kinds of special catalyst series connection uses, realized under middle pressure the high heavy of sulphur, nitrogen and aromaticity content and the processing of inferior raw material, can directly process nitrogen content and do stock oil more than 500 ℃ up to 1500ppmw, boiling range, the nitrogen content of hydrocracking charging allows up to 150ppmw, and this is that prior art institute is incomparable.
2. under the transformation efficiency of heavy or inferior raw material can the situation up to 80 body %, middle distillate oil product selectivity ≮ 50 body %, and good product quality, light naphthar fraction saturated hydrocarbon content height can be done ethylene raw; Heavy naphtha fraction nitrogen content＜0.5ppmw, virtue is dived high, is suitable for doing catalytic reforming raw material; Kerosene fraction aromaticity content is low, has good burning performance, and meets the rocket engine fuel specification; Fraction of diesel oil sulphur content＜0.05% reaches low-sulfur derv fuel oil specification; Tail oil fraction characterization factor＞12, aromatic hydrocarbons correlation index＜11, sulphur, nitrogen content are low, not only can do catalytically cracked material but also can make ethylene raw.
3. the selected and collocation of specific Hydrobon catalyst and hydrocracking catalyst has not only reduced the generation of coke, and has guaranteed that the stability of hydrocracking catalyst was not less than 1 year.
4. present method has the big advantage of other hydrocracking process production handiness equally, can with technology flexible combination such as coking, catalytic cracking, catalytic reforming and steam cracking, adjust products scheme as required.
5. the transformation that only needs existing medium-pressure hydrocracking refining plant slightly to be done a little necessity can be implemented the present invention.
Following example will give further instruction to the present invention, but not thereby limiting the invention.
Employed Hydrobon catalyst is to be that method described in 97112397.7 makes according to application number in the example.Specifically, that is: predecessor's hydrated aluminum oxide (Shandong Aluminum Plant's production) of the little porous aluminum oxide that will make with sodium metaaluminate-carbon dioxide process mixes according to 70: 30 weight ratios with predecessor's hydrated aluminum oxide (production of Chang Ling refinery catalyst plant) with the macroporous aluminium oxide that sodium metaaluminate-the Tai-Ace S 150 method makes, making circumscribed circle diameter is the trilobal cross bar of 1.4mm, dries back 550 ℃ of roastings 4 hours; Use NH then
4The F aqueous solution soaked 1 hour, dried back 500 ℃ of roastings 4 hours; Mixed aqueous solution with ammonium metawolframate and nickelous nitrate flooded 4 hours at last, dried back 480 ℃ of roastings 4 hours.This catalyst chemical consists of: NiO2.3 heavy %, WO
322.1 the Al of heavy % of heavy %, F4.1 and surplus
2O
3Carrier, this carrier A l
2O
3In the hole of 40～100A account for 84.5% of total pore volume.The specific surface of this catalyzer is 232 meters
2/ gram, pore volume are 0.31 milliliter/gram, and crushing strength is 23.1 Newton/millimeter.
Employed hydrocracking catalyst I and II are to be that method described in 97112396.9 makes according to application number in the example.Specifically, that is: be that acidity value is the Al of 0.7028 mmole/gram after the HY zeolite of 1.5672 mmole/grams and the roasting with acidity value
2O
3Predecessor's hydrated aluminum oxide mix according to certain weight ratio, making circumscribed circle diameter is the trilobal cross bar of 1.8mm, dries back 600 ℃ of roastings 4 hours; Burning the back acidity value then is the Al of 0.7028 mmole/gram
2O
3Predecessor's hydrated aluminum oxide mix according to certain weight ratio, making circumscribed circle diameter is the trilobal cross bar of 1.8mm, dries back 600 ℃ of roastings 4 hours; Use NH then
4The F aqueous solution soaked 1 hour, dried back 500 ℃ of roastings 4 hours; Mixed aqueous solution with ammonium metawolframate and nickelous nitrate flooded 4 hours at last, dried back 480 ℃ of roastings 4 hours.Catalyst I that makes and the composition of II and physico-chemical property are as follows:
Zeolite and hydration oxygen NiO, WO
3, F, specific surface, pore volume, crushing strength,
Change the heavy % rice of the heavy % of aluminium weight proportion %
210: 37 4.0 20.8 2.0 230 0.27 27.5 II of/gram milliliter/gram Newton/millimeter I 30: 37 4.6 19.0 2.1 242 0.22 31.0
Wherein used hydrated aluminum oxide prepares according to the CN85100218B disclosed method, that is: the aluminium isopropoxide that drips fusing in being heated to the ebullient isopropanol water solution carried out back flow reaction 6 hours, steam Virahol, add deionized water and wore out 16 hours for 80 ℃, 120 ℃ of oven dry of gained solid product are got final product.
Employed three kinds of stock oils in the example: the vacuum gas oil of matter crude oil in A-Saudi Arabia; B-China's intermediate base vacuum gas oil; The diesel oil of C-mix slag heavy oil fluid catalytic cracking gained and straight-run light gas oil are by the mixing oil of 69: 31 weight ratio gained, their character is all listed in down: stock oil numbering A B C boiling range, ℃ 299～553 267～532 204～402 density (20 ℃), g/cm
30.9235 0.8877 0.8425 carbon, heavy % 85.20 86.03 86.74 hydrogen, heavy % 11.61 12.98 13.13 sulphur, heavy % 3.10 0.66 0.07 nitrogen, ppm 898 1,300 548 alkali nitrogen, ppm 212 447 252 condensation points, ℃ 31 40 14 aniline points, ℃ 77.5 91.0 73.8 C
5Insolubles, heavy % 0.04 0.15-carbon residue
*, heavy % 0.23 0.10 0.05 viscosity (80 ℃), mm
2/ s 12.7 26.4 6.30 forms, heavy %
Alkane 18.2 69.2 41.4
Naphthenic hydrocarbon 26.5 29.4
Aromatic hydrocarbons 53.6 27.2 28.4
Colloid 1.7 3.6 0.8
*Electric furnace process records
Example 1
The explanation of this example the invention provides the enforcement of method when being raw material with Saudi Arabia's vacuum gas oil.
Process is to carry out on the middle-scale device of 0.4 liter, and operational condition is as follows: hydrogen dividing potential drop 9.6MPa, and stagnation pressure 11.3MPa, 383/380 ℃ of temperature of reaction (hydrofining/hydrocracking) is during liquid hourly space velocity 0.5
-1, hydrogen/oil volume is than 1000, and through the nitrogen content 25.3ppm of refining back end hydrogenation cracked charge, finishing agent is 50: 50 with the admission space ratio of cracking agent I, and two doses of filling cumulative volumes are 0.3 liter.What be converted into product below 350 ℃ is 63.7 body % by transformation efficiency once.The distribution and the character of products obtained therefrom are listed in table 1.
By table 1 data as can be known: the method for the invention provides can be under middle press strip spare changes into the light naphtha fraction of saturated hydrocarbon content up to 97 heavy % with the mink cell focus of high-sulfur, high aromaticity content; Nitrogen content＜0.5ppmw, virtue are dived up to the heavy naphtha fraction of 58 heavy %; Smoke point and aromatic hydrocarbons meet the kerosene(oil)fraction of rocket engine fuel specification; Sulphur content only is 21ppmw, condensation point-28 ℃, the diesel oil distillate of cetane value nearly 62; And the tail oil cut of characterization factor＞12, aromatic hydrocarbons correlation index＜11, sulphur content 23ppmw, nitrogen content 1.3ppmw.Boiling range is that the yield of 145～350 ℃ middle distillate oil reaches 46 heavy %, selectivity reaches 65.6 heavy %.
Table 1
| The cut scope, ℃ | ??＜65 | ??65～145 | ??145～260 | ???260～350 | ????＞350 |
| Product distributes, heavy % density (20 ℃), g/cm 3Sulphur, ppm nitrogen, the ppm stable hydrocarbon, heavy % virtue is dived, heavy % viscosity (20 ℃), mm 2/ S freezing point, ℃ condensation point, ℃ aromatic hydrocarbons, body % smoke point, the mm naphthalene is a hydrocarbon, body % cetane value characterization factor aromatic hydrocarbons correlation index | ??3.61 ??0.6546 ???- ??＜0.5 ??97.46 | ??20.57 ??0.7441 ???- ??＜0.5 ? ??58.59 | ????31.12 ????0.8042 ????9.2 ????0.8? ? ? ????1.7 ????＜-50 ? ????10.7 ????22.7 ????0.14 | ????14.98 ????0.8236 ????21 ????0.8 ? ? ????7.1 ? ????-28 ? ? ? ????61.8 | ????29.72 ????0.8359 ????23 ????1.3? ? ? ? ? ????39 ? ? ? ? ????12.85 ????10.4 |
Example 2
This example explanation the invention provides the enforcement of method when being raw material with China's intermediate base vacuum gas oil of high nitrogen-containing.
Reactor assembly, catalyst system therefor and filling ratio are with example 1.Operational condition is as follows: hydrogen dividing potential drop 6.4MPa, and stagnation pressure 7.5MPa, 391/384 ℃ of temperature of reaction (hydrofining/hydrocracking) is during liquid hourly space velocity 0.5
-1, hydrogen/oil volume is than 1000, and the nitrogen content through making with extra care the back end hydrogenation cracked charge is 46ppmw.What be converted into product below 350 ℃ is 55.9 body % by transformation efficiency once.The distribution and the character of products obtained therefrom are listed in table 2.
By table 2 data as can be known: the method for the invention provides can be under middle press strip spare changes into the mink cell focus of high nitrogen-containing and example 1 same high-quality various products.Boiling range is that the yield of 145～370 ℃ middle distillate oil reaches 46.7 heavy %, selectivity reaches 70.2 heavy %.
Table 2
| The cut scope, ℃ | ???＜65 | ??65～145 | ???145～215 | ??215～370 | ????＞370 |
| Product distributes, heavy % density (20 ℃), g/cm 3Sulphur, ppm nitrogen, the ppm stable hydrocarbon, heavy % virtue is dived, heavy % viscosity (20 ℃), mm 2/ S freezing point, ℃ condensation point, ℃ aromatic hydrocarbons, body % smoke point, the mm naphthalene is a hydrocarbon, body % cetane value characterization factor aromatic hydrocarbons correlation index | ???2.96? ? ? ???＜0.5 ???66.81 | ??16.85 ??0.7440 ? ??＜0.5 ? ??57.50 | ????18.26 ????0.8022 ????9.7 ????0.5? ? ? ????1.4 ????＜-50? ? ????16.0 ????20.7 ????＜1 | ????28.45 ????0.8266 ????29.6 ????1.0? ? ? ????5.1 ? ????-8 ? ? ? ????62.8 | ????33.48 ????0.8269 ????34 ????1.5? ? ? ? ? ????42? ? ? ? ? ????12.98 ????5.90 |
Example 3
This example explanation the invention provides the enforcement of method when being raw material with the diesel oil of mixing slag heavy oil fluid catalytic cracking gained and straight-run light gas oil by the mixing oil of 69: 31 weight ratios.
Reactor assembly is with example 1.Operational condition is as follows: hydrogen dividing potential drop 7.8MPa, and stagnation pressure 9.2MPa, 360/367 ℃ of temperature of reaction (hydrofining/hydrocracking) is during liquid hourly space velocity 0.85
-1, hydrogen/oil volume is than (hydrofining/hydrocracking) 807/1003, and finishing agent is 60: 40 with the admission space ratio of cracking agent II.What be converted into product below 350 ℃ is 77.0 body % by transformation efficiency once.The distribution and the character of products obtained therefrom are listed in table 3.
The invention provides method once more as can be known by table 3 data and can obtain various high-quality product under middle press strip spare, the yield of 145～350 ℃ of middle distillate oil reaches 67.8 heavy %, and selectivity reaches 75.4 heavy %.
Table 3
| The cut scope, ℃ | ????＜65 | ??65～145 | ??145～260 | ??260～350 | ????＞350 |
| Product distributes, heavy % density (20 ℃), g/ 3Sulphur, ppm nitrogen, the ppm stable hydrocarbon, heavy % virtue is dived, heavy % viscosity (20 ℃), mm 2/ S freezing point, ℃ condensation point, ℃ aromatic hydrocarbons, body % smoke point, mm cetane value characterization factor aromatic hydrocarbons correlation index | ????3.50 ????0.6494 ? ????＜0.5 ????99.52 | ????18.58 ????0.7265? ? ????＜0.5 ? ????48.87 | ????41.93 ????0.7920 ????4.5 ????＜0.5? ? ? ????2.0 ????-49? ? ????5.4 ????30? | ????25.91 ????0.7974 ????4.9 ????0.6? ? ? ????7.1? ? ????-8? ? ? ????＞75 | ????7.60 ????0.8117 ????4.5 ????4.1? ? ? ? ? ? ? ? ? ????12.95 ????3.6 |
Claims (10)
1. mink cell focus middle pressure hydrocracking method of producing middle distillate oil is characterized in that:
(1) heavy oil feed is that 6.0～10.0MPa, temperature are that 340～440 ℃, hydrogen/oil volume ratio are 400～1200, liquid hourly space velocity is 0.1～3.0 o'clock in the hydrogen dividing potential drop
-1Condition under contact with a kind of hydrocracking catalyst with a kind of Hydrobon catalyst successively and without intermediate section from, reacted effluent through cooling, separate, hydrogen-containing gas recycles, product liquid enters fractionating system;
(2) used Hydrobon catalyst consists of: 1～5 heavy %NiO, 12～35 heavy %WO
3, 1～9 heavy %F and surplus Al
2O
3, this Al
2O
3Be by one or more apertures Al
2O
3With one or more macropores Al
2O
3Be composited this aperture Al according to 75: 25～50: 50 weight ratios
2O
3The pore volume of median pore diameter＜80A accounts for total pore volume more than 95%, this macropore Al
2O
3The pore volume of median pore diameter 60～600A accounts for total pore volume more than 70%, and described pore volume is measured with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature;
(3) used hydrocracking catalyst consists of: 2.5～6.0 heavy %NiO, 10～38 heavy %WO
3, 0.5～5.0 heavy %F and balance carriers, this carrier is that the acidity value by 20～90 heavy % is the Al of 0.5～0.8 mmole/gram
2O
3With the acidity value of 10～80 heavy % be that the mesopore or the large pore zeolite of 1.0～2.0 mmole/grams formed, described acidity value is to use NH
3-TPD method records.
2. in accordance with the method for claim 1, wherein said heavy oil feed be boiling range do＞normal, vacuum gas oil, the coker gas oil of the heavy % in 500 ℃, nitrogen content ≯ 1500ppm, sulphur content ≯ 3.5, mix slag catalytic cracking turning oil.
3. in accordance with the method for claim 2, wherein the boiling range of said heavy oil feed to do be the heavy % in 500～580 ℃, nitrogen content ≯ 1300ppm, sulphur content ≯ 3.0.
4. in accordance with the method for claim 1, wherein said reaction conditions is: hydrogen dividing potential drop 6.5～9.5MPa, 350～420 ℃ of temperature, hydrogen/oil volume than 600～1000, liquid hourly space velocity 02～1.0 o'clock
-1
5. in accordance with the method for claim 1, wherein said Hydrobon catalyst is 25: 75～75: 25 with the admission space ratio of hydrocracking catalyst.
6. aperture and macropore Al in the wherein said Hydrobon catalyst in accordance with the method for claim 1,
2O
3Precursor be respectively a diaspore content greater than 60% with greater than 50% hydrated aluminum oxide.
7. wherein said hydrofining catalyst carrier Al in accordance with the method for claim 1,
2O
3Median pore diameter is that the pore volume of 40～100A accounts for more than 75% of total pore volume.
8. consisting of of said hydrocracking catalyst wherein in accordance with the method for claim 1: 2.6～5.0 heavy %NiO, 19～25 heavy %WO
3, 1.0～4.0 heavy %F and surplus carrier, this carrier is the Al by 50～80 heavy %
2O
3Form with mesopore or the large pore zeolite of 20～50 heavy %.
9. in accordance with the method for claim 1, mesopore in the wherein said carrier of hydrocracking catalyst or large pore zeolite are selected from the y-type zeolite and/or the mordenite of H type or RE type.
10. the Al in the wherein said carrier of hydrocracking catalyst in accordance with the method for claim 1,
2O
3Get through the roasting dehydration by one or more hydrated aluminum oxides that are selected from sodium metaaluminate-carbon dioxide process, sodium metaaluminate-Tai-Ace S 150 method, aluminum alkyls or the preparation of aluminum alkoxide hydrolysis method, diaspore content＞60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97112239A CN1045462C (en) | 1996-07-22 | 1997-07-17 | Middle-pressure hydrocracking process for heavy fractional oil |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109007 | 1996-07-22 | ||
| CN96109007.3 | 1996-07-22 | ||
| CN97112239A CN1045462C (en) | 1996-07-22 | 1997-07-17 | Middle-pressure hydrocracking process for heavy fractional oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1171430A true CN1171430A (en) | 1998-01-28 |
| CN1045462C CN1045462C (en) | 1999-10-06 |
Family
ID=25743982
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97112239A Expired - Lifetime CN1045462C (en) | 1996-07-22 | 1997-07-17 | Middle-pressure hydrocracking process for heavy fractional oil |
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| CN (1) | CN1045462C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072707C (en) * | 1998-12-16 | 2001-10-10 | 中国石油化工集团公司 | Medium pressure hydrocracking method |
| CN1088089C (en) * | 1999-10-13 | 2002-07-24 | 中国石油化工集团公司 | Process for hydrogenating raw material of hydrocarbon |
| CN100345945C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Two-stage hydrocracking method for increasing yield of middle distillate oil |
| CN100364668C (en) * | 2004-10-29 | 2008-01-30 | 中国石油化工股份有限公司 | Method for preparing surface modified IIB metal oxide hydrogenation catalyst |
| CN100381543C (en) * | 2004-10-29 | 2008-04-16 | 中国石油化工股份有限公司 | Hydrocracking method for composite catalyst bed layer |
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| CN101629098B (en) * | 2009-08-03 | 2012-12-26 | 中海石油炼化有限责任公司 | Hydrocracking equipment for high-acid-containing raw oil and hydrocracking method using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4572778A (en) * | 1984-01-19 | 1986-02-25 | Union Oil Company Of California | Hydroprocessing with a large pore catalyst |
| JPS62199687A (en) * | 1986-04-28 | 1987-09-03 | ユニオン・オイル・コンパニ−・オブ・カリフオルニア | Hydrogenation using catalyst having large pores |
| US4859312A (en) * | 1987-01-12 | 1989-08-22 | Chevron Research Company | Process for making middle distillates using a silicoaluminophosphate molecular sieve |
| GB8727777D0 (en) * | 1987-11-27 | 1987-12-31 | Shell Int Research | Heavy oil cracking process |
| US5089239A (en) * | 1989-04-18 | 1992-02-18 | Shin-Etsu Handotai Company Limited | Wire vibration prevention mechanism for a single crystal pulling apparatus |
| US5294330A (en) * | 1992-08-12 | 1994-03-15 | Mobil Oil Corp. | Hydrocracking process with a catalyst comprising MCM-36 |
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1997
- 1997-07-17 CN CN97112239A patent/CN1045462C/en not_active Expired - Lifetime
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| CN1072707C (en) * | 1998-12-16 | 2001-10-10 | 中国石油化工集团公司 | Medium pressure hydrocracking method |
| CN1088089C (en) * | 1999-10-13 | 2002-07-24 | 中国石油化工集团公司 | Process for hydrogenating raw material of hydrocarbon |
| CN100345945C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Two-stage hydrocracking method for increasing yield of middle distillate oil |
| CN100364668C (en) * | 2004-10-29 | 2008-01-30 | 中国石油化工股份有限公司 | Method for preparing surface modified IIB metal oxide hydrogenation catalyst |
| CN100381543C (en) * | 2004-10-29 | 2008-04-16 | 中国石油化工股份有限公司 | Hydrocracking method for composite catalyst bed layer |
| CN100439479C (en) * | 2005-10-24 | 2008-12-03 | 中国石油化工股份有限公司 | Combined processing method of faulty catalytic cracking diesel oil |
| CN101210195B (en) * | 2006-12-27 | 2012-05-30 | 中国石油化工股份有限公司 | Hydrocracking method for more producing chemical industry light oil from poor heavy raw material |
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| WO2013075850A1 (en) | 2011-11-22 | 2013-05-30 | Turkiye Petrol Rafinerileri A.S | A diesel production method and system |
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| CN1045462C (en) | 1999-10-06 |
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