CN100537720C - A kind of method for hydrogen cracking of voluminous intermediate oil - Google Patents
A kind of method for hydrogen cracking of voluminous intermediate oil Download PDFInfo
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Abstract
A kind of method for hydrogen cracking of voluminous intermediate oil, stock oil with react through Hydrobon catalyst and hydrocracking catalyst successively after hydrogen mixes, its resultant of reaction obtains naphtha fraction, intermediate oil and tail oil cut after cooling, separation and fractionation.Contain a kind of silica-alumina, a kind of y-type zeolite, at least a iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is selected from group VIII in the hydrocracking catalyst.The present invention can process the heavy distillate of high-sulfur, high nitrogen and high aromaticity content, under the demulcent reaction conditions, and intermediate oil that can be high-output qulified, wherein kerosene(oil)fraction sulphur content, aromaticity content are low, meet the rocket engine fuel specification; Sulphur content of diesel fraction, aromaticity content are low, and the cetane value height is the fine low-sulfur diesel fraction.
Description
Technical field
The invention belongs to a kind of is the cleavage method that obtains the low boiler cut hydrocarbon ils existing under the situation of hydrogen, and more particularly, the present invention is a kind of method for hydrogen cracking of voluminous intermediate oil.
Background technology
The crude oil of oil refining enterprise processing presents the trend of heaviness, poor qualityization day by day in the world wide, and social development has also been formulated more harsh specification standards from environmental angle to its quality product in kind and the continuous expansion of quantity demand to its product.Hydrocracking technology has that adaptability to raw material is strong, production decision flexibly and advantage such as good quality of product, be a kind of core processing means of heavy oil lighting.
In recent years, along with developing rapidly of diesel motor, market constantly increases the demand of high quality intermediate oil.Wherein the demand growth of diesel oil is fastest.This just needs to adjust the hydrocracking product and distributes, and meets the need of market, develop between the hydrocracking process of voluminous intermediate oil and suitable high reactivity thereof, senior middle school distillate optionally hydrocracking catalyst be effective solution.
US5464527 discloses a kind of method for hydrogen cracking of producing intermediate oil.This method adopts the higher hydrocracking catalyst of a kind of middle runnings selectivity, and this catalyzer contains the y-type zeolite and the nickel-tungsten metal component of decentralized sial, the processing of process rare earth ion exchanged.But the reaction conditions of this method is comparatively harsh, and reaction pressure is higher.
US6670295 discloses the method for hydrogen cracking of a kind of production high-quality rocket engine fuel and diesel oil.The carrier of the hydrocracking catalyst that this method adopts is made of modified zeolite of Y-type, modification zeolite beta, macroporous aluminium oxide, mesoporous aluminas and amorphous silicon aluminium, and adopting the hydrogenation activity component is nickel and tungsten.But this method reaction conditions is comparatively harsh, and reaction pressure is higher.
CN1072707C discloses a kind of middle pressure hydrocracking method of producing qualified boat product of coal.This method utilizes new hydrogen resource that the boat coal cut of middle pressure hydrocracking gained is carried out optionally deep hydrogenation saturated reaction on the middle pressure hydrocracking technology basis of routine, thereby makes the requirement that touches the mark of the quality of boat coal cut.This method intermediate oil selectivity is low.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method for hydrogen cracking of voluminous intermediate oil.
Method provided by the invention is: stock oil with react through Hydrobon catalyst and hydrocracking catalyst successively after hydrogen mixes, its resultant of reaction obtains naphtha fraction, intermediate oil and tail oil cut after cooling, separation and fractionation.Hydrocracking catalyst contains a kind of silica-alumina, a kind of y-type zeolite, at least a iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is selected from group VIII.
The present invention can process the heavy distillate of high-sulfur, high nitrogen and high aromaticity content, under the demulcent reaction conditions, and intermediate oil that can be high-output qulified, wherein kerosene(oil)fraction sulphur content, aromaticity content are low, meet the rocket engine fuel specification; Sulphur content of diesel fraction, aromaticity content are low, and the cetane value height is the fine low-sulfur diesel fraction.
Embodiment
Method provided by the invention comprises:
Stock oil mixes the back with hydrogen and contacts with Hydrobon catalyst, at hydrogen dividing potential drop 4.0～18.0MPa, and preferred 6.0～16.0MPa, 300～450 ℃ of temperature of reaction, preferred 340～400 ℃, hydrogen to oil volume ratio 300～1500Nm
3/ m
3, preferred 400～1200Nm
3/ m
3, volume space velocity 0.3～5.0h during liquid
-1, preferred 0.6～3.0h
-1Reaction conditions under, carry out hydrogenating desulfurization, hydrodenitrification and aromatic hydrocarbons saturated reaction.Resultant of reaction after the hydrofining directly contacts with hydrocracking catalyst without separating, at hydrogen dividing potential drop 4.0～18.0MPa, and preferred 6.0～16.0MPa, 350～450 ℃ of temperature of reaction, preferred 360～400 ℃, hydrogen to oil volume ratio 600～1500Nm
3/ m
3, preferred 700～1200Nm
3/ m
3, volume space velocity 0.3～5.0h during liquid
-1, preferred 0.6～3.0h
-1Reaction conditions under, carry out hydrocracking reaction.Resultant of reaction after the hydrocracking is after cooling, enter high-pressure separator and light pressure separator successively, isolated hydrogen rich stream is as the recycle hydrogen Returning reacting system, and isolated liquid phase stream enters fractionating system, obtains naphtha fraction, intermediate oil and tail oil cut after fractionation.All or part of tail oil cut Returning reacting system.
Stock oil of the present invention is any or several mixtures in atmospheric gas oil, vacuum gas oil, coker gas oil, heavy catalytic cycle oil, liquefied coal coil and the deasphalted oil.Stock oil can be sulphur content up to 30000 μ g/g, nitrogen content up to 2000 μ g/g, do and reach 560 ℃ poor heavy raw material.
The Hydrobon catalyst that uses among the present invention is a kind of VIB and/or VIII family non-precious metal catalyst that loads on the modified aluminas.The activity of such catalysts constituent element is the nickel of group VIII and the tungsten of group VIII, is benchmark with the catalyzer, and it consists of nickel oxide 1～5 heavy %, Tungsten oxide 99.999 12～35 heavy % and fluorine 1～9 heavy %.The carrier of catalyzer is composited according to the weight ratio of 75:25～50:50 for one or more little porous aluminum oxides and one or more macroporous aluminium oxides, to be bore dia account for the aluminum oxide of total pore volume more than 95% less than the pore volume of 80 dusts to wherein little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume of bore dia between 60～600 dusts accounts for the aluminum oxide of 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 volume in 40～100A hole 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 Hydrobon catalyst has higher desulfurization, denitrogenation and arene saturating activity.
The used hydrocracking catalyst of the present invention has higher anti-nitrogen ability and higher hydrogenation cracking activity, can process heavy, inferior raw material under mitigation reaction conditionss such as middle pressure.Contain a kind of silica-alumina, a kind of y-type zeolite, at least a iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is selected from group VIII in the hydrocracking catalyst.
Preferred hydrocracking catalyst composition and preparation method thereof is as follows:
The composition of this hydrocracking catalyst: with the catalyzer is benchmark, the content of silica-alumina is 15～70 heavy %, and the content of y-type zeolite is 1～55 heavy %, in oxide compound, the content of group VIII metal component is 2～8 heavy %, and the content of group vib metal component is 10～35 heavy %.
The preparation method of this hydrocracking catalyst is as follows:
(1) with the containing si molecular sieves or comprise that the composition that disordering contains si molecular sieves directly mixes of hydrated alumina and at least a disordering, obtain silica-alumina in 350～850 ℃ of roastings after 2～8 hours, its k value is 0.5～13A/ (cm
2G), said k=B/M
Sio2, B is the protonic acid amount of silica-alumina, M
Sio2Molar fraction for silicon oxide in the silica-alumina.B adopts Bio-RadIFS-3000 type determination of infrared spectroscopy; M
Sio2Calculate after adopting X fluorescent method [Yang Cuiding etc., petrochemical complex analytical procedure (RIPP test method), Science Press, 1990, P380] working sample to form.
(2) with the silica-alumina of step (1) gained and a kind of y-type zeolite mixing moulding, drying, 400～700 ℃ of roastings 1～8 hour under air again make carrier.
(3) carrier impregnation that step (2) is obtained after the drying, promptly obtained catalyst prod in 2～5 hours 400～650 ℃ of following roastings in containing at least a chosen from Fe, cobalt or nickel compound and at least a aqueous solution that is selected from molybdenum or tungsten compound.
The compound water solution of described cobalt, molybdenum, iron, nickel and tungsten can prepare according to a conventional method.The compound of cobalt, molybdenum, iron, nickel and tungsten is selected from one or more in their soluble compound respectively.The preferred ammonium molybdate of the compound of molybdenum wherein, one or more in the preferred ammonium tungstate of the compound of tungsten, ammonium metawolframate, ethyl ammonium metawolframate, the metatungstic acid nickel.The compound of iron, nickel and cobalt is preferably one or more in iron nitrate, nickelous nitrate, Xiao Suangu, iron(ic) chloride, nickelous chloride, cobalt chloride, basic carbonate iron, basic nickel carbonate, the cobaltous dihydroxycarbonate respectively.
Described aluminum oxide is selected from one or more the mixture among hibbsite, monohydrate alumina and the unformed aluminium hydroxide.Disordering contain silicon metal-aluminate, silicon-phosphorus-aluminate, faujusite, the ZSM series zeolite that si molecular sieves comprises disordering, be preferably a kind of and several in the ZSM series zeolite of the faujusite of disordering and disordering.The condition that the disordering molecular sieve should satisfy is: adopting XRD (X-ray diffraction method) when characterizing, is that 100% characteristic peak is a benchmark with original molecule sieve relative intensity, and the relative intensity that disordering contains this characteristic peak of si molecular sieves is below 15%.
Described y-type zeolite is selected from one or more in HY, USY, REY and the P-contained Y-zeolite.
Hydrobon catalyst is to fill in the same reactor with the form of connecting with hydrocracking catalyst, or fill in two or more independently reactors with the series connection form, the admission space of Hydrobon catalyst and hydrocracking catalyst is than being 30:70～70:30.The filling ratio of two kinds of catalyzer depends on the stock oil character of being processed, as foreign matter content, hydrocarbon compositions or the like such as the boiling range of stock oil, sulphur nitrogen, boiling range in the stock oil is heavy more, and foreign matter contents such as sulphur, nitrogen are high more, and the shared ratio of Hydrobon catalyst is just big more; In addition, also need to consider product is distributed and the requirement of quality product.
Cold hydrogen decanting point is all arranged between each beds that comprises Hydrobon catalyst bed and hydrocracking catalyst bed, come temperature of reaction and temperature rise are controlled with this.
If substances content such as the colloid in the device charging, bituminous matter, carbon residue and metal are higher, the very unsettled material of these character contacts with catalyzer, understand on first beds top green coke and caking apace, cause that bed and reactor pressure decrease rise.For falling, the pressure that prevents beds reaches the design limiting value too quickly; need load a certain amount of protective material in Hydrobon catalyst bed front; can the stable running of long period with assurance device; protectant loadings will be decided on the raw material oil properties, is generally 5～15% of Hydrobon catalyst cumulative volume.
Since no stripping measure between Hydrobon catalyst and the hydrocracking catalyst bed, the H that generates in the unifining process
2S and NH
3Enter the hydrocracking catalyst bed Deng impurity with the refining reaction product, H
2S can generate mercaptan with the olefine reaction that generates in the hydrocracking process.For the alkene that generates in the saturated hydrogenation crackate and remove H
2A small amount of mercaptan that S and olefine reaction generate improves the quality of products, and is effective means comparatively at the back of hydrocracking catalyst bed filling Hydrobon catalyst as the back finishing agent, and its loadings is generally 5～15% of hydrocracking catalyst cumulative volume.
The advantage of the inventive method is:
(1) the inventive method is depressed at other hydrogen branch of different pressures level and all can have been given play to high hydrogenation cracking activity and intermediate oil selectivity, all can process heavy, inferior raw material and highly selective and generate fine middle runnings in the high pressure range of the middle pressure scope of 6.0～12.0MPa and 12.0～18.0MPa.When once being 60 weight % by transformation efficiency, the ratio that intermediate oil (132～371 ℃ of boiling ranges) accounts for less than 371 ℃ of cuts can reach about 84 heavy %.
(2) the various quality product excellences that obtain of the present invention all have higher commodity value.As: naphtha fraction sulphur, nitrogen content＜0.5 μ g/g, arene underwater content〉50 heavy % are low-sulphur oil blend component or fine catalytic reforming raw material; Kerosene(oil)fraction sulphur content, aromaticity content are low, meet rocket engine fuel specification (GB6537-94, sulphur content in No. 3 rocket engine fuel standards＜2000 μ g/g, aromaticity content＜20 volume %); Sulphur content of diesel fraction＜20 μ g/g, the heavy % in total aromaticity content＜10, cetane value〉51, be the fine low-sulfur diesel fraction; Tail oil cut aromatic hydrocarbons correlation index (referring to the BMCI value)＜16, nitrogen content＜5 μ g/g is the fine catalytically cracked material, also is fine cracking ethylene preparation raw material.
(3) the inventive method production handiness is bigger, can carry out the production decision adjustment according to different product demands, as production diesel oil scheme, production tail oil scheme, production industrial chemicals scheme etc.
The following examples will give further instruction to present method, but therefore not limit present method.
The used hydrocracking catalyst C preparation method of embodiment is as follows:
1. be to soak 1 hour in 1.0 moles ammonium chloride (Beijing Chemical Plant's production) aqueous solution NaY type zeolite (production of Chang Ling catalyst plant) in concentration, after filtration, after washing and the drying, 550 ℃ of following roastings 4 hours.Behind twice of the repetition said process, it is in 0.2 mole Neutral ammonium fluoride (Beijing Chemical Plant's production) aqueous solution after 1 hour that resulting y-type zeolite is immersed in concentration, filter, wash and drying, after 4 hours, obtain the siliceous molecular sieve-4 A of disordering (the X ray diffracting characteristic peak of A disappears) through 600 ℃ of following roastings.
2. the siliceous molecular sieve-4 A of disordering and SB powder (diaspore that German Condea company produces) are mixed, add behind the water normal temperature stirring 30 minutes down, 550 ℃ of following roastings 4 hours, obtain silica-alumina B behind the filtration drying.
3. silica-alumina B and USY type zeolite (production of Chang Ling catalyst plant) are mixed, warp mixes and pinches, extrusion, makes three leaf stripe shapes.Extrudate 120 ℃ of oven dry down, again in 500 ℃ of following roastings 4 hours, is obtained carrier.
With carrier impregnation in the aqueous solution of ammonium metawolframate for preparing (Beijing Chemical Plant) and nickelous nitrate (Beijing Chemical Plant), flooded 4 hours, 120 ℃ of dryings 4 hours,, obtain hydrocracking catalyst C then 480 ℃ of following roastings 4 hours.
The composition of obtained catalyzer C: with the total catalyst weight is benchmark, silica-alumina 21.9 heavy %, and USY zeolite 50 heavy %, nickel oxide 5.6 heavy %, Tungsten oxide 99.999 22.5 heavy %, wherein the k value of silica-alumina is 6.4A/ (cm
2G).
The Hydrobon catalyst trade names of using among the embodiment are RN-10, for Sinopec catalyzer branch office Chang Ling catalyst plant is produced.
Embodiment 1
With a kind of vacuum gas oil is stock oil A, and its main raw material character is as shown in table 1.The sulphur content of stock oil A is up to 24400 μ g/g as can be seen from Table 1, and nitrogen content is 1000 μ g/g, is heavy distillate inferior.Stock oil A with react through Hydrobon catalyst and hydrocracking catalyst C successively after hydrogen mixes, its resultant of reaction is after cooling, separation and fractionation, obtain naphtha fraction, intermediate oil and tail oil cut, reaction conditions and product yield are listed in table 2, and the product main character is listed in table 3.As can be seen from Table 2, be under the demulcent reaction conditions of 8.0MPa in the hydrogen dividing potential drop, when once being 60 weight % by transformation efficiency, the intermediate oil selectivity is up to 84.36 heavy %.As can be seen from Table 3, the sulphur of naphtha fraction, nitrogen content all＜0.5 μ g/g, it is 55.3 heavy % that virtue is dived, be fine low-sulphur oil blend component also be the fine catalytic reforming raw material; The sulphur content of kerosene(oil)fraction＜10 μ g/g, aromaticity content is 5.1 volume %, meets the rocket engine fuel specification; The sulphur content of diesel oil＜20 μ g/g, total aromaticity content are 9.6 heavy %, and cetane value is 52, is the fine low-sulfur diesel fraction; The BMCI value of tail oil cut is 14.2, is fine catalytically cracked material or fine cracking ethylene preparation raw material.
Embodiment 2
With a kind of vacuum gas oil is stock oil B, and its main raw material character is as shown in table 1.The sulphur content of stock oil B is 11000 μ g/g as can be seen from Table 1, and nitrogen content is heavy distillates inferior up to 1700 μ g/g.Stock oil B with react through Hydrobon catalyst and hydrocracking catalyst C successively after hydrogen mixes, its resultant of reaction is after cooling, separation and fractionation, obtain naphtha fraction, intermediate oil and tail oil cut, reaction conditions and product yield are listed in table 2, and the product main character is listed in table 3.As can be seen from Table 2, when the hydrogen dividing potential drop was 14.5MPa, when once being 50.3 weight % by transformation efficiency, the intermediate oil selectivity was up to 85.6 heavy %.As can be seen from Table 3, the sulphur of naphtha fraction, nitrogen content all＜0.5 μ g/g, it is 50.1 heavy % that virtue is dived, be fine low-sulphur oil blend component also be the fine catalytic reforming raw material; The sulphur content of kerosene(oil)fraction＜10 μ g/g, aromaticity content is 4.2 volume %, meets the rocket engine fuel specification; The sulphur content of diesel oil＜20 μ g/g, aromaticity content are 2.7 heavy %, and cetane value is 51, is the fine low-sulfur diesel fraction; The BMCI value of tail oil cut is 13.6, is fine catalytically cracked material or fine cracking ethylene preparation raw material.
Table 1
| Stock oil | A | B |
| Density, g/cm 3 | 0.9069 | 0.9089 |
| Boiling range, ℃ | 232～545 | 250～556 |
| Sulphur content, μ g/g | 24400 | 11000 |
| Nitrogen content, μ g/g | 1000 | 1700 |
| Carbon residue, heavy % | 0.12 | 0.18 |
| Group composition, heavy % | ||
| Stable hydrocarbon | 66.6 | 72.2 |
| Aromatic hydrocarbons | 29.7 | 23.6 |
| Colloid | 3.7 | 4.2 |
Table 2
| Numbering | Embodiment 1 | Embodiment 2 |
| Stock oil | A | B |
| Reaction conditions | ||
| The hydrogen dividing potential drop, MPa | 8.0 | 14.5 |
| Temperature of reaction, ℃ | 380.0/375.9 | 380.0/380.0 |
| Volume space velocity during liquid, h -1 | 1.5 | 1.2 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 800 | 800 |
| Transformation efficiency, heavy % | 60 | 50.3 |
| Product distributes, heavy % | ||
| <65℃ | 2.52 | 1.57 |
| 65～135℃ | 10.35 | 7.60 |
| 135～260℃ | 29.42 | 24.03 |
| 260～370℃ | 28.90 | 26.06 |
| >370℃ | 28.81 | 40.74 |
| The intermediate oil selectivity, heavy % | 84.36 | 85.60 |
Table 3
| Numbering | Embodiment 1 | Embodiment 2 |
| Stock oil | A | B |
| The product main character | ||
| Naphtha fraction | ||
| Sulphur content, μ g/g | <0.5 | <0.5 |
| Nitrogen content, μ g/g | <0.5 | <0.5 |
| Virtue is dived, heavy % | 55.3 | 50.1 |
| Kerosene(oil)fraction | ||
| Sulphur content, μ g/g | <10 | <10 |
| Aromaticity content, heavy % | 5.1 | 4.2 |
| Diesel oil distillate | ||
| Sulphur content, μ g/g | <20 | <20 |
| Aromaticity content, heavy % | 9.6 | 2.7 |
| Cetane value | 52 | 51 |
| The tail oil cut | ||
| Nitrogen content, μ g/g | <5 | <5 |
| The BMCI value | 14.2 | 13.6 |
Claims (8)
1, a kind of method for hydrogen cracking of voluminous intermediate oil, stock oil with react through Hydrobon catalyst and hydrocracking catalyst successively after hydrogen mixes, its resultant of reaction is after cooling, separation and fractionation, obtain naphtha fraction, intermediate oil and tail oil cut, it is characterized in that hydrocracking catalyst contains a kind of silica-alumina, a kind of y-type zeolite, at least a iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is selected from group VIII, all or part of tail oil cut Returning reacting system.
2, in accordance with the method for claim 1, it is characterized in that described hydrocracking catalyst, with the catalyzer be benchmark its consist of: the content of silica-alumina is 15～70 heavy %, the content of y-type zeolite is 1～55 heavy %, in oxide compound, the content of group VIII metal component is 2～8 heavy %, and the content of group vib metal component is 10～35 heavy %.
3, according to claim 1 or 2 described methods, it is characterized in that described silica-alumina containing si molecular sieves or comprising that the composition that disordering contains si molecular sieves directly mixes by hydrated alumina and at least a disordering, obtained in 2～8 hours in 350～850 ℃ of roastings, its k value is 0.5～13A/ (cm
2G); Said k=B/M
Sio2, B is the protonic acid amount of silica-alumina, M
Sio2Molar fraction for silicon oxide in the silica-alumina.
4,, it is characterized in that described y-type zeolite is selected from one or more in HY, USY, REY and the P-contained Y-zeolite according to claim 1 or 2 described methods.
5, in accordance with the method for claim 1, it is characterized in that described stock oil is any or several mixtures in atmospheric gas oil, vacuum gas oil, coker gas oil, heavy catalytic cycle oil, liquefied coal coil and the deasphalted oil.
6, in accordance with the method for claim 1, it is characterized in that described hydrofining reaction condition is: hydrogen dividing potential drop 4.0～18.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～1500Nm
3/ m
3, volume space velocity 0.3～5.0h during liquid
-1The hydrocracking reaction condition is: hydrogen dividing potential drop 4.0～18.0MPa, 350～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 600～1500Nm
3/ m
3, volume space velocity 0.3～5.0h during liquid
-1
7,, it is characterized in that described hydrofining reaction condition is: hydrogen dividing potential drop 6.0～16.0MPa, 340～400 ℃ of temperature of reaction, hydrogen to oil volume ratio 400～1200Nm according to claim 1 or 6 described methods
3/ m
3, volume space velocity 0.6～3.0h during liquid
-1The hydrocracking reaction condition is: hydrogen dividing potential drop 6.0～16.0MPa, 360～400 ℃ of temperature of reaction, hydrogen to oil volume ratio 700～1200Nm
3/ m
3, volume space velocity 0.6～3.0h during liquid
-1
8, in accordance with the method for claim 1, it is characterized in that described Hydrobon catalyst and hydrocracking catalyst are to fill in the same reactor with the form of connecting, or fill in two or more independently reactors with the series connection form, the admission space of Hydrobon catalyst and hydrocracking catalyst is than being 30:70～70:30.
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| CN101733151B (en) * | 2008-11-20 | 2013-01-09 | 中国石油化工股份有限公司 | Distillate oil hydrorefining catalyst |
| CN102839019B (en) * | 2011-06-23 | 2015-05-20 | 中国石油化工股份有限公司 | Hydrogenation method for production of high quality middle distillate oil |
| CN103102966B (en) * | 2011-11-10 | 2015-07-22 | 中国石油化工股份有限公司 | High nitrogen raw material hydrocracking method |
| CN105542851B (en) * | 2014-10-29 | 2017-05-24 | 中国石油化工股份有限公司 | Aviation kerosene production method |
| CN109718834B (en) * | 2017-10-30 | 2022-03-11 | 中国石油化工股份有限公司 | Modified molecular sieve and preparation method and application thereof |
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| Title |
|---|
| 多产中间馏分油的中压加氢裂化技术的开发. 石亚华，石玉林，聂红，李大东.石油炼制与化工，第VOL.31卷第NO.11期. 2000 |
| 多产中间馏分油的中压加氢裂化技术的开发. 石亚华，石玉林，聂红，李大东.石油炼制与化工，第VOL.31卷第NO.11期. 2000 * |
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