CN1508230A - Hydrocracking process for producing clean product - Google Patents
Hydrocracking process for producing clean product Download PDFInfo
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- CN1508230A CN1508230A CNA021449554A CN02144955A CN1508230A CN 1508230 A CN1508230 A CN 1508230A CN A021449554 A CNA021449554 A CN A021449554A CN 02144955 A CN02144955 A CN 02144955A CN 1508230 A CN1508230 A CN 1508230A
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Abstract
The invention provides a trans-form once-through hydrocracking technique to produce clean hydrocracking product. Its character: adopting first-cracking after-refining flow, adopting once-through operating mode, and make raw material contact at least two grades of catalyzer to produce clean medium fractional oil and high-quality tail oil. Within the hydrocracking segment, it uses unformed hydrocracking catalyst or anti-nitrogen zeolite hydrocracking catalyst. It makes full use of double-functional catalyst within the hydrocracking segment, reduces the load for the hydrocracking catalyst, and improves the utilization ratio of the equipment.
Description
Technical field
The present invention relates to a kind of hydrocracking process of producing cleaning product, particularly adopt the once-through operation mode, produce the hydrocracking process that cleans intermediate oil and charging is provided for downstream unit.
Background technology
The density that present refinery is processed raw material is more and more heavier, and quality worse and worse.Refinery's crude oil average relative density in the world's rises to more than 0.86 at present, and sulphur content rises to more than the 1.6wt%, and other foreign matter contents in the crude oil (Fe, V, Ni etc.) are also in rising trend in addition.Secondly, in the face of the poor qualityization of raw material, the specification of quality of motor spirits such as vapour, coal, bavin is but being improved, the environmental protection restriction is strict more.In this case, the diesel oil that obtained of FCC technology can not satisfy specification of quality.Hydrocracking is a kind of main oil refining processing means of handling poor heavy raw material, improving quality product, hydrocracking not only has the raw material processing flexibility, and has a handiness in the production, adopt different operating procedures, hydrocracking process can obtain high-quality power fuel and industrial chemicals.
Hydrocracking is a kind of important refining of petroleum means, and after the hydrogen source of cheapness was resolved, hydrocracking technology was developed rapidly.The relevant manufacturer of in the world each has developed many hydrocracking technologies, integrates, and its technology generally can be divided into one-stage process and two-stage method.Operating method mainly can be divided into cyclical operation and once-through operation.So-called recycle to extinction mode is that maximum obtains intermediate oil by hydrocracking reactor is squeezed in unconverted tail oil circulation, One-through design is that unconverted tail oil is got rid of raw material as downstream unit outward, and unconverted generally speaking tail oil is mainly as the charging of lubricant base and preparing ethylene by steam cracking.
Specific technology and operating method thereof all have supporting special-purpose catalyst.Nobel metal hydrogen cracking catalyst is owing to the sulphur in the stock oil, nitrogen sensitivity, generally be used for two-stage method; And non-noble metal hydrocracking catalyst is widely used in the one-stage process technology except adopting the two-stage method, according to the characteristics at acidity of catalyst cracking center or the difference of anti-nitrogen poisoning performance, can be divided into one-stage serial or single hop technology again.Compare with two-stage process, do not establish gas in the middle of refining exactly section of so-called one-stage serial technology and the cracking zone and mention fractionating system; So-called single hop technology, the single hop list agent technology of saying so exactly is exactly no pre-refining section and have only the hydrocracking section in the flow process.
Hydrocracking catalyst is a kind of dual-function catalyst, promptly has hydrogenating function and has the cracking function again, so can produce clean fuel.On technology, because amorphous type hydrocracking catalyst acidic cleavage central characteristics can adapt to high nitrogen charging, thereby generally be used for single hop list agent technology more, shortcoming is the temperature of reaction height, generally more than 410 ℃.The amorphous type catalyzer is used for single hop list agent technology, generally to produce wide cut diesel fuel.The use of zeolite in hydrocracking catalyst is a qualitative leap of hydrocracking technology, it has changed the shortcoming that amorphous type hydrocracking catalyst activity was low in the past, running period is short, make the stability of catalyzer and life-span better and the flexibility of operation of catalyzer is strengthened, therefore present most hydrocracking full scale plant all uses the catalyzer that contains zeolite.The hydrocracking catalyst that contains zeolite component is easy to the nitrogen poisoning and deactivation, for making the cracking catalyst steady running, generally need under refining section Hydrobon catalyst cooperates cracking zone feed nitrogen content be reduced to below the 10ug/g.Above-mentioned two kinds of technologies in fact all can be described as single hop technology, and just for zeolite catalyst, the use Hydrobon catalyst of generally will connecting is called one-stage serial technology, with the single hop list agent technology formation difference of amorphous type catalyzer.
Along with the appearance and the enforcement of new environmental regulation, the oil fuel quality index is harsh day by day.In this case, when hydrocracking is being handled raw material very inferior when mixing the high aromatic hydrocarbons VGO of burnt wax CGO of high nitrogen or high-sulfur heavy recycle stock HCO, the rocket engine fuel smoke point of producing is lower, and aromatic content of diesel oil and sulphur content do not reach the quality index of low-sulfur diesel-oil yet.This problem is more outstanding on the SSOT technology of single hop list agent.Even adopt the single hop tandem process, when handling raw material very inferior, the product that is obtained still needs to re-refine, and this just needs to increase production units such as reactor, has improved production cost.The second stage reactor of two-stage method generally uses noble metal catalyst, have well to take off the aromatic hydrocarbons effect, but it has requirement to feed sulfur, nitrogen, so equipment and running cost is than higher, simultaneously neither be fine to the adaptability of raw material.
US4857169 has provided typical two-stage method hydrocracking process.US4990243 discloses a kind of multi-layer catalyst system, comprises the Ni-Mo-P/Al of the first layer
2O
3Or Co-Mo-P/Al
2O
3The Ni-W-P/Si-Al-zeolite of the denitrification catalyst and the second layer or Ni-Mo-P/Si-Al-zeolitic cracking catalyst.This is a normal sequence " hydrofining+hydrocracking " one-stage serial technology.US5593570 discloses a mixed hydrogenation process, and it is that hydrogenating desulfurization and/or hydrodenitrogenation catalyst and hydrocracking catalyst are mixed, thus hydrofining and hydrocracking process with become a dual-function catalyst system together.These technologies are all underused the difunctional of hydrocracking catalyst, and the overall performance of technology needs further to improve.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of produce cleaning hydrocracking product once pass through hydrocracking process, be used for the hydrocracking process treatment of heavy hydrocarbon material, technology of the present invention can obtain the high-quality clean fuel, and tail oil is a fine cracking of ethylene raw material.
Hydrocracking process of the present invention comprises: under hydrocracking condition, adopt the one-stage serial hydrocracking technical process, in the presence of hydrogen with the petroleum hydrocarbon material with 0.4-2.0hr
-1Volume space velocity earlier with after hydrocracking catalyst contacts, again with 1.0-6hr
-1Volume empty contact with Hydrobon catalyst, product passes through separation and obtains oil fuel and tail oil.
The hydrocracking catalyst that the present invention uses comprises amorphous type hydrocracking catalyst or high anti-nitrogen zeolite type hydrocracking catalyst, two kinds of catalyzer can use separately or be used, as material elder generation process amorphous type hydrocracking catalyst, and then by the zeolite type hydrocracking catalyst.
The amorphous type hydrocracking catalyst, its composition comprises: wherein amorphous type hydrocracking catalyst composition comprises: (a) acid sial 35-75wt%; (c) aperture aluminum oxide 10-30wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%.Wherein acid invisible sial has following feature: SiO
2Content is 20～60%, specific surface 350-600m
2/ g, pore volume 0.9～1.5ml/g, infrared acidity 0.30-0.60mmol/g.Pore volume 0.4～the 0.8ml/g of above-mentioned little porous aluminum oxide, specific surface 150～300m
2/ g.
The zeolite type hydrocracking catalyst, its composition comprises: (a) Y zeolite 1-15wt%; (b) macropore refractory oxide 10-65wt%; (c) aperture aluminum oxide 0-30wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%.Wherein Y zeolite has following feature: SiO
2/ Al
2O
3Mol ratio is 5-20, and the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume, specific surface 500-750m
2/ g, infrared acidity 0.25-0.50mmol/g, Na
2O content＜0.2wt%.Above-mentioned macropore refractory oxide mainly comprises macroporous aluminium oxide (pore volume 0.8～1.5ml/g, specific surface 300～500m
2/ g), macropore sial (pore volume 0.8～1.5ml/g, specific surface 350～600m
2/ g, silica weight content 20%～60%) etc., the pore volume 0.4～0.8ml/g of little porous aluminum oxide, specific surface 150～300m
2/ g.
Above-mentioned group vib metal oxide mainly comprises the oxide compound of tungsten or molybdenum, and the VIII metal oxide mainly comprises the oxide compound of cobalt or nickel.
(technological process is the cracking of first hydrofining back end hydrogenation to trans one-stage serial hydrocracking technology of the present invention usually, therefore flow process of the present invention is called " trans "), it is purified hydrocracking process flow process after the first cracking, it is based on hydrocracking catalyst is a kind of dual-function catalyst, has hydrogenation and cracking function concurrently.This trans flow process has been utilized the hydrogenation performance of catalyzer on the one hand more, on the other hand the lightweight cracking product of saturated, the certain desulfurization nitrogen of hydrogenation decreasing ratio is carried out hydrofining and will obtain better hydrofining effect, use less catalyst for refining can reach the deep refining effect, just be equivalent to improve the processing power of device.Need to prove that refining section has essence different after this trans arrangement and the traditional hydrocracking: this processing arrangement of the present invention is for the middle distillates oil selectivity that improves device and or meets the more high-quality hydrocracking product of cleaning of environmental protection standard on the purpose.Simultaneously, owing to utilized the hydrogenation performance of hydrocracking catalyst, thereby the loadings that not only can reduce Hydrobon catalyst to a certain extent corresponding increase hydrocracking catalyst loadings also improves the cracking processing power of device, and this flow arrangement and selection of catalysts thereof will help to improve from technology the middle distillates oil selectivity and the quality product of whole device.In addition, raw materials technology oil adaptability of the present invention is strong, can handle charging more inferior, produces clean fuel.
Embodiment
The handled petroleum hydrocarbon material of hydrocracking process is boiling range 200-600 ℃ best 250-550 ℃ a heavy crude hydrocarbon material, for example gas oil, vacuum gas oil (VGO), take off pitch prill oil, catalytic cracking turning oil, shale oil, coal tar wet goods.Below 370 ℃, preferably the cut of 60-80w% is below 370 ℃ through the cut of the product 40-90w% after the cracking.The per pass conversion of technology is at 50-80w%.
The volume space velocity of hydrocracking catalyst is generally 0.4-2.0hr in the trans one-stage serial hydrocracking technology that the present invention relates to
-1, best 0.5-1.5hr
-1The volume space velocity of the use of Hydrobon catalyst is general 1.0-6.0hr
-1, best 1.5-3.0hr
-1
Hydrocracking condition is the usual terms of this area,, stock oil is contacted system response pressure 5～20MPa, hydrogen-oil ratio 100～5000,360～440 ℃ of cracking zone temperature of reaction as in the presence of hydrogen with catalyzer.Hydrocracking catalyst of the present invention is used for the oil type hydrocracking process, be particularly suitable for treatment of heavy hydrocarbon material, the boiling range scope of heavy hydrocarbon material is at 200-600 ℃, generally at 250-550 ℃, hydrocracking catalyst of the present invention is when handling common VGO, reaction conditions is pressure 7～18MPa preferably, hydrogen-oil ratio 500～2500,380～400 ℃ of cracking zone temperature of reaction.Actual conditions can be adjusted according to this area general knowledge according to feedstock property and product requirement.
Hydrobon catalyst involved in the present invention is a kind of conventional non-noble metal hydrogenation catalyst for refining, 3936,3996 Hydrobon catalysts of producing as the Fushun Petrochemical Company catalyst plant etc.
For the requirement of hydrocracking catalyst, hydrocracking catalyst can use a kind of single amorphous type hydrocracking catalyst or a kind of single zeolite type hydrocracking catalyst in the trans one-stage serial hydrocracking technology that the present invention relates to; Also can be that two kinds of hydrocracking catalysts mix or grating is used, on the contrary comprise the mechanically mixing filling, successively load amorphous type and zeolite type hydrocracking catalyst or.But no matter use the sort of catalyzer or use which kind of catalyst combination loading mode, the hydrocracking catalyst of selection must have high anti-nitrogen/anti-nitrogen ability.Amorphous type hydrocracking catalyst itself just is to use under single hop list agent technology; The zeolite type hydrocracking catalyst is that certain range of choice is arranged.Usually, the employed zeolite component content of the so high anti-nitrogen/zeolite type of anti-nitrogen hydrocracking catalyst is lower, and acidity is also lower, and Y zeolite is used more generally.
A kind of modification processing method of the Y zeolite of the anti-nitrogen of above-mentioned height/anti-nitrogen ability is: with Na
2O content is raw material less than the Y zeolite of 3.0wt%, places the high-temperature roasting stove, at self water vapor or feed water vapor, and 450-600 ℃, under the 0.01-0.2MPa pressure water steam roasting 0.5-3.0 hour.Carry out ion-exchange techniques then and make Na
2O content is less than the Y zeolite of 0.2wt%.Na with above-mentioned preparation
2O content places the high-temperature roasting stove less than the Y zeolite of 0.2wt%, in self water vapor or feeding water vapor, 550-700 ℃, 0.01
-1.0MPa pressure water steam was handled 0.5-10 hour down, promptly got SiO
2/ Al
2O
3Mol ratio is the super-hydrophobic Y zeolite of 5.2-6.0.The above-mentioned super-hydrophobic Y zeolite that obtains with chemical process dealuminzation optionally, can be got SiO
2/ Al
2O
3Mol ratio is the super-hydrophobic Y zeolite of 5-20.The Y zeolite that aforesaid method is handled has lower acidity, and select suitable content to cooperate with other carrier component, make it on catalyzer, have moderate acid site density, the catalyzer coking inactivation of avoiding the multidigit condensation reaction of intensive strong acid center to cause, with suitable hydrogenation active centre synergy, therefore has stronger anti-nitrogen performance simultaneously.
Catalyzer air speed and other concrete processing condition can be determined according to main character, treatment capacity and the requirement of purpose product quality indicator of raw material according to this area general knowledge.For example, cracking burden requirement height or difficult cracked material should use more hydrocracking catalyst, should use more Hydrobon catalyst when high or difficult raw material that removes of processing sulphur nitrogen content or target level of product quality are demanding.In addition, above-mentioned reactor useful volume size, different catalysts bed size can design according to the use air speed of catalyzer and arrange, for existing apparatus, can satisfy the air speed service requirements of catalyzer by different beds or same bed loaded catalyst or level mixing ratio.
The present invention is trans can be an independent big reactor by the related reactor of hydrocracking method once: in superincumbent several beds of hydrocracking catalyst filling, Hydrobon catalyst is seated in the cracking case lower bed layer.The present invention is trans once also can to comprise at least two reactors by the related reactor of hydrocracking method: hydrocracking catalyst is seated in a hydrocracking reactor at least, and Hydrobon catalyst is seated in independent hydrofining reactor.
The operating method of one-stage serial technology mainly can be divided into recycle to extinction and once pass through in industrial production, the trans one-stage serial hydrocracking process using that the present invention relates to be that the once-through operation mode is produced, purpose is except obtaining intermediate oil, also for downstream unit provides the high-quality charging, for example charging of preparing ethylene by steam cracking.The trans one-stage serial hydrocracking processing arrangement that the present invention relates to is except obtaining the cleaning intermediate oil, because the result of deep refining, when the tail oil that obtains is used to produce the lubricant base raw material, even can directly use the isomerization dewaxing that carries out to the noble metal catalyst of sulfur sensitive.
Embodiment
This process program is handled a kind of heavy distillate: the wax tailings CGO of 90% heavy vacuum distillate VGO blending 10%, this petroleum hydrocarbon material main character is: proportion 0.9045cm
3/ g, 350 ℃-565 ℃ of boiling ranges, carbon residue 0.40wt%, sulphur 2.06wt%, nitrogen 2226 μ g/g.
This process program operational condition: reaction pressure 15MPa, hydrogen-oil ratio 1200 adopts the once-through operation mode, control per pass conversion 70wt%.It is to obtain divided by the liquid yield that has transformed (100 deduct tail oil) by intermediate oil (rocket engine fuel and/or diesel oil distillate) yield that middle distillates oil selectivity calculates.
Hydrobon catalyst is 3936 Hydrobon catalysts that Fushun petrochemical corporation (complex) catalyst plant is produced.Refining section medial temperature is 370 ℃.
Hydrocracking catalyst A:
The amorphous silicon Al catalysts consists of: (a) acid amorphous aluminum silicide 40wt%; (b) aperture aluminum oxide 25wt%; (c) Tungsten oxide 99.999 26wt%; (d) nickel oxide 9wt%.Wherein acid invisible sial has following feature: SiO
2Content is 45%, specific surface 480m
2/ g, pore volume 1.0ml/g, infrared acidity 0.55mmol/g.The pore volume 0.4ml/g of little porous aluminum oxide, specific surface 240m
2/ g.
Hydrocracking catalyst B:
The amorphous silicon catalyzer consists of: (a) acid amorphous aluminum silicide 60wt%; (b) aperture aluminum oxide 10wt%; (c) Tungsten oxide 99.999 21wt%; (d) nickel oxide 9wt%.Wherein acid invisible sial has following feature: SiO
2Content is 35%, specific surface 450m
2/ g, pore volume 1.1ml/g, infrared acidity 0.45mmol/g.The pore volume 0.4ml/g of little porous aluminum oxide, specific surface 240m
2/ g.
Hydrocracking catalyst C:
Y zeolite type hydrocracking catalyst consists of: Y zeolite 12wt%, sial (specific surface 520m
2/ g, SiO
235wt%, pore volume 1.2ml/g) 33wt%, little porous aluminum oxide (specific surface 240m
2/ g, pore volume 0.4ml/g) 25wt%, nickel oxide 8wt%, Tungsten oxide 99.999 22wt%.
Y zeolite modifying process wherein is as follows: with Na
2O content is less than the SiO of 3.0wt%
2/ Al
2O
3Be that 5 Y zeolite is a raw material, place the high-temperature roasting stove, feed water vapour, 580 ℃, roasting is 2.0 hours under the 0.12MPa pressure water steam.Carry out ion-exchange techniques then and make Na
2O content is less than the Y zeolite of 0.2wt%.Na with above-mentioned preparation
2O content places the high-temperature roasting stove less than the Y zeolite of 0.2wt%, is feeding water vapour, and 600 ℃, 0.4MPa pressure water steam was handled 3.0 hours down, got super-hydrophobic Y zeolite.With the above-mentioned super-hydrophobic Y zeolite concentration that obtains is the nitric acid treatment of 1.0mol/L, obtains SiO
2/ Al
2O
3Mol ratio is 18 super-hydrophobic Y zeolite.The secondary pore pore volume that obtains Y zeolite 2～10nm accounts for 45% of total pore volume, specific surface 705m
2/ g, infrared acidity 0.28mmol/g.
Hydrocracking catalyst D:
C is identical with catalyzer, and just Y zeolite content is 5wt%, and sial content is 40wt%.
Example 1～4 condition and the results are shown in Table
The hydrofining section air speed of the trans flow process of the present invention can be higher than the hydrofining section air speed of common sequence flow, can reach 1.0h as flow process hydrofining section air speed of the present invention
-1More than, and need at 1.0h usually
-1Followingly just can reach refining effect.
| Condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Cracking catalyst | ????A | ????B | ????D | A: C volume ratio layering in 2: 1 filling |
| Cracking zone cumulative volume air speed, hr -1 | ????0.64 | ????0.8 | ????0.92 | ???1.1 |
| Refining section cumulative volume air speed, hr -1 | ????2.5 | ????2.2 | ????2.0 | ???1.9 |
| The cracking zone weighted mean temperature, ℃ | ????415 | ????412 | ????405 | ???398 |
| Middle distillates oil selectivity, % | ????83.5 | ????82.5 | ????81 | ???80 |
| Quality product | ||||
| Diesel oil sulphur, μ g/g | ????＜50 | ????＜50 | ????＜50 | ???＜50 |
| Arylhydrocarbon in diesel oil, vl% | ????11.5 | ????9.8 | ????8.9 | ???7.5 |
* middle oil refers to rocket engine fuel and diesel oil, the cut coverage 138-282 of rocket engine fuel ℃ generally speaking, and the cut coverage 282-350 of diesel oil ℃.Data are not for cutting out rocket engine fuel among the embodiment, and diesel oil is 138-370 ℃ wide cut diesel fuel, and middle oil refers to this wide cut diesel fuel.
Claims (10)
1, a kind of hydrocracking process of producing cleaning product under hydrocracking condition, adopts the one-stage serial hydrocracking technical process, it is characterized in that in the presence of hydrogen the petroleum hydrocarbon material with 0.4-2.0hr
-1Volume space velocity earlier with after hydrocracking catalyst contacts, again with 1.0-6hr
-1Volume empty contact with Hydrobon catalyst, product passes through separation and obtains oil fuel and tail oil.
2, according to the described technology of claim 1, it is characterized in that described hydrocracking catalyst comprises amorphous type hydrocracking catalyst or high anti-nitrogen zeolite type hydrocracking catalyst, two kinds of catalyzer use separately or are used.
3,, it is characterized in that described amorphous type hydrocracking catalyst composition comprises: (a) acid sial 35-75wt% according to the described technology of claim 2; (c) aperture aluminum oxide 10-30wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%.
4,, it is characterized in that described acid sial character is: SiO according to the described technology of claim 3
2Content is 20～60%, specific surface 350-600m
2/ g, pore volume 0.9～1.5ml/g, infrared acidity 0.30-0.60mmol/g; Pore volume 0.4～the 0.8ml/g of little porous aluminum oxide, specific surface 150～300m
2/ g; The group vib metal oxide comprises the oxide compound of tungsten or molybdenum, and the VIII metal oxide comprises the oxide compound of cobalt or nickel.
5, according to the described technology of claim 2, it is characterized in that the composition of described zeolite type hydrocracking catalyst comprises: (a) Y zeolite 1-15wt%; (b) macropore refractory oxide 10-65wt%; (c) aperture aluminum oxide 0-30wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%.
6, according to the described technology of claim 5, it is characterized in that the character of described Y zeolite is: described group vib metal oxide comprises the oxide compound of tungsten or molybdenum, and the VIII metal oxide comprises the oxide compound of cobalt or nickel.
7,, it is characterized in that described petroleum hydrocarbon material is boiling range 200-600 ℃ a heavy crude hydrocarbon material according to the described technology of claim 1.
8, according to the described technology of claim 1, the volume space velocity that it is characterized in that described hydrocracking catalyst is 0.5-1.5hr
-1The volume space velocity of Hydrobon catalyst is 1.5-3.0hr
-1
9, according to the described technology of claim 1, it is characterized in that described hydrocracking condition is in the presence of hydrogen, stock oil is contacted system response pressure 5～20MPa, hydrogen-oil ratio 100～5000,360～440 ℃ of cracking zone temperature of reaction with catalyzer.
10,, it is characterized in that described Hydrobon catalyst is the non-noble metal hydrogenation catalyst for refining according to the described technology of claim 1.
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|---|---|---|---|
| CN 02144955 CN1221640C (en) | 2002-12-19 | 2002-12-19 | Hydrocracking process for producing clean product |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02144955 CN1221640C (en) | 2002-12-19 | 2002-12-19 | Hydrocracking process for producing clean product |
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| Publication Number | Publication Date |
|---|---|
| CN1508230A true CN1508230A (en) | 2004-06-30 |
| CN1221640C CN1221640C (en) | 2005-10-05 |
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ID=34232186
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703119A (en) * | 2012-06-19 | 2012-10-03 | 沧州华海炼油化工有限责任公司 | Preparation method for base oil of aluminium product rolling oil |
| CN104549345A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Active hydrocracking proppant and preparation method thereof |
| CN104650972A (en) * | 2013-11-20 | 2015-05-27 | 中国石油化工股份有限公司 | Hydrocracking method reducing content of sulfur in light fraction product |
| CN104650970A (en) * | 2013-11-20 | 2015-05-27 | 中国石油化工股份有限公司 | Hydrocracking technical method reducing the content of sulfur in light fraction product |
-
2002
- 2002-12-19 CN CN 02144955 patent/CN1221640C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703119A (en) * | 2012-06-19 | 2012-10-03 | 沧州华海炼油化工有限责任公司 | Preparation method for base oil of aluminium product rolling oil |
| CN104549345A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Active hydrocracking proppant and preparation method thereof |
| CN104549345B (en) * | 2013-10-23 | 2017-01-25 | 中国石油化工股份有限公司 | Active hydrocracking proppant and preparation method thereof |
| CN104650972A (en) * | 2013-11-20 | 2015-05-27 | 中国石油化工股份有限公司 | Hydrocracking method reducing content of sulfur in light fraction product |
| CN104650970A (en) * | 2013-11-20 | 2015-05-27 | 中国石油化工股份有限公司 | Hydrocracking technical method reducing the content of sulfur in light fraction product |
| CN104650972B (en) * | 2013-11-20 | 2016-08-17 | 中国石油化工股份有限公司 | Reduce the method for hydrogen cracking of light fraction product sulfur content |
| CN104650970B (en) * | 2013-11-20 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of hydrocracking method reducing light fraction product sulfur content |
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| Publication number | Publication date |
|---|---|
| CN1221640C (en) | 2005-10-05 |
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