CN1896181A - Production of high-bioctyl-value diesel oil by coal liquification - Google Patents
Production of high-bioctyl-value diesel oil by coal liquification Download PDFInfo
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- CN1896181A CN1896181A CN 200510083897 CN200510083897A CN1896181A CN 1896181 A CN1896181 A CN 1896181A CN 200510083897 CN200510083897 CN 200510083897 CN 200510083897 A CN200510083897 A CN 200510083897A CN 1896181 A CN1896181 A CN 1896181A
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Abstract
Production of high-cetane diesel oil from coal is carried out by filtering direct-liquefied diesel oil fraction of hydrogenated stabilized coal, mixing with hydrogen, contacting with hydrogenation refined catalyst and hydrogenation modified catalyst, separating out effluent from hydrogenation modified reactor to obtain naphtha fraction and diesel fraction, and returning hydrogen-enriched flow into diesel hydrogenation modified reactor. It is simple and fast, has better dearomatization and denitrification functions.
Description
Technical field
The present invention relates to the method that a kind of liquid hydrocarbon that coal destruction hydrogenation is obtained carries out hydrotreatment.More particularly, be a kind of method of producing diesel oil from liquefied coal coil.
Background technology
Just having begun DCL/Direct coal liquefaction produced the liquid hydrocarbon Study on Technology as far back as 1913 in Germany, and will make the skilled industryization of gasoline with the brown coal direct liquefaction in nineteen twenty-seven.Since the world oil crisis first time taking place in 1973, direct coal liquefaction technology is subjected to the attention of developed country, has developed multiple DCL/Direct coal liquefaction technology in succession.The IGOR technology of Germany's exploitation is with the online hydro-upgrading of coal direct liquefaction oil, processing condition are comparatively harsh, the production cetane value reaches 45 diesel product, Japan exploitation NEDO technology is carried out two step hydrogenation with coal direct liquefaction oil, processing condition comparatively relax, and the cetane value of coal diesel oil distillate can be brought up to 42.8.Reduce the cost of DCL/Direct coal liquefaction technology, will reduce the operating severity of DCL/Direct coal liquefaction technology and follow-up hydrogenation upgrading technology, as seen for being the technology that cetane value surpasses 45 diesel products under the demulcent processing condition, be that correlative study mechanism wants a difficult problem of making great efforts to solve with the upgrading of diesel oil distillates in direct coal liquefied oil hydrogenation always.
Generally, DCL/Direct coal liquefaction technology is wanted earlier coal direct liquefaction oil to be carried out stabilized hydrogenation, and saturation of olefins removes partial impurities, and the saturated aromatic hydrocarbons of shallow degree.The main purpose of stabilized hydrogenation is a production DCL/Direct coal liquefaction hydrogen supply dissolvent, therefore DCL/Direct coal liquefaction technology generally selects coal direct liquefaction oil last running as circulating solvent, and what can be used as that product goes out the DCL/Direct coal liquefaction device is mainly the following cut of coal direct liquefaction oil diesel oil.Stabilized hydrogenation coal direct liquefaction oil naphtha fraction virtue is dived high, be good reformer raw material, but sulphur and nitrogen content is higher, pass through deep desulfuration and nitrogen, just can advance reformer.Stabilized hydrogenation diesel oil distillates in direct coal liquefied oil aromaticity content height, generally more than 60m%, cycloalkanes stops content more than 20m%, and paraffinicity causes cetane value to be lower than 30 below 15m%, must by the degree of depth take off the virtue and the cracking open loop just can increase substantially cetane value, adopt hydrocracking process can realize above-mentioned purpose, but the yield of product diesel oil distillate is on the low side, causes the diesel oil of high value to become petroleum naphtha, and the hydrogen consumption increases, and Technological Economy is poor.
CN1493663A discloses a kind of combined technical method of being produced fine-quality diesel oil by liquefied coal coil, liquefied coal coil after the filtration and hydrogen enter the stable hydrogenation reactor, contact with hydrogenation protecting agent, Hydrobon catalyst, the stable hydrogenation reactor effluent obtains gas, naphtha fraction, diesel oil distillate and tail oil cut through separation, and hydrogen rich stream loops back the stable hydrogenation reactor; The diesel oil distillate and the hydrogen that obtain from the stable hydrogenation device enter the diesel oil hydrogenation modification reactor, contact with catalyst for hydro-upgrading, separate the hydro-upgrading reactor effluent and obtain naphtha fraction, diesel oil distillate, and hydrogen rich stream returns the diesel oil hydrogenation modification reactor.Reach diesel product more than 45 though this method can obtain cetane value,, influence on-stream time because the contained impurity such as nitrogen of coal direct liquefaction oil cause the catalyst for hydro-upgrading rapid deactivation.
Summary of the invention
The objective of the invention is on the prior art basis, to provide a kind of method of producing high hexadecane value diesel oil, to prolong on-stream time from coal direct liquefaction oil.
Method provided by the invention comprises: stabilized hydrogenation DCL/Direct coal liquefaction diesel oil distillate after filtering, mix with hydrogen, contact with Hydrobon catalyst, catalyst for hydro-upgrading successively, separate the hydro-upgrading reactor effluent and obtain naphtha fraction, diesel oil distillate, hydrogen rich stream returns the diesel oil hydrogenation modification reactor.
Method provided by the invention was loaded before catalyst for hydro-upgrading has the Hydrobon catalyst that well takes off virtue and nitrogen performance, remove the contained impurity such as nitrogen of coal direct liquefaction oil, prevent the catalyst for hydro-upgrading rapid deactivation, saturated aromatic hydrocarbons of while, reduce the difficulty of processing of catalyst for hydro-upgrading, prolong on-stream time, energy production cetane value reaches the diesel product more than 45 simultaneously.
Description of drawings
Accompanying drawing is a method synoptic diagram of producing high hexadecane value diesel oil from coal direct liquefaction oil provided by the invention.
Embodiment
Method of the present invention is a stabilized hydrogenation DCL/Direct coal liquefaction diesel fraction deep hydrogenation upgrading, and its flow process is:
After stabilized hydrogenation DCL/Direct coal liquefaction diesel oil distillate installs filtration after filtration, after mixing with hydrogen and being heated to temperature of reaction, enter hydrofining reactor, contact with Hydrobon catalyst, the hydrofining reactor effluent mainly is included in the H that generates in the hydrofining reactor
2S, NH
3And the treated oil after the hydrofining;
The hydrofining reactor effluent enters the hydro-upgrading reactor, contacts with catalyst for hydro-upgrading, and the saturated and ring-opening reaction of hydrogenation takes place in the hydro-upgrading reactor, and the hydro-upgrading reactor effluent mainly comprises H
2, lighter hydrocarbons, H
2S, NH
3, and hydro-upgrading after product oil; The hydro-upgrading reactor effluent enters high score, low branch, separation column in proper order; Isolate light naphthar, heavy naphtha fraction and diesel oil distillate by separation system.The isolated hydrogen rich stream of high score mixes with new hydrogen, and a part is mixed with raw material after delivering to feedstock pump, and remaining each reactor of delivering to is used for each beds temperature in of controlling reactor.
The deep hydrogenation method for modifying is that the two agent of single hop are operated, an anti-middle filling Hydrobon catalyst, two anti-middle filling catalyst for hydro-upgrading.Why the present invention adopts the two agent of single hop, is that Hydrobon catalyst has the saturated performance of good hydrogenation, can provide the reactant that can carry out ring-opening reaction easily to cracking reaction because the back of ring-opening reaction is the aromatic hydrogenation saturated reaction; Secondly, the cracking function of catalyst for hydro-upgrading comes from acidic components, and acidic components very easily are subjected to the nitride poisoning and deactivation, and the nitrogen content height is another characteristics of DCL/Direct coal liquefaction diesel oil, therefore, install finishing agent in the front of catalyst for hydro-upgrading additional and remove nitrogen in the coal direct liquefaction oil, guarantee the active relatively stable of catalyst for hydro-upgrading, prolong the life-span of catalyst for hydro-upgrading.
The Hydrobon catalyst that the present invention selects for use has good fragrant and the nitrogen performance of taking off, and removes the contained impurity such as nitrogen of coal direct liquefaction oil, prevents the catalyst for hydro-upgrading rapid deactivation, saturated aromatic hydrocarbons of while, the difficulty of processing of reduction catalyst for hydro-upgrading.The catalyst for hydro-upgrading of selecting for use possesses the coupling of good hydrogenation activity and open loop cracking activity, is fit to the above aromatic hydrocarbons of processing dicyclo, improves the cetane value of diesel oil distillate by open loop.The hydrogenation activity of catalyst for hydro-upgrading and cracking activity must mate, if hydrogenation activity hangs down the cracking activity height, then aromatic hydrocarbons can not get well saturated, can't obtain in a large number can be for the reactant of open loop, cause the cracking of " useful " hydro carbons such as straight-chain paraffin easily, cause the generation of small molecules product, diesel yield descends; And if the hydrogenation activity height, cracking activity is low, then the complete hydrogenation saturated reaction of aromatic hydrocarbons is deepened, ring-opening reaction is not enough, causes the hydrogen consumption to increase, but the cetane value increase rate is little.As seen, the catalyst for hydro-upgrading selected for use of the present invention has distinct characteristic.
Because the catalyst for hydro-upgrading that the deep hydrogenation modification technology adopts has certain cracking activity, therefore, doing of raw material can suitably be relaxed, and the highlyest is put into 390 ℃, to increase the Technological Economy of coal direct liquefaction oil hydrogenation upgrading technology.
Method of the present invention is applicable to the diesel oil distillate behind the various coal direct liquefaction oil stabilized hydrogenations of processing, and doing of raw material is not more than 390 ℃ (ASTM D-86).
The boiling range scope of the raw materials used coal direct liquefaction oil of method of the present invention should be preferably 165～370 ℃ (ASTM D-86) at 165～390 ℃ (ASTM D-86), and nitrogen content is not more than 0.2 heavy % in the raw material, preferably is not more than 0.1 heavy %; Sulphur content is not more than 2.0 heavy %.
Method flexibility of operation of the present invention largely depends on sternly product of raw material oil properties and purpose, and the hydrogen dividing potential drop is 6.0～20.0MPa, and temperature of reaction is 280～450 ℃, and liquid hourly space velocity is 0.1～10h
-1, hydrogen-oil ratio is 400～3000v/v.
Hydrobon catalyst is VIA and the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, has very strong hydrodenitrogenationactivity activity.
Preferred Hydrobon catalyst consists of: nickel oxide 1～5 heavy %, Tungsten oxide 99.999 12～35 heavy %, fluorine 1～9 heavy %, all the other are aluminum oxide, this aluminum oxide is to be composited by one or more little porous aluminum oxides and one or more macroporous aluminium oxides weight ratio according to 75: 25～50: 50, to be bore dia account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to wherein little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in bore dia 60～600 dust holes accounts for the aluminum oxide of total pore volume more than 70%.
Catalyst for hydro-upgrading is an active ingredient with the metal of VIII family, group vib in the periodic table of elements, is carrier with the mixture of aluminum oxide and zeolite.
Preferred catalyst for hydro-upgrading contains a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier.Preferred catalyzer is composed as follows: in oxide compound and with the catalyzer total amount is benchmark, and the content of molybdenum and/or tungsten is 10～35 heavy % preferred 18～32 heavy % in this hydrogenation catalyst, and the content of nickel and/or cobalt is 1～15 heavy % preferred 3～12 heavy %.Described carrier is made up of aluminum oxide and zeolite, the weight ratio of aluminum oxide and zeolite be 90: 10～50: 50 preferred 90: 10～60: 40.Described aluminum oxide is the aluminum oxide that is composited according to 75: 25～50: 50 weight ratio by little porous aluminum oxide and macroporous aluminium oxide, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 holes to wherein little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in diameter 60～600 holes accounts for the aluminum oxide of total pore volume more than 70%.Described zeolite is selected from one or more in faujusite, mordenite, erionite zeolite, zeolite L, omega zeolite, ZSM-4 zeolite, the Beta zeolite, preferred y-type zeolite, particularly preferred zeolite is that total acid content is 0.02 to less than 0.5 mmole/gram, the y-type zeolite of preferred 0.05～0.2 mmole/gram.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.
Accompanying drawing is the method flow synoptic diagram from coal direct liquefaction oil production high hexadecane value diesel oil provided by the invention, has omitted the equipment of many necessity among the figure, as pump, air cooler and valve etc.
Flow process is described in detail as follows:
Stabilized hydrogenation DCL/Direct coal liquefaction diesel oil distillate boosts to reaction pressure through pipeline 2 by feedstock pump, after hydrogen-rich gas from pipeline 3 mixes, enter interchanger 5 heat exchange through pipeline 4, again after pipeline 6 enters process furnace 7 heating, enter hydrofining reactor 8, by contacting with the Hydrobon catalyst bed, remove impurity such as sulphur and nitrogen in the stock oil, and fractional saturation aromatic hydrocarbons.Because hydrofining is strong exothermal reaction, need in the middle of reactor, to introduce cold hydrogen, control reaction temperature.The effluent of hydrofining reactor 8 enters hydro-upgrading reactor 10 through pipeline 9, and by contacting with the catalyst for hydro-upgrading bed, it is saturated to carry out open loop cracking and aromatic hydrocarbons.Because cracking reaction and aromatic hydrocarbons saturated reaction are strong exothermal reaction, need in the middle of reactor, to introduce cold hydrogen, control reaction temperature.The effluent of hydro-upgrading reactor 10 is after pipeline 11 enters interchanger 5 heat exchange, enter high-pressure separator 12, in high-pressure separator, be separated into two bursts of logistics, wherein one is a hydrogen-rich stream, wherein be mainly hydrogen, comprise partial vulcanization hydrogen, ammonia and lighter hydrocarbons simultaneously, hydrogen-rich stream compression is after pipeline 13 with after new hydrogen from pipeline 1 mixes, loops back reactor 8 and 10 through pipeline 3; Another burst logistics then enters light pressure separator 15 through pipeline 14, further remove lighter hydrocarbons, lighter hydrocarbons are through pipeline 17 caterpillars, and the bottom effluent of light pressure separator 15 enters fractionating column system 18 through pipeline 16, and naphtha fraction that fractionates out and diesel oil distillate are respectively through pipeline 19 and 20 caterpillars.
Method provided by the invention was loaded before catalyst for hydro-upgrading has the Hydrobon catalyst that well takes off aromatic hydrocarbons, nitrogen performance, remove the contained impurity such as nitrogen of coal direct liquefaction oil, prevent the catalyst for hydro-upgrading rapid deactivation, saturated aromatic hydrocarbons of while, reduce the difficulty of processing of catalyst for hydro-upgrading, prolong on-stream time, energy production cetane value reaches the diesel product more than 45 simultaneously.
The following examples will give further instruction to present method, but therefore not limit present method.
All through filtering, its character is listed in table 1 to diesel oil distillate A, B among the embodiment behind the used liquefied coal coil stabilized hydrogenation.The trade names of Hydrobon catalyst, catalyst for hydro-upgrading are respectively RN-10, RIC-1, produce by Sinopec Chang Ling catalyst plant.Test is carried out on medium-sized fixed bed hydrogenation device.
Embodiment 1
Test raw material is the diesel oil distillate A behind the coal direct liquefaction oil stabilized hydrogenation, stock oil deep hydrogenation modification technology is that flow process is once passed through in the two agent of single hop, and promptly stock oil, hydrogen are RN-10, catalyst for hydro-upgrading RIC-1 contact reacts with Hydrobon catalyst successively.The processing condition of deep hydrogenation modification technology and product diesel oil distillate character are listed in table 2 and table 3 respectively.By table as seen, the density of stabilized hydrogenation diesel oil distillates in direct coal liquefied oil is not too high, do is 342 ℃, the processing condition that the deep hydrogenation modification technology is adopted comparatively relax, the sulphur of product diesel oil distillate and the content of nitrogen are very low, aromaticity content is lower, has reached the index request of " world's fuel oil standard " III class diesel oil, and it is qualified diesel products that its cetane value surpasses 45.Catalyst for hydro-upgrading is that be 36 months the running period of RIC-1.
Test raw material is stabilized hydrogenation diesel oil distillates in direct coal liquefied oil B, and stock oil character is listed in table 1.The deep hydrogenation modification technology is that flow process is once passed through in the two agent of single hop, and promptly stock oil, hydrogen are RN-10, catalyst for hydro-upgrading RIC-1 contact reacts with Hydrobon catalyst successively.The processing condition of deep hydrogenation technology and diesel product character are listed in table 2 and table 3 respectively.By table as seen, the density of diesel oil distillates in direct coal liquefied oil is higher, the foreign matter content height, the processing condition of deep hydrogenation upgrading are comparatively harsh, the sulphur of product diesel oil distillate and the content of nitrogen are very low, aromaticity content is lower, has reached the index request of " world's fuel oil standard " III class diesel oil, and it is qualified diesel products that its cetane value surpasses 45.Be 24 months the running period of catalyst for hydro-upgrading RIC-1.
Comparative Examples
Experiment process is that the agent of single hop list is once passed through, promptly stock oil, hydrogen only with catalyst for hydro-upgrading RIC-1 contact reacts.Test raw material, processing condition are all identical with embodiment 1, and under the close situation of product property and embodiment 1, only be 12 months the running period of catalyst for hydro-upgrading RIC-1.
Table 1, raw material oil properties
| Project | Embodiment 1 | |
| The stock oil numbering | A | B |
| Density (20 ℃), g/cm 3 | 0.9161 | 0.9211 |
| S，ppm | 23 | 138 |
| N，ppm | 506 | 1200 |
| Total aromaticity content, m% | 52.0 | 60.8 |
| Polycyclic aromatic hydrocarbon content, m% | 21.3 | 22.5 |
| Boiling range (ASTM D-1160) ℃ | ||
| Initial boiling point/10% | 193/222 | 180/212 |
| 50％/90％ | 266/312 | 286/344 |
| Do | 342 | 370 |
Table 2, deep hydrogenation modifying process parameter
| Processing condition | Embodiment 1 | |
| Temperature of reaction, ℃ | 365 | 370 |
| The hydrogen dividing potential drop, MPa | 14.0 | 14.0 |
| Volume space velocity, h -1 | 1.0 | 0.75 |
| Hydrogen-oil ratio, v/v | 1000 | 1000 |
The character of table 3, diesel product
| Diesel product character | Embodiment 1 | |
| Density (20 ℃), g/cm 3 | 0.8609 | 0.8674 |
| S，ppm | ＜10 | ＜10 |
| Total aromaticity content, m% | 12.5 | 14.2 |
| Polycyclic aromatic hydrocarbon content, m% | 1.8 | 2.2 |
| Boiling range (ASTM D-86), ℃ | ||
| Initial boiling point | 184 | 187 |
| 50％ | 258 | 267 |
| 90％ | 305 | 330 |
| Do | ||
| Cetane value | 46.2 | 47.3 |
Claims (11)
1, a kind of method of producing high hexadecane value diesel oil from coal direct liquefaction oil, it is characterized in that stock oil after filtering, mix with hydrogen, contact with Hydrobon catalyst, catalyst for hydro-upgrading successively, separate the hydro-upgrading reactor effluent and obtain naphtha fraction, diesel oil distillate, hydrogen rich stream returns the diesel oil hydrogenation modification reactor.
2, according to the method for claim 1, it is characterized in that described stock oil is stabilized hydrogenation DCL/Direct coal liquefaction diesel oil distillate, its boiling range is 165～390 ℃.
3, according to the method for claim 1, it is characterized in that reaction conditions is: hydrogen dividing potential drop 6.0～20.0MPa, 280～450 ℃ of temperature of reaction, liquid hourly space velocity 0.1～10h-1, hydrogen-oil ratio 400～3000v/v.
4,, it is characterized in that Hydrobon catalyst is VIA and the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports according to the method for claim 1.
5, according to the method for claim 1 or 4, it is characterized in that described Hydrobon catalyst consists of nickel oxide 1～5 heavy %, Tungsten oxide 99.999 12～35 heavy %, fluorine 1～9 heavy %, all the other are aluminum oxide, this aluminum oxide is to be composited by one or more little porous aluminum oxides and one or more macroporous aluminium oxides weight ratio according to 75: 25～50: 50, to be bore dia account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to wherein little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in bore dia 60～600 dust holes accounts for the aluminum oxide of total pore volume more than 70%.
6, according to the method for claim 1, it is characterized in that described catalyst for hydro-upgrading is an active ingredient with the metal of VIII family, group vib in the periodic table of elements, be carrier with the mixture of aluminum oxide and zeolite.
7, method according to claim 1 or 6, it is characterized in that described catalyst for hydro-upgrading contains a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, described carrier is made up of aluminum oxide and zeolite, the weight ratio of aluminum oxide and zeolite is 90: 10～50: 50, described aluminum oxide is the aluminum oxide that is composited according to 75: 25～50: 50 weight ratio by little porous aluminum oxide and macroporous aluminium oxide, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 holes to wherein little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in diameter 60～600 holes accounts for the aluminum oxide of total pore volume more than 70%.
8, method according to claim 7 is characterized in that in oxide compound and is benchmark with the catalyzer total amount that the content of molybdenum and/or tungsten is 10～35 heavy %, and the content of nickel and/or cobalt is 1～15 heavy %.
9, method according to claim 8, the content that it is characterized in that molybdenum and/or tungsten are 18～32 heavy %, and the content of nickel and/or cobalt is 3～12 heavy %.
10, method according to claim 7, the weight ratio that it is characterized in that described aluminum oxide and zeolite is 90: 10～60: 40.
11,, it is characterized in that described zeolite is a y-type zeolite according to claim 7 or 10 described methods.
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| CN101928600A (en) * | 2009-06-25 | 2010-12-29 | 中国石油化工股份有限公司 | Method for producing diesel oil or diesel oil blending component |
| CN101144026B (en) * | 2007-10-23 | 2011-09-07 | 神华集团有限责任公司 | Method for producing cleaning diesel oil from coal directly liquidized oil |
| CN102206511A (en) * | 2011-04-26 | 2011-10-05 | 神华集团有限责任公司 | Method for producing diesel fuel by using coal direct liquefication oil and delayed coking heavy diesel fuel fraction and application of method |
| CN102533323A (en) * | 2012-01-10 | 2012-07-04 | 神华集团有限责任公司 | Method for preparing light weight oil by using high-nitrogen and high-sulfur low-quality oil |
| CN101591564B (en) * | 2008-05-29 | 2014-04-09 | 北京三聚环保新材料股份有限公司 | Hydrofining method of diesel oil distillates in direct coal liquefied oil |
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| CN101144026B (en) * | 2007-10-23 | 2011-09-07 | 神华集团有限责任公司 | Method for producing cleaning diesel oil from coal directly liquidized oil |
| CN101591564B (en) * | 2008-05-29 | 2014-04-09 | 北京三聚环保新材料股份有限公司 | Hydrofining method of diesel oil distillates in direct coal liquefied oil |
| CN101928600A (en) * | 2009-06-25 | 2010-12-29 | 中国石油化工股份有限公司 | Method for producing diesel oil or diesel oil blending component |
| CN101928600B (en) * | 2009-06-25 | 2013-06-05 | 中国石油化工股份有限公司 | Method for producing diesel oil or diesel oil blending component |
| CN102206511A (en) * | 2011-04-26 | 2011-10-05 | 神华集团有限责任公司 | Method for producing diesel fuel by using coal direct liquefication oil and delayed coking heavy diesel fuel fraction and application of method |
| CN102206511B (en) * | 2011-04-26 | 2014-07-09 | 神华集团有限责任公司 | Method for producing diesel fuel by using coal direct liquefication oil and delayed coking heavy diesel fuel fraction and application of method |
| CN102533323A (en) * | 2012-01-10 | 2012-07-04 | 神华集团有限责任公司 | Method for preparing light weight oil by using high-nitrogen and high-sulfur low-quality oil |
| CN102533323B (en) * | 2012-01-10 | 2014-08-13 | 神华集团有限责任公司 | Method for preparing light weight oil by using high-nitrogen and high-sulfur low-quality oil |
| CN111097552A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for restoring activity of low-activity hydrogenation modified catalyst |
| CN111097552B (en) * | 2018-10-29 | 2022-03-08 | 中国石油化工股份有限公司 | Method for restoring activity of low-activity hydrogenation modified catalyst |
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