CN102465014B - Hydrocracking method for processing low-sulfur raw material - Google Patents
Hydrocracking method for processing low-sulfur raw material Download PDFInfo
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- CN102465014B CN102465014B CN201010539020.8A CN201010539020A CN102465014B CN 102465014 B CN102465014 B CN 102465014B CN 201010539020 A CN201010539020 A CN 201010539020A CN 102465014 B CN102465014 B CN 102465014B
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Abstract
The invention discloses a hydrocracking method for processing a low-sulfur raw material. The method comprises the steps of: hydroprocessing a high-sulfur raw material, and performing gas-liquid separation on a reaction effluent to obtain sulfur-containing hydrogen-enriched gas; hydrocracking low-sulfur raw oil, and performing gas-liquid separation on a reaction effluent to obtain a low-sulfur hydrogen-enriched gas; and mixing the sulfur-containing hydrogen-enriched gas and the low-sulfur hydrogen-enriched gas, selectively performing hydrogen sulfide removal treatment on the gas mixture, and circulating the treated gas mixture to a reactor inlet. According to the invention, two paths of hydrogen-enriched gas of the hydroprocessing process and the hydrocracking process are effectively combined, and the sulfur-containing hydrogen-enriched gas subjected to hydroprocessing is fully utilized to replenish sulfur for a low-sulfur raw material hydrocracking device, so that the problem of sulfur loss of the catalyst during long-term operation of the low-sulfur hydrocracking device is effectively solved. The hydrocracking method disclosed by the invention has the advantages of simplified process flow, low operation cost, low total investment and the like.
Description
Technical field
The present invention relates to a kind of Unionfining technique, mainly refer to that hydrotreater combines with hydroeracking unit, especially for the hydroeracking unit of processing treatment low-sulfur raw material.
Background technology
Hydrocracking is that heavy distillate faces a kind of catalytic conversion process that carries out the reactions such as hydrogenation, desulfurization, denitrogenation, molecular structure rearrangement and cracking under hydrogen and catalyzer existence in High Temperature High Pressure.There is the plurality of advantages such as adaptability to raw material is strong, products scheme is flexible, liquid product yield is high, good product quality, be subject to for many years the favor of countries in the world oil refining enterprise always.As the hydrocracking of one of the main technique of heavy oil deep processing not only can direct production vapour, the clean automotive fuel such as coal, bavin, and light, heavy naphtha and hydrocracking tail oil or the industrial chemicals of high-quality in its product, therefore, hydrocracking technology progressively develops into the bridge technology that the modern times refine oil and petroleum chemical enterprise's oil, change, fibre organically combine in recent years, more than hydrocracking throughput in the world's has reached 200Mt/a at present.
The core of hydrocracking technology is catalyzer, and the hydrogenation catalyst (except indivedual catalyzer) that Present Domestic is produced is oxidized form substantially.Industrial raw catalyst regenerated catalyst alive (except the outer prevulcanized type catalyzer of device), its contained active metal component (Mo, Ni, Co, W), is all with oxidation state (MoO
3, NiO, CoO, WO
3) form exist.The practice of fundamental research and industrial application shows, the active metal component (base metal) of most hydrogenation catalysts, its sulphided state has higher hydrogenation activity and stability, hydrogenation catalyst is before it contacts with hydrocarbon raw material, must first use vulcanizing agent, catalyst activity metal is converted into corresponding sulphided state by oxidation state, carries out catalyst vulcanization; In operation process, catalyzer also needs to exist with the form of sulphided state for a long time, is beneficial to the stable and performance of its activity.
At present, a lot of oil refining enterprise hydroeracking unit is all processed low-sulfur raw material (sulphur nitrogen is than < 0.5), in the past for a long time, certainly will cause sulphur loss, active metal valence state in catalyzer change and even are reduced, the permanent inactivation that finally causes catalyzer, hydroeracking unit is forced to a series of losses such as shut-down.In actual production process, for the running of holding device long-term stability, for the hydroeracking unit of processing low-sulfur raw material, often all adopt the high reactivity that the mode of injecting dimethyl disulfide (DMDS) in alignment system maintains catalyzer, its injection rate is decided by the hydrogen sulfide content in the sulphur in processed raw material, nitrogen content, recycle hydrogen amount and the recycle hydrogen that will maintain etc.Although this method can be guaranteed the activity of catalyzer, can increase material consumption, people's consumption, energy consumption etc.
CN99112819.2 has introduced a kind of method of hydrorefining paraffin wax method benefit sulphur, although can the hydrogenation activity of sulfurized hydrogenation catalyst is restored in the situation that device is not stopped work, needs extra a certain amount of vulcanizing agent that consumes.
CN93121026.7 has introduced a kind of benefit sulphur mode, although mending sulphur mode, its hydrocarbon ils can guarantee catalyst activity, but need to consume a certain amount of hydrocarbon ils, although mending sulphur mode, its gas do not need to consume hydrocarbon ils, but need extra system to inject hydrogen sulfide to reactive moieties, energy consumption is larger, easily makes raw oil pump produce vapour lock simultaneously, is difficult to long-term operation.
Summary of the invention
The problem existing for prior art, the invention provides a kind of combined hydrogenation method, sour feedstock hydroprocessing technique and low-sulfur raw material hydroeracking unit are carried out organic assembling by the method, can be keeping to greatest extent catalyst activity in low-sulfur hydroeracking unit, when reaching safety, long-term, steady running object, reduce investment, reduce cost, can not reduce again the hydrogen purity in reactive system simultaneously.
Combined hydrogenation method provided by the invention, comprises the steps:
A) under hydroprocessing condition, after high-sulfur feed mixes with hydrogen by containing the beds of hydrotreating catalyst, first reaction effluent enters in high pressure hot separator and separates, obtain gas phase and liquid phase, gas phase enters cold high pressure separator and again separates, and obtains hydrogen-rich gas and lighter hydrocarbons;
B) under hydrocracking condition, after low-sulfur raw material oil mixes with hydrogen by containing the beds of hydrocracking catalyst, reaction effluent enters in high pressure hot separator and separates, obtain gas phase and liquid phase, gas phase enters cold high pressure separator and again separates, and obtains hydrogen-rich gas and lighter hydrocarbons;
C) hydrogen-rich gas that recycle hydrogen step a) being obtained b) obtains with step mixes, and after circulating hydrogen compressor mixes with new hydrogen, recycles.
Wherein step a) boiling range of described sour feedstock be generally 150~700 ℃, sulphur content is more than 1wt%, more than being generally 1.5wt%.Described sour feedstock can be selected from various vacuum gas oils (VGO), coker gas oil (CGO), the deasphalted oil (DAO) that processing middle-eastern crude obtains, as Iranian VGO, Iranian CGO, Iranian DAO, Saudi Arabia VGO, Saudi Arabia CGO, Saudi Arabia DAO, one or several in Kuwait VGO, Kuwait CGO, Kuwait DAO.
Step b) the boiling range of described low-sulfur raw material is generally 150~550 ℃, and sulphur content, below 0.1%, is generally 0.01~0.08wt%.Described low-sulfur raw material is generally selected from the vacuum gas oil (VGO) that the crude oil such as processing grand celebration or the Liaohe River obtain, as one or several in grand celebration VGO, Liaohe River VGO.
The hydrotreating catalyst of step described in a) comprises the hydrogenation metal of carrier and institute's load.Take the weight of catalyzer as benchmark, generally include group vib metal component in the periodic table of elements, count 10%~35% as tungsten and/or molybdenum with oxide compound, be preferably 15%~30%; Group VIII metal counts 1%~7% as nickel and/or cobalt with oxide compound, is preferably 1.5%~6%.Carrier is porous, inorganic refractory oxide, is generally selected from aluminum oxide, amorphous silicon aluminium, silicon-dioxide, titanium oxide etc.Wherein conventional hydrotreating catalyst can be selected existing various commercial catalysts, the Hydrobon catalyst such as FF-14, FF-24,3936,3996, FF-16, FF-26, FF-36, FF-46 that such as Fushun Petrochemical Research Institute (FRIPP) develops; Also can be prepared by the general knowledge of this area as required.
The beds of step described in b) can also comprise hydrotreating catalyst simultaneously, and described hydrotreating catalyst is with described in step a).The hydrocracking catalyst of step described in b) comprises cracking component and hydrogenation component.Cracking component generally includes amorphous aluminum silicide and/or molecular sieve, as Y type or USY molecular sieve.Tackiness agent is generally aluminum oxide or silicon oxide.Hydrogenation component is selected from metal, metal oxide or the metallic sulfide of VI family, VII family or VIII family, more preferably one or more in iron, chromium, molybdenum, tungsten, cobalt, nickel or its sulfide or oxide compound.Take the weight of catalyzer as benchmark, the content of hydrogenation component is 5~40wt%.Conventional hydrocracking catalyst can be selected existing various commercial catalysts, the catalyzer such as such as FC-12, the FC-14 of FRIPP development, FC-16, FC-24, FC-26, ZHC-02, FC-28.Also can prepare specific hydrocracking catalyst by the general knowledge of this area as required.
Step a) described in the typical operational condition of hydrotreatment be: reaction pressure 8.0~16.0MPa, hydrogen to oil volume ratio 200: 1~600: 1, volume space velocity is 0.1~5.0h
-1, 260 ℃~455 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 12.0~15.5MPa, hydrogen to oil volume ratio 300: 1~500: 1, volume space velocity 0.5~2.0h
-1, 310 ℃~400 ℃ of temperature of reaction.
Step b) described in the typical operational condition of hydrocracking be: reaction pressure 8.0~16.0MPa, hydrogen to oil volume ratio 600: 1~1500: 1, volume space velocity is 0.1~5.0h
-1, 260 ℃~455 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 12.0~15.5MPa, hydrogen to oil volume ratio 800: 1~1300: 1, volume space velocity 0.3~2.0h
-1, 310 ℃~430 ℃ of temperature of reaction.
The reaction pressure of the hydrotreatment of step described in a) and the step hydrocracking described in b) can be identical or not identical, preferably adopts identical reaction pressure.A) the high pressure hot separator working pressure described in b) is identical with reacting system pressure with step for step, temperature is generally 180~400 ℃, preferably 200~350 ℃, the isolated light hydrocarbons of high pressure hot separator enters cold high pressure separator after condensation; The isolated liquid phase hydro carbons of high pressure hot separator enters thermal low-pressure separators, enters afterwards fractionating system.
Step c) in, the hydrogen-rich gas that the recycle hydrogen that step a) obtains b) obtains with step mixes, and enters in recycle hydrogen surge tank.After mixing with new hydrogen by circulating hydrogen compressor supercharging (supercharging is 0.2~0.4MPa preferably) afterwards, circulation enters reactive system.
Compared with prior art, the present invention is organically combined processing the hydroprocessing technique of sour feedstock and the hydrocracking process of low-sulfur raw material, make different inferior raw materials on the basis of normal processing processing, can make full use of its feature separately, carry out Combinatorial Optimization, on the basis of improving the quality of products, obtain desirable comprehensive process effect.
In technical process, the inventive method is that hydrotreatment is effectively combined with the two-way gas circuit of hydrocracking process, the high-sulfur hydrogen-rich gas that makes full use of high-sulfur hydrotreater is that low-sulfur raw material hydroeracking unit is mended sulphur, has effectively solved low-sulfur and has added the catalyzer mistake sulphur problem of splitting device long-term operation.Because two covering devices share hydrogen gas buffer, circulating hydrogen compressor and make-up hydrogen compressor, the inventive method can be saved facility investment simultaneously; Reduce total steam consumption of circulating hydrogen compressor, thereby reduce energy consumption.Because adding, low-sulfur splits device without injecting DMDS, total flow simultaneously that can also save poor amine liquid compared with independent processing sour feedstock hydrotreater, even can save in some cases desulphurization of recycle hydrogen device, therefore the inventive method has the advantages such as the low and overall investment of technical process simplification, process cost is low.
Accompanying drawing explanation
Fig. 1 is the principle process schematic diagram of the inventive method.For the combination process of hydrotreater and hydroeracking unit.
Embodiment
Below in conjunction with accompanying drawing, Unionfining technique of the present invention is elaborated.
As shown in Figure 1, a kind of embodiment of Unionfining technical process of the present invention is as follows:
Sour feedstock 1 enters hydrotreater 2 after mixing with hydrogen 30, reaction effluent 3 enters high pressure hot separator 4, the liquid 6 that hot high score obtains removes separation column, the gas 7 obtaining injects washing water 8, by entering cold high pressure separator 10 after high-pressure air cooler 9, isolate the waste liquid 11 of Containing Sulfur amine and sulphur hydrogenated amines, hydrogen-rich gas 12 enters desulphurization of recycle hydrogen tower 13 and contacts with poor amine liquid 15, the rich amine liquid 14 obtaining is discharged thionizer and is entered regeneration system rapidly, obtains having the hydrogen-rich gas 16 of certain concentration of hydrogen sulfide simultaneously; Low-sulfur raw material 17 enters hydroeracking unit 18 after mixing with hydrogen 30, and gained reaction effluent 19 enters high pressure hot separator 20 and separates, and gained liquid 21 removes separation column; The gas 22 that high pressure hot separator 20 obtains injects washing water 23, after high-pressure air cooler 24, enter cold high pressure separator 25, isolate the waste liquid 26 of Containing Sulfur amine and sulphur hydrogenated amines, hydrogen-rich gas 27 with after 16 mix through circulating hydrogen compressor 28, after new hydrogen 29 supplements, obtain hydrogen 30, be circulated to reactor inlet or use as quenching hydrogen simultaneously.
Below by specific embodiment, Unionfining technique of the present invention is further described.
Comparative example 1
Comparative example 1 comprises independently conventional hydroeracking unit A and B and a set of hydrotreater C of two covers---hydroeracking unit processing low-sulfur raw material 1, hydrotreater processing sour feedstock 2, independent operation between three, comprise separately hot high score and cold high score, wherein install A and do not carry out the measure of any benefit sulphur, device B uses DMDS as sulfur supplementary agent, and catalyzer, raw material, operational condition that three cover hydrogenation units use are all identical with the corresponding part in embodiment 1.Operation result is listed in respectively table 2~4.
Embodiment 1
Adopt the technical process shown in Fig. 1, the hydroeracking unit recycle hydrogen gas circuit of the hydrotreater of processing sour feedstock 2 and processing low-sulfur raw material 1 is organically combined.The character of the catalyzer using in embodiment is listed in table 1.Catalyzer is the commercial catalyst of Fushun Petrochemical Research Institute's development and production.
Raw material oil properties is in table 2, and hydrogenation technique operational condition is in table 3, concentration of hydrogen sulfide in recycle hydrogen, and DMDS consumption, poor amine liquid inject cycle and device running period etc. in table 4.
The main physico-chemical property of table 1 catalyzer
Project | FF-36 | FC-14 | FF-14 |
Face shaping | Trifolium bar | Cylindrical bars | Trifolium bar |
Particle diameter, mm | 1.1~1.3 | 1.5~1.7 | 1.1~1.3 |
Bar is long, |
3~8 | 3~8 | 3~8 |
Crushing strength, N/cm | ≥180 | >185 | ≥180 |
Chemical constitution, m%: | Mo-Ni | W-Ni | Mo-Ni-Co |
NiO | 4.0 | 5.5 | 2.1 |
MoO 3 | 25.0 | 23.6 | |
WO 3 | 22.0 | ||
CoO | 1.5 |
Table 2 stock oil property list
Project | Stock oil-1 | Stock oil-2 |
Source | Decompressed wax oil | Decompressed wax oil+deasphalted oil |
Density (20 ℃)/gcm -3 | 0.9105 | 0.9404 |
Boiling range scope/℃ | 300~580 | 300~680 |
Sulphur/μ gg -1 | 600 | 19900 |
Nitrogen/μ gg -1 | 1600 | 1800 |
Table 3 reaction conditions
Low-sulfur raw material hydrocracking | Sour feedstock hydrotreatment | |
Stock oil | Stock oil-1 | Stock oil-2 |
Catalyzer | FF-36/FC-14 | FF-14 |
Reaction pressure/MPa | 14.0 | 14.0 |
Average reaction temperature/℃ | 385 | 365 |
Volume space velocity/h -1 | 1.2 | 1.5 |
Hydrogen to oil volume ratio/℃ | 1200∶1 | 500∶1 |
Table 4
Can find out from above embodiment, the maximum feature of this combination process is, adopts gas circuit to mend the device of sulphur mode, and compared with the hydroeracking unit of not taking the measure of any benefit sulphur with processing low-sulfur raw material, can increase substantially running period; Compared with adopting the hydroeracking unit of DMDS processing low-sulfur raw material, can save the injection link of DMDS, reduce the poor amine liquid total flow of high-sulfur hydrotreater simultaneously, improve Business Economic Benefit, gas circuit associating simultaneously can also be saved investment on equipment, in human and material resources, energy consumption, there is very large advantage, make every covering device when Each answers the purpose intended, meet to greatest extent enterprise to the rationally object of processing of different material.
Claims (9)
1. a method for hydrogen cracking of processing low-sulfur raw material, comprises the following steps:
A) under hydroprocessing condition, after high-sulfur feed mixes with hydrogen by containing the beds of hydrotreating catalyst, first reaction effluent enters in high pressure hot separator and separates, obtain gas phase and liquid phase, gas phase enters cold high pressure separator and again separates, and obtains hydrogen-rich gas and lighter hydrocarbons; The sulphur content of described high-sulfur feed is more than 1wt%;
B) under hydrocracking condition, after low-sulfur raw material oil mixes with hydrogen by containing the beds of hydrocracking catalyst, reaction effluent enters in high pressure hot separator and separates, obtain gas phase and liquid phase, gas phase enters cold high pressure separator and again separates, and obtains hydrogen-rich gas and lighter hydrocarbons; The sulphur content of described low-sulfur raw material is below 0.1%;
C) hydrogen-rich gas that hydrogen-rich gas step a) being obtained b) obtains with step mixes, and after circulating hydrogen compressor mixes with new hydrogen, recycles.
2. in accordance with the method for claim 1, it is characterized in that, the step a) boiling range of described high-sulfur feed is 150~700 ℃; Step b) the boiling range of described low-sulfur raw material oil is 150~550 ℃.
3. in accordance with the method for claim 1, it is characterized in that, step a) sulphur content of described sour feedstock more than 1.5wt%, step b) sulphur content of described low-sulfur raw material at 0.01~0.08wt%.
4. in accordance with the method for claim 1, it is characterized in that, the hydroprocessing condition of step described in a) is: reaction pressure 8.0~16.0MPa, and hydrogen to oil volume ratio 200:1~600:1, volume space velocity is 0.1~5.0h
-1, 260 ℃~455 ℃ of temperature of reaction.
5. in accordance with the method for claim 1, it is characterized in that, the hydrocracking condition of step described in b) is: reaction pressure 8.0~16.0MPa, and hydrogen to oil volume ratio 600:1~1500:1, volume space velocity is 0.1~5.0h
-1, 260 ℃~455 ℃ of temperature of reaction.
6. in accordance with the method for claim 1, it is characterized in that, the hydrotreating catalyst of step described in a) comprises the hydrogenation metal of carrier and institute's load, take the weight of catalyzer as benchmark, tungsten and/or molybdenum count 10%~35% with oxide compound, and nickel and/or cobalt count 1%~7% with oxide compound.
7. in accordance with the method for claim 1, it is characterized in that, the hydrocracking catalyst of step described in b) comprises cracking component and hydrogenation component, and take the weight of catalyzer as benchmark, the content of hydrogenation component is 5~40wt%.
8. in accordance with the method for claim 1, it is characterized in that, step a) described in hydrotreatment and step b) described in the reaction pressure of hydrocracking identical or not identical.
9. in accordance with the method for claim 1, it is characterized in that, step c) in, after the hydrogen-rich gas that the hydrogen-rich gas that step a) obtains b) obtains with step mixes, enter in recycle hydrogen surge tank.
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CN103725306B (en) * | 2012-10-10 | 2017-06-06 | 中国石油化工集团公司 | The separation method and device of reforming reaction product |
CN103725313B (en) * | 2012-10-10 | 2017-07-07 | 中国石油化工集团公司 | The B-grade condensation separation method and device of catalytic reforming pre-hydrotreating reaction product |
CN103789030B (en) * | 2012-11-03 | 2015-07-22 | 中国石油化工股份有限公司 | Hydrocracking method of low-sulfur raw materials |
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US6096191A (en) * | 1998-10-28 | 2000-08-01 | Uop Llc | Process for hydrocracking a hydrocarbonaceous feedstock |
CN1952069A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Combined hydrogenation method |
CN101768469A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Combined hydrogenation method for mineral oil and animal and vegetable oil |
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US6096191A (en) * | 1998-10-28 | 2000-08-01 | Uop Llc | Process for hydrocracking a hydrocarbonaceous feedstock |
CN1952069A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Combined hydrogenation method |
CN101768469A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Combined hydrogenation method for mineral oil and animal and vegetable oil |
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