CN100513532C - Technology of heavy oil floating bed hydrocracking - Google Patents
Technology of heavy oil floating bed hydrocracking Download PDFInfo
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- CN100513532C CN100513532C CNB021178356A CN02117835A CN100513532C CN 100513532 C CN100513532 C CN 100513532C CN B021178356 A CNB021178356 A CN B021178356A CN 02117835 A CN02117835 A CN 02117835A CN 100513532 C CN100513532 C CN 100513532C
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Abstract
A suspended-bed hydrocracking technology for heavy oil is characterized by that its hydrocracking reactor is a back-mix-recirculating reactor, a fixed-bed hydrorefining reactor is also used, its catalyst is prepared from the water-soluble salts of multiple metals (Fe, Ni, Mn, Mo and Co), multiple cyclone separators are used in product separating system, and a solvent separating system is used for treating solvent and recovering catalyst.
Description
Technical field:
The present invention relates to a kind of suspension bed hydrogenation process that adopts the composite liquid catalyst of multiple metal water soluble salt, it is the improvement that belongs to the heavy oil hydroprocessing process process in the refining of petroleum technology.It mainly is that floating bed hydrocracking circulation (or empty tube) reactor, many metals of suspension bed high dispersive water soluble salt are catalyst compounded by adopting, the online multistage shearing pump of the online hydrofining reactor of fixed bed and raw material residual oil, catalyzer, promotor mixes and the cryogenic vulcanization system.In the separation system of product, use many cover cyclone separators and solvent treatment and catalyst recovery technology, thereby improved the yield of heavy oil lighting greatly, the cost of product quality and reduction catalyzer.
Background technology:
Suspension bed hydrogenation process research at present is very active in the world, now existing ten kinds of processes are in pilot scale and industrial demonstration unit stage, possessed industrialized condition individually, but these technologies all exist weak point separately, for example 1. German VCC (VEBA-Combi-Cracking) technology of developing, it is to adopt red mud (a kind of ferruginous solids or title Baeyer material) and brown coal finely-ground coke to make catalyzer, and this technology is reaction pressure height (30～75Mpa) but also catalyst levels big (add-on be about raw material 5%) not only.2. the Micro-Cat technology of U.S. Exxon company exploitation, this technology is catalyzer with phospho-molybdic acid and molybdenum naphthenate mainly, though the degree of scatter of catalyzer and activity are all higher, the cost that also rests on lab scale stage (1 barrel/day) and catalyzer so far is very high, economic benefit is not high.3. the entrust HDH technology of Nei Ruina INTEVEP company exploitation, it be with committee's Nei Ruina existing a kind of cheap natural crystal through pulverize and levigate after as catalyzer, though catalyzer low price, but consumption also very big (2～5m%), and the separation system complexity of the solid matter of catalyzer and unconverted tail oil, it is peculiar that this ore only limits to this institute of country simultaneously.4. Canadian CANMET technology, the used catalyzer of this technology is FeSO
4H
2O, add-on is big (1～5%) also, and the desulfurization removing nitric rate of this technology is not high simultaneously, quality product is good inadequately, and catalysis separates also existing problems with the unreacted tail oil.5. the SOC technology that Japanese Asahi Chemical Industry Co., Ltd developed is though this technology has adopted the ultrafine powder of high dispersive type and the catalyzer that transistion metal compound is formed, reactive behavior height.It is better to press down burnt effect, has built up industrial demonstration unit at present, and (20～22Mpa), the plant investment cost is higher but the reaction pressure of this process is still very high.6. for example also has other technology in the world at present in addition: the MRH technology that goes out the common exploitation of wide product company and U.S. Kai Luoge company by Japan; The Aurabon technology of American UOP company exploitation; The small-scale test stage that is in that these technologies such as (HC3) technology of Canada's exploitation have, the catalyst levels that has is big, has plenty of the employing solid catalyst, having plenty of catalyzer costs an arm and a leg, the reaction pressure height, and most of catalyst system therefors are that single catalyst or 1～2 kind of catalyzer are composite in these technologies, and the raw material overwhelming majority that these technology is processed is sulphur-bearing crude, for the bad adaptability of these technologies of sweet crude oil residual oil raw material.
Summary of the invention:
Purpose of the present invention just is to avoid above-mentioned the deficiencies in the prior art part, and has proposed the new technology of heavy oil floating bed hydrocracking of the catalyst compounded floating bed hydrocracking circulation of a kind of multiple metal water soluble salt of employing (or empty tube) reactor.It has mainly carried out multinomial technological innovation and has constituted complete new technology of heavy oil floating bed hydrocracking on hydrocracking process.This technology is catalyst compounded by the multiple metallic salt that adopts full back-mixing formula heavy oil floating bed hydrogenation loop reactor, polymolecularity, and the fixed bed hydrogenation refining reaction device of product, and stock oil and catalyzer, promotor online multistage emulsification pretreatment system of blended and cryogenic vulcanization system mutually.In product separation system, have many cover cyclone separators and solvent treatment and catalyst recovery system, and the freshening treatment technology of wax oil or circulation tail oil etc., thereby heavy oil lighting yield improved greatly, product quality and reduction catalyzer cost.This technology both can solve low sulphur heavy oil, also can solve the processing of high-sulfur heavy oil, and it is effective especially for viscous crude that contains high nitrogen, high metal, high viscosity, high acid value, high carbon residue and residual oil processing.
It mainly is to have adopted the floating bed hydrocracking reactor, the method that online fixed bed hydrogenation refining reaction device combines with product separation system, it is characterized in that having adopted in the floating bed hydrocracking reactor by the composite catalyzer that forms of multiple metal water soluble salt, what the floating bed hydrocracking reactor adopted is full backmixed reactor, described full backmixed reactor is a loop reactor, promptly have guide shell in this reactor, utilize the inside and outside fluid density difference of guide shell to realize that fluid is at the reactor internal recycle, the reaction liquid product of this loop reactor is from the reactor bottom discharge or discharge at the top or top and bottom is discharged simultaneously, or described full backmixed reactor is the sky barrel reactor, and promptly Fan Ying product liquid is discharged through reactor bottom; Described product separation system has adopted many covers cyclone separator that solid-liquid is separated; In the pre-treatment of raw material, adopt multistage shearing tube mixer, raw material and catalyzer and promotor are mixed and cryogenic vulcanization fully, described promotor promptly adds in raw material residual oil and catalyst mix, its purpose is to improve the dispersiveness and the cryogenic vulcanization effect of raw material, and promotor is a water-soluble sulfide; On to the processing of wax oil and tail oil, then adopted the circulation cracking or made the disposable method of raw material by reactor; On to the processing of residue, then adopted the separated from solvent system, made residue further to carry out solvent treatment and catalyzer is reclaimed; The reaction conditions of floating bed hydrocracking reactor is: reaction pressure 8-15Mpa, 420～460 ℃ of temperature of reaction, gross space speed 0.8～1.4, the recycle ratio of tail oil or wax oil/fresh feed is 0～0.8, catalyst levels is 30～2000ppm, promotor agent consumption is 0.01～0.5% of a raw material, and hydrogen is 500～1200 to the fresh feed ratio; The reaction conditions of the online hydrofining reactor of fixed bed is: 300～420 ℃ of temperature of reaction, reaction pressure are a little less than the pressure of floating bed hydrocracking reactor, and air speed is 1.0～2.0h
-1, hydrogen/oil ratio is 300～1500.
The flow process of this technology is: stock oil and catalyzer and promotor enter the floating bed hydrocracking reactor by the bottom after thorough mixing and heating, the top effluent of hydrocracking reactor then enters hot high sub-system to be separated, the vapor phase stream at the high sub-system of heat top enters online fixed bed hydrogenation refining reaction device with the overhead stream of atmospheric flash tower, logistics after refining then enters cold high sub-system again, cold high sub-system overhead stream is handled through oil-poor absorption tower, can obtain product oil, its bottoms then enters atmospheric fractional tower and directly isolates needed product behind water-and-oil separator; The liquid phase stream of hydrocracking reactor bottom then enters primary cyclone, the primary cyclone overhead stream enters the thermal low separation system, the liquid phase stream of thermal low separation system then enters atmospheric flash tower, the bottoms of atmospheric flash tower then enters the secondary cyclone separator, secondary cyclone separator overhead stream both can divide as the circulation tail oil and carried out freshening, also can directly enter vacuum still and once isolate product by flow process, secondary cyclone separator bottoms then enters the three swirler separator with the bottoms of primary cyclone, and the overhead stream of three swirler separator carries out freshening as the circulation tail oil, bottoms enters slag treatment system, thereby obtains demetalization residual oil and metallic sulfide.
The reaction conditions of this floating bed hydrocracking reactor is: reaction pressure 8-15Mpa, 420～460 ℃ of temperature of reaction, gross space speed 0.8～1.4, the recycle ratio of tail oil or wax oil/fresh feed is 0～0.8, catalyst levels is 30～2000ppm, the promotor consumption is 0.01～0.5% of a raw material, and hydrogen is 500～1200 to the fresh feed ratio; The reaction conditions of the online hydrofining reactor of fixed bed is: 300～420 ℃ of temperature of reaction, reaction pressure are a little less than the pressure of floating bed hydrocracking reactor, and air speed is 1.0～2.0h
-1, hydrogen/oil ratio is 300～1500.
In order to realize above-mentioned purpose of the present invention better, it can be that loop reactor (promptly has guide shell in this reactor that the inventor is designed to the full backmixed reactor that is adopted, utilize the inside and outside fluid density difference of guide shell to realize that fluid is at the reactor internal recycle, the reaction liquid product of this loop reactor can be discharged or discharge at the top or top and bottom is discharged simultaneously from reactor bottom), also can be sky barrel reactor (promptly Fan Ying product liquid is discharged through reactor bottom).That is adopted mainly comprises composite dose of two components by the composite catalyzer that forms of multiple metal water soluble salt, as iron-nickel salt, iron-molybdenum salt, iron-manganese salt, iron-cobalt salt etc.; Composite dose of three components, as iron-nickel-molybdenum, iron-nickel-manganese, iron-nickel-cobalt etc.; Composite dose of many components are as based on iron-nickel-molybdenum-manganese.
For dispersiveness and the cryogenic vulcanization effect that improves raw material, the method that raw material is adopted is that promotor is promptly added in raw material residual oil and catalyst mix.Promotor is that its add-on of water-soluble sulfide is 0.01～0.5% of a stock oil; Raw material and mixing of catalyzer, promotor are to adopt multi-level tubular emulsification pretreatment machine and carry out under high rotating speed, after the mixing through the dehydration tower dehydration, thereby reduce the fineness of dispersion of catalyzer greatly, improve the cryogenic vulcanization effect.
A plurality of cyclone separators are set in the separation system of product, thereby most of solid product is separated with product liquid, reduce the solid content in circulation tail oil and the decompression tail oil greatly.
For the processing of circulation tail oil or wax oil is to mix back circulation cracking again with stock oil, also can adopt once by flow process, and promptly raw material is through the hydrocracking after product freshening that do not circulate.
In the end the residue of primary cyclone bottom discharge can be handled with solvent method, to reclaim active princlples such as demetalization residue and metallic sulfide.
Description of drawings:
Accompanying drawing is technical process schematic diagram of the present invention.
The drawing of accompanying drawing is described as follows:
L-1 residual oil process furnace L-2 hydrogen process furnace K-1 floating bed hydrogenation loop reactor
The hot high score K-3 heat of K-2 is low divides K-4 online hydrofining reactor
The cold high score K-7 of K-5 atmospheric flash tower K-6 atmospheric fractional tower
Oil-poor absorption tower 0-1 first cyclone separator of K-8 vacuum still K-9
The 0-2 second cyclone separator 0-3 the 3rd cyclone separator 0-4 catch pot
The 0-5 water-and-oil separator
Embodiment:
Come enumeration design philosophy of the present invention and design advantage below in conjunction with accompanying drawing.
In practical design and in service, planner of the present invention adopts technical process as shown in drawings, and in the floating bed hydrocracking loop reactor, used many metals of high dispersive compositional liquor body catalyst (UPC series), in fixed bed hydrogenation refining reaction device, used industrial commonly used 3936 or 3996 or the RN-2 Hydrobon catalyst.Like this, raw material residual oil (containing high dispersing and the catalyzer behind cryogenic vulcanization) mixes (raw material residual oil can not mix with wax oil or tail oil yet and adopts and once pass through flow process) after fresh feed pump is mixed into residual oil process furnace L-1 with fresh hydrogen again with wax oil or circulation tail oil, after being heated to 380～480 ℃, enter from floating bed hydrogenation loop reactor K-1 bottom (or top).Circulating hydrogen removes hydrogen sulfide and is heated to that the bottom from reactor K-1 enters after 380～480 ℃ after recycle compressor boosts and sends into hydrogen process furnace L-2.
The gaseous stream that comes out from circulation (or empty tube) reactor K-1 top separates through overheated high score K-2, and gas phase partly enters online hydrofining reactor K-4 with the gas phase of atmospheric flash tower K-5 after partially mixed in the lump.The liquid phase stream that comes out from loop reactor K-1 bottom enters the hot low K-3 of branch through its top stream part of cyclone separator 0-1 separation back and after the liquid phase stream of hot high score K-2 mixes, and then enter atmospheric flash tower K-5, isolated gaseous stream enters online hydrofining reactor K-4, its part was as the circulation tail oil during the top that liquid phase stream is separated through cyclone separator 0-2 at the bottom of the tower of atmospheric flash tower K-5 was flowed partly, and remainder enters vacuum still K-8 and isolates wax slop and decompression tail oil.The underflow of separating from cyclone separator 0-1 and cyclone separator 0-2 enters cyclone separator 0-3 in the lump further to be separated, the top stream of 0-3 is also as the circulation tail oil, after the residue of underflow is discharged, can get part demetalization residual oil and little metal sulfide after solvent treatment, this sulfide can be used as the raw material that reclaims catalyzer.
Through the refining after product of online hydrofining reactor K-4 through water Xian with after cold high score K-6 separates, liquid phase stream enters water-and-oil separator 0-5 and isolates sour water, oil phase enters atmospheric fractional tower K-7, fractionate out petroleum naphtha, solar oil and light wax oil, the gaseous stream of cold high score K-6 is through behind the oil-poor absorption tower K-9, and the unabsorbed gases major part is as circulating hydrogen.From the liquid phase process oil-gas separator 0-4 that oil-poor absorption tower K-9 comes out, isolated absorption gas (i.e. reaction generates gas) is further recycled.
By actual motion operation, new technology of the present invention compared with prior art, this following outstanding advantage:
1. since the present invention adopt many metals compositional liquor body catalyst to have the high dispersive performance, catalyst grain size little (0.1～0.5 micron), active high, consumption few (consumption is lower than 0.1%) is many metal components source in the catalyst in addition The cost that is easy to get is low, thereby greatly reduces the running cost of this technology. Simultaneously, because catalyst can adopt two components Metal, three component metals or multicomponent metal water soluble salt built agent, thereby enlarged the selection model of catalyst Enclose, be conducive to the different regions factories and miness and gather materials on the spot.
2. the present invention is owing to adopt co-catalyst greatly to improve the cure efficiency of catalyst under low temperature (being lower than 250 ℃), Thereby further improve the active of catalyst and avoid at high temperature vulcanizing some engineering problems that bring.
3. the present invention has adopted the heavy oil floating bed hydrogenation circulation flow reactor, and this reactor not only makes in the reactor for full back-mixing formula Each position logistics reaction temperature homogeneous; And, owing to adopt continuously lower row's reaction liquid product, thereby from all On solved reactor bottom coke laydown problem, make reactor keep continuous run in long period.
Thereby 4. in product separation system many cover cyclone separators are installed in the technological process of the present invention and are greatly reduced recycle oil And the solid content in the decompression tail oil, improved the device operating condition and also carried for the reasonable utilization of decompression tail oil Having supplied may.
5. the residue of telling in the bottom of cyclone separator 0-3 in the technology of the present invention is processed not only recyclable through solvent Thereby the active principle of part residue oil and recyclable a part of catalyst will further improve the recovery of oil Rate and reduction catalyst cost.
Claims (6)
1. heavy oil floating bed hydrocracking technology, it mainly is to have adopted the floating bed hydrocracking reactor, the method that online fixed bed hydrogenation refining reaction device combines with product separation system, it is characterized in that having adopted in the floating bed hydrocracking reactor by the composite catalyzer that forms of multiple metal water soluble salt, describedly mainly comprise composite dose of composite dose of two components or composite dose of three components or many components by the composite catalyzer that forms of multiple metal water soluble salt, described two components are iron-nickel salt for composite dose, iron-molybdenum salt, iron-manganese salt, iron-cobalt salt, described three components are iron-nickel-molybdenum for composite dose, iron-nickel-manganese, iron-nickel-cobalt, described many components are iron-nickel-molybdenum-manganese for composite dose; What described floating bed hydrocracking reactor adopted is full backmixed reactor, described full backmixed reactor is a loop reactor, promptly have guide shell in this reactor, utilize the inside and outside fluid density difference of guide shell to realize that fluid is at the reactor internal recycle, the reaction liquid product of this loop reactor is from the reactor bottom discharge or discharge at the top or top and bottom is discharged simultaneously, or described full backmixed reactor is the sky barrel reactor, and promptly Fan Ying product liquid is discharged through reactor bottom; Described product separation system has adopted many covers cyclone separator that solid-liquid is separated; In the pre-treatment of raw material, adopt multistage shearing tube mixer, raw material and catalyzer and promotor are mixed and cryogenic vulcanization fully, described promotor promptly adds in raw material residual oil and catalyst mix, its purpose is to improve the dispersiveness and the cryogenic vulcanization effect of raw material, and described promotor is a water-soluble sulfide; On to the processing of wax oil and tail oil, then adopted the circulation cracking or made the disposable method of raw material by reactor; On to the processing of residue, then adopted the separated from solvent system, made residue further to carry out solvent treatment and catalyzer is reclaimed; The reaction conditions of floating bed hydrocracking reactor is: reaction pressure 8-15Mpa, 420～460 ℃ of temperature of reaction, gross space speed 0.8～1.4, the recycle ratio of tail oil or wax oil/fresh feed is 0～0.8, catalyst levels is 30～2000ppm, promotor agent consumption is 0.01～0.5% of a raw material, and hydrogen is 500～1200 to the fresh feed ratio; The reaction conditions of the online hydrofining reactor of fixed bed is: 300～420 ℃ of temperature of reaction, reaction pressure are a little less than the pressure of floating bed hydrocracking reactor, and air speed is 1.0～2.0h
-1, hydrogen/oil ratio is 300～1500.
2. heavy oil floating bed hydrocracking technology according to claim 1, it is characterized in that described technical process is: stock oil and catalyzer and promotor enter the floating bed hydrocracking reactor by the bottom after thorough mixing and heating, the top effluent of hydrocracking reactor then enters hot high sub-system to be separated, the vapor phase stream at the high sub-system of heat top enters online fixed bed hydrogenation refining reaction device with the overhead stream of atmospheric flash tower, logistics after refining then enters cold high sub-system again, cold high sub-system overhead stream is handled through oil-poor absorption tower, can obtain product oil, its bottoms then enters atmospheric fractional tower and directly isolates needed product behind water-and-oil separator; The liquid phase stream of hydrocracking reactor bottom then enters primary cyclone, the primary cyclone overhead stream enters the thermal low separation system, the liquid phase stream of thermal low separation system then enters atmospheric flash tower, the bottoms of atmospheric flash tower then enters the secondary cyclone separator, secondary cyclone separator overhead stream both can divide as the circulation tail oil and carried out freshening, also can directly enter vacuum still and once isolate product by flow process, secondary cyclone separator bottoms then enters the three swirler separator with the bottoms of primary cyclone, and the overhead stream of three swirler separator carries out freshening as the circulation tail oil, bottoms enters slag treatment system, thereby obtains demetalization residual oil and metallic sulfide.
3. heavy oil floating bed hydrocracking technology according to claim 1, it is characterized in that the raw material that is adopted is employing multi-level tubular emulsification pretreatment machine with mixing of catalyzer, promotor and carries out under high rotating speed, dewater through dehydration tower after the mixing, thereby reduce the fineness of dispersion of catalyzer greatly, improve the cryogenic vulcanization effect.
4. heavy oil floating bed hydrocracking technology according to claim 1, it is characterized in that in the separation system of product a plurality of cyclone separators being set, thereby most of solid product is separated with product liquid, reduce the solid content in circulation tail oil and the decompression tail oil greatly.
5. heavy oil floating bed hydrocracking technology according to claim 1, it is characterized in that circulating tail oil or wax oil are mixed back circulation cracking again with stock oil, or adopt once by flow process, and promptly raw material is through the hydrocracking after product freshening that do not circulate.
6. heavy oil floating bed hydrocracking technology according to claim 1 is characterized in that handling with solvent method through the residue that discharge last step cyclone separator bottom, to reclaim demetalization residue and metallic sulfide active princlple.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021178356A CN100513532C (en) | 2002-05-23 | 2002-05-23 | Technology of heavy oil floating bed hydrocracking |
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| CNB021178356A CN100513532C (en) | 2002-05-23 | 2002-05-23 | Technology of heavy oil floating bed hydrocracking |
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| CN1459490A CN1459490A (en) | 2003-12-03 |
| CN100513532C true CN100513532C (en) | 2009-07-15 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148613B (en) * | 2006-09-20 | 2010-10-27 | 中国石油化工股份有限公司 | Hydrocarbons hydrocracking technique |
| CN101294104B (en) * | 2008-06-05 | 2012-02-01 | 华东理工大学 | Hydrocracking recycle hydrogen deoiling, dewatering separation method and apparatus |
| CN102197116B (en) * | 2008-09-18 | 2014-05-14 | 雪佛龙美国公司 | Systems and methods for producing crude product |
| CN102417826B (en) * | 2010-09-27 | 2014-03-26 | 中国石油化工股份有限公司 | Heavy oil hydrogenation conversion method |
| CN103657463B (en) * | 2012-09-21 | 2016-03-30 | 李华 | A kind of gas-liquid mixing processes and application thereof and gas-liquid reaction method |
| CN103254934B (en) * | 2013-06-07 | 2015-03-25 | 上海华畅环保设备发展有限公司 | Rotational flow-washing-rotational flow combined hot high-pressure separation method and device in suspended bed hydrogenation process |
| CN104017601B (en) * | 2014-06-19 | 2016-11-09 | 北京中科诚毅科技发展有限公司 | A kind of residual oil slurry bed system method for hydrogen cracking and device |
| CN104388116B (en) * | 2014-11-10 | 2016-07-06 | 陕西延长石油（集团）有限责任公司 | A kind of heavy poor oil Efficient Conversion technique |
| CN104388117B (en) * | 2014-11-10 | 2016-06-22 | 陕西延长石油（集团）有限责任公司 | A kind of hydrocracking heavy oil produces the method for high-quality fuel oil |
| CN111575054A (en) * | 2020-06-29 | 2020-08-25 | 陕西延长石油（集团）有限责任公司 | Reaction and separation integrated counter-flow type hydrogenation reaction process |
| CN113416578B (en) * | 2021-07-13 | 2023-04-14 | 海南盈科生物科技有限公司 | Refining method of methyl ester residual oil |
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