CN102260527B - New catalytic hydroprocessing thermal cracking-hydrotreating process of high-sulfur high-acid inferior heavy oil - Google Patents
New catalytic hydroprocessing thermal cracking-hydrotreating process of high-sulfur high-acid inferior heavy oil Download PDFInfo
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Abstract
The invention relates to a novel catalytic hydroprocessing thermal cracking-hydrotreating process of high-sulfur high-acid inferior heavy oil. In the process, a tail oil circulating method in which heavy oil catalytic hydroprocessing thermal cracking, distillate hydrotreatment and liquid cyolonic separation treatment of vacuum tail oil are combined is adopted. The novel catalytic hydroprocessing thermal cracking-hydrotreating process of high-sulfur high-acid inferior heavy oil has the characteristics of simple complexing agent dispersion, high distillate yield, good product property and less tailings throwing amount, and can be used for treating high-sulfur high-acid high-metal, high-carbon-residue high-asphaltene inferior heavy oil which is difficultly treated by using the existing processes such as fixed bed hydrocarcking, catalytic cracking and the like; and the yield of the distillate is up to 85%-90%, and the property of the product is good, thus the novel catalytic hydroprocessing thermal cracking-hydrotreating process of high-sulfur high-acid inferior heavy oil has great popularization and application prospects.
Description
Technical field
The invention belongs to the heavy oil lighting technological process in refining of petroleum technique, specifically, relate to a kind of catalytic hydroprocessing thermal cracking of high-sulfur, acid inferior heavy oil and novel process that hydrotreatment is coupled processed.
Background technology
At present, the poor quality oil output of China constantly increases, and in while imported crude oil, high-sulfur, the shared ratio of high-acid crude oil are also the trend of growth.These crude oil with poor quality have high metal, high carbon residue, high-sulfur, high nitrogen, high acid value, high viscosity and light oil containing the low feature of rate, are difficult to, by existing processing technology, it is carried out to cost-effective processing.
Very active to the research of inferior heavy oil hydrocracking or hydrogenation modifying process both at home and abroad, but most of in pilot scale and commerical test degree, only indivedual technique possesses industrialized condition, and, all there is weak point separately in these techniques, the for example 1. EST technology of Italian ENI company, the decompression tail oil of this technology adopts C3 or C4 to carry out solvent deasphalting, de-oiled asphalt (being mainly bituminous matter and catalyzer) circulating reaction, although this technology has possessed industrialized condition, but reaction severity is low, de-oiled asphalt internal circulating load is large, fresh feed air speed is little, economy is not good.2. the HDHPLUS-SHP technology of French Axens/IFP and Venezuela Intevep/PDVSA cooperative development, this technology is the one-pass scheme of fresh feed, use water-soluble catalyst, 2 reactors in series, mode by decompression deep drawing is processed decompression tail oil, and this technique has completed industrial test at present, is just carrying out basic design, but exist facility investment large, the high deficiency of running energy consumption.3. the VRSH technique of Chevron company, 3 reactors in series of this process using, a small amount of catalyzer returns to use by side line continuous separate after, reactivate, rely on the combination of polystep reaction/separating step, make weight components different in stock oil realize substep and transform, this technique is in the industrial test stage at present, but operation is comparatively complicated, quality product is good not, and the separation of catalyzer, activation also existing problems.4. the UniflexTM technique of Uop Inc., this technique is used iron-based nano-dispersed type catalyzer, and add-on is large, and the mode of wax slop circulation cracking makes the decompression tail oil content in the finished product high, and economy is not strong.5. the heavy oil floating bed hydrocracking technique of PetroChina Company Ltd. and Petroleum Univ.'s joint development, this technique has completed industrial test, but owing to using water-soluble catalyst and wax oil recycle scheme, make catalyzer disperse energy consumption high, the tail oil content that reduces pressure in the finished product is large, and economic rate of return is not high.6. in addition, also has at present other similar technique both at home and abroad, for example: VCC floating bed hydrocracking technology and (HCAT/HC) 3 techniques of Headwater company etc. that KBR company and the cooperation of BP company are released, these techniques are mostly all in lab scale and pilot scale stage, exist problem at aspects such as catalyzer, product property or the processing of decompression tail oil, and the raw materials that above-mentioned technique great majority are processed are not inferior heavy oil, but the long residuum of low-sulfur or sulphur-bearing crude.
Summary of the invention
The object of the invention is to avoid above-mentioned the deficiencies in the prior art, and proposed a kind of novel process that uses high-sulfur, acid inferior heavy oil catalytic hydroprocessing thermal cracking and the hydrotreatment of oil soluble recombiner and tail oil recycle scheme to be coupled.This technique be process high-sulfur, acid inferior heavy oil is object, adopt the heavy oil lighting technique that heavy oil catalytic hydroprocessing thermal cracking, distillate hydrogenation are processed and spinning liquid separating treatment decompression tail oil combines, there is recombiner and disperse the feature simple, distillate yield is high, product property good, the tailings amount of getting rid of is little.
Technical solution of the present invention is as follows:
A kind of high-sulfur, acid inferior heavy oil catalytic hydroprocessing thermal cracking-hydrotreatment novel process, this process using the tail oil circulation means that heavy oil catalytic hydroprocessing thermal cracking, distillate hydrogenation are processed and spinning liquid separating treatment decompression tail oil combines, its concrete technology is:
(1) in catalytic hydroprocessing thermal cracking reactor, adopted a kind of oil soluble recombiner, described catalytic hydroprocessing thermal cracking reactor operating condition is: reaction pressure 10～20MPa, 425～455 ℃ of temperature of reaction, combined feed total feed volume space velocity 0.5～1.5h
-1, hydrogen/oil volume ratio is 600～1200, the mass ratio 0.2～0.7 of circulation tail oil/fresh feed, recombiner consumption is 0.1%～0.4% of fresh feed, described catalytic hydroprocessing thermal cracking reactor head material enters the first hot high score, the first hot high score bottom material and catalytic hydroprocessing thermal cracking reactor bottom material enter low point of the first heat in the lump, low point of top noncondensable gas of the first heat removes pipe network, the first low point of heat bottom material enters vacuum fractionation tower, vacuum fractionation tower side stream oil, the cold oil at the first hot high score top material and the first low point of top of heat enters online fixed bed hydrogenation treatment reactor in the lump,
(2) in online fixed bed hydrogenation treatment reactor, contain the conventional hydrotreating catalyst such as hydrofining and hydrocracking that provides, reaction pressure is than the low 1～2MPa of the pressure in catalytic hydroprocessing thermal cracking reactor, temperature of reaction is 320～420 ℃, and volume space velocity is 0.6～2.0h
-1, hydrogen/oil volume ratio is 500～1000, the hot high score of product introduction second of described online fixed bed hydrogenation treatment reactor, the second hot high score top material enters cold high score, cold high score top gas desulfurization enters recycle hydrogen system through circulating hydrogen compressor after processing, cold high score bottom material enters cold low point, cold low point of top gas removed pipe network, cold low point of bottom material enters stripping tower, stripping tower top material is gas and liquid hydrocarbon product, the second hot high score bottom material enters low point of the second heat, low point of top gas of the second heat removed pipe network, the second low point of heat bottom material and stripping tower bottom material enter atmospheric fractional tower in the lump, atmospheric fractional tower top material is naphtha product, side line material is diesel product, bottom material is that vacuum distillate is wax oil product,
(3) the decompression tail oil that wet cyclone flows out for the treatment of vacuum fractionation tower bottom, decompression tail oil mixes with solvent for 1: 1 in mass ratio～1: 4, enter wet cyclone, 80～150 ℃ of temperature, under pressure 0.5～2.0MPa condition, carry out spinning liquid separation, spinning liquid top flows to into top stream solvent recovery tower, spinning liquid underflow enters underflow solvent recovery tower, top stream solvent recovery tower and underflow solvent recovery tower service temperature are 200～250 ℃, working pressure is normal pressure, top stream solvent recovery tower and underflow solvent recovery tower top material are as circulating solvent, mix with decompression tail oil in the lump with fresh solvent, top stream solvent recuperation tower bottom material is as circulation tail oil, with fresh feed, recombiner, hydrogen mixes, underflow solvent recuperation tower bottom material goes out device as outer last person's slag.
Further preferably, the oil soluble recombiner described in step (1) mainly comprises the auxiliary agent of two components or three component oil solube metallic catalyzer, vulcanizing agent and inhibition coking.Two described components or three component oil solube metallic catalyzer are oil-soluble molybdenum-nickel salt, oil soluble cobalt-nickel salt, oil-soluble molybdenum-Ni-Fe salt, oil soluble Co-Ni-Fe salt; Described vulcanizing agent is sulphur powder or dithiocarbonic anhydride; The auxiliary agent of described inhibition coking is a kind of or several mixture of cationic surfactant, anion surfactant, lipid acid and aliphatic amide.
High-sulfur of the present invention, acid inferior heavy oil catalytic hydroprocessing thermal cracking-hydrotreatment novel process, described in step (1), catalytic hydroprocessing thermal cracking reactor is the reactor with upper and lower discharge function.
High-sulfur of the present invention, acid inferior heavy oil catalytic hydroprocessing thermal cracking-hydrotreatment new technological flow are: certainly install external stock oil and come from recombiner that recombiner pump extracts out after multistage static mixer and multi-buffer tank mix, with the turning oil incoming stock oily surge tank in the lump in circulation oil tank, surge tank adopts the mode of mechanical stirring or pump circulation, and recombiner, stock oil and turning oil are fully mixed.Mixed raw material with High pressure feeding pump extract out after heat exchange with from the external fresh hydrogen of device and come from the recycle hydrogen incoming stock oily process furnace in the lump of circulating hydrogen compressor, enter again catalytic hydroprocessing thermal cracking reactor after being heated to 425～455 ℃ of predetermined temperature of reaction.In catalytic hydroprocessing thermal cracking reactor, mix hydrogen and stock oil catalytic hydroprocessing thermal cracking reaction occurs under the effect of high temperature, high pressure and catalyzer.The reaction product temperature flowing out from catalytic hydroprocessing thermal cracking reactor head reaches 420～440 ℃, in order to prevent coking in in-line and high pressure hot separator, inject light cycle oil at reactor head pipeline and enter the first hot high score after being chilled to 400 ℃, the gas flashing off from the first hot high score top with come from the first heat cold oil at low point of top and the vacuum distillate of vacuum fractionation tower side line and enter in the lump online fixed bed hydrogenation treatment reactor and carry out hydrotreatment.The reaction product flowing out from catalytic hydroprocessing thermal cracking reactor bottom enters in the lump low point of the first heat with the first hot high score bottom material after being chilled to 400 ℃, the gas flashing off from first low point of top of heat enters online fixed bed hydrogenation treatment reactor in the lump through the side stream oil of cooled cold oil and vacuum fractionation tower, non-condensable gas enters pipe network, and the generation oil of the first low point of bottom of heat enters decompression process furnace.Online fixed bed hydrogenation treatment reactor bottoms enters the second hot high score, the gas that the second hot high score top flashes off enters cold high score, cold high score top gas desulfurization enters recycle hydrogen system through circulating hydrogen compressor after processing, cold high score bottom cold oil enters cold low point, cold low point of top gas enters pipe network, and cold low point of bottom cold oil enters fractionating system; The second hot high score bottom material enters low point of the second heat, and low point of top gas of the second heat enters pipe network, and the second low point of heat bottom material enters fractionating system.
The generation oil of the first low point of bottom of heat enters decompression process furnace and enter vacuum fractionation tower after heating, the cold oil at the gas that tower side line vacuum distillate and the first hot high score top flash off and the first low point of top of heat enters in the lump online fixed bed hydrogenation treatment reactor after heat exchange, and at the bottom of tower, vacuum residuum enters decompression tail oil solvent treatment system.Cold low point of bottom cold oil enters stripping tower, tower top effluent is gas and liquid hydrocarbon product, low point of bottom material of materials at bottom of tower and the second heat enters in the lump atmospheric pressure kiln and enter atmospheric fractional tower after heating, after atmospheric fractional tower fractionation, tower top is that naphtha fraction is as ethylene cracking material or catalytic reforming raw material, tower side line flows out diesel oil distillate directly as diesel product, and it is the stock oil of wax oil as catalytic cracking unit that tower bottom flow goes out vacuum distillate.
It is, after the solvent of 1: 1～1: 4, to enter wet cyclone that vacuum residuum at the bottom of vacuum fractionation tower tower mixes its mass ratio, revolves a point top and flows to into top stream solvent recovery tower, revolves a point underflow and enters underflow solvent recovery tower.The recovery solvent that top stream solvent recovery tower and underflow solvent recuperation column overhead obtain is in the lump as circulating solvent, after circulating solvent mixes with fresh solvent, with vacuum residuum by certain mass than mixing, after top stream solvent recuperation tower bottom material mixes with fresh feed, recombiner as circulation tail oil, enter stock oil surge tank, underflow solvent recuperation tower bottom material is as outer last person's residue product.
The difference of high-sulfur of the present invention, acid inferior heavy oil catalytic hydroprocessing thermal cracking one hydrotreatment novel process and existing all kinds of hydrogenation techniques is:
(1) handling object of this technique is high-sulfur, peracid, high metal, high carbon residue, high bitum inferior heavy oil.
(2) the catalytic hydroprocessing thermal cracking reactor of this technique uses a kind of oil soluble recombiner, this oil soluble recombiner mainly comprises the auxiliary agent of two components or three component oil solube metallic catalyzer, vulcanizing agent and inhibition coking, and described two components or three component oil solube metallic catalyzer are oil-soluble molybdenum-nickel salt, oil soluble cobalt-nickel salt, oil-soluble molybdenum-Ni-Fe salt, oil soluble Co-Ni-Fe salt; Described vulcanizing agent is sulphur powder or dithiocarbonic anhydride; The auxiliary agent of described inhibition coking is a kind of or several mixture of cationic surfactant, anion surfactant, lipid acid and aliphatic amide.The dispersing technology simple possible of this recombiner in stock oil, energy consumption is low.
(3) this process using tail oil recycle scheme, main products is petroleum naphtha, diesel oil, vacuum distillate and a small amount of outer last person's slag.
(4) mode that this process using catalytic hydroprocessing thermal cracking reactor and online fixed bed hydrogenation treatment reactor combine, not only takes full advantage of existing temperature of reaction and pressure, and makes product property good.
(5) this process using spinning liquid separate mode process tail oil, make loop tail oil nature better, be difficult for green coke, reduced the outer discharge capacity of tailings simultaneously.
Compared with prior art, beneficial effect of the present invention is:
(1) dispersing technology of oil soluble recombiner is simple, and energy consumption is little, and recombiner consumption is little, and cost is low, processes the recombiner cost that fresh feed per ton uses and is less than 100 yuans.
(2) catalytic hydroprocessing thermal cracking temperature of reaction is high is 425～455 ℃, and distillate yield is high is 85%～90%, and few its of system green coke is less than 1%.
(3) be less than 480 ℃ of cuts through online fixed bed hydrogenation processing, product characteristics is good, naphtha fraction can be used as catalytic reforming or ethylene cracking material, and diesel oil distillate can be directly as high-quality clean diesel product, and vacuum distillate can be used as the raw material of catalytic cracking unit.
The present invention can process the reluctant high-sulfur of technique, peracid, high metal, high carbon residue, the high bitum inferior heavy oil such as existing fixed bed hydrogenation cracking, catalytic cracking, its distillate yield is up to 85%～90%, product property is good, therefore has great popularizing application prospect.
Accompanying drawing explanation
Fig. 1 is the schema of high-sulfur of the present invention, acid inferior heavy oil catalytic hydroprocessing thermal cracking-hydrotreatment novel process.
Embodiment
Below in conjunction with the drawings and specific embodiments, novel process of the present invention is described in further detail.In actual design and in service, planner of the present invention adopts technical process as shown in drawings, fresh feed, circulation tail oil and oil soluble recombiner mix through multi-buffer tank and multistage static mixer, and this hybrid mode can guarantee that a small amount of recombiner is evenly dispersed in a large amount of raw materials.Compound is mixed into process furnace with fresh hydrogen and recycle hydrogen again, after being heated to 425～455 ℃, process furnace enters catalytic hydroprocessing thermal cracking reactor from bottom, at reaction pressure 10～20MPa, under 425～455 ℃ of conditions of temperature of reaction, carry out catalytic hydroprocessing thermal cracking reaction, higher temperature of reaction can guarantee higher transformation efficiency, the existence of recombiner can reduce green coke and the coking in reactor, guarantees the long-term operation of technique.
The reaction product temperature flowing out from catalytic hydroprocessing thermal cracking reactor head reaches 420～440 ℃, in order to prevent coking in in-line and high pressure hot separator, inject light cycle oil at reactor head pipeline and enter the first hot high score after being chilled to 400 ℃, the gas flashing off from the first hot high score top with come from the first heat cold oil at low point of top and the vacuum distillate of vacuum fractionation tower side line and enter in the lump online fixed bed hydrogenation treatment reactor and carry out hydrotreatment.The reaction product flowing out from catalytic hydroprocessing thermal cracking reactor bottom enters in the lump low point of the first heat with the first hot high score bottom material after being chilled to 400 ℃, the gas flashing off from first low point of top of heat enters online fixed bed hydrogenation treatment reactor in the lump through the side stream oil of cooled cold oil and vacuum fractionation tower, non-condensable gas enters pipe network, and the generation oil of the first low point of bottom of heat enters decompression process furnace.Online fixed bed hydrogenation treatment reactor bottoms enters the second hot high score, the gas that the second hot high score top flashes off enters cold high score, cold high score top gas desulfurization enters recycle hydrogen system through circulating hydrogen compressor after processing, cold high score bottom cold oil enters cold low point, cold low point of top gas enters pipe network, and cold low point of bottom cold oil enters fractionating system; The second hot high score bottom material enters low point of the second heat, and low point of top gas of the second heat enters pipe network, and the second low point of heat bottom material enters fractionating system.This technology mode can guarantee all can obtain hydrotreatment through the reacted petroleum naphtha of catalytic hydroprocessing thermal cracking, diesel oil and reduced pressure distillate oil production, improves product property.
The generation oil of the first low point of bottom of heat enters decompression process furnace and enter vacuum fractionation tower after heating, the cold oil at the gas that tower side line vacuum distillate and the first hot high score top flash off and the first low point of top of heat enters in the lump online fixed bed hydrogenation treatment reactor after heat exchange, and at the bottom of tower, vacuum residuum enters decompression tail oil solvent treatment system.Cold low point of bottom cold oil enters stripping tower, tower top effluent is gas and liquid hydrocarbon product, low point of bottom material of materials at bottom of tower and the second heat enters in the lump atmospheric pressure kiln and enter atmospheric fractional tower after heating, after atmospheric fractional tower fractionation, tower top is that naphtha fraction is as ethylene cracking material or catalytic reforming raw material, tower side line flows out diesel oil distillate directly as diesel product, and tower bottom flow goes out the stock oil of vacuum distillate (wax oil) as catalytic cracking unit.
It is, after the solvent of 1: 1～1: 4, to enter wet cyclone that vacuum residuum at the bottom of vacuum fractionation tower tower mixes its mass ratio, revolves a point top and flows to into top stream solvent recovery tower, revolves a point underflow and enters underflow solvent recovery tower.The recovery solvent that top stream solvent recovery tower and underflow solvent recuperation column overhead obtain is in the lump as circulating solvent, after circulating solvent mixes with fresh solvent, with vacuum residuum by certain mass than mixing, after top stream solvent recuperation tower bottom material mixes with fresh feed, recombiner as circulation tail oil, enter stock oil surge tank, underflow solvent recuperation tower bottom material is as outer last person's residue product.This decompression tail oil processing mode can guarantee to circulate in tail oil and contain less easy green coke component, and reduces the outer discharge capacity of tailings.
The example that by technical process of the present invention, Venezuela's oil fuel is carried out pilot scale below:
The reaction conditions of Venezuela's oil fuel on 30 tons/year of catalytic hydroprocessing thermal crackings and hydrotreatment pilot plant is: 440 ℃ of catalytic hydroprocessing thermal cracking temperature, and reaction pressure 12.0MPa, hydrogen/oil volume is than 800: 1, combined feed total feed air speed 1.0h
-1, fresh feed air speed 0.74h
-1; Fixed bed hydrogenation is processed 365 ℃ of average reaction temperature, reactor outlet stagnation pressure 11.0MPa, and hydrogen/oil volume is than 800: 1, charging air speed 0.8h
-1.In product, be less than 90% left and right that 480 ℃ of products account for fresh feed, concrete data are as follows:
(1) Venezuela's oil fuel reaction after product distributes
| Products distribution, w% | Numerical value |
| Dry gas | 2.31 |
| Liquefied gas | 3.75 |
| Petroleum naphtha (IBP～180 ℃) | 9.75 |
| Diesel oil distillate (180～350 ℃) | 40.26 |
| Vacuum distillate (350～480 ℃) | 33.75 |
| Outer last person's slag | 10.18 |
| Add up to | 100 |
| Hydrogen consumption | 2.30 |
(2) naphtha fraction (IBP～180 ℃) composition and character
| Project | Numerical value |
| Fractions consisting, ℃ | IBP～180 |
| Hydrocarbon system's composition, w% | |
| Normal paraffin | 17.02 |
| Isoparaffin | 37.15 |
| Alkene | 0.00 |
| Naphthenic hydrocarbon | 26.01 |
| Aromatic hydrocarbon | 19.82 |
| Density (20 ℃), gcm -3 | 0.7723 |
| Acidity, mgKOH/100ml | 0.21 |
| S，μg·ml -1 | 38.22 |
| N，μg·ml -1 | 14.21 |
| Basic nitrogen, μ gg -1 | 5.03 |
| Octane value (organon) | 78 |
(3) diesel oil distillate (180～350 ℃) composition and character
| Project | Numerical value |
| Fractions consisting, ℃ | 180～350 |
| Density (20 ℃), gcm -3 | 0.8568 |
| Viscosity (50 ℃), mm 2·s -1 | 3.31 |
| Condensation point, ℃ | -24.0 |
| Acidity, mgKOH/100ml | 0.50 |
| S，μg·g -1 | 39.71 |
| N，μg·g -1 | 19.54 |
| Basic nitrogen, μ gg -1 | 7.42 |
| Colourity, number | 0.5 |
| Flash-point, ℃ | 87.0 |
| Cetane value | 50 |
(4) reduced pressure distillate oil distillate (350～480 ℃) composition and character
| Project | Numerical value |
| Fractions consisting, ℃ | 350～480 |
| Density (20 ℃), gcm -3 | 0.8912 |
| Viscosity (50 ℃), mm 2·s -1 | 32.42 |
| Viscosity (80 ℃), mm 2·s -1 | 8.76 |
| Condensation point, ℃ | 26 |
| Acid number, mgKOH/g | 0.06 |
| Carbon residue, w% | 0.12 |
| C，w％ | 86.61 |
| H，w％ | 13.10 |
| S，μg·g -1 | 237.61 |
| N，μg·g -1 | 54.83 |
Claims (1)
1. a high-sulfur, acid inferior heavy oil catalytic hydroprocessing thermal cracking one hydrotreatment novel process, it is characterized in that, this process using the tail oil circulation means that heavy oil catalytic hydroprocessing thermal cracking, distillate hydrogenation are processed and spinning liquid separating treatment decompression tail oil combines, its concrete technology is:
(1) in catalytic hydroprocessing thermal cracking reactor, adopted a kind of oil soluble recombiner, described catalytic hydroprocessing thermal cracking reactor operating condition is: reaction pressure 10～20MPa, 425～455 ℃ of temperature of reaction, combined feed total feed volume space velocity 0.5～1.5h
-1, hydrogen/oil volume ratio is 600～1200, the mass ratio 0.2～0.7 of circulation tail oil/fresh feed, recombiner consumption is 0.1%～0.4% of fresh feed, described catalytic hydroprocessing thermal cracking reactor head material enters the first hot high score, the first hot high score bottom material and catalytic hydroprocessing thermal cracking reactor bottom material enter low point of the first heat in the lump, low point of top noncondensable gas of the first heat removes pipe network, the first low point of heat bottom material enters vacuum fractionation tower, vacuum fractionation tower side stream oil, the cold oil at the first hot high score top material and the first low point of top of heat enters online fixed bed hydrogenation treatment reactor in the lump,
(2) in online fixed bed hydrogenation treatment reactor, contain the conventional hydrotreating catalyst that hydrofining and hydrocracking are provided, reaction pressure is than the low 1～2MPa of the pressure in catalytic hydroprocessing thermal cracking reactor, temperature of reaction is 320～420 ℃, and volume space velocity is 0.6～2.0h
-1, hydrogen/oil volume ratio is 500～1000, the hot high score of product introduction second of described online fixed bed hydrogenation treatment reactor, the second hot high score top material enters cold high score, cold high score top gas desulfurization enters recycle hydrogen system through circulating hydrogen compressor after processing, cold high score bottom material enters cold low point, cold low point of top gas removed pipe network, cold low point of bottom material enters stripping tower, stripping tower top material is gas and liquid hydrocarbon product, the second hot high score bottom material enters low point of the second heat, low point of top gas of the second heat removed pipe network, the second low point of heat bottom material and stripping tower bottom material enter atmospheric fractional tower in the lump, atmospheric fractional tower top material is naphtha product, side line material is diesel product, bottom material is that vacuum distillate is wax oil product,
(3) the decompression tail oil that wet cyclone flows out for the treatment of vacuum fractionation tower bottom, decompression tail oil mixes with solvent for 1: 1 in mass ratio～1: 4, enter wet cyclone, 80～150 ℃ of temperature, under pressure 0.5～2.0MPa condition, carry out spinning liquid separation, spinning liquid top flows to into top stream solvent recovery tower, spinning liquid underflow enters underflow solvent recovery tower, top stream solvent recovery tower and underflow solvent recovery tower service temperature are 200～250 ℃, working pressure is normal pressure, top stream solvent recovery tower and underflow solvent recovery tower top material are as circulating solvent, mix with decompression tail oil in the lump with fresh solvent, top stream solvent recuperation tower bottom material is as circulation tail oil, with fresh feed, recombiner, hydrogen mixes, underflow solvent recuperation tower bottom material goes out device as outer last person's slag,
Oil soluble recombiner described in step (1) mainly comprises the auxiliary agent of two components or three component oil solube metallic catalyzer, vulcanizing agent and inhibition coking, and two described components or three component oil solube metallic catalyzer are oil-soluble molybdenum-nickel salt, oil soluble cobalt-nickel salt oil-soluble molybdenum-Ni-Fe salt, oil soluble Co-Ni-Fe salt; Described vulcanizing agent is sulphur powder or dithiocarbonic anhydride; The auxiliary agent of described inhibition coking is a kind of or several mixture of cationic surfactant, anion surfactant, lipid acid and aliphatic amide;
Described in step (1), catalytic hydroprocessing thermal cracking reactor is the reactor with upper and lower discharge function.
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| CN104164255A (en) * | 2013-05-20 | 2014-11-26 | 中国石油大学(华东) | Inferior heavy oil hydro-thermal cracking and tail oil decarbonization composite process and device |
| CN104888666A (en) * | 2015-05-07 | 2015-09-09 | 北京中科诚毅科技发展有限公司 | Temperature control method for slurry bed reactor, design method and application thereof |
| CN108587668A (en) * | 2018-03-29 | 2018-09-28 | 南京大学连云港高新技术研究院 | A kind of method of inferior heavy oil cracking waste plastics desulfurization visbreaking production light petroleum gas |
| CN112500917B (en) * | 2020-11-12 | 2022-04-26 | 青岛翌星环保技术有限公司 | Waste lubricating oil hydrogenation recycling method |
| CN112500916B (en) * | 2020-11-12 | 2022-04-15 | 中国石油大学(华东) | Method for purifying waste lubricating oil by hydrogen pretreatment |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295112A (en) * | 2000-11-02 | 2001-05-16 | 中国石油天然气股份有限公司 | Novel normal-pressure heavy oil suspension bed hydrogenation process adopting multi-metal liquid catalyst |
| CN1324917A (en) * | 2000-05-19 | 2001-12-05 | 中国石油化工集团公司 | Heavy oil and residual oilk hydrogenating conversion process |
| CN1386826A (en) * | 2002-05-23 | 2002-12-25 | 中国石油天然气股份有限公司 | Cyclone separation technology for on-line separation of solid-phase substances in hydrogenated tail oil |
| CN1459489A (en) * | 2002-05-23 | 2003-12-03 | 中国石油天然气股份有限公司 | Method for treating heavy oil suspension bed hydrogenation tail oil by solvent extraction technology |
| CN1594509A (en) * | 2004-07-02 | 2005-03-16 | 中国科学院山西煤炭化学研究所 | Process for hydrocracking of Fischer-Tropsch synthesized heavy hydrocarbon and/or kettle bottom wax |
-
2011
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324917A (en) * | 2000-05-19 | 2001-12-05 | 中国石油化工集团公司 | Heavy oil and residual oilk hydrogenating conversion process |
| CN1295112A (en) * | 2000-11-02 | 2001-05-16 | 中国石油天然气股份有限公司 | Novel normal-pressure heavy oil suspension bed hydrogenation process adopting multi-metal liquid catalyst |
| CN1386826A (en) * | 2002-05-23 | 2002-12-25 | 中国石油天然气股份有限公司 | Cyclone separation technology for on-line separation of solid-phase substances in hydrogenated tail oil |
| CN1459489A (en) * | 2002-05-23 | 2003-12-03 | 中国石油天然气股份有限公司 | Method for treating heavy oil suspension bed hydrogenation tail oil by solvent extraction technology |
| CN1594509A (en) * | 2004-07-02 | 2005-03-16 | 中国科学院山西煤炭化学研究所 | Process for hydrocracking of Fischer-Tropsch synthesized heavy hydrocarbon and/or kettle bottom wax |
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