CN101892075A - Method for transforming, separating and processing heavy oil - Google Patents
Method for transforming, separating and processing heavy oil Download PDFInfo
- Publication number
- CN101892075A CN101892075A CN2010102403579A CN201010240357A CN101892075A CN 101892075 A CN101892075 A CN 101892075A CN 2010102403579 A CN2010102403579 A CN 2010102403579A CN 201010240357 A CN201010240357 A CN 201010240357A CN 101892075 A CN101892075 A CN 101892075A
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- Prior art keywords
- heavy oil
- chloride
- catalyzer
- separating
- reactor
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/08—Halides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
The invention discloses a new method for transforming, separating and processing heavy oil. The separation of heavy oil components is realized by a catalytic conversion and separation method. The method comprises the following steps of: dissolving the heavy oil by taking methylbenzene or dimethylbenzene and the like as solvents; adding a catalyst into the dissolved heavy oil to separate heavier components out of the heavy oil in different phases so as to fulfill the aim of separating heavy components; and separating colloid and asphaltene from the heavy oil by catalytic precipitation to obtain a light oil product with higher quality. Precipitated materials can be taken as raw materials of resin, plastic, paint, filler and the like or asphalt for special purpose. The method has the advantages of small investment, low running cost, flexible process design, capability of excellently solving the problem of the utilization of the heavy oil in a refinery and very high industrial application value.
Description
Technical field
The present invention relates to the isolating novel process of a kind of heavy oil upgrading, mainly is to come heavy oil such as process residual oils, pitch by the isolating method of catalyzed conversion.
Background technology
Mink cell focus mainly refers to long residuum or the vacuum residuum in the crude oil, and it is the most complicated part of relative molecular mass maximum, The Nomenclature Composition and Structure of Complexes in the oil.At present in the laboratory, generally all be to be that solvent comes mink cell focus is separated with low molecule normal paraffin, will wherein be insoluble to low molecule normal paraffin (Skellysolve A, normal hexane or normal heptane etc.) and the material that is dissolved in benzene is defined as bituminous matter.Along with the difference of solvent for use, be called Skellysolve A bituminous matter, normal hexane bituminous matter or normal heptane bituminous matter accordingly.Low molecule normal paraffin can the dissolved part then become " solvent ".With the bituminous matter that solvent method obtains, be relative molecular mass maximum in the mink cell focus, part that polarity is the strongest.This method is called solvent deasphalting.But saturated branch and fragrance divide content more in the pitch that this method obtains, because the performance of solvent is limit the component lighter in the pitch that removes that can't nearlyer goes on foot.
Patent CN1297980 discloses a kind of delayed coking method of de-oiled asphalt, be that de-oiled asphalt is mixed into the delayed coker fractionator bottom separately or with other conventional coking raw material, mix with＞330 ℃ wax oil, be heated to 480～500 ℃ through process furnace, enter the coke drum reaction again, the oil gas that generates enters separation column to be separated, and＞330 ℃ wax oil all mixes with de-oiled asphalt as turning oil and enters process furnace again.This method has guaranteed on-stream time, has overcome, colloid big owing to de-oiled asphalt viscosity and the high problem that causes the delay coking heating furnace coking of asphalt content.But this method need be reacted under hot conditions, and power consumption is high, and is uneconomical economically.
Patent CN1382766 discloses a kind of process for viscosity breaking of deoiled asphalt, be that de-oiled asphalt with solvent deasphalting unit production is a raw material, mix 1～50% fluid catalytic cracking decant oil, enter the upflow visbreaking cracking unit, adopt the operating method of low temperature long residence time, both reduce the viscosity of de-oiled asphalt, guaranteed the macrocyclic running of visbreaking process furnace again.But this quadrat method is just improved the part of viscosity breaking, and oil content is higher in the residual oil that obtains, and heavy constituent such as bituminous matter are dispersed in the oil with a kind of colloidal state usually, do not realize the further separation of heavy oil.
The method of the heavy oil modification that patent CN101007970 provides is: by heavy oil, diesel oil, emulsifying agent, contain benzene compound, contain the printworks trade effluent of aniline and phosphoric acid is reinforced according to a certain ratio, order is carried out circulate repeatedly spray mixing emulsification and the filtration of four steps and is made modification heavy oil in four placed in-line spray mixing emulsors.This invention is to produce oil fuel by the method for circulating emulsion, but its emulsifying process complexity, the industrial investment cost is higher.
Summary of the invention
Technical problem to be solved by this invention is the defective that will overcome above technology, develops a kind of novel process of catalyzed conversion separating and processing heavy oil, reaches the purpose of the separation trans-utilization of heavy constituent in the heavy oil such as residual oil, pitch.
The present invention solves the technological line that its technical problem takes: adopt the isolating method of catalyzed conversion to realize separation to heavy oil component.With toluene or dimethylbenzene is dissolution with solvents heavy oil, adding catalyzer in the heavy oil after dissolving separates out component heavier in the heavy oil at a certain temperature, thereby realize the isolating purpose of heavy constituent, and the heavy constituent of separating out can be used as the raw material or the special purpose pitch of resin, plastics, coating, weighting material etc. from solution.
Concrete technical scheme is: at first with solvent heavy oil is dissolved, solvent comprises tetracol phenixin, chloroform, benzene, toluene, dimethylbenzene, trimethylbenzene, durene, pyridine, quinoline, alkane and the naphthenic hydrocarbon of carbon more than eight, mononuclear aromatics, two rings and trinucleated aromatic hydrocarbon etc., after the heavy oil dissolving, heavy oil and solvent are moving phase, join dissolved heavy oil in the reactor this moment, at 0 ℃～380 ℃, pressure is under 0～10MPa, adds catalyzer in reactor, the part by weight of raw material and catalyzer is 100: (0.1～1000), catalyzer is an anhydrous chloride, is included as iron trichloride, bismuth chloride, aluminum chloride, zinc chloride, calcium chloride, cobalt chloride, cupric chloride, magnesium chloride, nickelous chloride, silver chloride, tin chloride is or/and lithium chloride etc., and the adding mode of catalyzer is to join in the reactor after one or more of above-mentioned anhydrous chloride mix.Catalyzer stirs after adding, and makes reactant react the static again separation that can realize heavy oil component in 1 hour after 10 minutes～6 hours in still.
The present invention is owing to adopt the modification of the isolating method realization of catalyzed conversion to mink cell focus, the heavy constituent in the heavy oil such as residual oil, pitch have been separated preferably, and with low cost, resulting heavy constituent can be used as the raw material or the special purpose pitch of resin, plastics, coating, weighting material etc.
Embodiment
Describe the present invention in detail below in conjunction with embodiment.
Embodiment 1:
Use raw material: blue refining refinery de-oiled asphalt
Concrete steps:
1. the quality of the good anhydrous chlorides of rase zinc catalyst of weighing, about 8 grams are placed in the baking oven dry earlier.
2. heating and melting de-oiled asphalt 101.5 restrains to good fluidity, with 400 gram xylene soluble de-oiled asphalts, in the reactor of packing into after treating to dissolve fully.
With the de-oiled asphalt constant temperature in the reactor at 30 ℃, in reactor, add the catalyzer Zinc Chloride Anhydrous, stirred 6 hours.
4. left standstill one hour, and poured out supernatant liquid.
5. surplus materials in the reactor is transferred in the beaker, clean with distilled water wash, again beaker is put in the baking oven, dry 6 hours, weighing obtained dry weight 8.5 grams.
Embodiment 2:
Use raw material: the Jinan Refinery de-oiled asphalt
Concrete steps:
1. the quality of the good Anhydrous Ferric Chloride of weighing, anhydrous cupric chloride, Zinc Chloride Anhydrous and four kinds of catalyzer of Aluminum chloride anhydrous, every kind of each about 8 gram are placed in the baking oven dry earlier.
2. heating and melting de-oiled asphalt 100 restrains to good fluidity, with 150 gram xylene soluble de-oiled asphalts, in the reactor of packing into after treating to dissolve fully.
With the de-oiled asphalt constant temperature after the dissolving in the reactor at 80 ℃, four kinds of catalyzer of adding in the reactor stirred 3 hours successively.
4. left standstill one hour, and poured out supernatant liquid.
5. surplus materials in the reactor is transferred in the beaker, clean with distilled water wash, again beaker is put in the baking oven, dry 6 hours, weighing obtained dry weight 12.5 grams.
Embodiment 3:
Use raw material: blue refining refinery de-oiled asphalt
Concrete steps:
1. the quality of the good Anhydrous Ferric Chloride of weighing, anhydrous cupric chloride, Zinc Chloride Anhydrous and four kinds of catalyzer of Aluminum chloride anhydrous, every kind of each about 30 gram are placed in the baking oven dry earlier.
2. heating and melting de-oiled asphalt 100 restrains to good fluidity, with 150 gram toluene dissolving de-oiled asphalts, in the reactor of packing into after treating to dissolve fully.
With the de-oiled asphalt constant temperature in the reactor at 80 ℃, add four kinds of catalyzer successively in the reactor, stirred 6 hours.
4. left standstill one hour, and poured out supernatant liquid.
5. surplus materials in the reactor is transferred in the beaker, clean with distilled water wash, again beaker is put in the baking oven, dry 6 hours, weighing obtained dry weight 54.5 grams.
Embodiment 4:
Use raw material: the Jinan Refinery de-oiled asphalt
Concrete steps:
1. the quality of the good Anhydrous Ferric Chloride of weighing, anhydrous cupric chloride, Zinc Chloride Anhydrous and four kinds of catalyzer of Aluminum chloride anhydrous, every kind of each about 8 gram are put in the baking oven dry earlier.
2. heating and melting de-oiled asphalt 100 restrains to good fluidity, with 150 gram toluene dissolving de-oiled asphalts, puts into reactor after the dissolving fully.
With dissolved de-oiled asphalt constant temperature in the reactor at 30 ℃, add four kinds of catalyzer successively in the reactor, stirred 3 hours.
4. left standstill one hour, and poured out supernatant liquid.
5. surplus materials in the reactor is transferred in the beaker, clean with distilled water wash, again beaker is put in the baking oven, dry 6 hours, weighing obtained dry weight 14 grams.
Embodiment 5:
Use raw material: Ji refining refinery de-oiled asphalt
Concrete steps:
1. the quality of the good Anhydrous Ferric Chloride of weighing, anhydrous cupric chloride, Zinc Chloride Anhydrous, Aluminum chloride anhydrous and five kinds of catalyzer of anhydrous chlorides of rase bismuth, every kind of each about 15 gram are placed in the baking oven dry earlier.
2. heating and melting de-oiled asphalt 101.5 restrains to good fluidity, with 200 gram toluene dissolving de-oiled asphalts, in the reactor of packing into after treating to dissolve fully.
With the de-oiled asphalt constant temperature in the reactor at 80 ℃, add five kinds of catalyzer successively in the reactor, stirred 6 hours.
4. left standstill one hour, and poured out supernatant liquid.
5. surplus materials in the reactor is transferred in the beaker, clean with distilled water wash, again beaker is put in the baking oven, dry 6 hours, weighing obtained dry weight 34.98 grams.
See that by experimental result the catalysis settling process can effectively remove the heavy constituent in the pitch.
Method provided by the present invention has realized the advanced treating to de-oiled asphalt, has the following advantages:
1. technological process is simple, and one-time investment is little, and operating cost is low.
2. the restructuring in the pitch can be divided comparatively thoroughly to remove out, the material that settles down can be used as raw material or the specific use pitch of resin, plastics, coating, filler etc.
With the colloid in the mink cell focus, asphalitine after the catalysis sedimentation separation is come out, obtained preferably light-end products of quality.
Claims (3)
1. the method for a transforming, separating and processing heavy oil, it is characterized in that: raw material heavy oil is dissolved with solvent, solvent comprises tetracol phenixin, chloroform, benzene,toluene,xylene, trimethylbenzene, durene, pyridine, quinoline, carbon alkane and the naphthenic hydrocarbon more than eight, mononuclear aromatics, two ring and trinucleated aromatic hydrocarbon.Heavy oil after the dissolving is joined in the reactor, temperature is 0 ℃～380 ℃, pressure is 0～10MPa, add catalyzer in reactor, catalyzer is an anhydrous chloride, and the weight of catalyzer is 0.1%～1000% of raw material, after mixing, the component that is insoluble in the solution is separated out in static phase-splitting, realizes the separation to heavy oil component.
2. heavy oil method of modifying according to claim 1 is characterized in that: said catalyzer is an iron trichloride, bismuth chloride, aluminum chloride, zinc chloride, calcium chloride, cobalt chloride, cupric chloride, magnesium chloride, nickelous chloride, silver chloride, tin chloride or/and lithium chloride a kind of, two or more, mix by weight 1: 0.1～10.
3. heavy oil method of modifying according to claim 1 is characterized in that: used raw material heavy oil comprises vacuum residuum, long residuum and pitch.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102403579A CN101892075A (en) | 2010-07-27 | 2010-07-27 | Method for transforming, separating and processing heavy oil |
| PCT/CN2011/077630 WO2012013142A1 (en) | 2010-07-27 | 2011-07-26 | Heavy oil processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102403579A CN101892075A (en) | 2010-07-27 | 2010-07-27 | Method for transforming, separating and processing heavy oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101892075A true CN101892075A (en) | 2010-11-24 |
Family
ID=43101426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102403579A Pending CN101892075A (en) | 2010-07-27 | 2010-07-27 | Method for transforming, separating and processing heavy oil |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101892075A (en) |
| WO (1) | WO2012013142A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012013142A1 (en) * | 2010-07-27 | 2012-02-02 | 中国石油大学(华东) | Heavy oil processing |
| CN102676217A (en) * | 2012-05-09 | 2012-09-19 | 刘群 | Preparation method of fuel oil |
| CN108187759A (en) * | 2018-01-09 | 2018-06-22 | 商洛学院 | A kind of catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102601A (en) * | 1986-04-10 | 1987-05-13 | 泰州炼油厂 | Process for producing refinly of liquid paraffin by cooling pressure filtration aluminium salt |
| CN1093736A (en) * | 1993-04-16 | 1994-10-19 | 抚顺石油化工公司石油二厂 | The processing method of Pyrolysis gas oil PGO upgrading |
| CN1403539A (en) * | 2002-10-18 | 2003-03-19 | 大连理工大学 | Chemical refining process of eliminating unsoluble oxides and gum from diesel oil |
| CN101921614A (en) * | 2009-04-16 | 2010-12-22 | 通用电气公司 | Remove the method for impurity from hydrocarbon ils |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237151C (en) * | 2002-05-23 | 2006-01-18 | 中国石油天然气股份有限公司 | Treatment technology of residual oil used for heavy oil floating bed hydrocracking |
| CA2428995A1 (en) * | 2003-05-16 | 2004-11-16 | Speros E. Moschopedis | Separation of asphaltenes from bitumen and heavy oils using a metal salt catalyst |
| CN101892075A (en) * | 2010-07-27 | 2010-11-24 | 中国石油大学(华东) | Method for transforming, separating and processing heavy oil |
-
2010
- 2010-07-27 CN CN2010102403579A patent/CN101892075A/en active Pending
-
2011
- 2011-07-26 WO PCT/CN2011/077630 patent/WO2012013142A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102601A (en) * | 1986-04-10 | 1987-05-13 | 泰州炼油厂 | Process for producing refinly of liquid paraffin by cooling pressure filtration aluminium salt |
| CN1093736A (en) * | 1993-04-16 | 1994-10-19 | 抚顺石油化工公司石油二厂 | The processing method of Pyrolysis gas oil PGO upgrading |
| CN1403539A (en) * | 2002-10-18 | 2003-03-19 | 大连理工大学 | Chemical refining process of eliminating unsoluble oxides and gum from diesel oil |
| CN101921614A (en) * | 2009-04-16 | 2010-12-22 | 通用电气公司 | Remove the method for impurity from hydrocarbon ils |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012013142A1 (en) * | 2010-07-27 | 2012-02-02 | 中国石油大学(华东) | Heavy oil processing |
| CN102676217A (en) * | 2012-05-09 | 2012-09-19 | 刘群 | Preparation method of fuel oil |
| CN108187759A (en) * | 2018-01-09 | 2018-06-22 | 商洛学院 | A kind of catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012013142A1 (en) | 2012-02-02 |
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Application publication date: 20101124 |