CN1237151C - Treatment technology of residual oil used for heavy oil floating bed hydrocracking - Google Patents
Treatment technology of residual oil used for heavy oil floating bed hydrocracking Download PDFInfo
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- CN1237151C CN1237151C CN 02117838 CN02117838A CN1237151C CN 1237151 C CN1237151 C CN 1237151C CN 02117838 CN02117838 CN 02117838 CN 02117838 A CN02117838 A CN 02117838A CN 1237151 C CN1237151 C CN 1237151C
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Abstract
The present invention relates to a technology for processing residual oil produced by the suspended bed hydrocracking of heavy oil, which is a special technology for processing residual oil separated by a liquid-liquid rotational flow in the suspended bed hydrocracking technology of heavy oil. The technology is characterized in that a solvent with strong polarity is used for extracting the residue oil, and the extract is post-treated with a specific mixed acid, and thus, clean scrap metal compounds and demetallized oil are obtained. The technology is suitable for treating the residual oil developed by the suspended bed hydrocracking of various kinds of heavy crude, extra-thick and super-thick crude oil and residual oil thereof (atmospheric residual oil and vacuum residual oil) comprising various kinds of heavy oil with high sulfur and high metal, various kinds of thick residual oil with high metal, high carbon residue, high viscosity and high nitrogen and various kinds of extra-thick and super-thick crude oil.
Description
The present invention relates to a kind of treatment technology that is used for the residual oil of heavy oil floating bed hydrocracking, it belongs to the dedicated processes technology to the residual oil after the liquid-liquid cyclonic separation in the heavy oil floating bed hydrocracking technology of present exploitation.It mainly is by the stronger solvent of employing polarity residual oil to be carried out extracting, and carries out aftertreatment by specific mixing acid, thereby obtains comparatively clean scrap metal compound and metal removal oil.
At present, heavy oil floating bed hydrocracking technology is one of inferior heavy oil deep processing effective ways, the charging of this technology is generally the inferior heavy oil and special thick, the high viscous crude of high metal, high carbon residue, high viscosity, high nitrogen, the catalyzer that uses is disperse type catalyzer, carry out under 420～490 ℃ of temperature of reaction and 7.0～14Mpa reaction pressure, fraction oil yield is up to 70～95%.Though the floating bed hydrocracking reaction conversion ratio is very high, but still have 5～10% even more unconverted oil, this part unconverted oil is exactly the vacuum residuum of floating bed hydrocracking synthetic oil, it is except containing oil content, colloid, bituminous matter and toluene insoluble beyond the region of objective existence, also contain most metals and all metal catalysts in the reaction feed, thereby this unconverted oil character is relatively poor, and reprocessing or processing are also just very difficult.Split the change catalyzer that uses in the technology at heavy oil floating bed hydrogenation and divide solid powder th-1 catalyst, water-soluble catalyst, oil-soluble catalyst.Because the catalyst activity that floating bed hydrocracking uses is not very high, hydrocracking process mainly is based on heat cracking reaction, the purpose of adding catalyzer is to suppress colloid and the reaction of bitum condensation green coke, therefore no matter use the catalyzer of that type, a certain amount of Jiao of inevitable generation in the hydrogenation process.When pressed powder type catalyzer is used in the floating bed hydrogenation reaction, because the solid powder th-1 catalyst dispersity is limited, add-on is big (accounting for reaction raw materials 2～5%), thereby contain thing in the unconverted oil admittedly and account for more than 10%, admittedly containing thing through the residue after the de-oiling accounts for more than 50%, this residue generally be burn, landfill or catalyst recovery, as using the local rich a kind of cheap natural crystal that produces as catalyzer in the exploitation HDH of the Venezuela INTEVEP company technology, add-on is 2～5m%, and unconverted oil need be isolated spent catalyst.The spent catalyst of separating can landfill, also can manipulation of regeneration.Though the floating bed hydrocracking technology of oil soluble and water-soluble catalyst is in the research and development stage at present.(HC) as the proposition of the husky mechanism of Canadian Alberta oil
3Technology, the catalyzer of use is the colloid iron carbonyl, and dispersity is higher, and add-on is few, and this technology is in the lab scale stage; Chevron research company and Exxon research engineering company have done more research work to water-soluble catalyst as hydrocracking catalyst for suspension bed, still be in the laboratory study stage at present, relevant floating bed hydrocracking adopts the Residual oil treatment technology of these catalyzer not appear in the newspapers.Because floating bed hydrocracking is based on heat cracking reaction, generate burnt phase (toluene insolubles) except containing because of condensation reaction in the reaction system, also contain and add metal component in catalyst solid phase and the raw material, these out-phase material concentrations will further improve in the unconverted oil, utilize the spinning liquid isolation technique major part in the floating bed hydrocracking unconverted oil can be contained thing admittedly and separate (the present invention separates material with spinning liquid and is defined as residue), this part contains thing admittedly and contains most metals in the unconverted oil, most of toluene insolubles and part bituminous matter, colloid, therefore, the unconverted oil carbon residue and the metal content that take off residue will obviously reduce, character also improves, can freshening or act as a fuel oil and other purposes, and the residue of telling still need further be handled.
Purpose of the present invention provides a kind of treatment technology that is used for the residual oil of heavy oil floating bed hydrocracking with regard to being to avoid above-mentioned the deficiencies in the prior art part, mainly be by adopting the stronger solvent of polarity that residual oil is carried out extracting, and carry out aftertreatment, thereby obtain comparatively clean scrap metal compound and metal removal oil by specific mixing acid.In actually operating, the temperature of extracting solvent for use can be at 20～200 ℃, and its agent-oil ratio can be 1～10: 1; Employed mixing acid can be the mixing acid of sulfuric acid and nitric acid, and its blended volume ratio is 0.05～10: 1.
Technical characterstic of the present invention and effect are described in detail in detail below in conjunction with specific embodiments:
In reality is implemented, the residue of separating with the unconverted oil spinning liquid in Petroleum Univ. (East China) exploitation " heavy oil floating bed hydrocracking technology " (being called for short UPC-RSHC technology) (this part residue generally account for suspension bed fresh feed 2～7%) is an object, adopt the stronger solvent treatment residual oil of polarity, obtain demetalization residual oil and scrap metal compound after filtration, the demetalization residual oil is directly made fuel or is transferred in the coal as industrial fuel and uses or as the raw material of secondary processing, the scrap metal compound adopts mixing acid to handle, and obtains recycling hydrocracking catalyst for suspension bed raw material.Below table 1 and table 2 be exactly respectively to the do not circulate treatment effect of Residual oil and to floating bed hydrocracking unconverted oil circulation back Residual oil treatment effect of floating bed hydrocracking unconverted oil:
The table 1 pair floating bed hydrocracking unconverted oil Residual oil result that do not circulate
| The oil sample title | Kelamayi, Xinjiang long residuum |
| Reaction conditions: temperature of reaction reaction pressure fresh feed air speed＞524 ℃ of unconverted oil yield unconverted oil circulations | 440℃ 12Mpa 1.0h -118% is not |
| The residue yield ①(accounting for fresh feed) | 8％ |
| Residue treatment is used solvent demetallization residue yield (accounting for residue) scrap metal compound yield (accounting for residue) | Quinoline 85% 15% |
| The utilization of demetalization residue | Call in and subtract slag as coking raw material |
| Handling the scrap metal compound uses acid treatment acid to form | Mixing acid sulfuric acid: nitric acid=3: 2 (V/V) |
| The catalyzer raw material M rate of recovery (accounting for residue) | 75％ |
Table 2 floating bed hydrocracking unconverted oil circulation back Residual oil result
| The oil sample title | Kelamayi, Xinjiang long residuum |
| Reaction conditions: temperature of reaction reaction pressure fresh feed air speed＞524 ℃ of unconverted oil yield unconverted oil circulations | 440℃ 12Mpa 0.5h -17% circulation |
| The residue yield ②(accounting for fresh feed) | 4％ |
| Residue treatment is used solvent demetallization residue yield (accounting for residue) scrap metal compound yield (accounting for residue) | Quinoline 80% 20% |
| The utilization of demetalization residue | Call in and subtract slag as coking raw material |
| Handling the scrap metal compound uses acid treatment acid to form | Mixing acid sulfuric acid: nitric acid=3: 2 (V/V) |
| The catalyzer raw material M rate of recovery (accounting for residue) | 79％ |
Compared with prior art, the present invention has following outstanding characteristics:
(1) raw material of Chu Liing is the residual oil that floating bed hydrocracking unconverted oil spinning liquid is separated, rather than unconverted oil or cracking tail oil, greatly reduces treatment capacity.
(2) adopt the very strong solvent of polarity, can peel off the carbon distribution (toluene insolubles) on the scrap metal compound, obtain the scrap metal compound (overwhelming majority is spent catalyst) of comparison " totally ".
(3) demetalization residue metal content is very low, ash oontent is very low, has improved the performance of utilizing of demetalization Residual oil greatly.
(4) adopt nitration mixture to handle the scrap metal compound, reduce cost, improved the rate of recovery of catalyzer raw material.
The treatment technology that is used for the residual oil of heavy oil floating bed hydrocracking of the present invention is applicable to various heavy crude, special thick, high viscous crude and residual oil (long residuum, vacuum residuum) thereof, comprises the residue treatment of the viscous crude residual oil and special thick, that high viscous crude the is developed heavy oil floating bed hydrocracking of the heavy oil of various high-sulfurs, high metal and high metal, high carbon residue, high viscosity, high nitrogen.Along with heavy crude, high-sulfur crude oil and special thick, high viscous crude produced quantity increase in the world wide, heavy oil floating bed hydrocracking technology has wide application prospect, and heavy oil and viscous crude floating bed hydrocracking residue treatment technology also have wide application prospect.
Claims (2)
1. the treatment technology that is used for the residual oil of heavy oil floating bed hydrocracking, it mainly is to adopt the very strong solvent of polarity that the residual oil of heavy oil floating bed hydrocracking is handled, handle with mixing acid again, it is characterized in that handling to as if heavy oil floating bed hydrogenation technology in the Residual oil after spinning liquid separates, the intensive polar solvent that is adopted in treating processes mainly is a quinoline, arsenic is coughed up, tetracol phenixin, dithiocarbonic anhydride, obtain scrap metal compound and demetalization Residual oil after filtration, then also to adopt mixing acid to carry out aftertreatment to the scrap metal compound, thereby obtain comparatively clean scrap metal compound; The processing condition of its processing are: service temperature is 20～200 ℃, and agent-oil ratio is 1～10: 1.
2. the treatment technology that is used for the residual oil of heavy oil floating bed hydrocracking according to claim 1 is characterized in that described mixing acid can be the mixing acid of sulfuric acid and nitric acid, and its blended volume ratio is 0.05～10: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02117838 CN1237151C (en) | 2002-05-23 | 2002-05-23 | Treatment technology of residual oil used for heavy oil floating bed hydrocracking |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02117838 CN1237151C (en) | 2002-05-23 | 2002-05-23 | Treatment technology of residual oil used for heavy oil floating bed hydrocracking |
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| CN1459488A CN1459488A (en) | 2003-12-03 |
| CN1237151C true CN1237151C (en) | 2006-01-18 |
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| CN 02117838 Expired - Fee Related CN1237151C (en) | 2002-05-23 | 2002-05-23 | Treatment technology of residual oil used for heavy oil floating bed hydrocracking |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101265414B (en) * | 2008-04-08 | 2011-06-29 | 中国石油兰州石油化工公司 | Oil soluble coke cleaning agent and preparation thereof |
| CN101892075A (en) * | 2010-07-27 | 2010-11-24 | 中国石油大学(华东) | Method for transforming, separating and processing heavy oil |
| CN103364361B (en) * | 2013-04-09 | 2016-05-25 | 江苏国创环保科技有限公司 | A kind of infrared spectrophotometry that does not use oils in CFC class reagent Fast Measurement water |
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Granted publication date: 20060118 Termination date: 20210523 |