CN101921608B - Method for removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent - Google Patents
Method for removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent Download PDFInfo
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- CN101921608B CN101921608B CN 200910062624 CN200910062624A CN101921608B CN 101921608 B CN101921608 B CN 101921608B CN 200910062624 CN200910062624 CN 200910062624 CN 200910062624 A CN200910062624 A CN 200910062624A CN 101921608 B CN101921608 B CN 101921608B
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Abstract
The invention discloses a method for removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent, which comprises the following steps: diluting catalytic slurry oil with hydrocarbon solvent, adding solid-phase adsorbent, adsorbing and filtering to obtain the solid-phase adsorbent with adsorbed asphalt and the filtrate containing asphalt oil solution; washing the solid-phase adsorbent with adsorbed asphalt by using hydrocarbon solvent, mixing the washed solution with the filtrate, and removing the solvent to obtain the deasphalted oil; and eluting the washed solid-phase adsorbent with alkyl halide to elute the adsorbed colloid asphalt, filtering, and removing the solvent from the solution to obtain the colloid asphalt. In the invention, the solid-phase adsorbent is added to remove the colloid asphalt from the catalytic slurry oil; and the solid-phase adsorbent can be separated from the oil phase by common filtering, thereby effectively solving the problems of difficult separation of two phases and long standing time required in the traditional technique. The method for removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent in the invention not only reduces the loss of deasphalted oil in the traditional technique, but also can obtain high-content colloid asphalt. The solid-phase adsorbent and the solvent can be recycled.
Description
Technical field
The present invention relates to a kind of method that removes pitch, specifically a kind of method of removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent.
Background technology
Catalytic slurry is the remainder of crude oil behind catalytic cracking, catalytic pyrolysis, accounts for about 10% of processing crude oil, wherein contains a large amount of bituminous matters and a small amount of metal-powder.And bituminous matter is a kind of fused ring compound of high ratio of carbon-hydrogen, it is in catalytic cracking process, almost all be converted into coke, in the catalytic slurry hydrodesulfurization process, for preventing that bituminous matter from generating coke in reactor, must adopt very high hydrogen dividing potential drop, cause the construction investment of hydrodesulfurization unit and process cost all very high.In the catalysis engineering, the metal in the catalytic slurry can be deposited on and make the catalyzer permanent deactivation on the catalyzer, causes catalyzer to consume in a large number.
Thus, in Crude Oil Processing, the bituminous matter that how to remove in the catalytic slurry usually is stubborn problem.Usually, bituminous matter is present in wherein with the form of micella, the solvated layer that is made of colloid and condensed-nuclei aromatics is arranged around it, therefore, pitch mass-energy is dispersed in well in the mink cell focus and with mink cell focus and forms stable colloidal solution, and when adding low molecule alkane gradually in catalytic slurry, condensed-nuclei aromatics and colloid around the bituminous matter are drawn out of, stable colloidal state is destroyed, and the bituminous matter cohesion is separated out.
Solvent deasphalting can make bituminous matter in the catalytic slurry, metal etc. concentrate in the pitch, and resulting deasphalted oil has the characteristics such as foreign matter content is low, cracking performance is good.Its byproduct de-oiled asphalt is to produce preferably raw material of asphaltic products. or gas making, and therefore, in recent years, the use of solvent deasphalting in catalytic slurry processing comes into one's own day by day.The solvent that solvent deasphalting is commonly used has propane, Trimethylmethane, normal butane, pentane and their mixture.There are some researches show that the resulting deasphalted oil of different solvents diasphaltene is at yield with there is qualitatively a very big difference.When take propane as solvent, deasphalting selectivity is best, and carbon residue and the metal content of deasphalted oil are low, is the desirable feedstock of producing residual lubricating oil.At present, the solvent deasphalting of producing lube stock both at home and abroad nearly all adopts propane to make solvent, and the residual oil solvent deasphalting take the production lightweight oil as purpose often adopts the heavy hydrocarbons such as butane or pentane to make solvent.
Although solvent deasphalting is method commonly used at present, but the problem that exists is apparent in view, mainly is that diasphaltene oil phase and pitch are separated very long time of repose need be arranged, and usually needs 5～6 hours, and the two-phase separation difficulty, the deasphalted oil that obtains and asphalt content are not high.
Summary of the invention
For two-phase separation difficulty and the long-time static shortcoming of need that conventional solvent diasphaltene technique exists, the invention provides a kind of method of removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent, used sorbent material is easy to get, treatment process is simple and practical.
The method of removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent provided by the invention is characterized in that, described method comprises:
(1) first catalytic slurry is added solid-phase adsorbent after with the dilution of the varsol of C3～C7, stir solid liquid phase is fully contacted, adsorbed 10～30 minutes, then sedimentation or direct filtration obtain the filtrate of solid-phase adsorbent and the bituminous oil solution of adsorptive pitch;
(2) solid-phase adsorbent of adsorptive pitch washs with the varsol of C3～C7, and the solution after the washing is mixed into deasphalted oil solution mutually with filtrate, and solvent removal is got deasphalted oil;
(3) with the varsol solvent recuperation of C3～C7, recycle;
(4) the haloalkane kind solvent wash-out of the solid-phase adsorbent after the washing, the colloidal bitumen wash-out with adsorbing filters out solid-phase adsorbent, and solvent removal in the solution after wash-out, the filtration is obtained colloidal bitumen;
(5) solid-phase adsorbent behind the wash-out can directly utilize, and the haloalkane kind solvent reclaims, and recycles.The varsol of used C3～C7 is selected from a kind of or its mixture of ethyl acetate, sherwood oil, condensate oil, light naphthar.
The varsol of C3～C7 that described dilution catalytic slurry is used and the weight ratio of catalytic slurry are 0.5: 1～5: 1.
The solid-phase adsorbent of described adsorptive pitch washs with the varsol of C3～C7, and the weight ratio of solid-phase adsorbent and solvent is 1: 2～1: 4.
Described solid-phase adsorbent is silica gel or the solid mixture take silica gel as one of composition, and the weight ratio of solid-phase adsorbent and catalytic slurry is 0.05: 1～1: 1.
Described adsorption process is carried out in settling vessel or extraction tower, and temperature is 20～100 ℃.
The eluting solvent of described solid-phase adsorbent is a kind of or its mixture in the haloalkane, and the weight ratio of solid-phase adsorbent and haloalkane kind solvent is 1: 3～1: 10.
Described solid-phase adsorbent and solvent be recyclable recycling all.
The present invention removes colloidal bitumen in the catalytic slurry by adding solid-phase adsorbent, solid-phase adsorbent gets final product and separation of oil by common filtration, effectively solve the two-phase separation difficulty of conventional solvent diasphaltene technique existence and needed long-time static shortcoming, greatly shortened the time of whole technique; Solid-phase adsorbent has selectivity to the absorption of component in the catalytic slurry, the solid-phase adsorbent that filters out is rear with haloalkane kind solvent wash-out with the varsol washing, not only reduce the loss of deasphalted oil in the solvent de-asphalting process, and can obtain the colloidal bitumen of high-content.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, and following examples are explanation of the invention and the present invention is not limited to following examples.The present invention limits its add-on, just is convenient to enforcement of the present invention, does not illustrate outside limited range of the present invention and can not implement.
Embodiment 1
The 100g catalytic slurry is poured in the 250ml beaker, stir after adding the 100ml sherwood oil, 60～100 order silica gel that add 15g, after whip attachment, suction filtration, silica gel 20ml petroleum ether after the absorption that filters out, washings is mixed into deasphalted oil solution mutually with filtrate, gets deasphalted oil through solvent extraction.Behind the silica dehydrator, weighing is also calculated adsorptive capacity after the absorption.Adsorptive capacity deducts the weight of the front silica gel of absorption for the weight of the rear silica gel of absorption.Adsorptive capacity is 6.8g, accounts for 6.8% of catalytic slurry.
Silica gel, reclaims ethylene dichloride and obtains high-quality colloidal bitumen the colloidal bitumen wash-out that adsorbs with 50ml ethylene dichloride wash-out after the absorption.
Content (the unit: weight percent) be listed in the table 1 of stable hydrocarbon, aromatic hydrocarbons, colloid and pitch in catalytic slurry and the gained deasphalted oil.
Table 1 moiety result
Data can be found out from table, and it is about 80% that the deasphalted oil Asphalt Content of processing gained through solid-phase adsorbent reduces, and gum level reduces about 20%.
Embodiment 2
Take by weighing the catalytic slurry sample of 4 parts of 15g, respectively with 15ml sherwood oil, ethyl acetate, methylene dichloride and furfural dissolving, after fully stirring, with the 4g silica gel adsorption, behind the filtration drying, weight after the weighing silica gel adsorption, obtain the adsorptive capacity of silica gel, further calculate the colloidal bitumen yield.Test-results sees Table 2.
Table 2 different solvents is on the impact of silica gel adsorption amount
Silica gel is different to bitum adsorption in different solvents, present embodiment has been investigated different solvents as the impact of the solvent that dilutes catalytic slurry on the silica gel adsorption amount, discovery silica gel in sherwood oil is maximum to the adsorptive capacity of colloidal bitumen, so the preferred sherwood oil of the present invention is as the diluting solvent of catalytic slurry.
Embodiment 3
Take by weighing the catalytic slurry sample of 4 parts of about 10g, each use the 20ml petroleum ether dissolution, and fully after the stirring, respectively with the silica gel adsorption of inequality, behind the filtration drying, weight after the weighing silica gel adsorption obtains the adsorptive capacity of silica gel, further calculates the colloidal bitumen yield.Test-results sees Table 3.
The different silica gel amounts of table 3 are on the impact of silica gel adsorption amount
Data can be found out from table, when the weight ratio of silica gel weight and handled catalytic slurry reaches 1: 5, just can reach good adsorption effect, and continuing increases the silica gel consumption, and the colloidal bitumen yield slightly rises.
Claims (8)
1. the method for a removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent is characterized in that, described method comprises:
(1) first catalytic slurry is added solid-phase adsorbent after with the dilution of the varsol of C3～C7, stir solid liquid phase is fully contacted, adsorbed 10～30 minutes, then sedimentation or direct filtration obtain the filtrate of solid-phase adsorbent and the bituminous oil solution of adsorptive pitch;
(2) solid-phase adsorbent of adsorptive pitch washs with the varsol of C3～C7, and the solution after the washing is mixed into deasphalted oil solution mutually with filtrate, and solvent removal is got deasphalted oil;
(3) with the varsol solvent recuperation of C3～C7, recycle;
(4) the haloalkane kind solvent wash-out of the solid-phase adsorbent after the washing, the colloidal bitumen wash-out with adsorbing filters out solid-phase adsorbent, and solvent removal in the solution after wash-out, the filtration is obtained colloidal bitumen;
(5) solid-phase adsorbent behind the wash-out can directly utilize, and the haloalkane kind solvent reclaims, and recycles.
2. according to the method for claim 1, it is characterized in that: the varsol of used C3～C7 is selected from a kind of or its mixture of ethyl acetate, sherwood oil, condensate oil, light naphthar.
3. according to the method for claim 1, it is characterized in that: the varsol of C3～C7 that the dilution catalytic slurry is used and the weight ratio of catalytic slurry are 0.5: 1～5: 1.
4. according to the method for claim 1, it is characterized in that: the solid-phase adsorbent of described adsorptive pitch washs with the varsol of C3～C7, and the weight ratio of solid-phase adsorbent and solvent is 1: 2～1: 4.
5. according to the method for claim 1, it is characterized in that: described solid-phase adsorbent is silica gel or the solid mixture take silica gel as one of composition, and the weight ratio of solid-phase adsorbent and catalytic slurry is 0.05: 1～1: 1.
6. according to the method for claim 1, it is characterized in that: described adsorption process is carried out in settling vessel or extraction tower, and temperature is 20～100 ℃.
7. according to the method for claim 1, it is characterized in that: the eluting solvent of described solid-phase adsorbent is a kind of or its mixture in the haloalkane, and the weight ratio of solid-phase adsorbent and haloalkane kind solvent is 1: 3～1: 10.
8. according to the method for claim 1, it is characterized in that: described solid-phase adsorbent and solvent be recyclable recycling all.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200910062624 CN101921608B (en) | 2009-06-09 | 2009-06-09 | Method for removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent |
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| CN 200910062624 CN101921608B (en) | 2009-06-09 | 2009-06-09 | Method for removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent |
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| CN101921608B true CN101921608B (en) | 2013-05-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102262150B (en) * | 2011-04-28 | 2015-04-22 | 山东东明石化集团有限公司 | Method for detecting solid content of oil slurry |
| CN104593034B (en) * | 2013-10-31 | 2016-07-27 | 神华集团有限责任公司 | The method of coal liquefaction aromatic hydrocarbons is obtained and coal liquefaction aromatic hydrocarbons that the method obtains from coal liquefaction residue |
| CN109233902A (en) * | 2018-11-08 | 2019-01-18 | 黑龙江省能源环境研究院 | A kind of method of catalyst fines in removing catalytic slurry |
| CN112480959B (en) * | 2020-11-17 | 2022-06-17 | 茂名市鹰鹏机电设备有限公司 | Method for removing solid impurities in catalytic oil slurry through low-temperature coalescence |
| CN113817498A (en) * | 2021-09-20 | 2021-12-21 | 中海油天津化工研究设计院有限公司 | Crude oil or heavy oil pretreatment combined process method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075496A (en) * | 1992-02-20 | 1993-08-25 | 唐文祥 | In the ceresine clay dregs, reclaim cereous method |
| US5599381A (en) * | 1993-03-08 | 1997-02-04 | Whitlock; David R. | Separation of solutes in gaseous solvents |
| CN1600833A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method for eliminating arene from kerosene distillation fraction |
| CN1718689A (en) * | 2004-07-06 | 2006-01-11 | 中国石油化工股份有限公司 | Pretreatment method of lubricating oil hydrogenation isomeric dewax raw material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075496A (en) * | 1992-02-20 | 1993-08-25 | 唐文祥 | In the ceresine clay dregs, reclaim cereous method |
| US5599381A (en) * | 1993-03-08 | 1997-02-04 | Whitlock; David R. | Separation of solutes in gaseous solvents |
| CN1600833A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method for eliminating arene from kerosene distillation fraction |
| CN1718689A (en) * | 2004-07-06 | 2006-01-11 | 中国石油化工股份有限公司 | Pretreatment method of lubricating oil hydrogenation isomeric dewax raw material |
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