CN102181303B - Method for refining solvent oil No.200 - Google Patents
Method for refining solvent oil No.200 Download PDFInfo
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- CN102181303B CN102181303B CN 201010592791 CN201010592791A CN102181303B CN 102181303 B CN102181303 B CN 102181303B CN 201010592791 CN201010592791 CN 201010592791 CN 201010592791 A CN201010592791 A CN 201010592791A CN 102181303 B CN102181303 B CN 102181303B
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Abstract
The invention discloses a method for refining num.200 miscella, including: (1) pretreating: fully contacting the miscella and sodium hydroxide and reacting; (2) adsorbing and denitrifying on a fixed bed: fully contacting and reacting the miscella treated after the step (1) and a compound nitrogen adsorption agent; (3) oxidizing and promoting: fully mixing and treating the miscella treated after the step (2) and an oxidation promoter; and (4) oxidizing, catalyzing and deodorizing on the fixed bed: fully contacting and reacting the miscella treated after the step (3) and a catalyst. By using the method, an alkaline nitride content of the refined miscella is removed to less than 1PPm, a mercaptan content is removed to less than 1PPm, the refined oil is colourless and odourless, and Sybolt chroma thereof is not less than 25, and storage stability is good.
Description
Technical field
The invention belongs to the refining of petroleum field, relate to a kind of process for purification of No. 200 solvent oils, relate in particular to a kind of not only the decolouring but also the solvent oil process for purification of deodorization.
Background technology
No. 200 solvent oils generally are 140 ~ 200 ℃ distillates in the crude oil, have the advantages that dissolving power is strong, volatilization is fast, mainly as the solvent and the thinner of paint industry.By standard, No. 200 colourless, the odorlesses of solvent oil, transparent, stable in properties.Because the diversity that oil property changes, particularly along with the poor qualityization of crude oil, No. 200 solvent oils that the refinery produces usually occur that color stability is relatively poor, colourity does not conform to quality problems such as customer requirements; It is more obvious that the solvent oil peculiar smell of the high crude production of peculiar smell, particularly sulfur-bearing appears in solvent oil sometimes that produce.
No. 200 the color of prime city naphtha stability is relatively poor, mainly cause owing to containing basic nitrogen compound in the solvent oil, because basic nitrogen compound very easily variable color under the effect of light or oxygen, and the stink in the solvent oil mainly is to contain the thio-alcohol material to cause.Light oil products deodorizing technology such as gasoline deodorization extensively adopt the deodorization of Merox catalyzed oxidation, this technology is under catalyst action, mercaptan is oxidized to disulphide under alkaline condition, be characterized in that technology is simple, mercaptan removal is effective, but the refined oil color burn, and it is big to exist the caustic alkali consumption, the environmental issue distinct issues.Chinese patent application CN101063042A discloses a kind of alkali-free sulfur removal technology, this technology is with hydrogen peroxide as oxidant, with heteropolyacid as catalyzer, with methyl-sulphoxide as extraction agent, mercaptan oxidation and extraction are removed, and this technology is by removing sulfur compound the purpose that reaches deodorization, but complex process, the big cost height of operation easier, and can not solve the relatively poor problem of color of prime city naphtha stability.Chinese patent application CN101265420A discloses a kind of fixed bed decoloration process, this process using modified activated carbon adsorption solvent basic nitrogen in oils thing, reach the effect of stabilizing color of prime city naphtha, but this technology denitrification percent only 90%, and can not solve the solvent oil bad-smell problem.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, not only decoloured but also the process for purification of No. 200 solvent oils of deodorization thereby provide a kind of.The present invention is by carrying out pre-treatment to No. 200 solvent oil distillates of straight run, handles pretreated solvent oil through denitrogenation-deodorization combination process again, reached good, the no stink of production colourity, technique effect that stability in storage is good.
In order to realize purpose of the present invention, the contriver has finally obtained following technical scheme by a large amount of experimental studies:
A kind of process for purification of No. 200 solvent oils comprises the steps:
(1) pre-treatment: with the abundant contact reacts of the aqueous sodium hydroxide solution of solvent oil and 1%-15%, or solid sodium hydroxide is carried on the gac, charge capacity is 5%-30%, then with the abundant contact reacts of solvent oil.
(2) ADSORPTION IN A FIXED BED denitrogenation: with solvent oil and the abundant contact reacts of compound adsorption denitrifier after step (1) processing, reaction conditions is air speed 1/h-10/h, 0 ℃-70 ℃ of adsorption temps, adsorptive pressure 0.1MPa-1.0Mpa, described compound adsorption denitrifier is to be carrier with the activated carbon, and effective constituent is the mixture of heteropolyacid and mineral acid; Employing ADSORPTION IN A FIXED BED denitride technology can be removed the most basic nitrogen compounds in the solvent oil, denitrification percent can reach 95%, basic nitrogen compound is a unstable component in the oil product, the unsettled major cause of color particularly, after basic nitrogen compound removes, no matter be oxidation stability or light stability, the chromaticity stability of solvent oil is bright all to show raising.
(3) oxidation promotes: solvent oil and oxidation promotor thorough mixing after step (2) is handled; described oxidation promotor is by activeconstituents and solvent composition; wherein activeconstituents is a benzoyl peroxide or/and hydrogen peroxide, and solvent is selected from one or more of ethanol, methyl alcohol, acetone, ethylene glycol and water.
(4) fixed bed oxidation catalysis deodorization: with oil miscible solvent compound and the abundant contact reacts of catalyzer after step (3) processing, reaction conditions is air speed 1/h-5/h, temperature 0-70 ℃, pressure 0.1-1.0Mpa, described catalyzer are the phthalein cyanine compound that is carried on cobalt on the activated carbon, nickel, molybdenum.Adopting fixed bed oxidation catalysis deodorization technique is that the mercaptan in the solvent oil is oxidized to disulfide under catalyzer and oxidation promotor agent effect, and mercaptan has stench, and the disulfide odorless, tasteless, thereby reaches the purpose of deodorization.
The process for purification of No. 200 above-mentioned solvent oils, the total content of heteropolyacid and mineral acid accounts for the 10%-30% of carrier activated carbon weight described in the step (2).
The process for purification of No. 200 above-mentioned solvent oils, heteropolyacid is selected from one or more of phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid and silicomolybdic acid described in the step (2).
The process for purification of No. 200 above-mentioned solvent oils, mineral acid is selected from one or more of phosphoric acid, sulfuric acid and hydrochloric acid described in the step (2).
The process for purification of No. 200 above-mentioned solvent oils, the described catalyst content of step (4) accounts for the 0.1%-5% of solvent oil gross weight, and catalyzer is carried on the carrier in the mode of match or dipping.
The process for purification of No. 200 above-mentioned solvent oils, catalyst content accounts for the 0.2%-2% of solvent oil gross weight described in the preferred steps (4).
The process for purification of No. 200 above-mentioned solvent oils, described carrier activated carbon is sheet or column, and particle diameter is 1-5 centimetre, and length is 2-8 centimetre.
Above-mentioned used activated carbon can be that sheet also can be that column is, its big I determines that according to treatment capacity general particle diameter is at 1-5 centimetre, and length is at 2-8 centimetre.
[0016]The present invention implements like this: the solvent oil raw material enters pretreater from the pretreater bottom, fully contact with the pre-treatment sorbent material, in the preprocessing process, the coalescent back of moisture is regularly discharged by water port in the raw material, and pretreated solvent oil enters denitrification column from the denitrification column bottom, with the abundant contact reacts of denitrification adsorbent in the fixed bed, air speed was controlled at 1-10/ hour, preferably at 1-5/ hour, temperature was controlled at 0-70 ℃, and pressure-controlling is at 0.1-1.0Mpa.The waste residue that denitrogenation produces is regularly discharged by slag-drip opening, and the denitrogenation solvent oil goes out tower from the denitrification column top, advances subsequent processing.After the denitrogenation solvent oil and oxidation promotor in static mixer behind the thorough mixing bottom from the deodorization tower enter the deodorization tower, under the fixed bed catalyst effect, carry out oxidizing reaction, reaction velocity was controlled at 1-5/ hour, and temperature is controlled at 0-70 ℃, and pressure-controlling is at 0.1-1.0Mpa.Solvent oil goes out tower from the deodorization top of tower after the deodorization becomes the refining solvent oil production.
The process for purification of No. 200 solvent oils that provide of the present invention has following beneficial technical effects: adopt this method that the basic nitrogen compound content of refining back solvent oil is removed to below the 1PPm, mercaptan is reduced to below the 1PPm; Colourless, the no stink of treated oil, its Saybolt color is not less than 25, and stability in storage is good.
Description of drawings
Fig. 1 is the associating process for purification schematic flow sheet of solvent oil decolouring and deodorization
1 solvent oil raw material; 2 oxidation promotors; 3 solvent-refined oils; 4 drainings, 5 deslagginves; 6 deslagginves.
A: pretreater B: denitrification column C: mixing tank D: deodorization tower.
Embodiment
Below be specific embodiments of the invention, technical scheme of the present invention is done further the description, but protection scope of the present invention is not limited to these embodiment.Every do not deviate from the change of the present invention design or be equal to substitute include within protection scope of the present invention.
Making with extra care of No. 200 solvent oils of embodiment 1 wuhan petrochemical industry
No. 200 solvent oils of wuhan petrochemical industry, the content of basic nitrogen is 25PPm, mercaptans content is 11 PPm, the pre-treatment sorbent material adopts solid alkali, denitrification adsorbent adopts the acid of phospho-wolframic acid composite inorganic to load on the activated carbon, and active component content 15%, deodorizing catalyst are the phthalocyanine cobalt.5 centimetres of the diameters of tower A, B, C, 40 centimetres of height, raw material solvent oil feeding temperature 40 degree, pressure 0.4Mpa, the parameter change air speed of pressing table 1, colourity, the smell of the final treated oil that obtains all meet state quality standard.Concrete effect sees Table 1.
The refining effect of No. 200 solvent oils of table 1 wuhan petrochemical industry
| The solvent oil air speed, hour -1 | Treated oil alkali nitrogen, PPm | Treated oil mercaptan, PPm | The treated oil Saybolt color | The treated oil smell |
| 1 | 0 | 0.8 | 30 | Odorless |
| 2 | 0 | 0.8 | 30 | Odorless |
| 3 | 0 | 0.9 | 30 | Odorless |
| 4 | 0 | 0.9 | 30 | Odorless |
| 6 | 0 | 1.0 | 30 | Odorless |
| 8 | 0 | 1.2 | 30 | Odorless |
| 10 | 0.5 | 1.5 | 29 | Odorless |
Making with extra care of No. 200 solvent oils of embodiment 2 Jingmen petrochemical industry
No. 200 solvent oils of Jingmen petrochemical industry, the content of basic nitrogen is 21PPm, mercaptans content is 13 PPm, the pre-treatment sorbent material adopts activated carbon to carry alkali, denitrification adsorbent adopts the acid of phospho-molybdic acid composite inorganic to load on the activated carbon, and active component content 10%, deodorizing catalyst are phthalocyanine nickel.5 centimetres of the diameters of tower A, B, C, 40 centimetres of height, raw material solvent oil feeding temperature 20 degree, pressure 0.2Mpa, the parameter change air speed of pressing table 2, colourity, the smell of the final treated oil that obtains all meet state quality standard.Concrete effect sees Table 2.
The refining effect of No. 200 solvent oils of table 2 Jingmen petrochemical industry
| The solvent oil air speed, hour -1 | Treated oil alkali nitrogen, PPm | Treated oil mercaptan, PPm | The treated oil Saybolt color | The treated oil smell |
| 1 | 0 | 0.8 | 30 | Odorless |
| 2 | 0 | 0.8 | 30 | Odorless |
| 3 | 0 | 0.9 | 30 | Odorless |
| 4 | 0 | 0.9 | 30 | Odorless |
| 6 | 0 | 1.0 | 30 | Odorless |
| 8 | 0.5 | 1.1 | 30 | Odorless |
| 10 | 0.5 | 1.4 | 29 | Odorless |
Making with extra care of No. 200 solvent oils of embodiment 3 Luoyang Petrochemical
No. 200 solvent oils of Luoyang Petrochemical, the content of basic nitrogen is 40PPm, mercaptans content is 25 PPm, the pre-treatment sorbent material adopts solid alkali, denitrification adsorbent adopts the acid of P-Mo-Wo acid composite inorganic to load on the activated carbon, and active component content 25%, deodorizing catalyst are the phthalocyanine cobalt.5 centimetres of the diameters of tower A, B, C, 40 centimetres of height, raw material solvent oil feeding temperature 50 degree, pressure 0.6Mpa, the parameter change air speed of pressing table 3, colourity, the smell of the final treated oil that obtains all meet state quality standard.Concrete effect sees Table 3.
The refining effect of No. 200 solvent oils of table 3 Luoyang Petrochemical
| The solvent oil air speed, hour -1 | Treated oil alkali nitrogen, PPm | Treated oil mercaptan, PPm | The treated oil Saybolt color | The treated oil smell |
| 1 | 0 | 0.8 | 30 | Odorless |
| 2 | 0 | 0.8 | 30 | Odorless |
| 3 | 0 | 0.9 | 30 | Odorless |
| 4 | 0 | 0.9 | 30 | Odorless |
| 6 | 0.5 | 1.0 | 30 | Odorless |
| 8 | 0.8 | 1.5 | 30 | Odorless |
| 10 | 1.5 | 2.0 | 29 | Odorless |
Making with extra care of No. 200 solvent oils of embodiment 4 wuhan petrochemical industries
No. 200 solvent oils of wuhan petrochemical industry, the content of basic nitrogen is 25PPm, mercaptans content is 11 PPm, the pre-treatment sorbent material adopts solid alkali, denitrification adsorbent adopts the acid of phospho-wolframic acid composite inorganic to load on the activated carbon, and active component content 15%, deodorizing catalyst are the phthalocyanine cobalt.5 centimetres of the diameters of tower A, B, C, 40 centimetres of height, raw material solvent oil feeding temperature 10 degree, pressure 0.4Mpa, the parameter change air speed of pressing table 4, colourity, the smell of the final treated oil that obtains all meet state quality standard.Concrete effect sees Table 4.
The refining effect of No. 200 solvent oils of table 4 wuhan petrochemical industry
| The solvent oil air speed, hour -1 | Treated oil alkali nitrogen, PPm | Treated oil mercaptan, PPm | The treated oil Saybolt color | The treated oil smell |
| 1 | 0 | 0.8 | 30 | Odorless |
| 2 | 0 | 0.8 | 30 | Odorless |
| 3 | 0 | 0.9 | 30 | Odorless |
| 4 | 0 | 0.9 | 30 | Odorless |
| 6 | 0.2 | 1.0 | 30 | Odorless |
| 8 | 0.5 | 1.5 | 30 | Odorless |
| 10 | 0.8 | 1.6 | 29 | Odorless |
Claims (7)
1. the process for purification of No. 200 solvent oils is characterized in that: comprise the steps:
(1) pre-treatment: with the abundant contact reacts of the aqueous sodium hydroxide solution of solvent oil and 1%-15%, or solid sodium hydroxide is carried on the gac, charge capacity is 5%-30%, then with the abundant contact reacts of solvent oil;
(2) ADSORPTION IN A FIXED BED denitrogenation: with solvent oil and the abundant contact reacts of compound adsorption denitrifier after step (1) processing, reaction conditions is air speed 1/h-10/h, 0 ℃-70 ℃ of adsorption temps, adsorptive pressure 0.1MPa-1.0Mpa, described compound adsorption denitrifier is to be carrier with the gac, and effective constituent is the mixture of heteropolyacid and mineral acid;
(3) oxidation promotes: solvent oil and oxidation promotor thorough mixing after step (2) is handled, described oxidation promotor is by activeconstituents and solvent composition, wherein activeconstituents is a benzoyl peroxide or/and hydrogen peroxide, and solvent is selected from one or more of ethanol, methyl alcohol, acetone, ethylene glycol and water;
(4) fixed bed oxidation catalysis deodorization: with oil miscible solvent compound and the abundant contact reacts of catalyzer after step (3) processing, reaction conditions is air speed 1/h-5/h, temperature 0-70 ℃, pressure 0.1-1.0Mpa, described catalyzer are the phthalein cyanine compound that is carried on cobalt on the gac, nickel, molybdenum.
2. the process for purification of No. 200 solvent oils as claimed in claim 1 is characterized in that: the total content of heteropolyacid and mineral acid accounts for the 10%-30% of carrier active carbon weight described in the step (2).
3. the process for purification of No. 200 solvent oils as claimed in claim 1 or 2 is characterized in that: heteropolyacid is selected from one or more of phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid and silicomolybdic acid described in the step (2).
4. the process for purification of No. 200 solvent oils as claimed in claim 1 or 2 is characterized in that: mineral acid is selected from one or more of phosphoric acid, sulfuric acid and hydrochloric acid described in the step (2).
5. the process for purification of No. 200 solvent oils as claimed in claim 1 is characterized in that: the described catalyst content of step (4) accounts for the 0.1%-5% of solvent oil gross weight, and catalyzer is carried on the carrier in the mode of match or dipping.
6. the process for purification of No. 200 solvent oils as claimed in claim 5 is characterized in that: catalyst content accounts for the 0.2%-2% of solvent oil gross weight described in the step (4).
7. the process for purification of No. 200 solvent oils as claimed in claim 1 is characterized in that: described carrier active carbon is sheet or column, and particle diameter is 1-5 centimetre, and length is 2-8 centimetre.
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| CN 201010592791 CN102181303B (en) | 2010-12-17 | 2010-12-17 | Method for refining solvent oil No.200 |
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| CN 201010592791 CN102181303B (en) | 2010-12-17 | 2010-12-17 | Method for refining solvent oil No.200 |
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| CN102492464A (en) * | 2011-12-02 | 2012-06-13 | 甘肃蓝科石化高新装备股份有限公司 | Gasoline desulfuration and deodorization process |
| CN106311134B (en) * | 2015-06-24 | 2019-03-26 | 中国石油化工股份有限公司 | Solid purificant and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143667A (en) * | 1995-08-21 | 1997-02-26 | 寿光市文家乡建筑安装公司 | Method and use for producing civil liquid fuel and leadless gasoline from C5 fraction oil |
| CN1302845A (en) * | 1999-10-28 | 2001-07-11 | 中国石油化工集团公司 | Process for chemically refining gasoline or diesel oil |
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| US8246814B2 (en) * | 2006-10-20 | 2012-08-21 | Saudi Arabian Oil Company | Process for upgrading hydrocarbon feedstocks using solid adsorbent and membrane separation of treated product stream |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143667A (en) * | 1995-08-21 | 1997-02-26 | 寿光市文家乡建筑安装公司 | Method and use for producing civil liquid fuel and leadless gasoline from C5 fraction oil |
| CN1302845A (en) * | 1999-10-28 | 2001-07-11 | 中国石油化工集团公司 | Process for chemically refining gasoline or diesel oil |
Non-Patent Citations (2)
| Title |
|---|
| 国内溶剂油精制技术现状;张晓侠;《工业催化》;20070715;第15卷(第7期);21-23 * |
| 张晓侠.国内溶剂油精制技术现状.《工业催化》.2007,第15卷(第7期),21-23. |
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