CN1644655A - Method for low temperature and low pressure hydrogenated refinment of low boiling point solvent oil - Google Patents
Method for low temperature and low pressure hydrogenated refinment of low boiling point solvent oil Download PDFInfo
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- CN1644655A CN1644655A CN 200410065881 CN200410065881A CN1644655A CN 1644655 A CN1644655 A CN 1644655A CN 200410065881 CN200410065881 CN 200410065881 CN 200410065881 A CN200410065881 A CN 200410065881A CN 1644655 A CN1644655 A CN 1644655A
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Abstract
A method achieves one step removal of unsaturated and aromatic hydrocarbons in solvent oil with their contents <10ppm and bromine index of <1mg by hydrogenation refinement. Its raw materials is light oil from natural gas plant or oil finery with boiling point <120 degC, working condition as following: reaction temperature 100-140 degC, operation pressure 0.15-0.3 MPa, H: oil = 40-70, space rate 2-4/h, with Ni-Al catalysts. Its products are of high standard and low cost.
Description
Technical field: the invention belongs to the petrochemical technology field, be specifically related to a kind of production method of low temperature and low pressure hydrogenated refinment of low boiling point solvent oil.
Background technology: technology related to the present invention mainly contains:
1. " petrochemical complex Journal of Chinese Universities ", 98,11 (2), 36～39, the aromatic hydrocarbons shortening system high-quality solvent oil of raffinating oil adopts modified catalyst Pt (Al
2O
3) to raffinate oil No. 6, No. 120 solvent oils that carry out low-voltage hydrogenation production high-quality of aromatic hydrocarbons, at 175～185 ℃ of temperature of reaction, reaction pressure 0.2～0.25Mpa, hydrogen-oil ratio (V) 340～360, air speed LHSV2.8～3.0h
-1Under the condition of loaded catalyst 100ml, carry out the continuous hydrogenation test, the result is bromine index＜10mg/100g, olefin(e) centent 0.2%, aromaticity content 0.2%.This technology only can manufacture level solvent oil, belongs to thick hydrogenation technique.
2, " Speciality Petrochemicals progress ", 2000,1 (7): 32～35, utilize the modification Pt catalyzer MH-705 hydrogenation and olefin hydrocarbon removal technology of raffinating oil, its working condition is: 180 ℃ of temperature of reaction, reaction pressure 1.6Mpa, hydrogen-oil ratio (V) 400, air speed LHSV 4h
-1Utilize modification Pt catalyzer MH-508 to carry out recapitalization generating oil hydrogenation and make with extra care, the hydrogenation technique condition is: 200～220 ℃ of temperature of reaction, reaction pressure 2.0Mpa, hydrogen-oil ratio (V) 250, air speed 4h
-1, aromaticity content is 0.12% in the 6# solvent oil product.
3, " Daqing Petroleum Institute's journal ", 2000,24 (2): 28～30, use the Ni-Al catalyzer, on 100ml hydrogenation reaction device, investigate the effect of straight run mixed solvent oil shortening.At 130～160 ℃ of temperature of reaction, reaction pressure 0.3～1.0Mpa, hydrogen-oil ratio (V) 60～90, air speed 1.0～2.5h
-1In the operating restraint of broad, in the solvent oil product benzene content less than 0.02%, toluene level is less than 0.05%.
4, " oil refining design ", 2000,30 (8): 21～23, adopt NCG or HPA-1 hydrogenation catalyst, at hydrogen dividing potential drop 1.0～5.0Mpa, 120～180 ℃ of temperature of reaction, volume space velocity 0.5～2.0h
-1, hydrogen-oil ratio (V) 300～500 condition under, can obtain aromaticity content less than 0.01% solvent-refined oil.
5, CN1351982A, a kind of process for refining of normal hexane solvent oil, proposition utilizes nickel-alumina catalyst, under the condition of hydrogen dividing potential drop 0.2～0.3Mpa, 140～280 ℃ of temperature of reaction, hydrogen-oil ratio (V) 120～180, by the secondary hydrogenation reaction, can obtain the normal hexane solvent oil oil of aromaticity content less than 1ppm.
Summary of the invention: the production method that the purpose of this invention is to provide hydrofining lower boiling flux oil under a kind of low-temp low-pressure.With Sweet natural gas and refinery processing the light oil products mid-boiling point be lower than 120 ℃ solvent oil, react by one-stage hydrogenation, remove impurity such as wherein unsaturated hydrocarbons, aromatic hydrocarbons once, produce and meet the solvent oil that developed country's food sanitation requires, aromaticity content＜10ppm in the product, bromine index＜1mgBr/100g sample.
Low boiling point solvent oil (for example, 6# solvent oil) is widely used in edible oil, printing-ink, leather, agricultural chemicals, sterilant, rubber school, makeup, spices, chemical industry polymerization, medicine and at the aspects such as cleaning of IC electronic unit.The solvent oil aromaticity content that developed country's requirement is used for food and health industry is lower (as the solvent oil product aromaticity content＜100ppm of Exxon/Mobil company, Shell company solvent oil product aromaticity content＜10ppm), and that China is used for the low boiling point solvent oil aromaticity content of food and health industry is generally higher, is 1000-2000ppm.After the China joined WTO, to the quality standard of solvent oil will be further with integrate with the direction that to develop the eco-friendly petroleum hydrocarbon solvent oil of low arene content more be Future Development abroad.
The present invention is achieved like this: adopt the technical process of " solvent oil gasification → hydrogenation and olefin hydrocarbon removal and aromatic hydrocarbons → solvent oil condensation → hydrogen recycle ", adopt the nickel-alumina catalyst of nickel content, at 100 ℃～140 ℃ temperature and the working pressure of 0.15～0.3Mpa and hydrogen dividing potential drop 0.04～0.07MPa (hydrogen to oil volume ratio 40～70), air speed 2～4h greater than 40% (w%)
-1Condition under, boiling point is carried out hydrofining at the solvent oil below 120 ℃, remove unsaturated hydrocarbons, aromatic hydrocarbon impurities in the solvent oil once, make the low boiling point solvent oil production.
For the solvent oil product after the rectifying cutting, adopt nickel-alumina catalyst, nickel content 〉=40% (w%) in this catalyzer carries out hydrofining under the pressure of 100-140 ℃ temperature and 0.15-0.3Mpa (gauge pressure), remove impurity such as unsaturated hydrocarbons in the solvent oil, aromatic hydrocarbons once.General one-stage hydrogenation deolefination and the aromatic hydrocarbons of adopting, disposable with alkene and arene engaging scraping in hydrogenation and olefin hydrocarbon removal and aromatic hydrocarbons reactor.Aromaticity content＜10ppm, bromine index＜1mgBr/100g sample in the product that makes.
Description of drawings: accompanying drawing 1 is an embodiment of the invention process flow diagram.Among the figure, the 1-interchanger; The 2-vaporizer; The 3-reactor; The 4-water cooler; The 5-separating tank; The 6-compressor.
Embodiment: the present invention is described in detail below in conjunction with embodiment and accompanying drawing.
Embodiment: use the oil plant pump with 6 in the storage tank
#Solvent oil is squeezed into interchanger 1 after metering, and with entering vaporizer 2 from hydrogen gas cylinder and through the hydrogen of spinner-type flowmeter, mixture enters hydrogenator 3 after vaporization, remove alkene and aromatic hydrocarbons after the preliminary preheating.After reacted gaseous mixture material and raw material heat exchange tentatively are condensed, enter water cooler 4 further condensations, carry out gas-liquid separation through separating tank 5, liquid product is the high standard 6 that the degree of depth is taken off virtue
#Solvent oil, Returning evaporimeter recycles after compressed machine 6 superchargings of remaining hydrogen.
(1), process of the test
The stock oil that this test is adopted is: 6
#Solvent oil: benzene 800-1100ppm wherein, bromine index≤20mg/100g.
Select modification nickel catalyst (NCG-B) for use, loaded catalyst is: 100ml, and bed height 200mm, the conversion zone length-to-diameter ratio is 7.Under as the operational condition of table one, carry out hydropyrolysis experiment.
Table one 6# mineral spirit platreating condition
| Working pressure Mpa (table) | ????0.15-0.3 |
| Temperature, ℃ | ????100-140 |
| Liquid air speed (LHSV) h -1 | ????1-4 |
| Hydrogen-oil ratio, V/V | ????40-70 |
(2), test-results
Hydrorefined test-results sees Table two.Test-results shows, adopts different temperature of reaction, air speed and hydrogen-oil ratio, and the major impurity content of its product all can reach requirement.
Table two 6
#The mineral spirit platreating result
| Project | ????6 #Solvent oil | High standard 6 #Solvent oil | |
| Boiling range | Initial boiling point ℃ | Be not less than 65.0 | Be not less than 65.0 |
| 98% recovered temperature ℃ | Be not more than 69.0 | Be not more than 69.0 | |
| Aromatic hydrocarbons % (ppm) | ????800～1000 | ????＜10 | |
| Density (20 ℃), kg/m 3 | ????675.0～686.0 | ????675.0～686.0 | |
| Bromine index, mgBr/100g | Be not more than 20.0 | ????＜1 | |
| Colourity, number | Be not less than+30 | Be not less than+30 | |
| Non-volatile matter, mg/100ml | Be not more than 3 | Be not more than 3 | |
| Sulphur content w, 10 -6 | Be not more than 1 | Be not more than 1 | |
| Mechanical impurity and moisture content | Do not have | Do not have | |
| Copper corrosion (50 ℃, 3h), level | Be not more than 1 | Be not more than 1 | |
| Water-soluble acid or alkali | Do not have | Do not have | |
| Spot test for fat | Qualified | Qualified | |
Adopt 1500 tons of/year high standards 6 of a cover of Technology of the present invention
#The solvent oil production equipment.Under 100 ℃～140 ℃ temperature of reaction and the working pressure of 0.15Mpa, can be reduced to below the 10PPm bromine index＜1mgBr/100g sample with the benzene content in the solvent oil from 800～1100PPm.
The present invention compares with similar technology, have lower reaction temperature, lower operating pressure, the less characteristics such as hydrogen-oil ratio, can property the impurity such as the unsaturated hydrocarbons in the low boiling point solvent oil, aromatic hydrocarbons be taken off to 10PPm in the operating condition of milder next time. The suitability for industrialized production application result shows that technology of the present invention is mature and feasible, and production run is reliable and stable, and operating condition is gentle, and production cost is low, remarkable in economical benefits.
Claims (3)
1, a kind of method of low temperature and low pressure hydrogenated refinment of low boiling point solvent oil, it is characterized in that the technical process of " solvent oil gasification → hydrogenation and olefin hydrocarbon removal and aromatic hydrocarbons → solvent oil condensation → hydrogen recycle ", adopt the nickel-alumina catalyst of nickel content, at 100 ℃～140 ℃ temperature and the working pressure of 0.15～0.3Mpa and hydrogen dividing potential drop 0.04～0.07MPa (hydrogen to oil volume ratio 40～70), air speed 2～4h greater than 40% (w%)
-1Condition under, boiling point is carried out hydrofining at the solvent oil below 120 ℃, remove unsaturated hydrocarbons, aromatic hydrocarbon impurities in the solvent oil once, make the low boiling point solvent oil production.
2, a kind of method of low temperature and low pressure hydrogenated refinment of low boiling point solvent oil as claimed in claim 1 is characterized in that one-stage hydrogenation deolefination and aromatic hydrocarbons, and is disposable with alkene and arene engaging scraping in hydrogenation and olefin hydrocarbon removal and aromatic hydrocarbons reactor.
3, a kind of method of low temperature and low pressure hydrogenated refinment of low boiling point solvent oil as claimed in claim 1, aromaticity content＜10ppm, bromine index＜1mgBr/100g in the product that it is characterized in that making.
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| CNB2004100658811A CN100427570C (en) | 2004-12-24 | 2004-12-24 | Method for low temperature and low pressure hydrogenated refinment of low boiling point solvent oil |
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| CNB2004100658811A CN100427570C (en) | 2004-12-24 | 2004-12-24 | Method for low temperature and low pressure hydrogenated refinment of low boiling point solvent oil |
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| CN1644655A true CN1644655A (en) | 2005-07-27 |
| CN100427570C CN100427570C (en) | 2008-10-22 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993727A (en) * | 2010-11-26 | 2011-03-30 | 开滦能源化工股份有限公司 | Method for producing solvent oil |
| CN101608133B (en) * | 2009-06-18 | 2012-04-18 | 广州中元石油化工工程有限公司 | Preparation method of vegetable oil extraction solvent |
| CN101875854B (en) * | 2009-04-30 | 2012-12-19 | 中国海洋石油总公司 | Method for preparing narrow fraction low-aromatic hydrocarbon No.6 solvent oil |
| CN103468304A (en) * | 2013-09-29 | 2013-12-25 | 东北农业大学 | Method for removing arene and unsaturated hydrocarbon from hydrogenation solvent oil |
| CN105754650A (en) * | 2014-12-18 | 2016-07-13 | 中国石油天然气集团公司 | System and method for preparing solvent oil |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5642612A (en) * | 1995-12-19 | 1997-07-01 | Hughes; Ceiriog | Replaceable tip cable handler |
| CN100357401C (en) * | 2003-12-26 | 2007-12-26 | 南化集团研究院 | Process for producing hydrogenation refining solvent oil |
-
2004
- 2004-12-24 CN CNB2004100658811A patent/CN100427570C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875854B (en) * | 2009-04-30 | 2012-12-19 | 中国海洋石油总公司 | Method for preparing narrow fraction low-aromatic hydrocarbon No.6 solvent oil |
| CN101608133B (en) * | 2009-06-18 | 2012-04-18 | 广州中元石油化工工程有限公司 | Preparation method of vegetable oil extraction solvent |
| CN101993727A (en) * | 2010-11-26 | 2011-03-30 | 开滦能源化工股份有限公司 | Method for producing solvent oil |
| CN103468304A (en) * | 2013-09-29 | 2013-12-25 | 东北农业大学 | Method for removing arene and unsaturated hydrocarbon from hydrogenation solvent oil |
| CN105754650A (en) * | 2014-12-18 | 2016-07-13 | 中国石油天然气集团公司 | System and method for preparing solvent oil |
| CN105754650B (en) * | 2014-12-18 | 2017-09-01 | 中国石油天然气集团公司 | A kind of system and method for preparing solvent naphtha |
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| Publication number | Publication date |
|---|---|
| CN100427570C (en) | 2008-10-22 |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: Nanhua Group Research Institute |