CN100427570C - 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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- CN100427570C CN100427570C CNB2004100658811A CN200410065881A CN100427570C CN 100427570 C CN100427570 C CN 100427570C CN B2004100658811 A CNB2004100658811 A CN B2004100658811A CN 200410065881 A CN200410065881 A CN 200410065881A CN 100427570 C CN100427570 C CN 100427570C
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Abstract
The present invention belongs to the technical field petrochemical industry. The method of the present invention comprises: a nickel aluminum catalyst is used for hydrofinishing white oil with a boiling point lower than 120DEG C in natural gas processing plants and oil refineries under the conditions that a reaction temperature is between 100 DEG C to 140 DEG C, operation pressure is between 0.15 to 0.3MPa, the proportion of hydrogen to oil is 40 to 70, and air speed is 2 to 4 h<-1> so as to produce solvent oil with high standards. The present invention is characterized in that impurities such as unsaturated hydrocarbon, aromatic hydrocarbon, etc., are hydrofinished to be reduced below 10 PPm under the condition of moderate operation conditions, and a sample with a bromine index lower than 1 mg Br/100 g is formed. The application result of industrial production indicates that the technical technology has the advantages of maturity, feasibility, stable production operation, moderate operation conditions, low production cost of products, and obvious economic benefit.
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 nickel content weight percent greater than 40% nickel-alumina catalyst, 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
-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% (wt%) 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;
Below in conjunction with embodiment and accompanying drawing the present invention is described in detail.
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
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 (2)
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 nickel content weight percent greater than 40% nickel-alumina catalyst, 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
-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.
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| Application Number | Priority Date | Filing Date | Title |
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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 CN1644655A (en) | 2005-07-27 |
| CN100427570C true CN100427570C (en) | 2008-10-22 |
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Families Citing this family (5)
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159418A (en) * | 1995-12-19 | 1997-09-17 | C·休斯 | Replaceable tip cable handler |
| CN1554729A (en) * | 2003-12-26 | 2004-12-15 | 南化集团研究院 | Process for producing hydrogenation refining solvent oil |
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- 2004-12-24 CN CNB2004100658811A patent/CN100427570C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159418A (en) * | 1995-12-19 | 1997-09-17 | C·休斯 | Replaceable tip cable handler |
| CN1554729A (en) * | 2003-12-26 | 2004-12-15 | 南化集团研究院 | Process for producing hydrogenation refining solvent oil |
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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 |
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