CN1177019C - Chemical refining process of eliminating unsoluble oxides and gum from diesel oil - Google Patents
Chemical refining process of eliminating unsoluble oxides and gum from diesel oilInfo
- Publication number
- CN1177019C CN1177019C CNB021332312A CN02133231A CN1177019C CN 1177019 C CN1177019 C CN 1177019C CN B021332312 A CNB021332312 A CN B021332312A CN 02133231 A CN02133231 A CN 02133231A CN 1177019 C CN1177019 C CN 1177019C
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- Prior art keywords
- diesel oil
- refining
- quaternary ammonium
- chemical
- reagent
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a chemically refining method of a petroleum product, particularly to a chemically refining method for eliminating oxidated total insoluble substances and colloidal matters in diesel oil, which belongs to the technical field of petrochemical industry. The method is characterized in that catalytically cracked diesel oil, etc. containing more oxidated total insoluble substances and more colloidal matters is chemically refined, and simultaneously, the chrominance of the diesel oil chemically refined is kept relatively stable with the prolonged time. In the method, a compound chemical refining reagent composed of an inorganic hydroxide solution, thiosulfates and quaternary ammonium salt surface active agent or a quaternary ammonium hydroxide surface active agent according to certain proportions is adopted; the compound chemical refining reagent and the diesel oil are thoroughly mixed according to certain proportions to react with each other at a certain temperature; mixed liquid at the bottom of the delaminated mixture is separated after the mixture is sedimentated for a certain time and delaminated, and the chemical refining process of the diesel oil is completed. Compared with a hydrogenation refining method, the chemically refining method of diesel oil has the advantages of simple process, little investment, low cost (6 to 10 yuan/ton) for diesel oil treatment, and no industrial pollution. The yield of the diesel oil of the method is higher than 99.5%.
Description
Technical field
The invention belongs to petrochemical industry, relate to a kind of petroleum products chemical refining method, specially refer to catalytic cracking etc. is contained the method that more oxidation total insoluble substance and gelationus diesel oil carry out chemical refining.
Background technology
The diesel oil that oil is produced through refining, the diesel oil of producing by methods such as catalytic cracking, coking, thermally splitting particularly, the heterogeneous ring compound, olefin(e) compound and the aldehydes matter that contain more sulphur, nitrogen, oxygen, the existence of above-mentioned substance reduces the stability of diesel oil greatly.Because diesel oil stability is poor, placing for some time is variable color, muddiness, and produces a large amount of sediments.The vehicle that uses this diesel oil can cause filtering system to stop up, and causes failure of fuel system, simultaneously because combustion efficacy missionary society causes topsoil.This kind diesel oil is along with increase storage period, and oxidation total insoluble substance and colloid also constantly increase in the diesel oil.For this reason, above-mentioned diesel oil is generally all adopted the hydrofining technology, promptly than removing sulphur, nitrogen, oxygen, heterogeneous ring compound and phenolic compound under the severe condition, make alkene saturated simultaneously, improve the diesel oil stability in storage, hydrofining is effective, but the one-time investment cost is big, the processing cost height.
Disclosed at present CN1058038A, CN1287149A and CN1279269A only can handle catalytic diesel oil, and can not and contain more oxidation total insoluble substance and the gelationus finished diesel fuel is handled to other diesel oil such as coker gas oil, thermally splitting diesel oil.
Summary of the invention
The purpose of this invention is to provide and a kind ofly remove oxidation total insoluble substance and gelationus chemical refining method in the diesel oil, and the diesel oil colourity after the chemical refining is kept relative stability along with the increase of time.
Technical scheme of the present invention is to adopt the composite chemical of being made up of greater than the inorganic alkali solution of 30% (m/m) and thiosulphate and quaternary ammonium salt or quaternary ammonium hydroxide tensio-active agent concentration to make with extra care reagent, with the refining reagent of diesel oil and composite chemical by 100: 1-1000: 1 under normal pressure and 30 ℃ of-80 ℃ of temperature hybrid reaction 1-10 minute, after treating the layering of sedimentation certain hour, layering bottom mixing liquid cut release, promptly finish the diesel oil chemical refining process.
Effect benefit of the present invention is to adopt this kind method that diesel oil is carried out chemical refining oxidation total insoluble substance and the colloid major part that contains in the diesel oil to be removed, decreasing ratio reaches more than 90%, improve the diesel oil stability in storage, can delay again simultaneously that diesel oil oxidation total insoluble substance and colloid generate after the chemical refining, and can make diesel oil colourity increase and keep relative stability along with the time.Simultaneously, the present invention is simple than hydrofining technology, less investment, processing diesel oil cost are low, and does not have industrial pollution.
Embodiment
A kind ofly remove oxidation total insoluble substance and gelationus chemical refining method in the diesel oil, in diesel oil, add the refining reagent of forming by mineral alkali and thiosulphate and quaternary ammonium salt or quaternary ammonium hydroxide tensio-active agent of composite chemical by a certain percentage, under normal pressure and certain temperature, mixed stirring reaction 1-10 minute, after the layering of sedimentation certain hour, layering bottom mixed solution cut release, promptly finish oxidation total insoluble substance and the gelationus chemical refining method in the diesel oil of removing.Upper solution is the diesel oil after chemical refining is handled, lower floor is diesel oil chemical refining reaction product (dirty oil) and the refining reagent of residue composite chemical, diesel oil chemical refining reaction product (dirty oil) can be used as the fuel utilization, and the refining reagent of residue composite chemical can be recycled.Said mineral alkali can be the alkaline solution of sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, and its concentration range is 30%-50% (m/m); Said thiosulphate can be Sulfothiorine, Potassium Thiosulphate, and its concentration in the refining reagent of composite chemical is 100ppm-10000ppm; Said quaternary ammonium salt or quaternary ammonium hydroxide tensio-active agent can be these series product tensio-active agents such as tetramethyl ammonium chloride, etamon chloride, 4-propyl ammonium chloride, tetrabutylammonium chloride, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, and its concentration in the refining reagent of composite chemical is 20ppm-10000ppm; Refining reagent of said composite chemical and diesel oil blended certain proportion are 1: 100-1: 1000; The chemical refining reaction times is 1-10 minute; Said certain temperature is 30 ℃-80 ℃; Said certain hour is 2-4 hour.
The present invention carries out chemical refining to containing more oxidation total insoluble substance and gelationus diesel oil, oxidation stability of diesel oil and colourity etc. all can reach oxidation total insoluble substance among the GB252-2000 and is not more than 2.5mg/100ml, colourity and is not more than 3.5 the diesel oil standard of dispatching from the factory after chemical refining, it is wide that this kind method is handled diesel range, the refined diesel oil yield is greater than 99.5%, diesel oil chemical refining reaction product (dirty oil) productive rate is less than 0.5%, diesel oil consumption agent 1.5-3 kilogram per ton, processing cost are 6-10 unit, less investment, and do not have industrial pollution.
The present invention is further illustrated below in conjunction with embodiments of the invention.
Embodiment
Use concentration and be 35% liquid sodium hydroxide and be mixed and made into the refining reagent of composite chemical with Sulfothiorine and tetraethyl ammonium hydroxide by 1000: 2: 1 (weight ratio), following example all adopts the composite chemical of this proportioning to make with extra care reagent and experimentizes.
Getting certain catalytic diesel oil 1000ml of petrochemical industry branch office pours in the beaker, be heated to 60 ℃, add the refining reagent 1.67ml of composite chemical, stirring reaction 8 minutes, sedimentation 2 hours, upper strata diesel oil is separated with lower floor's reactant and residue reagent, get refining forward and backward diesel oil and analyze, the result is shown in table 1, table 2.
Table 1, two urges the diesel oil chemical refining to handle forward and backward every index (finish was than 600: 1)
After project is handled pre-treatment
Colloid mg/100ml 248 23
Oxidation sediment mg/100ml 10.54 0.79
Density g/cm
30.9160 0.9159
Viscosity (20 ℃) mm
2/ s 4.82 4.82
Sulphur content % (m/m) 0.2103 0.2075
The mechanical impurity nothing
N(ppm) 951 906
Iodine number gI/100g 27.10 2.41
Water-soluble soda acid nothing
Copper corrosion 1a 1a
(50 ℃ of 3h) level
Heat up in a steamer 50% 274.4 274.4
Journey 90% 342 341
℃ 95％ 352 351
Table 2, three urges the diesel oil chemical refining to handle forward and backward every index (finish was than 600: 1)
After project is handled pre-treatment
Colloid mg/100ml 145 13
Oxidation sediment mg/100ml 12.63 0.86
Density g/cm
30.8704 0.8698
Viscosity (20 ℃) mm
2/ s 3.79 3.78
Sulphur content % (m/m) 0.14 0.14
The mechanical impurity nothing
N(ppm) 801 798
Cetane value 40.0 40.3
Iodine number gI/100g 31.1 16.33
Water-soluble soda acid nothing
Copper corrosion
(50 ℃ of 3h) level 1a 1a
Heat up in a steamer 50% 265 265
Journey 90% 332 332
℃ 95％ 343.5 343
Adopt above-mentioned composite chemical to make with extra care reagent, certain petrochemical industry branch office finished diesel fuel (diesel oil and normal pressure diesel oil were concocted by 82: 18 after the hydrofining) is carried out chemical refining to be handled, its finish is than pressing 600: 1 (m/m), stirring reaction 6 minutes, sedimentation 2.5 hours, upper strata diesel oil is separated with lower floor's reactant and residue reagent, refining forward and backward oxidation total insoluble substance and colloid are analyzed, the result is as shown in table 3.
Finished diesel fuel carries out chemical refining and handles forward and backward Measurement results behind table 3, the hydrogenation
After project is handled pre-treatment
The oxidation total insoluble substance
5.2 0.38
mg/100ml
Colloid mg/100ml 132 12
Adopt the refining reagent of composite chemical of the present invention that certain petrochemical industry branch office catalytic diesel oil is carried out chemical refining, finish is than pressing 600: 1 (m/m), stirring reaction 8 minutes, sedimentation 2 hours, upper strata diesel oil is separated with lower floor's reactant and residue reagent, and result of variations is as shown in table 4 in time for refining back diesel oil oxidation total insoluble substance and colourity.
Table 4, oxidation stability total insoluble substance and colourity change in time
The total insoluble mg/100ml colourity of time oxidation
Chemical refining preceding 8.2 1.0
After the chemical refining 0.56 1.0
After one month 0.61 1.0
After two months 0.94 1.5
After three months 1.03＜2.0
Claims (1)
1, a kind ofly remove oxidation total insoluble substance and gelationus chemical refining method in the diesel oil, be in diesel oil, to add in proportion by inorganic alkali solution, thiosulphate, and the refining reagent of composite chemical of quaternary ammonium salt or quaternary ammonium hydroxide composition, normal pressure and 30 ℃-80 ℃ following reactions 1-10 minute, then after the layering in sedimentation 2-4 hour, layering bottom mixed solution cut release, promptly finish the diesel oil chemical refining process, it is characterized in that: described quaternary ammonium salt or quaternary ammonium hydroxide are tetramethyl ammonium chlorides, etamon chloride, 4-propyl ammonium chloride, tetrabutylammonium chloride, Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide, described quaternary ammonium salt or the quaternary ammonium hydroxide concentration in the refining reagent of composite chemical is 20ppm-10000ppm; Described thiosulphate is Sulfothiorine or Potassium Thiosulphate, and the concentration of described thiosulphate in the refining reagent of composite chemical is 100ppm-10000ppm; Described mineral alkali is sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood, and the concentration of described inorganic alkali solution is 30%-50%; The ratio of the refining reagent of diesel oil and composite chemical is 100: 1-1000: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021332312A CN1177019C (en) | 2002-10-18 | 2002-10-18 | Chemical refining process of eliminating unsoluble oxides and gum from diesel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021332312A CN1177019C (en) | 2002-10-18 | 2002-10-18 | Chemical refining process of eliminating unsoluble oxides and gum from diesel oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1403539A CN1403539A (en) | 2003-03-19 |
| CN1177019C true CN1177019C (en) | 2004-11-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021332312A Expired - Fee Related CN1177019C (en) | 2002-10-18 | 2002-10-18 | Chemical refining process of eliminating unsoluble oxides and gum from diesel oil |
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| Country | Link |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892075A (en) * | 2010-07-27 | 2010-11-24 | 中国石油大学(华东) | Method for transforming, separating and processing heavy oil |
| US8828218B2 (en) | 2011-10-31 | 2014-09-09 | Exxonmobil Research And Engineering Company | Pretreatment of FCC naphthas and selective hydrotreating |
| CN102876362A (en) * | 2012-10-22 | 2013-01-16 | 常州大学 | Diesel refinement and decolorization method |
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2002
- 2002-10-18 CN CNB021332312A patent/CN1177019C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1403539A (en) | 2003-03-19 |
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Granted publication date: 20041124 Termination date: 20131018 |