CN1177019C - A chemical refining method for removing oxidized total insolubles and colloids in diesel oil - Google Patents
A chemical refining method for removing oxidized total insolubles and colloids in 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
- Authority
- CN
- China
- Prior art keywords
- diesel oil
- chemical refining
- quaternary ammonium
- reagent
- refining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000126 substance Substances 0.000 title claims abstract description 65
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 63
- 238000007670 refining Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000000084 colloidal system Substances 0.000 title claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical group [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims 1
- 235000019345 sodium thiosulphate Nutrition 0.000 claims 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 239000003209 petroleum derivative Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 19
- 238000007254 oxidation reaction Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明属于石油化工技术领域，涉及到石油产品的化学精制方法，特别涉及一种脱除柴油中氧化总不溶物及胶质的化学精制方法，该方法主要是对催化裂化等含有较多氧化总不溶物及胶质的柴油进行化学精制，同时使化学精制后的柴油色度随着时间的增加保持相对稳定。该方法采用由无机碱溶液与硫代硫酸盐及季铵盐或季铵碱表面活性剂按一定比例组成的复合化学精制试剂，将该种复合化学精制试剂与柴油按一定比例、在一定温度下，充分混合反应，待沉降一定时间分层后，将分层底部混合液体切放出来，即完成柴油化学精制过程。该种柴油化学精制方法较加氢精制，工艺简单、投资少、处理柴油成本低(6-10元/吨)，其柴油收率大于99.5%，且无工业污染。The invention belongs to the technical field of petrochemical industry and relates to a chemical refining method for petroleum products, in particular to a chemical refining method for removing oxidized total insolubles and colloids in diesel oil. The insoluble and colloidal diesel oil is chemically refined, and at the same time, the color of the chemically refined diesel oil remains relatively stable with the increase of time. The method adopts a composite chemical refining reagent composed of inorganic alkali solution, thiosulfate, quaternary ammonium salt or quaternary ammonium alkali surfactant in a certain proportion, and the compound chemical refining reagent and diesel oil are mixed in a certain proportion at a certain temperature. , fully mixed and reacted, after settling for a certain period of time and stratified, the mixed liquid at the bottom of the stratified layer was cut out, and the diesel chemical refining process was completed. Compared with hydrogenation refining, this kind of diesel oil chemical refining method has simple process, less investment, low cost of processing diesel oil (6-10 yuan/ton), and its diesel oil yield is greater than 99.5%, and there is no industrial pollution.
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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021332312A CN1177019C (en) | 2002-10-18 | 2002-10-18 | A chemical refining method for removing oxidized total insolubles and colloids in diesel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021332312A CN1177019C (en) | 2002-10-18 | 2002-10-18 | A chemical refining method for removing oxidized total insolubles and colloids in diesel oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1403539A CN1403539A (en) | 2003-03-19 |
| CN1177019C true CN1177019C (en) | 2004-11-24 |
Family
ID=4747103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021332312A Expired - Fee Related CN1177019C (en) | 2002-10-18 | 2002-10-18 | A chemical refining method for removing oxidized total insolubles and colloids in diesel oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1177019C (en) |
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) | A method for converting, 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 |
-
2002
- 2002-10-18 CN CNB021332312A patent/CN1177019C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1403539A (en) | 2003-03-19 |
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