CN101705124B - Diesel oxidized stabilizer composite - Google Patents
Diesel oxidized stabilizer composite Download PDFInfo
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- CN101705124B CN101705124B CN 200910230970 CN200910230970A CN101705124B CN 101705124 B CN101705124 B CN 101705124B CN 200910230970 CN200910230970 CN 200910230970 CN 200910230970 A CN200910230970 A CN 200910230970A CN 101705124 B CN101705124 B CN 101705124B
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- diesel
- diesel oil
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- oxidized
- antioxidizer
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- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 239000003381 stabilizer Substances 0.000 title claims abstract description 16
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 13
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 14
- 239000000654 additive Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 6
- 239000013049 sediment Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000007792 addition Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 239000002283 diesel fuel Substances 0.000 description 59
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- RWLPWUBCXLUUNY-UHFFFAOYSA-N 9,10-dimethoxy-3,6-di(propan-2-yl)-1,2,3,4-tetrahydroanthracene-2,7-diol Chemical compound CC(C)C1CC2=C(C3=CC(=C(C=C3C(=C2CC1O)OC)O)C(C)C)OC RWLPWUBCXLUUNY-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
- 238000004523 catalytic cracking Methods 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229940125725 tranquilizer Drugs 0.000 description 4
- 239000003204 tranquilizing agent Substances 0.000 description 4
- 230000002936 tranquilizing effect Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- IBIRPPFWAAOERN-UHFFFAOYSA-N CC(C)c1c(Cc(c(C2)c3)c(C(C)C)cc3O)c2cc(O)c1 Chemical compound CC(C)c1c(Cc(c(C2)c3)c(C(C)C)cc3O)c2cc(O)c1 IBIRPPFWAAOERN-UHFFFAOYSA-N 0.000 description 1
- WLQBULPWCSJJCC-UHFFFAOYSA-N CC(C)c1cc(C(c(c(C2OC)c3)cc(C(C)C)c3O)OC)c2cc1O Chemical compound CC(C)c1cc(C(c(c(C2OC)c3)cc(C(C)C)c3O)OC)c2cc1O WLQBULPWCSJJCC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a diesel oxidized stabilizer composite which is prepared from the following raw materials in percentage by weight: 20-40 percent of screening phenols antioxidizer, 30-60 percent of amine antioxidizer, 10-20 percent of phosphate-contained antioxidizer, 5-10 percent of sulpho-esters antioxidizer and 5-10 percent of carboxylic acid compound. The diesel oxidized stabilizer composite can effectively reduce total insoluble substances of diesel oxidized sediments to effectively improve the color grade of the diesel. An additive for the composite has low manufacture cost, good intersolubility with the diesel, and simple adding method without using new equipment; the additive has synergistic effect with other additions of the diesel and low solidifying point, being beneficial to winter storage and addition; moreover, the additive has the cleaning action on engines.
Description
Technical field
The present invention relates to a kind of composition of additive for diesel oil, be specifically related to the compositions of additives that a kind of active ingredient that is used for suppressing diesel oil generates oxidation sediment, improves the oxidation stability of diesel oil.
Background technology
Along with the quickening of vehicle diesel oil trend in the world wide, the demand of diesel oil is increasing, and is also increasingly high to the specification of quality of diesel oil.Because crude production rate is limited, present widely used diesel oil generally all is the composite of perfectly straight diesel oil and catalytic cracking diesel oil.For a long time, the stability of catalytic cracking diesel oil is people's questions of common concern.Compare with perfectly straight diesel oil; Urge and contain a large amount of destabilization components in the bavin, like non-hydrocarbon compounds such as alkene, condensed-nuclei aromatics and sulphur, nitrogen, under the effect of these compounds oxygen in air; Be easy to take place condensation or oxidizing reaction; Generating various macromolecular cpds, i.e. total insoluble substance or oxidation sediment---the oxidation stability total insoluble substance is to indicate diesel oil in storage and transportation, and generation throw out and gelationus trend in the presence of air and the less water are being arranged.It is diesel oil colourity that the oxidation stability of diesel oil total insoluble substance shows the most intuitively.Along with the storage time prolongs, diesel colour is deepened, and diesel quality descends.Mainly show as and accelerate sediment, colloid increases, darken etc.The existence of total insoluble substance will influence the use properties of diesel oil, and when diesel oil burnt in mover, compositions such as total insoluble substance will be with the form of coking material attached on the inwall of combustion chamber, cause filtering system to stop up thus and cause failure of fuel system.Nitride and sulfide and naphthenic acid etc. play an important role in urging the deterioration by oxidation of bavin.Modern petroleum refining industry requires fuel to develop to eco-friendly aspect, and foreign matter contents such as the sulphur in the finished diesel fuel, nitrogen, aromatic hydrocarbons will be tried to achieve strict more in new national standard.Simultaneously, the existence of sulphur, nitrogen is prone to make poisoning of catalyst, thereby removes impurity such as sulphur, nitrogen and become and improve the oxidation stability of diesel oil top priority.
As everyone knows; Diesel oil is the complicated mixture of a kind of component; Mostly the diesel oil of China is to be formed by two or more components mediations in perfectly straight diesel oil, catalytic cracking diesel oil, coker gas oil and the hydrogenated diesel oil now; Except that hydrogenated diesel oil and perfectly straight diesel oil, contain the active nitrogenous and sulfocompound of the 1000-10000ppm that has an appointment in catalytic cracking diesel oil and the coker gas oil.These compounds are easy to react with airborne oxygen and generate total insoluble substance.New diesel oil standard GB 250-2000 and new car with strict regulation among the diesel oil standard GB/T19147-2003 total insoluble substance must be not more than the index of 2.5mg/100ml, the regulation of this index, the gap of having dwindled China's diesel oil and developed country's diesel oil.
Improve the stability of diesel oil, adopt unifining, chemical refining and use diesel oil tranquilizer at present usually.Unifining can improve the stability of diesel oil greatly, but production cost is too high, and equipment requirements is strict; Chemical refining can improve the stability of diesel oil to a certain extent, but refining effect is not ideal enough, and has the waste residue problem; And in diesel oil, add suitable additive, and can improve the stability of diesel oil to a certain extent, be a kind of economical and practical method.
Summary of the invention
The cost that the present invention is directed to present raising diesel oil stability is high, the problem of DeGrain, has proposed a kind of diesel oxidized stabilizer composite that can effectively improve diesel oil stability.
Technical scheme of the present invention is following:
Diesel oxidized stabilizer composite of the present invention is made up of following weight percentages:
Shielding phenolic antioxidant 20-40%, amine antioxidants 30-60%, phosphorus-containing antioxidant 10-20%, monothioester kind antioxidant 5-10%, carboxylic acid cpd 5-10%.
Wherein said shielding phenolic antioxidant select for use have structural formula (1) 2,7-dihydroxyl-4,5-di-isopropyl-9,10-tetrahydro-anthracene with have 2 of structural formula (2), 7-dihydroxyl-3,6-di-isopropyl-9, one or both in the 10-dimethoxy tetrahydro-anthracene;
Said amine antioxidants is triphen phenolic group ammonia with structural formula (3) and the N-propyl group-3 with structural formula (4), at least a in the 6-dimethoxy carbazole;
Said phosphorus-containing antioxidant is a tricresyl phosphite methoxyl group methyl esters, and molecular formula is P (OCOCH
3)
3Said monothioester kind antioxidant comprises at least a in the two dodecyl esters of thio-2 acid, the two tetradecyl esters of thio-2 acid, the two stearyl of thio-2 acid for the thio-2 acid alkyl ester; Said carboxylic acid cpd is an oxalic acid.
The preparation of diesel oxidized stabilizer composite of the present invention is each raw materials mix to be stirred get final product, and is benchmark with diesel oil weight in use, and add-on is 10-20000ppm, is preferably 20-15000ppm.
Diesel oxidized stabilizer composite of the present invention can effectively reduce diesel oil oxidation sediment total insoluble substance, and meets GB252-2000 and GB/T19147-2003 standard; Effectively improve the look level of diesel oil; Additive cost of manufacture of the present invention is low, and good with the diesel oil mutual solubility, addition means is simple, need not go up new installation, has synergistic effect with other additives of diesel oil, and zero pour is low, is beneficial to storage in winter and interpolation, and mover is had peace and quiet effect.
Embodiment
Embodiment 1
The weight of each raw material is formed as follows in the stabilizer composite:
2,7-dihydroxyl-4,5-di-isopropyl-9,10-tetrahydro-anthracene 20%
Triphen phenolic group ammonia 50%
Tricresyl phosphite methoxyl group methyl esters 10%
The two dodecyl esters 10% of thio-2 acid
Oxalic acid 10%
Embodiment 2
The weight of each raw material is formed as follows in the stabilizer composite:
2,7-dihydroxyl-3,6-di-isopropyl-9,10-dimethoxy tetrahydro-anthracene 40%
N-propyl group-3,6-dimethoxy carbazole 30%
Tricresyl phosphite methoxyl group methyl esters 10%
The two dodecyl esters 5% of thio-2 acid
The two stearyl 5% of thio-2 acid
Oxalic acid 10%
Embodiment 3
The weight of each raw material is formed as follows in the stabilizer composite:
2,7-dihydroxyl-4,5-di-isopropyl-9,10-tetrahydro-anthracene 10%
2,7-dihydroxyl-3,6-di-isopropyl-9,10-dimethoxy tetrahydro-anthracene 30%
N-propyl group-3,6-dimethoxy carbazole 30%
Tricresyl phosphite methoxyl group methyl esters 10%
The two stearyl 10% of thio-2 acid
Oxalic acid 10%
Embodiment 4
The weight of each raw material is formed as follows in the stabilizer composite:
2,7-dihydroxyl-4,5-di-isopropyl-9,10-tetrahydro-anthracene 30%
2,7-dihydroxyl-3,6-di-isopropyl-9,10-dimethoxy tetrahydro-anthracene 10%
N-propyl group-3,6-dimethoxy carbazole 10%
Triphen phenolic group ammonia 20%
Tricresyl phosphite methoxyl group methyl esters 15%
The two stearyl 5% of thio-2 acid
Oxalic acid 10%
Embodiment 5
The weight of each raw material is formed as follows in the stabilizer composite:
2,7-dihydroxyl-4,5-di-isopropyl-9,10-tetrahydro-anthracene 10%
2,7-dihydroxyl-3,6-di-isopropyl-9,10-dimethoxy tetrahydro-anthracene 10%
N-propyl group-3,6-dimethoxy carbazole 30%
Triphen phenolic group ammonia 20%
Tricresyl phosphite methoxyl group methyl esters 10%
The two dodecyl esters 2% of thio-2 acid
The two tetradecyl esters 4% of thio-2 acid
The two stearyl 4% of thio-2 acid
Oxalic acid 10%
Test case 1
The oxidation stability of the diesel oil after the mediation is measured with the EN14112:2003 method, uses the 743 type Oxidation of Fat and Oils stability determinators of instrument as Switzerland Wan Tong company.The result sees table one.
Table one
The result shows that diesel oxidized stabilizer composite provided by the invention can effectively improve the oxidation stability of diesel oil, and improvement effect is remarkable.
Adopt SH/T0175 or ASTM D2274 analytical procedure not to measure result such as table two to diesel oil is always tolerant:
Table two
| Test item | Add dosage (ppm) | Add the preceding total insoluble substance (mg/100ml) of agent | Add total insoluble substance (mg/100ml) after the agent |
| Add the diesel oil of embodiment 1 product | 80 | 3.8 | 1.3 |
| Add the diesel oil of embodiment 2 products | 80 | 3.8 | 1.0 |
| Add the diesel oil of embodiment 3 products | 80 | 3.8 | 1.2 |
| Add the diesel oil of embodiment 4 products | 80 | 3.8 | 0.9 |
| Add the diesel oil of embodiment 5 products | 80 | 3.8 | 0.8 |
The result shows, diesel oxidized stabilizer composite of the present invention can reduce the amount of diesel oil oxidation sediment total insoluble substance greatly, and improvement effect is good.
Investigated the stabilization of tranquilizer, tranquilizer add-on 300ugg to diesel colour
-1, normal temperature is measured.The result sees table three.
Table three
| Test item | 0 week | 1 week | 2 weeks | 3 weeks |
| Not additivated diesel oil | 0.5 | 1.0 | 2.8 | 3.6 |
| Add the diesel oil of embodiment 1 product | 0.5 | 0.7 | 1.5 | 2.4 |
| Add the diesel oil of embodiment 1 product | 0.5 | 0.9 | 1.4 | 2.3 |
| Add the diesel oil of embodiment 1 product | 0.5 | 0.8 | 1.7 | 2.4 |
| Add the diesel oil of embodiment 1 product | 0.5 | 0.6 | 1.3 | 2.2 |
| Add the diesel oil of embodiment 1 product | 0.5 | 0.7 | 1.3 | 2.3 |
The result shows, behind the adding tranquilizer, can suppress the discoloration problem of diesel oil greatly.
Claims (1)
1. diesel oxidized stabilizer composite is characterized in that being made up of following weight percentages:
Shielding phenolic antioxidant 20-40%, amine antioxidants 30-60%, phosphorus-containing antioxidant 10-20%, monothioester kind antioxidant 5-10%, carboxylic acid cpd 5-10%;
Said shielding phenolic antioxidant is 2,7-dihydroxyl-9,10-tetrahydro-anthracene and 2,7-dihydroxyl-3,6-di-isopropyl-9, one or both in the 10-dimethoxy tetrahydro-anthracene;
Said amine antioxidants is triphen phenolic group ammonia and N-propyl group-3, at least a in the 6-dimethoxy carbazole;
Said phosphorus-containing antioxidant is a tricresyl phosphite methoxyl group methyl esters;
Said monothioester kind antioxidant is the thio-2 acid alkyl ester;
Said carboxylic acid cpd is an oxalic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910230970 CN101705124B (en) | 2009-11-27 | 2009-11-27 | Diesel oxidized stabilizer composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910230970 CN101705124B (en) | 2009-11-27 | 2009-11-27 | Diesel oxidized stabilizer composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101705124A CN101705124A (en) | 2010-05-12 |
| CN101705124B true CN101705124B (en) | 2012-10-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910230970 Expired - Fee Related CN101705124B (en) | 2009-11-27 | 2009-11-27 | Diesel oxidized stabilizer composite |
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| Country | Link |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275775B (en) * | 2013-06-25 | 2013-12-25 | 咸阳东庆石油化工有限公司 | Harmonic ingredient of high-power clean diesel oil |
| CN106318525B (en) * | 2015-06-19 | 2019-09-24 | 中国石油化工股份有限公司 | Diesel engine oil composition and its manufacturing method |
| CN111607439A (en) * | 2020-06-22 | 2020-09-01 | 金浦新材料股份有限公司 | Heat stability additive for aviation kerosene fuel |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314459A (en) * | 2000-03-20 | 2001-09-26 | 英菲诺姆国际有限公司 | Lubrication oil composition |
| CN1413985A (en) * | 2001-10-26 | 2003-04-30 | 乙基公司 | Dithio-carbamate containing alkythio group and hydroxy substituting group |
| CN1425743A (en) * | 2002-12-28 | 2003-06-25 | 李盛秋 | Non-toxic oxidation and deterioration preventing process for finished oil made from petroleum |
| CN1712494A (en) * | 2005-07-26 | 2005-12-28 | 张喜文 | Coke inhibitor of high-temperature refining equipment |
-
2009
- 2009-11-27 CN CN 200910230970 patent/CN101705124B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314459A (en) * | 2000-03-20 | 2001-09-26 | 英菲诺姆国际有限公司 | Lubrication oil composition |
| CN1413985A (en) * | 2001-10-26 | 2003-04-30 | 乙基公司 | Dithio-carbamate containing alkythio group and hydroxy substituting group |
| CN1425743A (en) * | 2002-12-28 | 2003-06-25 | 李盛秋 | Non-toxic oxidation and deterioration preventing process for finished oil made from petroleum |
| CN1712494A (en) * | 2005-07-26 | 2005-12-28 | 张喜文 | Coke inhibitor of high-temperature refining equipment |
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