CN1148436C - Process for refining gasoline or diesel oil by oxidation method - Google Patents
Process for refining gasoline or diesel oil by oxidation method Download PDFInfo
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- CN1148436C CN1148436C CNB991199049A CN99119904A CN1148436C CN 1148436 C CN1148436 C CN 1148436C CN B991199049 A CNB991199049 A CN B991199049A CN 99119904 A CN99119904 A CN 99119904A CN 1148436 C CN1148436 C CN 1148436C
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- diesel oil
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Abstract
The present invention relates to a method for refining gasoline or diesel oil by an oxidation method. Hydrogen peroxide is added into processed oil, and ternary heteropoly acid is used as a catalyst to carry out oxidation reaction under the existence condition of low-carbon alcohol of C1 to C4. The material filling ratio of the gasoline or the diesel oil to the hydrogen peroxide to the catalyst to the low-carbon alcohol is 100: (0.5 to 10): (0.05 to 1.5): (5 to 65). Oil and water phase materials are separated after the reaction is finished. The general formula of the catalyst is Hm(U<X>M<Y>N<Z>On), wherein U is P, Si or Ge, M is Mo, and N is W or V; X is from 1 to 2, Y and Z are from 0 to 18, and m and n are chemical coordination equilibrium numbers determined according to the values of X, Y and Z. The present invention is not only suitable for refining common straight distillation and catalytic cracking gasoline or diesel oil, but also for refining coking gasoline or diesel oil.
Description
Technical field
The present invention relates to the fine purification treatment process of gasoline or diesel oil.
Background technology
Along with the aggravation of crude oil heaviness and poor qualityization phenomenon, for improving light oil yield, oil refining production firm adopts this class heat processing technique of delayed coking to handle crude oil much more more and more.The coker gasoline that delayed coking obtains is a kind of fraction oil of poor quality, as reforming or the cracked raw material as mediation fraction oil or conduct, must carry out refinement treatment to reach decolouring, deodorization desulfurization, denitrogenation and to remove the purpose of alkene, industrial normal employing catalytic hydrogenation process carries out refinement treatment at present.Catalytic hydrofinishing is the comparatively harsh technological process of a kind of reaction conditions, and general hydrogen pressure will reach more than the 6MPa, and temperature of reaction is then up to 350 ℃.This just requires higher facility investment, and needs a large amount of sources of hydrogen, so the running cost of catalytic hydrofinishing technology is also corresponding higher.The report that non-hydrogenation technique treated gasoline or diesel oil were once arranged in the prior art has been released the technology of a kind of oxidation-solvent extraction two-step approach as European patent EP 0482841.Its process is earlier oil product to be carried out oxidizing reaction with hydrogen peroxide in the presence of the catalyzer and under the effect of phase transition promotor, and catalyst system therefor is the binary heteropolyacid, and general formula is H
e(X
kM
nO
y), wherein X is P, Ge, Ga, Si or B, M is Mo, W or V; E, k, y are respectively corresponding atomicity, and used phase transition promotor is quaternary ammonium salt or quaternary alkylphosphonium salt.Second step was carried out extracting with the oxidation oil product with low-carbon alcohol or water.There is following shortcoming in this method: catalytic performance is low, and generally effectively desulfurization, and denitrogenation, deactivation alkene weak effect are seen from its example of quoting just to be used for desulfurization.This method is generally used for handling catalytically cracked gasoline, is used to handle then poor effect of coker gasoline more inferior or diesel oil.This method uses the quaternary ammonium salt or the quaternary alkylphosphonium salt that can't recycle in a large number to do phase transition promotor in oxidation reaction process in addition, and processing cost is higher, and the emulsifying effect of quaternary ammonium salt or quaternary alkylphosphonium salt might make the oily water separation difficulty.
Summary of the invention
The purpose of this invention is to provide a kind of method of treated gasoline or diesel oil of non-hydrogenation, it has remedied the deficiency of existing non-hydrogenation method, its reaction conditions gentleness, and technological process is more easy, and can make with extra care coker gasoline or diesel oil effectively.
The method of treated gasoline provided by the invention or diesel oil comprises following process:
The adding concentration expressed in percentage by weight is 20～80% aqueous hydrogen peroxide solution in processed gasoline or diesel oil, and optimum concn is 30～50%, is catalyzer with the ternary heteropolyacid with following general formula, and at C
1～C
4Low-carbon alcohol carry out oxidizing reaction under existing, low-carbon alcohol is preferably used methyl alcohol or ethanol.
The add-on of hydrogen peroxide in the quality of pure hydrogen peroxide is:
Gasoline or diesel oil: hydrogen peroxide=100: (0.5～10), the best are 100: (2～5);
Catalyst consumption is by quality ratio:
Gasoline or diesel oil: catalyzer=100: (0.05～1.5), the best are 100: (0.5～1);
The consumption of low-carbon alcohol is by quality ratio:
Gasoline or diesel oil: low-carbon alcohol=100: (5～65), the best are 100: (10～30);
Temperature of reaction is 0～80 ℃, and the best is 20～60 ℃, and the reaction times is 0.2～5 hour, and the best is 2～4 hours, and reaction pressure is a normal pressure, and reaction finishes the back and separates oil phase and water material.
The general formula of above-mentioned catalyzer is:
H
m(U
xM
YN
ZO
n)
Wherein U=P, Si or Ge, M=Mo, N=W or V, X=1～2, Y, Z=1～17, m=3～5, n are for according to m, X, Y, the fixed chemical coordination equilibrium number of Z value.
Preferably use H
3PMo
(12-X)W
XO
40Or H
(3+X)PMo
(12-X)V
XO
40, X=1～2 wherein.
Catalyzer can be made by U, M, the corresponding high oxide of N or water-soluble salt back flow reaction under acidic conditions, and with ether complexometric extraction purifying in addition.
In treated gasoline provided by the invention or diesel oil method, hydrogen peroxide is oxidized to the bigger and more stable compound of polarity with materials such as gasoline or sulfide in diesel oil, nitride, active olefins under the catalysis of ternary heteropolyacid, for example:
Mercaptan is oxidized to disulphide:
；
Thioether is oxidized to sulfoxide compound:
Nitride is oxidized to oxynitride (tertiary amine oxide):
Active olefin is oxidized to epoxide, acid and pure:
These oxidation productss are easily removed to water by extracting, in this treating process, add low-carbon alcohol and have dual function, and on the one hand, it promotes that hydrogen peroxide fully contacts with gasoline or diesel oil; Promote the polarity oxidation products to be arrived aqueous phase on the other hand by extracting.
Compared with prior art, the invention has the advantages that reaction conditions is comparatively gentle, and be a kind of technology of single stage method.Can not only be suitable for the refining of general straight run and catalytically cracked gasoline or diesel oil, and can carry out refinement treatment to coker gasoline or diesel oil preferably.Iodine number decline 10～30%, the appearance color of gasoline after the processing or diesel oil sulphur content decline 40～80%, basic n content decline 98～100%, sign active olefin content obviously shoals, smell becomes odorless by stench, and can not descend with the coker gasoline octane value that the inventive method was handled.For example, undressed coker gasoline is placed for about 30 ℃ just had tangible green coke in one day, and the coker gasoline of handling Exposure to Sunlight in clear-glass bottle did not have tangible green coke phenomenon in six months yet.
Below we will further describe details of the present invention and effect thereof by embodiment.In straight run, cracking, cracking and coking oil, the highest and the most difficult with coking oil nuisance content, following embodiment will be refining object with coker gasoline or diesel oil.
The measuring method of each analytical data is as follows among the embodiment:
1, basic nitrogen: measure by the specialized standard ZBE 3003-86 of the People's Republic of China (PRC) with the perchloric acid titration method;
2, iodine number: press the SY-66 standard method with the iodo-Ethanol Method and measure;
3, transmittance: with 721 type spectrophotometric determinations;
4, octane value: the octane value (MON) of measuring oil product with motor method;
5, sulphur content: press GB 380-77 with Ignition Lamp Method and measure;
6, colloid: press GB 509-77 with SYD-509 motor spirit apparatus for determining existent gum and measure.
Embodiment
Embodiment 1:
In flask at the bottom of the garden that band stirs, add 800 gram coker gasolines (boiling range be fore-running～165 ℃), add 30% (w.t.) H
2O
280 grams, methyl alcohol 80 grams, ternary heteropolyacid H
3PMo
6W
6O
404 grams, reaction is 4 hours under 20～40 ℃ temperature, standing demix, the upper strata is a treated oil, lower floor is the water layer that contains catalyzer, methyl alcohol, oxidation impurities and unreacted hydrogen peroxide, with water trap water phase separated material.
Refining yield is greater than 96%, and treated oil is colourless, odorless, transparent, the energy stably stored, and other test data sees Table 1.
Embodiment 2:
In flask at the bottom of the garden that band stirs, add 500 gram coker gasolines (boiling range is 50～70 ℃), add 30% (w.t.) H
2O
250 grams, methyl alcohol 50 grams, H
3PMo
8W
4O
403 grams, reaction is 2 hours under 20～40 ℃ temperature, and other is with embodiment 1.
Refining yield 93.6%, treated oil is colourless, odorless, transparent, the energy stably stored, other test data sees Table 1.
Embodiment 3:
Methanol usage is 2 times of consumption among the embodiment 1, and all the other are with embodiment 1.
Refining yield is greater than 96%, and treated oil is colourless, odorless, transparent, the energy stably stored, and other test data sees Table 1.
Embodiment 4:
In flask at the bottom of the garden that band stirs, add 1780 gram coker gasolines (boiling range be fore-running～197 ℃), add 30% (w.t.) H
2O
2160 grams, methyl alcohol 160 grams, heteropolyacid H
3PMo
8W
4O
407 grams, 20～40 ℃ of reactions 2 hours, other was with embodiment 1.
Make with extra care yield greater than 97%, treated oil odorless, transparent, the energy stably stored, other test data sees Table 1.
Embodiment 5:
H with 50% (w.t.)
2O
2150 grams, all the other are with embodiment 4.
Make with extra care yield greater than 97%, treated oil odorless, transparent, the energy stably stored, other test data sees Table 1.
Embodiment 6:
In flask at the bottom of the garden that band stirs, add 1600 gram coker gas oils, add the H of 50% (w.t.)
2O
2160 grams, methyl alcohol 160 grams, heteropolyacid H
3PMo
8W
4O
407.5 gram reacted 2 hours down at 50～60 ℃, all the other are with embodiment 1.
The essential oil yield is greater than 97%, and treated oil odorless, reddish brown transparent can stably stored, and other test data sees Table 1.
Embodiment 7:
With H
5PMo
10V
2O
40Be catalyzer, all the other are with example 6.
Refining yield is greater than 97%.Treated oil odorless, reddish brown transparent, the energy stably stored, other test data sees Table 1.
Comparative example:
With binary heteropolyacid H
3PW
12O
40Be catalyzer, consumption is 4 grams, and all the other are with embodiment 1.
Refining yield is greater than 96%.
Table 1.
| Weight ratio feeds intake | Colloid (mg/100ml) | Sulphur content (%) | Basic nitrogen (PPM) | Iodine number (gI 2/100g) | Transmittance (%) | Outward appearance | |
| Comparative example | 100∶3∶10∶0.5 | 19.6 (43.4) | 0.46(0.61) | 0 (41.2) | 79.6 (94.1) | 91.0 (58.0) | Pale yellow (reddish brown) |
| Embodiment 1 | 100∶3∶10∶0.5 | 13.2 (43.4) | 0.37 (0.61) | 0 (41.2) | 72.2 (94.1) | 98.0 (58.0) | Colourless (reddish brown) |
| Embodiment 2 | 100∶3∶10∶0.6 | 0 (0.4) | 0.13 (0.53) | 0.37 (19.1) | 84.6 (107.7) | 98.5 (82.0) | Colourless (pale yellow) |
| Embodiment 3 | 100∶3∶20∶0.5 | 7.2 (43.4) | 0.23 (0.61) | 0 (41.2) | 70.3 (94.1) | 99.0 (58.0) | Colourless (reddish brown) |
| Embodiment 4 | 100∶2.7∶9∶0.39 | 30.8 (44.8) | 0.41 (0.75) | 0.78 (210) | 84.8 (100.8) | 79 (41) | Pale yellow (reddish brown) |
| Embodiment 5 | 100∶4.2∶9∶0.39 | 26.5 (44.8) | 0.24 (0.75) | 0.95 (210) | 72.6 (100.8) | 83.8 (41) | Pale yellow (reddish brown) |
| Embodiment 6 | 100∶5∶10∶0.47 | - - | 0.22 (0.72) | 1.9 (230.2) | 81.3 (97.5) | 39.5 (16) | Reddish brown (brown) |
| Embodiment 7 | 100∶5∶10∶0.47 | - - | 0.20 (0.72) | 2.6 (230.2) | 79.6 (97.5) | 42.6 (16) | Reddish brown (brown) |
Annotate: the weight ratio that feeds intake is: oil: H
2O
2(in 100%): low-carbon alcohol: catalyzer, data are oil product corresponding index before refining in the table bracket.
Claims (7)
1, the method for a kind of oxidation style treated gasoline or diesel oil comprises following process:
The adding concentration expressed in percentage by weight is 20～80% aqueous hydrogen peroxide solution in processed gasoline or diesel oil, is catalyzer with the ternary heteropolyacid with following general formula, and at C
1～C
4Low-carbon alcohol carry out oxidizing reaction under existing,
The add-on of hydrogen peroxide in the mass ratio of pure hydrogen peroxide is:
Gasoline or diesel oil: hydrogen peroxide=100: (0.5～10),
Catalyst consumption is by quality ratio:
Gasoline or diesel oil: catalyzer=100: (0.05～1.5),
The consumption of low-carbon alcohol is by quality ratio:
Gasoline or diesel oil: low-carbon alcohol=100: (5～65),
Temperature of reaction is 0～80 ℃, and reaction pressure is a normal pressure, and the reaction times is 0.2～5 hour, and reaction finishes the back and separates oil phase and water material,
The general formula of above-mentioned catalyzer is:
H
m(U
xM
YN
ZO
n)
Wherein U is P, Si or Ge, and M is Mo, and N is W or V, X=1～2, and Y, Z=1～17, m=3～5, n are for according to m, X, Y, the fixed chemical coordination equilibrium number of Z value.
2, the method for treated gasoline according to claim 1 or diesel oil is characterized in that described ternary heteropolyacid catalyst is H
3PMo
(12-X)W
XO
40Or H
(3+X)PMo
(12-X)V
XO
40, X=1～2 wherein.
3, the method for treated gasoline according to claim 1 and 2 or diesel oil is characterized in that described hydrogen peroxide concentration expressed in percentage by weight concentration is 30～50%, and its add-on in the mass ratio of pure hydrogen peroxide is:
Gasoline or diesel oil: hydrogen peroxide=100: (2～5).
4, the method for treated gasoline according to claim 1 and 2 or diesel oil is characterized in that catalyst consumption is by quality ratio:
Gasoline or diesel oil: catalyzer=100: (0.5～1).
5, the method for treated gasoline according to claim 1 and 2 or diesel oil is characterized in that the consumption of low-carbon alcohol is by quality ratio:
Gasoline or diesel oil: low-carbon alcohol=100: (10～30).
6, the method for treated gasoline according to claim 1 and 2 or diesel oil is characterized in that described C
1～C
4Low-carbon alcohol is methyl alcohol or ethanol.
7, the method for treated gasoline according to claim 1 and 2 or diesel oil is characterized in that described oxidizing reaction temperature is 20～60 ℃, and the reaction times is 2～4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991199049A CN1148436C (en) | 1999-10-28 | 1999-10-28 | Process for refining gasoline or diesel oil by oxidation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991199049A CN1148436C (en) | 1999-10-28 | 1999-10-28 | Process for refining gasoline or diesel oil by oxidation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1302844A CN1302844A (en) | 2001-07-11 |
| CN1148436C true CN1148436C (en) | 2004-05-05 |
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|---|---|---|---|
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040178121A1 (en) * | 2003-03-13 | 2004-09-16 | Leyshon David W. | Organosulfur oxidation process |
| CN1331987C (en) * | 2004-07-09 | 2007-08-15 | 石油大学(北京) | Oxidation and desulfurization method of petroleum oil product |
| CN100429295C (en) * | 2005-06-21 | 2008-10-29 | 大连理工大学 | Fixed bed oxidation desulfur reaction method |
| CN101063043B (en) * | 2006-04-27 | 2011-04-20 | 中国石油化工股份有限公司 | Oxidation deodorizing method for benzine |
| CN101063044B (en) * | 2006-04-27 | 2010-06-23 | 中国石油化工股份有限公司 | Diesel oxidation desulfurizing method |
| CN101376821B (en) * | 2007-08-27 | 2012-05-30 | 中国石油天然气股份有限公司 | Method for removing sulfur in gasoline and diesel oil through photocatalytic oxidation |
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1999
- 1999-10-28 CN CNB991199049A patent/CN1148436C/en not_active Expired - Fee Related
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Granted publication date: 20040505 Termination date: 20091130 |