CN1105768C - Refining additive for lubricating oil solvent and its compounding process and application in refining - Google Patents
Refining additive for lubricating oil solvent and its compounding process and application in refining Download PDFInfo
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- CN1105768C CN1105768C CN98111730A CN98111730A CN1105768C CN 1105768 C CN1105768 C CN 1105768C CN 98111730 A CN98111730 A CN 98111730A CN 98111730 A CN98111730 A CN 98111730A CN 1105768 C CN1105768 C CN 1105768C
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Abstract
The present invention relates to a refining additive for a lubricating oil solvent and a compounding process and a process for refining the lubricating oil solvent by the additive. The additive of the present inveniton is composed of the following materials (by weight): 100 portions of phosphate ester or sulfuric acid ester surface active agent, 25 to 400 portions of water soluble salt containing divalent metal or metal which is more than bivalence, and 0 to 1000 portions of water. After the water soluble salt is mixed with the water in the proportion and is mixed with the surface active agent at the temperature of 40 to 70DEGC in the proportion so as to obtain the additive of the present inveniton. The additive of the present invention is used for refining the lubricating oil solvent, refined oil yield can be enhanced by 2 to 6%, and a basic nitrogen elimination rate in refined oil can reach 92 to 99%. Physical and chemical performance indexes, such as the viscosity, the corrosion, a flashing point, an inclined point, a benzene ammonia point, the residual carbon of an oil product are all improved to a certain extent. The present invention has the advantages of lubricating oil refining process simplification, obvious effect of energy saving, and obvious economic benefits.
Description
The present invention relates to the solvent treatment additive in the refining of petroleum field, particularly relate to a kind of lubricating oil solvent additive and use the lubricating oil solvent method of this additive.
The production of general lubricant base comprises solvent treatment, solvent dewaxing, hydrofinishing or clay finishing, and wherein solvent treatment is an important step in the production process.Because the most of crude oil nitrogen content of China is about 0.3%, belong to high nitrogenous crude oil, nitrogenous compound mainly is distributed in the high boiling fraction district in the oil, wherein about 80% nitrogen concentrates in the distillate more than 400 ℃, promptly concentrate in the lubricant base oil fraction, the oxidation stability of many bibliographical information lubricant bases both domestic and external and its chemical constitution are closely related, and nitride wherein, especially basic nitrogen compound is to the having the greatest impact of the hydrogenation stability of base oil, because basic nitrogen compound can quicken the oxidation of oil product.Present solvent treatment can only remove the basic nitrogen compound of 50%-60%, the denitrification percent of hydrofinishing is lower, and cost is higher, and the denitrification percent of clay finishing is higher, but the treated oil loss is bigger, and the residue oil fraction denitrification effect is not good and the problem of environmental pollution of useless carclazyte is difficult to solve.Chinese patent CN1103106 adopts sulfur-preserving and denitrifying additive, to improve the oxidation stability of lubricant base, but settlement separate being difficult to of base oil and waste oil realizes in the denitrogenation of frivolous material, and all there is waste residue to produce after each line oil denitrogenation, the waste residue that is produced has pollution and is difficult for handling, need can handle with the treatment agent that Chinese patent CN1103660 is given, still needing after each line oil denitrogenation in addition can be qualified through clay treatment, and just the carclazyte consumption obviously reduces.U.S. Pat 4381234 is reported in the solvent treatment of lubricating oil furfural and adds dodecylbenzene sulfonate, can improve the yield and the viscosity index of treated oil." daily chemical industry " first phase nineteen ninety-five has reported that South China Science ﹠ Engineering University also is used for dodecylbenzene sulfonate the grand celebration lube oil finishing, proof adds dodecylbenzene sulfonate in the furfural treatment solvent of Daqing oil, treated oil yield and alkali nitrogen removed all certain improvement, wherein second line of distillation improves yield 2～3%, alkali nitrogen is reduced to 27.95PPM from 73.27PPM, but to subtracting three-way especially subtract four lines and the not significantly improvement of frivolous oil.Can end up till now, in each oil refining enterprise of China, each line lube cut oil, especially subtract four and frivolous material in alkali nitrogen still be difficult to break away from and use carclazyte to come effective elimination.
The object of the present invention is to provide a kind of lube oil finishing additive, it can remove alkali nitrogen effectively, improve the oxidation stability and the treated oil yield of lubricant base, even to subtract four or frivolous material also can omit clay finishing, thereby the environmental pollution of having avoided useless carclazyte to bring reduces the treated oil loss.
Another object of the present invention is to provide the compound method of this lube oil finishing additive.
A further object of the present invention is to provide the lubricating oil solvent method of using additive of the present invention.
Additive provided by the invention is mixed and formed by A, B, C three components, and is specifically composed as follows:
(A) tensio-active agent of phosphoric acid or sulfuric acid ester, consumption are 100 parts (by weight);
(B) contain the water-soluble salt of divalence or the above metal of divalence, consumption is 25～400 parts, is preferably 100～200 parts (all by weight);
(C) water, consumption are 0～1000 part, and suitable consumption is 25～60 parts (all by weight).
Can be alkyl phenol ether polyoxyethylene phosphate, alkyl phenol ether polyoxyethylene sulfuric ester, alkylbenzene phosphoric acid ester, alkylbenzene sulfuric ester as the phosphoric acid of A component or the tensio-active agent of sulfuric acid ester, its alkyl carbon atoms number is 1-20, is preferably 8～12; Oxygen ethene number is 0-30, is preferably 8～12.Alkyl carbon atoms number and oxygen ethene number are too little or too mostly will cause the active variation of its face, influence effect of extracting.Above-mentioned tensio-active agent is the commercially available prod.
Water-soluble salt as the B component is the salt of divalence or the above metal of divalence, they can be cupric chloride, cupric bromide, copper sulfate, cupric nitrate, zinc chloride, zinc sulfate, zinc bromide, zinc nitrate, iron(ic) chloride, iron protochloride, iron bromide, ferric sulfate, ferrous sulfate, iron nitrate, Iron nitrate or titanium tetrachloride etc., are preferably zinc chloride.Above-mentioned metal-salt also is the commercially available prod.
The C component is the general industry fresh water, as tap water etc.
Additive of the present invention can adopt following method to prepare:
When additive of the present invention contains the C component, water-soluble salt (B) and water (C) are pressed described mixed, the mixture with gained mixes under 40～70 ℃ in described ratio with tensio-active agent (A) more then.
When additive of the present invention does not contain the C component, directly water-soluble salt (B) is mixed under 40～70 ℃ in described ratio with tensio-active agent (A).
Additive of the present invention can be used for lubricating oil solvent technology, has improved refining effect.The used lubricating oil solvent method of the present invention is:
(1) the above-mentioned additive for preparing is mixed mutually with refining solvent, additive concentration can be decided according to used stock oil in the mixed solution, and the stock oil of heavier (being that boiling point is higher) needs higher additive concentration.According to the present invention, additive concentration is generally 0.01～5%, is 0.05～2% preferably, is preferably 0.2～1%, all by weight;
(2) mixed solution enters the lube oil finishing extraction tower from the top;
(3) stock oil therefrom, hypomere enters the lube oil finishing extraction tower, contacts with said mixture through adverse current;
(4) treated oil is extracted out from cat head, raffinates oil and discharges at the bottom of tower.
Wherein being used for the purified solvent is phenol, N-methyl pyrrole slightly alkane ketone or furfural etc., is preferably furfural.
Adopt additive provided by the invention, can improve essential oil yield 2～6%, basic nitrogen removal rate can reach 92～99% in the treated oil, thereby not only can improve the oxidation stability of lubricant base, and can significantly improve the treated oil yield, and physical and chemical indexs such as the viscosity of oil product, burn into flash-point, pour point, phenylamino point, carbon residue are all had some improvement, and the treated oil that obtains its rotary oxygen bomb after benzol-kentone dewaxing was brought up to 132 minutes from 73 minutes.
Alkali nitrogen content of the present invention, rotary oxygen bomb, treated oil acid number and yield all adopt the conventionally test method to obtain.
Additive provided by the invention, it is convenient to implement, and it is remarkable to improve oil quality, and can simplify lube oil finishing technology, and energy conservation and consumption reduction effects is obvious, remarkable in economical benefits.
Following embodiment and Comparative Examples will further specify the present invention, but not limit the present invention in any way.
Embodiment 1～7 shows the influence of the different proportionings of binder component to refining result with comparative example 1.
The lubricating oil solvent additive by (A) nonyl phenolic ether polyoxyethylene phosphate (oxygen ethene number is 10), (B) zinc chloride and (C) water formed, three's amount ratio sees Table 1.
Component (B) with after (C) mixes, is mixed with (A) component down at 50 ℃ again.
The additive of gained is mixed with the solvent furfural; And additive concentration was 0.2% (by weight) .The furfural that contains above-mentioned additive of gained is used for grand celebration and subtracts the refining of four line stock oils; And solvent ratio is 2.2:1 (volume ratio); 130 ℃ of and tower top temperature is, 95 ℃ of and column bottom temperature is. acquired results see Table 1. table 1 embodiment A B C basic nitrogen rotary oxygen bomb sequence numbers (parts by weight) (parts by weight) (parts by weight) (PPM) (minute) embodiment 141 0.2 80.08 131 embodiment 242 0.5 67.72 139 embodiment 343 0.8 45.20 145 embodiment 444 0.9 26.75 171 embodiment 545 1.2 17.82 166 embodiment 612 0.8 15.57 157 embodiment 714 2.1 16.71 161 comparative examples 1000 191.00 85
As can be seen from Table 1, the present invention in given each amounts of components scope of additive, all can obtain refining effect preferably, compare with not additivated situation, its alkali nitrogen content drops to below the 80PPM from 191PPM, and rotary oxygen bomb was brought up to more than 130 minutes from 85 minutes.
Embodiment 8～14 and comparative example 2 show that the concentration of additive in solvent is to subtracting the refining result's of third fractional oil influence.
The lubricating oil solvent additive by (A) nonyl phenolic ether polyoxyethylene phosphate (oxygen ethene number is 10), (B) zinc chloride and (C) water formed, three's amount ratio is 4: 4: 1 (by weight).
Component (B) with after (C) mixes, is mixed with (A) component down at 50 ℃ again.
The additive of gained is mixed with the solvent furfural, and additive concentration sees Table 2.The furfural that contains above-mentioned additive of gained is used for grand celebration and subtracts the refining of three-way stock oil, and solvent ratio is 2.0: 1 (volume ratio), and tower top temperature is 125 ℃, and column bottom temperature is 90 ℃.Gained the results are shown in Table 2.
Table 2 embodiment additive concentration basic nitrogen refined oil acid number yield sequence number % (by weight) is (mgKOH/g) (%) embodiment 8 0.04 77.27 0.022 83.65 embodiment 9 0.06 55.96 0.028 84.07 embodiment 10 0.08 38.97 0.028 85.00 embodiment 11 0.10 36.69 0.022 86.45 embodiment 12 0.12 26.41 0.028 86.67 embodiment 13 0.14 13.90 0.028 86.56 embodiment 14 0.16 21.56 0.034 86.65 comparative examples 20 120.65 0.028 82.50 (PPM)
As can be seen from Table 2, for subtracting three-way material, the present invention in the given additive concentration scope, all can obtain refining effect preferably, compare with not additivated situation, its alkali nitrogen content drops to below the 77PPM from 120PPM, and yield is brought up to more than 86.6% from 82.5%.
Example 1.5～19 and comparative example 3 show the influence of the concentration of additive in solvent to the refining result of frivolous stock oil.
The lubricating oil solvent additive by (A) nonyl phenolic ether polyoxyethylene phosphate (oxygen ethene number is 10), (B) zinc chloride and (C) water formed, three's amount ratio is 4: 4: 1 (by weight).
Component (B) with after (C) mixes, is mixed with (A) component down at 50 ℃ again.
The additive of gained is mixed with the solvent furfural, and the furfural that contains above-mentioned additive that additive concentration sees Table 3. gained is used for the refining of the frivolous stock oil of grand celebration, and solvent ratio is 3.5: 1 (volume ratio), and tower top temperature is 140 ℃, and column bottom temperature is 105 ℃.Gained the results are shown in Table 3.
Table 3 embodiment additive concentration basic nitrogen rotary oxygen bomb sequence number % (by weight) (PPM) (minute) embodiment 15 0.12 143.03 108 embodiment 16 0.16 133.85 112 embodiment 17 0.20 46.83 129 embodiment 18 0.24 33.34 144 embodiment 19 0.30 23.61 132 comparative examples 30 315.06 79
As can be seen from Table 3,,, can obtain refining effect preferably, its alkali ammonia content≤50PPM, rotary oxygen bomb 〉=110 minute at concentration 〉=0.2% of additive o'clock for frivolous material.
Embodiment 20～25 shows the refining result's of different solvents comparison influence.
The lubricating oil solvent additive by (A) nonyl phenolic ether polyoxyethylene phosphate (oxygen ethene number is 10), (B) zinc chloride and (C) water formed, three's amount ratio is 4: 4: 1 (by weight).
Component (B) with after (C) mixes, is mixed with (A) component down at 50 ℃ again.
The additive of gained is mixed with the solvent furfural, and additive concentration and solvent ratio see Table 4.The furfural that contains above-mentioned additive of gained is used for grand celebration and subtracts three-way and subtract the refining of four line stock oils, and tower top temperature and gained the results are shown in Table 4.
Table 4 embodiment feedstock oil additive concentration tower top temperature ratio of solvent basic nitrogen yield sequence number % (by weight) (℃) (volume ratio) (PPM) (%) embodiment 20 grand celebrations subtract 3 0.16 115 2.0: 1 26.73 85.50 embodiment, 21 grand celebrations subtract 3 0.16 115 1.8: 1 39.44 88.00 embodiment, 22 grand celebrations subtract 3 0.16 115 1.5: 1 44.64 88.33 embodiment, 23 grand celebrations subtract 4 0.20 120 2.2: 1 28.03 86.50 embodiment, 24 grand celebrations subtract 4 0.20 120 2.0: 1 46.64 88.43 embodiment, 25 grand celebrations subtract 4 0.20 120 1.7: 1 67.08 89.69
As can be seen from Table 4, adopt additive that the present invention gave to carry out under the less situation of solvent ratio, still can obtaining refining effect preferably when special, show energy-saving and cost-reducing good action.
Embodiment 26～29 shows the influence of tower top temperature to refining result.
The lubricating oil solvent additive by (A) nonyl phenolic ether polyoxyethylene phosphate (oxygen ethene number is 10), (B) zinc chloride and (C) water formed, three's amount ratio is 4: 4: 1 (by weight).
Component (B) with after (C) mixes, is mixed with (A) component down at 50 ℃ again.
The additive of gained is mixed with the solvent furfural, and additive concentration and tower top temperature see Table 5.The furfural that contains above-mentioned additive of gained is used for grand celebration and subtracts three-way and subtract the refining of four line stock oils, and solvent when gained the results are shown in Table 5
Table 5 embodiment feedstock oil additive concentration ratio of solvent tower top temperature basic nitrogen yield sequence number % (by weight) (volume ratio) (℃) (PPM) (%) embodiment 26 grand celebrations subtract 3 0.16 2.0: 1 125 16.47 82.33 embodiment, 20 grand celebrations subtract 3 0.16 2.0: 1 115 26.73 85.50 embodiment, 27 grand celebrations subtract 3 0.16 2.0: 1 105 18.95 88.00 embodiment, 28 grand celebrations subtract 4 0.20 2.2: 1 130 26.89 83.31 embodiment, 23 grand celebrations subtract 4 0.20 2.2: 1 120 28.03 86.50 embodiment, 29 grand celebrations subtract 4 0.20 2.2: 1 110 31.10 89.50
As can be seen from Table 5, when the employing additive that the present invention gave is made with extra care, under the situation of low tower top temperature, still can obtain refining effect preferably, demonstrate energy-saving and cost-reducing good action.
Claims (11)
1, a kind of lubricating oil solvent additive, it is composed as follows:
(A) alkyl phenol ether polyoxyethylene phosphate, consumption is 100 parts by weight;
(B) zinc chloride, consumption is 25～400 parts by weight;
(C) water, consumption is 0～1000 part by weight.
2, according to the described additive of claim 1, wherein the consumption of (A) is 100 parts, and consumption (B) is 100～200 parts, and the consumption of water (C) is 25～60 parts, all by weight.
3, according to the described additive of claim 1, wherein the alkyl carbon atoms number of alkyl phenol ether polyoxyethylene phosphate is 8～12.
4, according to the described additive of claim 1, wherein the oxygen ethene number of alkyl phenol ether polyoxyethylene phosphate is 8～12.
5, a kind of compound method of additive as claimed in claim 1 the steps include:
(1) with zinc chloride (B) and (C) by described mixed;
(2) mixture with above-mentioned (1) mixes under 40～70 ℃ in described ratio with (A) again.
6, a kind of compound method of additive as claimed in claim 1, its method is for directly mixing zinc chloride in described ratio with the alkyl phenol ether polyoxyethylene phosphate under 40～70 ℃.
7, a kind of lubricating oil solvent method of using the described additive of claim 1 the steps include:
(1) additive that is prepared is mixed mutually with refining solvent, additive concentration is 0.01～5 part by weight in the mixed solution;
(2) mixed solution enters the lube oil finishing extraction tower from the top;
(3) stock oil therefrom, hypomere enters the lube oil finishing extraction tower, contacts with above-mentioned mixed solution through adverse current;
(4) treated oil is extracted out from cat head, raffinates oil and discharges at the bottom of tower.
8, according to the described lubricating oil solvent method of claim 7, additive concentration is 0.05～2% in the wherein said mixed solution.
9, according to the described lubricating oil solvent method of claim 7, additive concentration is 0.2～1% in the wherein said mixed solution.
10, according to the described lubricating oil solvent method of one of claim 7～9, wherein being used for the purified solvent is phenol, N-Methyl pyrrolidone or furfural.
11, according to the described lubricating oil solvent method of claim 10, wherein being used for the purified solvent is furfural.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111730A CN1105768C (en) | 1998-12-29 | 1998-12-29 | Refining additive for lubricating oil solvent and its compounding process and application in refining |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111730A CN1105768C (en) | 1998-12-29 | 1998-12-29 | Refining additive for lubricating oil solvent and its compounding process and application in refining |
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| CN1258716A CN1258716A (en) | 2000-07-05 |
| CN1105768C true CN1105768C (en) | 2003-04-16 |
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| CN98111730A Expired - Fee Related CN1105768C (en) | 1998-12-29 | 1998-12-29 | Refining additive for lubricating oil solvent and its compounding process and application in refining |
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| CN115637191A (en) * | 2022-09-09 | 2023-01-24 | 湖北大江润业再生资源有限公司 | Auxiliary agent for improving oxidation stability of regenerated base oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4329222A (en) * | 1980-09-26 | 1982-05-11 | Exxon Research & Engineering Co. | Method for selectively removing basic nitrogen compounds from lube oils using transition metal halides or transition metal tetrafluoroborates |
| CN86100790A (en) * | 1985-02-01 | 1986-07-30 | 美国银行公司 | The high-content that is used for alcohol engine lubricating oil is peace and quiet/dispersing additive |
| CN87101001A (en) * | 1987-03-23 | 1988-10-12 | 上海工业大学 | Ash-free, Wear-resistant phosphorus-nitrogen (P-N) type additibve for lubricating oil |
| CN88103104A (en) * | 1987-05-26 | 1988-12-07 | 埃克森化学专利公司 | Prepare improving one's methods of stable oleaginous composition |
-
1998
- 1998-12-29 CN CN98111730A patent/CN1105768C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4329222A (en) * | 1980-09-26 | 1982-05-11 | Exxon Research & Engineering Co. | Method for selectively removing basic nitrogen compounds from lube oils using transition metal halides or transition metal tetrafluoroborates |
| CN86100790A (en) * | 1985-02-01 | 1986-07-30 | 美国银行公司 | The high-content that is used for alcohol engine lubricating oil is peace and quiet/dispersing additive |
| CN87101001A (en) * | 1987-03-23 | 1988-10-12 | 上海工业大学 | Ash-free, Wear-resistant phosphorus-nitrogen (P-N) type additibve for lubricating oil |
| CN88103104A (en) * | 1987-05-26 | 1988-12-07 | 埃克森化学专利公司 | Prepare improving one's methods of stable oleaginous composition |
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