CN1060206C - Combined denitrification process for base oil of lubricant oil - Google Patents
Combined denitrification process for base oil of lubricant oil Download PDFInfo
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- CN1060206C CN1060206C CN97111776A CN97111776A CN1060206C CN 1060206 C CN1060206 C CN 1060206C CN 97111776 A CN97111776 A CN 97111776A CN 97111776 A CN97111776 A CN 97111776A CN 1060206 C CN1060206 C CN 1060206C
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Abstract
The present invention relates to a method for denitrifying lube base oil, which is characterized in that the method is a combined process comprising organic acidic solvent extraction and clay refining. Nitrides, especially alkaline nitrides, are extracted from base oil by using a low-molecular organic acid, and sulfides in the base oil are retained. Thus, the method enhances theoxidation stability of the lube base oil.
Description
The invention belongs to petroleum refining process, more particularly, the present invention is low carbon organic acid solvent extraction and clay-filtered process integration, optionally to remove the nitride in the lubricant base, improves the oxidation stability of lubricant base.
Lubricant base often normally adopts, vacuum distillate or deasphalted oil is through solvent treatment, solvent dewaxing and clay-filtered explained hereafter.For the lubricant base of the nitrogenous crude production of height, often owing to the nitrogen content height, sulphur content is low, and oxidation stability is poor.Hydrofinishing can be taken off lower level with nitrogen content, but the nitride that removes in the oil product is relatively more difficult, remove the nitride in the oil product, must improve the hydrofining degree of depth, this moment, the sulfide in the oil product then can't keep, because the fracture of C-S key is easy more than the fracture of C-N key during hydrofining.But sulfide particularly thioether and epithio ether is natural oxidation inhibitor, therefore adopt hydrogenation post-refining process to produce lubricating oil, base oil with the higher crude production of nitrogen content, its oxidation stability is generally relatively poor, inaccessible base oil standard-required is so exploitation sulfur-preserving and denitrifying technology becomes an important topic with high nitrogenous crude production lubricant base.
In order to remove the nitride in the oil product, people have done number of research projects, UK Patent Application GB2114997A utilizes metal halides such as fourth, fifth, six, seven subgroups, eight families or copper, zinc, cadmium, mercury, or the solution of the anhydrous polar solvent of a tetrafluoro borate removes the basic nitrogen compound in the base oil, effect is remarkable, but its technology more complicated, except that above-mentioned solution extracting, oil product after the extracting also needs with the polar solvent washing, and then carries out solvent recuperation etc.The solution that Chinese patent application CN1107875A adopts organic solvents such as titanium sulfate and alcohols, ether, ketone, furfural to be made into removes nitride in the oil product to improve the oxidation stability of base oil, shortcoming is that titanium sulfate is the oxide catalyst of these organic solvents, be easy to make these oxidation in organic solvent, if and the oil product after the extracting does not wash, remaining in a small amount of titanium sulfate in the base oil also can influence the use properties of base oil, and titanium sulfate solution also needs to reclaim.Chinese patent application CN1103106A adopts the sulfur-preserving and denitrifying agent of the solvent composition of 6～85% acidizer, 0.1～85% complexing agent and 0.1～85%, removes the basic nitrogen compound in the base oil, to improve its oxidation stability.This agent is except that the shortcoming with above-mentioned two patent applications, and agents useful for same is various.U.S. Pat P4,985,139 propose to remove the two-stage process of the nitride in oil and the distillate thereof, and first section with C1～C15 organic acid extracting, second section hydrotreatment under the mitigation condition, the main purpose of this patent are to provide nitrogen content lower stock oil for subsequent technique.
Purpose of the present invention is in order to overcome the deficiencies in the prior art, and it is simple to propose a kind of process, the single combined denitrification process for base oil of lubricant oil of agents useful for same.
Characteristics of the present invention are before existing clay-filtered technology, adopt nitride, particularly basic nitrogen compound in the organic acidity solvent extraction base oil, to reach the purpose that improves the lubricant base oxidation stability.
The present invention is actually a kind of organic acid extracting and clay-filtered process integration, concrete steps are as follows: (1) lubricant base is with after acid solvent mixes in mixing tank, through settlement separate fuel-displaced liquid layer and acid solution layer, the acid solvent consumption is 1～20% of a lube base weight of oil, best 3～15%, 20～90 ℃ of extraction temperatures; (2) the fluid layer 150～280 ℃ down directly and the carclazyte contact treatings, oil and carclazyte mixture after clay-filtered obtain finished product base oil and clay dregs after filtration; (3) acid solution of step (1) gained is carried out solvent recuperation, and solvent cycle is used, and extracts oil out as oil fuel.
The described lube stock oil plant that to be normal, vacuum distillate and deasphalted oil obtain through solvent treatment and solvent dewaxing.Described acid solvent is a low molecular organic acids, comprises formic acid, acetate and propionic acid, preferably formic acid.
Further specify characteristics of the present invention below in conjunction with accompanying drawing.
Accompanying drawing is technical process of the present invention.As shown in the figure, the lube stock I enters slurry tank 2 sedimentations with the acid solvent II after mixing tank 1 mixes, tank deck is isolated the fluid III, the acid solution IV is isolated at the jar end, the fluid III enters clay-filtered jar 3 and the contact treating of carclazyte V by pipeline, acid solvent in the fluid is in clay-filtered temperature therapeutic method to keep the adverse qi flowing downward formation gas VI, distillate from clay-filtered jar 3 top, after condensate cooler 4 condensations cooling, recycle as extraction solvent, oil after clay-filtered and carclazyte mixture VII enter filter 5 and filter, obtain finished product base oil VIII and clay dregs IX, the acid solution IV is carried out solvent recuperation in solvent recovery unit 6, the acid solvent X recycles as extraction solvent, extracts oily XI out and goes out device and can make the oil fuel blend component.
Advantage of the present invention:
1. to adopt low molecular organic acids be the solvent extracted lube base oil in the present invention, and solvent boiling point is low, is convenient to recycling use, and energy consumption is little, compares with inorganic acid, and is also little to the corrosion of equipment;
2. the present invention utilizes clay-filtered temperature more than the high characteristics of acid flux material boiling point, and fluid does not need to reclaim first solvent, and reclaims in clay treatment, saves solvent recovery unit;
3. technique of the present invention is remarkable to lubricant base-oil denitrification and dealkalize nitrogen effect, and desulfurization degree is very low, reaches the purpose of sulfur-preserving and denitrifying, has increased substantially the oxidation stability of lube base oil;
4. technological process of the present invention is simple, convenient operation, and equipment investment is few.
Further describe characteristics of the present invention below in conjunction with example.
The used carclazyte of following example is the industrial atlapulgite that chemical industry two factories in Fushun produce, and organic acid is the commercially available prod.
Example 1
This example is that employing formic acid is extraction solvent, and according to refining grand celebration 500SN solvent treatment of technical process of the present invention and solvent dewaxed oil, condition and result are as shown in table 1.
Example 2
This example is to adopt same stock oil to carry out clay-filtered and hydrofining, condition and the results are shown in Table 1.
By example 1 and example 2 data as can be known: compare with clay-filtered, the formic acid extracting---clay-filtered technology dealkalize nitrogen rate improves 49.5% and 60.7% respectively, denitrification percent improves 28.6% and 36.2% respectively, desulfurization degree remains unchanged substantially, and rotary oxygen bomb improves 34.8% and 47.8% respectively.Make with extra care with low temperature hydrogenation (280 ℃, catalyzer is produced by the CN85104438.7 patent, the trade mark is RN-1) compare, dealkalize nitrogen rate and denitrification percent are higher, and desulfurization degree is much lower, and the increase rate of rotary oxygen bomb is also much bigger; With refining (320 ℃ of high temperature hydrogenation, catalyzer RN-1) compare, though dealkalize nitrogen rate and denitrification percent maintain an equal level, hydrorefined desulfurization degree is higher more than 60% than desulfurization degree of the present invention, high temperature hydrogenation purified oxidation stability also has only 138 minutes, far less than oxidation stability of the present invention.
Example 3
It is extraction solvent that this example adopts formic acid, and refining grand celebration 650SN solvent treatment and solvent dewaxed oil the results are shown in table 2.
Example 4
This example is the stock oil that only carries out clay-filtered example 3, condition and the results are shown in Table 2.
Example 3 and example 4 data show, compare the formic acid extracting with clay-filtered---clay-filtered dealkalize nitrogen and denitrification effect highly significant, and desulfurization degree remains basically stable, oxidation stability increases substantially.
Example 5
This example is only used the formic acid extracting, and does not carry out clay-filtered, as shown in table 2.The result shows single effective not as the clay-filtered process integration of formic acid extracting with the formic acid extracting.
Example 6
It is extraction solvent that this example adopts acetate, refining grand celebration 500SN and 650SN solvent treatment and solvent dewaxed oil, condition and the results are shown in table 3.
By data in the table as can be known, the denitrogenation of the clay-filtered technology of acetate extracting and dealkalize nitrogen effect are than clay-filtered height, and the amplitude that oxidation stability improves is also much bigger than clay-filtered technology.
Table 1
| Example 1 | Example 2 | Raw material | ||||
| Extraction solvent | Formic acid | Formic acid | - | - | - | - |
| Stock oil | 500SN | 500SN | 500SN | 500SN | 500SN | 500SN |
| Condition: sour consumption, heavy % extraction temperature, ℃ carclazyte consumption, heavy % extraction temperature, ℃ hydrogenation reaction temperature, ℃ hydrogen dividing potential drop, the MPa air speed, / h hydrogen-oil ratio, the v/v base oil yield, % character: alkali nitrogen, ppm nitrogen, ppm sulphur, ppm dealkalize nitrogen rate, the % denitrification percent, the % desulfurization degree, the % rotary oxygen bomb, the min acid number, mgKOH/g rotary oxygen bomb increase rate, % density (20 ℃), g/cm
3Color, | 5 70 3 200 - - - - 95.7 51 123 593 74.2 55.4 11.9 208 0.005 80.9 0.8799 2.0 | 10 70 3 200 - - - - 95.2 29 102 584 85.4 63.0 13.2 223 0.005 93.9 0.8798 1.5 | - - 3 200 - - - - 96.4 149 202 605 24.7 26.8 10.1 168 0.006 46.1 0.8805 ＜2.5 | - - - - 280 3.5 1.0 200∶1 99.9 158 234 404 20.2 15.2 40.0 123 0.006 7.0 0.8808 - | - - - - 320 3.5 1.0 200∶1 99.9 54 99 152 72.7 64.1 77.4 138 0.005 20.0 0.8801 - | - - - - - - - - - 198 276 673 - - - 115 0.02 - 0.8808 2.5 |
Table 2
| Example 3 | Example 4 | Example 5 | Raw material | ||
| Extraction solvent | Formic acid | Formic acid | - | Formic acid | - |
| Stock oil | 650SN | 650SN | 650SN | 650SN | 650SN |
| Condition: sour consumption, heavy % extraction temperature, ℃ carclazyte consumption, heavy % extraction temperature, ℃ base oil yield, % character: alkali nitrogen, ppm nitrogen, ppm sulphur, ppm dealkalize nitrogen rate, the % denitrification percent, the % desulfurization degree, the % rotary oxygen bomb, the min acid number, mgKOH/g rotary oxygen bomb increase rate, % density (20 ℃), g/cm
3Color, | 5 70 5 210 95.6 74 280 902 77.0 54.8 16.6 183 0.006 72.6 0.8851 4.5 | 10 70 5 210 95.1 43 257 880 86.6 58.5 18.6 202 0.006 90.6 0.8849 4.5 | - - 5 210 96.3 235 516 890 27.0 16.8 17.7 125 0.006 17.9 0.8857 5.0 | 10 70 - - 98.8 78 342 895 75.8 44.8 17.2 168 0.009 58.5 0.8851 5.5 | - - - - - 322 620 1081 - - - 106 0.02 - 0.8860 6.5 |
Table 3
| Example 6 | ||||
| Extraction solvent | Acetate | Acetate | Acetate | Acetate |
| Stock oil | 500SN | 500SN | 650SN | 650SN |
| Condition: sour consumption, heavy % extraction temperature, ℃ carclazyte consumption, heavy % extraction temperature, ℃ base oil yield, % character: alkali nitrogen, ppm nitrogen, ppm sulphur, ppm dealkalize nitrogen rate, the % denitrification percent, the % desulfurization degree, the % rotary oxygen bomb, the min acid number, mgKOH/g rotary oxygen bomb increase rate, % density (20 ℃), g/cm
3Color, | 5 80 3 200 95.8 101 176 595 49.0 36.2 11.6 179 0.005 55.6 0.8802 ＜2.5 | 10 80 3 200 95.4 82 146 577 58.6 47.1 14.3 196 0.006 70.4 0.8799 2.0 | 3 80 5 210 95.8 183 422 873 43.2 31．9 19．2 156 0.006 47.2 0.8855 5.0 | 10 80 5 210 95.3 161 401 859 50.0 35.3 20.5 175 0.006 65.1 0.8854 5.0 |
Claims (4)
1, a kind of combined denitrification process for base oil of lubricant oil, it is characterized in that concrete steps are followed successively by: (1) lubricant base is with after acid solvent mixes in mixing tank, through settlement separate fuel-displaced liquid layer and acid solution layer, the acid solvent consumption is 1～20% of a lube base weight of oil, 20～90 ℃ of extraction temperatures, described acid solvent is selected from formic acid, acetate or propionic acid; (2) the fluid layer 150～280 ℃ down directly and the carclazyte contact treatings, oil and carclazyte mixture after clay-filtered obtain finished product base oil and clay dregs after filtration; (3) acid solution of step (1) gained is carried out solvent recuperation, and solvent cycle is used, and extracts oil out as oil fuel.
2,, it is characterized in that described acid solvent is a formic acid according to the described process integration of claim 1.
3,, it is characterized in that described acid solvent consumption is 3～15% of a base oil weight according to the described process integration of claim 1.
4,, it is characterized in that the lubricant base oil plant that to be normal, vacuum distillate and deasphalted oil obtain through solvent treatment and solvent dewaxing according to the described process integration of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111776A CN1060206C (en) | 1997-05-13 | 1997-05-13 | Combined denitrification process for base oil of lubricant oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111776A CN1060206C (en) | 1997-05-13 | 1997-05-13 | Combined denitrification process for base oil of lubricant oil |
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| CN1199082A CN1199082A (en) | 1998-11-18 |
| CN1060206C true CN1060206C (en) | 2001-01-03 |
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| CN97111776A Expired - Lifetime CN1060206C (en) | 1997-05-13 | 1997-05-13 | Combined denitrification process for base oil of lubricant oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102485842B (en) * | 2010-12-03 | 2014-01-15 | 中国石油天然气股份有限公司 | Processing method for supplementing refined coker gas oil by fixed bed |
| CN102277191A (en) * | 2011-07-14 | 2011-12-14 | 烟台大学 | Method for decoloring catalytic cracking diesel oil |
| CN102559252B (en) * | 2012-03-07 | 2013-10-09 | 抚顺石化北天集团众兴公司鸿远达精细化工厂 | Non-hydrodenitrogeneration method for catalytically cracked gasoline |
| CN110627623B (en) * | 2019-09-06 | 2020-09-22 | 陕西煤业化工集团神木天元化工有限公司 | Separation system and method for alkaline nitride in phenol product |
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59147083A (en) * | 1983-02-10 | 1984-08-23 | Idemitsu Kosan Co Ltd | Production of lubricant base oil |
| CN1103106A (en) * | 1994-09-20 | 1995-05-31 | 中国石油化工总公司 | Additives for base oil of lubricating oil |
| CN1139146A (en) * | 1996-02-12 | 1997-01-01 | 吕洪民 | Refining process of base oil for lubricating oil |
-
1997
- 1997-05-13 CN CN97111776A patent/CN1060206C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59147083A (en) * | 1983-02-10 | 1984-08-23 | Idemitsu Kosan Co Ltd | Production of lubricant base oil |
| CN1103106A (en) * | 1994-09-20 | 1995-05-31 | 中国石油化工总公司 | Additives for base oil of lubricating oil |
| CN1139146A (en) * | 1996-02-12 | 1997-01-01 | 吕洪民 | Refining process of base oil for lubricating oil |
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| CN1199082A (en) | 1998-11-18 |
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