CN102041034B - Method for reducing neutralization value of base oil - Google Patents
Method for reducing neutralization value of base oil Download PDFInfo
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- CN102041034B CN102041034B CN 200910197590 CN200910197590A CN102041034B CN 102041034 B CN102041034 B CN 102041034B CN 200910197590 CN200910197590 CN 200910197590 CN 200910197590 A CN200910197590 A CN 200910197590A CN 102041034 B CN102041034 B CN 102041034B
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Abstract
The invention relates to a method for reducing a neutralization value of base oil, which mainly solves the problems that the neutralization value of base oil is high due to acidic crude oil and that metal corrosion is caused and other performance indexes of the base oil are influenced in the process of reducing the neutralization value by using a common alkaline deacidification agent in the prior art. The method for reducing the neutralization value of the base oil comprises the steps of: mixing the base oil and the deacidification agent; and filtering and refining to obtain low-neutralization value base oil, wherein the used deacidification agent comprises the following components in part by weight: a) 0.01 to 15 parts of at least one of magnesium silicate and magnesium aluminum silicate; and b) 0 to 96 parts of clay; and the quality index of the low-neutralization value base oil is that: for the base oil with the neutralization value of 250 or below, the quality index of the neutralization value is less than 0.03mg of KOH per gram; and for the base oil with the neutralization value of 500 or more, the quality index of the neutralization value is less than 0.05mg of KOH per gram. The technical scheme better solves the problems, and can be used for industrial production for reducing the neutralization value of the base oil.
Description
Technical field
The present invention relates to a kind of method that reduces the base oil neutralization value.
Background technology
Neutralization value (or acid number) is a critical nature index of lubricant base.For 250 and following base oil, the quality index of neutralization value is＜0.03 milligram of KOH/ gram; For 500 and above base oil, the quality index of its neutralization value is＜0.05 milligram of KOH/ gram.
In recent years, along with the rapid expansion of crude oil in China demand, the variation day by day of crude oil source, the ratio of crude oil with high acid value increases gradually, causes the refinery feedstock quality to descend, and wherein the too high problem of acid number becomes increasingly conspicuous.For existing oil refining apparatus, this also make component oil particularly the acid number of lubricating oil increase.The existence of lubricant base PetroChina Company Limited. acid has a strong impact on the use properties of lubricating oil, increases its corrodibility, has reduced the quality of lubricating oil.Therefore the depickling technology of studying lubricant base has bigger realistic meaning.
For the crude oil deacidification method, mainly contain two kinds: a kind of is that another kind is to adopt the neutralizing agent depickling, adopts the method for solvent extraction and separation by the petroleum acid in the method destruction crude oil of thermolysis.Document US 5891325 discloses a kind of technology with thermolysis destruction petroleum acid, but its temperature height causes the decomposition of other components in the crude oil easily, and does not reach the required refining depth of lubricant base.Document US 4424158, CN90107685.6, CN01135182.9, CN99804557.8 and CN99804502.0 disclose and have adopted neutralizing agent and solvent extraction and separation to remove the method for crude oil PetroChina Company Limited. acid, but ubiquity needs a large amount of extraction solvents, neutralizing agent costliness, cost height, complex technical process, long flow path, and lubricant base had problems such as pollution.Document CN96196526.6 and CN96195273.4 disclose a kind of employing metal oxide, mainly are CaO and Ca (OH)
2Remove the method for crude oil PetroChina Company Limited. acid.But the metal ring alkyl salt of its generation still remains in the crude oil, causes other indexs of lubricant base defective; And the used method of these two patents only can be used for neutralization value greater than the depickling of the above high acid value oil of 0.2 milligram of KOH/ gram, and can not realize the degree of depth depickling requirement of lubricant base.The crude oil with high acid value neutralization value generally all is higher than 1.5 milligrams of KOH/ grams, even is higher than 10.0 milligrams of KOH/ grams.Lubricant base is because the process part depickling processing of raw material sources and crude oil, its neutralization value generally all is lower than 0.2 milligram of KOH/ gram, but still the 0.05 milligram of KOH/ that does not reach index request restrains, need the deep refining depickling, and remain in the lubricant base this a part of petroleum acid difficulty remove.Because the otherness of lubricant base and crude oil, namely lubricant base is after being in harmonious proportion, and directly as manufactured consumer goods, and crude oil also has the oil refining process in downstream, causes the index of lubricant base requirement many and tight.So the various acid stripping methods of crude oil can not be applicable to fully that the degree of depth depickling of lubricant base is refining.
Reduce the base oil neutralization value at present and mainly contain following three kinds of methods.Document " refining of petroleum and chemical industry, 2008,39 (10), 14～17 " discloses a kind of denitrogenation and absorption acid stripping method of intermediate base lubricant base, adopts WK-1 denitrfying agent and WK-3 sorbent material to carry out the denitrogenation depickling.But the concrete composition of itself and unexposed WK-1 denitrfying agent and WK-3 sorbent material, and it is bigger to add dosage, and deacidification effect is slightly poor.Document " petrochemical technology and application, 2005,23 (3), 199～202 " discloses at lube oil furfural refining unit and has adopted the de-acidying agent depickling.This method can improve furfural to the dissolving power of crude oil middle acid substance by the acidic substance that reduce the circulation furfural really, thereby reduces the neutralization value of lubricating oil to a certain extent.But the neutralising capacity of the acidic substance in the different crude oils of its employed de-acidying agent DY-06 is different, and is better to Weizhou oil effect, then relatively poor to Oman's oil effect; And this method comes down to annotate the alkali neutralization, causes metallic corrosion easily.Document " oil refining design, 2001,31 (2), 48～50 " discloses to adopt the composite deacidifying solvent and contain sour lubricating oil distillate and has reacted the method that removes its middle acid substance.But this method needs two kinds of solvents to carry out a procedure compound, many, operation inconvenience; When the raw material acid number was higher than 0.2 milligram of KOH/ gram, oil product was difficult to reach the base oil index request; There is residue, unfavorable environmental protection.
Summary of the invention
Technical problem to be solved by this invention be exist in the prior art owing to acid-containing raw oil causes the base oil neutralization value higher, and use general alkaline de-acidying agent when reducing neutralization value, also can cause metallic corrosion and influence the problem of other performance index of base oil, a kind of method of new reduction base oil neutralization value is provided.But the petroleum acid in this method effective elimination base oil reduces its neutralization value, thereby makes base oil meet service requirements; Simultaneously can not cause metallic corrosion, influence other performance index of base oil.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that reduces the base oil neutralization value, and comprise base oil is mixed with de-acidying agent, obtain low neutralization value base oil after making with extra care after filtration; Used de-acidying agent wherein in parts by weight, comprises following component:
A) 0.01～15 part be selected from least a in Magnesium Silicate q-agent or the neusilin;
B) 0～96 part carclazyte;
Wherein the quality index of low neutralization value base oil is: for 250 and following base oil, the quality index of neutralization value be that＜0.03 milligram of KOH/ restrains; For 500 and above base oil, the quality index of neutralization value is＜0.05 milligram of KOH/ gram.
In the technique scheme, in parts by weight, at least a consumption preferable range that is selected from Magnesium Silicate q-agent or the neusilin is 0.1～10 part, and more preferably scope is 0.3～5 part; The consumption preferable range of carclazyte is 50～95 parts, and more preferably scope is 80～90 parts.Base oil is 90～200 ℃ with the temperature preferable range that contacts of de-acidying agent, and more preferably scope is 100～190 ℃, and most preferred range is 150～180 ℃; Duration of contact, preferable range was 0.1～20 hour, and more preferably scope is 0.2～10 hour, and most preferred range is 0.3～5 hour.The consumption preferable range of described de-acidying agent is 0.01～10% of base oil weight, and more preferably scope is 0.1～8%, most preferred range 0.3～5%.
The inventive method is applicable to the lubricant base in all kinds crude oil source, as paraffinic base, intermediate base or naphthenic base crude.
The refining base oil that obtains of the inventive method can be used for being in harmonious proportion each class lubricating oil.For industrial lubricant, its consumption can account for 80～100% of lubricating oil weight, and preferable range is 90～99.9%, and more preferably scope is 95～99%; For I. C. engine oil, its consumption can account for 50～99% of lubricating oil weight, and preferable range is 70～98%, and more preferably scope is 80～95%.
In the inventive method, owing to Magnesium Silicate q-agent, neusilin are strong base-weak acid salts, after base oil contacts, can reduce the acidity of base oil.The inventor also finds uncannily, in base oil, add be selected from least a in Magnesium Silicate q-agent or the neusilin after, when reducing the base oil neutralization value, can not cause metallic corrosion, can not influence simultaneously other performance index of base oil, for example demulsification performance, antioxidant property, viscosity temperature characteristic and the metal content to base oil do not have disadvantageous effect.Use the inventive method, can make the highest the gram from 0.28 milligram of KOH/ of neutralization value of 500 base oils drop to 0.00 milligram of KOH/ gram, make the neutralization value of 250 base oils drop to 0.01 milligram of KOH/ gram from 0.13 milligram of KOH/ gram, obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Be that Oman's 500 treated oils of 0.28 fully mix with de-acidying agent with neutralization value, obtain the low base oil of neutralization value after the filtration.In parts by weight, de-acidying agent consist of 10 parts of neusilins, 90 parts of carclazytes.Base oil is 160 ℃ with the temperature that contacts of de-acidying agent, and be 1 hour duration of contact.The consumption of de-acidying agent is 5.0% of base oil weight.The neutralization value of base oil is reduced to 0.04 milligram of KOH/ gram from 0.28 milligram of KOH/ gram.De-acidying agent does not cause metallic corrosion, and demulsification performance, antioxidant property, viscosity temperature characteristic and the metal content to base oil do not have disadvantageous effect simultaneously.
[embodiment 2～9]
Change the consumption that contacts temperature, time and de-acidying agent of feed of base oil, de-acidying agent composition, base oil and de-acidying agent, specifically see Table 1.De-acidying agent does not cause metallic corrosion, and demulsification performance, antioxidant property, viscosity temperature characteristic and the metal content to base oil do not have disadvantageous effect simultaneously.
[Comparative Examples 1]
With [embodiment 2], just de-acidying agent is 10 parts carclazyte, and the consumption of carclazyte is 1.0% of base oil, and the neutralization value of base oil is reduced to 0.09 milligram of KOH/ gram from 0.10 milligram of KOH/ gram.
[Comparative Examples 2]
With [embodiment 3], just de-acidying agent is 10 parts carclazyte, and the consumption of carclazyte is 4.0% of base oil, and the neutralization value of base oil is reduced to 0.11 milligram of KOH/ gram from 0.14 milligram of KOH/ gram.
[Comparative Examples 3]
With [embodiment 5], just de-acidying agent is 10 parts carclazyte, and the consumption of carclazyte is 0.5% of base oil, and the neutralization value of base oil is reduced to 0.12 milligram of KOH/ gram from 0.13 milligram of KOH/ gram.
[Comparative Examples 4]
With [embodiment 5], just de-acidying agent is 10 parts alkaline wilkinite, and its consumption is 0.5% of base oil, and the neutralization value of base oil is reduced to 0.072 milligram of KOH/ gram from 0.13 milligram of KOH/ gram, and effect is not as Magnesium Silicate q-agent.Because it is alkaline wilkinite contains higher alkalescence, influenced to the basic nitrogen effect that removes in the base oil simultaneously, so the basic n content in the base oil is higher, thus cause the antioxidant property to base oil to affect adversely.Compare with [embodiment 5], the rotary oxygen bomb of base oil dropped to 174 minutes from 205 minutes (the antioxidant property index of 250 base oils is that rotary oxygen bomb was not less than 180 minutes), reduced by 31 minutes.
Claims (7)
1. a method that reduces the base oil neutralization value comprises base oil is mixed with de-acidying agent, obtains low neutralization value base oil after making with extra care after filtration; Wherein used de-acidying agent is selected from least a in Magnesium Silicate q-agent or the neusilin; Wherein the quality index of low neutralization value base oil is: for 250 and following base oil, the quality index of neutralization value be that＜0.03 milligram of KOH/ restrains; For 500 and above base oil, the quality index of neutralization value is＜0.05 milligram of KOH/ gram.
2. according to the method for the described reduction base oil of claim 1 neutralization value, it is characterized in that base oil is 90～200 ℃ with the temperature that contacts of de-acidying agent, be 0.1～20 hour duration of contact.
3. according to the method for the described reduction base oil of claim 2 neutralization value, it is characterized in that base oil is 100～190 ℃ with the temperature that contacts of de-acidying agent, be 0.2～10 hour duration of contact.
4. according to the method for the described reduction base oil of claim 3 neutralization value, it is characterized in that base oil is 150～180 ℃ with the temperature that contacts of de-acidying agent, be 0.3～5 hour duration of contact.
5. according to the method for the described reduction base oil of claim 1 neutralization value, the consumption that it is characterized in that described de-acidying agent is 0.01～10% of base oil weight.
6. according to the method for the described reduction base oil of claim 5 neutralization value, the consumption that it is characterized in that described de-acidying agent is 0.1～8% of base oil weight.
7. according to the method for the described reduction base oil of claim 6 neutralization value, the consumption that it is characterized in that described de-acidying agent is 0.3～5% of base oil weight.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5891325A (en) * | 1998-08-11 | 1999-04-06 | Exxon Research And Engineering Co. | Process for reducing total acid number of crude oil |
| CN1353167A (en) * | 2000-11-03 | 2002-06-12 | 石油大学(北京) | Modified argil as denitrifying agent and its preparing process |
| CN101148602A (en) * | 2007-09-10 | 2008-03-26 | 蒋玉珊 | Alkaline purifying agent |
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2009
- 2009-10-23 CN CN 200910197590 patent/CN102041034B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5891325A (en) * | 1998-08-11 | 1999-04-06 | Exxon Research And Engineering Co. | Process for reducing total acid number of crude oil |
| CN1353167A (en) * | 2000-11-03 | 2002-06-12 | 石油大学(北京) | Modified argil as denitrifying agent and its preparing process |
| CN101148602A (en) * | 2007-09-10 | 2008-03-26 | 蒋玉珊 | Alkaline purifying agent |
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