CN1333049C - Esterizing acid lowering method for acid containing raw oil or fraction oil - Google Patents
Esterizing acid lowering method for acid containing raw oil or fraction oil Download PDFInfo
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- CN1333049C CN1333049C CNB2004100483499A CN200410048349A CN1333049C CN 1333049 C CN1333049 C CN 1333049C CN B2004100483499 A CNB2004100483499 A CN B2004100483499A CN 200410048349 A CN200410048349 A CN 200410048349A CN 1333049 C CN1333049 C CN 1333049C
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Abstract
The present invention relates to an esterification acid lowering method for crude oil containing acid or distillate oil. The crude oil containing acid or the distillate oil and C1 to C6 alcohol are in contact reaction under the existence of a catalyst at the temperature of 200 to 270 DEG C; the acid in the crude oil is converted into ester, and the catalyst is SnO or heteropoly acid. The method can effectively reduce the acid value of the crude oil containing acid or the distillate oil and can reduce the corrosiveness of processing materials to equipment.
Description
Technical field
The present invention is the acid reduction method of a kind of acid-containing raw oil or distillate, specifically, is a kind of acid content by esterification reduction acid-containing raw oil or distillate, reduces its corrosive method.
Background technology
Along with crude oil becomes heavy gradually, acid number improves constantly, and has increased the weight of the corrosion of crude oil to refining equipment.Acidic components in the oil mainly are oxygen containing acidic cpds, comprise naphthenic acid, lipid acid, aromatic acid, phenols and mercaptan etc., and wherein naphthenic acid content is maximum, and content is greater than 90%, so the acid in the oil refers generally to naphthenic acid.The method of naphthenic acid corrosion control mainly contains four kinds: 1, adopt corrosion resisting alloy, as 317 stainless steels.This method is the may command naphthenic acid corrosion in a short time, but when the character of crude oil and source changed, naphthenic acid corrosion still may take place; 2, crude oil mixing.Select for use low acid number crude oil to mix, total acid mumber of crude oil is reduced to below the critical acid number, but limited by oil product source and kind with crude oil with high acid value; 3, add alkali neutralization or depickling from crude oil.In adding alkali and in the process of naphthenic acid,, cause emulsification easily because the naphthenate that generates has surfactivity; 4, filling inhibiter.But the caducous problem of the protective film that this method forms when high temperature also is not resolved.
Because increasing of acid-containing raw oil, the traditional technology deacidification effect is undesirable.Develop some in recent years both at home and abroad in succession and use the novel process that methods such as esterification process, hydrogenation method, thermal treatment are carried out crude oil deacidification, as US6251305B
1By the acid-containing raw oil esterification being reduced the acidity in the crude oil, the temperature of esterification treatment is that 25～350 ℃, pressure are 100～300kPa, and the used alcohol of esterification is C
1～C
6Alkanol, its acid/pure mol ratio is 1: 0.5～20, does not add catalyzer in the esterification reaction process.
US 5948238 discloses a kind of petroleum acid esterification process, adds alcohol or dibasic alcohol in crude oil, is that catalyzer makes petroleum acid carry out esterification with the metal carboxylate, and described metal carboxylate comprises naphthenate, stearate or 16 carbonate of metal.Described catalyzer can directly add in the crude oil, also can add metal oxide, oxyhydroxide and acetylacetonate, by the carboxylate salt promotion esterification of the synthetic metal of original position in crude oil.
Summary of the invention
The esterification acid reduction method that the purpose of this invention is to provide a kind of acid-containing raw oil or distillate, this method can effectively reduce the acid number of stock oil, and is simple to operate, mild condition.
The esterification acid reduction method of acid-containing raw oil provided by the invention or distillate comprises acid-containing raw oil or distillate and C
1～C
6Alcohol in the presence of catalyzer, 200～270 ℃ of contact reactss make the acid in the crude oil be converted into ester, described catalyzer is SnO or heteropolyacid.
The present invention is with acidiferous stock oil--and crude oil or distillate and lower alcohol carry out esterification, make carboxylic acid wherein change into corresponding ester.The ash content that produces behind the burning crude oil that esterification technique is handled is less, and the fat of generation and unreacted alcohols are harmless components, can not cause the problem on downstream processing and the quality product, and excessive alcohol can also reclaim, utilize.
Embodiment
Crude oil that the inventive method is lower with calcium content and acid content is higher or distillate react with alcohol in the presence of special catalyst, making raw material is that organic acid in crude oil or the distillate is transformed into corresponding ester, thereby reduced the acid number of raw material, reduced the corrodibility of raw material equipment.
Acid number in the described raw material has reflected amount of acidic substances wherein.Acid number＞0.5mgKOH the g of crude oil is thought in initial research
-1Can cause equipment corrosion, usually with acid number＞0.5mgKOH g
-1Crude oil be referred to as high-acid crude oil.The someone studied and thought acid value for crude oil≤1.0mgKOH g afterwards
-1Only have low corrosion, acid number reaches 1.5～2.0mgKOHg
-1Just can cause comparatively serious naphthenic acid corrosion.
Calcium salt in the raw material has inorganic calcium and two kinds of existing waies of organic calcium, and inorganic calcium is mainly CaCl
2, CaSO
4, CaCO
3Deng salt, organic calcium mainly contains fatty calcium, calcium naphthenate, phenol calcium etc., wherein based on calcium naphthenate.Calcium naphthenate has self-catalysis to esterification acid reduction, and calcium contents is 120～600 μ g g in raw material
-1, preferred 140～350 μ g g
-1The time, calcium salt wherein mainly is that calcium naphthenate has self-catalysis to esterification acid reduction.Can directly carry out esterification acid reduction and handle without catalyzer for high acid starting material with above-mentioned calcium contents.Calcium contents surpasses 600 μ g g in the raw material
-1The time, calcium salt wherein plays restraining effect to esterification, should carry out decalcification earlier and handle, and calcium contents in the crude oil is reduced in the OK range, carries out esterification acid reduction again and handles, and the raw material decalcification can adopt the chelating method to carry out.Raw material calcium contents after decalcification is handled is less than 140 μ g g
-1, or for calcium contents less than 140 μ g g
-1Raw material then is applicable to method of the present invention, adds catalyzer and carry out effective esterification in low calcium raw material, reduces acid.
The described reaction pressure of the inventive method is 0.1～0.3MPa.Preferred 220～250 ℃ of temperature of reaction, to density bigger contain acid starting material, optional higher temperature of reaction is as carrying out esterification at 250～270 ℃.
The time of esterification of the present invention is 0.5～2.0 hour, preferred 1.0～2.0 hours.The consumption of reaction time catalizer is 0.1～5.0 milligram of every gram raw material, preferred 0.1～2.5 milligram.To acid number is 2～6mgKOH g
-1Raw material, catalyst levels is 0.1～0.25 milligram of every gram raw material, is 6～10mgKOH g to acid number
-1Raw material, catalyst levels is 0.2～0.5 milligram of every gram raw material, is 10～15mgKOH g to acid number
-1Raw material, catalyst levels is 0.5～1.0 milligram of every gram raw material.Described esterifying catalyst is better with SnO, and heteropolyacid can be selected any known heteropolyacid for use, preferred H
3PO
412WO
3XH
2O, wherein x is 9～17.
The preferred C of used alcohol in the inventive method
1～C
6Primary alconol, secondary alcohol or dibasic alcohol, selected alcohol sterically hindered more little, esterification is easy more to be carried out, corresponding productive rate is also higher.Therefore the esterification yied of primary alconol is than secondary alcohol height.In addition, the boiling point of primary alconol is higher relatively, and catalyzer is active better when high temperature.So the preferred alcohol of the inventive method is methyl alcohol, ethanol or ethylene glycol.Alcohol is 1.0～4.0: 1 with the mol ratio of acid in the reaction, preferred 1.5～3.0: 1.
The degree of esterification of carboxylic acid can be with infrared spectra by carboxyl peak 1708cm in the raw material
-1With ester group peak 1742cm
-1The variation of functional group's peak value size is estimated.The residual acid substance of raw material can calculate conversion rate of esterification by following formula again by the acid number of ASTM D664 potentiometric determination sample after the esterification:
The inventive method is not subjected to the restriction of acid-containing raw oil or distillate kind and acid number size, is applicable to the pre-treatment of various acid-containing raw oils or distillate, reduces the content of raw material middle acid substance by esterification acid reduction, and then reduces its corrodibility in the course of processing.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Following case expedition is the esterification acid reduction effect of catalyzer of the same race not.
200 milliliters of (190 gram) low calcium high-acid crude oils of adding, 6.8 milliliters of (7.56 gram) ethylene glycol and 0.05 restrain SnO as catalyzer in 1 liter airtight autoclave reactor, stirring reaction is 1 hour under 250 ℃, 0.1～0.3MPa, alcohol/condition of 3: 1 of sour mol ratio, carry out chilling with water coolant then, take out oil sample, according to the acid number of the potentiometric determination oil product of ASTM D664, the calcium contents in the crude oil, the catalytic amount of adding and reaction result see Table 1.
Example 2
Method according to example 1 is carried out esterification to low calcium high-acid crude oil, is not both to add 0.20 heteropolyacid that restrains as catalyzer, and described heteropolyacid consists of H
3PO
412WO
314H
2O, reaction result sees Table 1.
Comparative Examples
Method according to example 1 is carried out esterification to low calcium high-acid crude oil, but does not add catalyzer, and reaction result sees Table 1.
By table 1 data as can be known, for low calcium high-acid crude oil, behind adding catalyst S nO or the heteropolyacid, the transformation efficiency of esterification is respectively 81.7%, 82.6%, and reaction back acid number all is lower than 0.5mgKOHg
-1, and do not add catalyzer, and directly petroleum acid being carried out esterification, transformation efficiency only is 54.3%, reaction back acid number is 1.05mgKOH g
-1Illustrate that the catalyzer of the inventive method use can effectively reduce the acid number of acid-containing raw oil.
Example 3～12
Following case expedition catalyst levels is to the influence of esterification.
Get 200 milliliters of crude oil (190 gram) after the decalcification, its calcium contents is 67.5 μ gg
-1, carry out the esterification acid reduction reaction by the method for example 1, different is to add 7 milliliters of (5.52 gram) ethanol to replace ethylene glycol to react, wherein used heteropolyacid is H
3PO
412WO
314H
2O, catalyzer that each example is used and consumption and reaction result see Table 2.
As shown in Table 2, two kinds of catalyzer of SnO and heteropolyacid to decalcification after the esterification of crude oil good catalytic effect is all arranged, the catalytic effect of SnO is good slightly, adds 0.025 gram SnO conversion rate of esterification and can reach 93.6%, reaction back acid number is reduced to 0.95mgKOH g
-1, suitable SnO catalyst levels is 0.025～0.1 gram.And the catalytic effect of heteropolyacid is poor slightly, and the conversion rate of esterification that adds 0.20 gram heteropolyacid can reach 93.4%, and reaction back acid number is reduced to 0.98mgKOH g
-1Suitable heteropolyacid catalyst consumption is 0.2～0.4 gram, and when catalyst levels increased to 0.8 gram, reaction back acid number was higher.
Table 1
| Instance number | Feedstock property | Catalyzer | Reaction result | |||
| Acid number, mgKOHg -1 | Calcium contents, μ gg -1 | Title | Consumption, g | Acid number, mgKOHg -1 | Transformation efficiency, quality % | |
| 1 | 2.30 | 6.0 | SnO | 0.05 | 0.42 | 81.7 |
| 2 | 2.30 | 6.0 | Heteropolyacid | 0.20 | 0.40 | 82.6 |
| Comparative Examples | 2.30 | 6.0 | - | - | 1.05 | 54.3 |
Table 2
| Instance number | Catalyzer | Reaction result | ||
| Title | Consumption, g | Acid number, mgKOHg -1 | Transformation efficiency, quality % | |
| 3 | SnO | 0 | 4.1 | 72.4 |
| 4 | SnO | 0.025 | 0.95 | 93.6 |
| 5 | SnO | 0.05 | 0.86 | 94.2 |
| 6 | SnO | 0.10 | 0.98 | 93.4 |
| 7 | SnO | 0.15 | 1.05 | 92.9 |
| 8 | Heteropolyacid | 0 | 4.1 | 72.4 |
| 19 | Heteropolyacid | 0.1 | 3.05 | 79.5 |
| 10 | Heteropolyacid | 0.2 | 0.98 | 93.4 |
| 11 | Heteropolyacid | 0.4 | 1.05 | 92.9 |
| 12 | Heteropolyacid | 0.8 | 1.20 | 91.9 |
Claims (10)
1, the esterification acid reduction method of a kind of acid-containing raw oil or distillate comprises acid-containing raw oil or distillate and C
1～C
6Alcohol in the presence of catalyzer, 200～270 ℃ of contact reactss make the acid in crude oil or the distillate be converted into ester, described catalyzer is SnO or heteropolyacid.
2, in accordance with the method for claim 1, it is characterized in that described temperature of reaction is 220～250 ℃, pressure is 0.1～0.3MPa, and the time is 0.5～2.0 hour.
3,, it is characterized in that catalyst consumption is 0.1～5.0 milligram of every gram crude oil or a distillate according to claim 1 or 2 described methods.
4, in accordance with the method for claim 3, it is characterized in that catalyst consumption is 0.1～2.5 milligram of every gram crude oil or a distillate.
5, in accordance with the method for claim 1, the mol ratio that it is characterized in that in the described reaction acid in alcohol and crude oil or the distillate is 1.0～4.0: 1.
6, in accordance with the method for claim 5, the mol ratio that it is characterized in that in the described reaction acid in alcohol and crude oil or the distillate is 1.5～3.0: 1.
7, in accordance with the method for claim 1, it is characterized in that described alcohol is selected from C
1～C
6Primary alconol, secondary alcohol or dibasic alcohol.
8, in accordance with the method for claim 7, it is characterized in that described alcohol is selected from methyl alcohol, ethanol or ethylene glycol.
9, in accordance with the method for claim 1, it is characterized in that described heteropolyacid is H
3PO
412WO
3XH
2O, wherein x is 9～17.
10, in accordance with the method for claim 1, it is characterized in that calcium contents is less than 140 μ gg in described crude oil or the distillate
-1
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|---|---|---|---|
| CNB2004100483499A CN1333049C (en) | 2004-06-29 | 2004-06-29 | Esterizing acid lowering method for acid containing raw oil or fraction oil |
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|---|---|---|---|
| CNB2004100483499A CN1333049C (en) | 2004-06-29 | 2004-06-29 | Esterizing acid lowering method for acid containing raw oil or fraction oil |
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| CN1333049C true CN1333049C (en) | 2007-08-22 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314729B (en) * | 2007-05-31 | 2013-01-30 | 中国石油化工股份有限公司 | Esterification acid reduction method for primary oil or distillate oil |
| CN101537363B (en) * | 2009-04-24 | 2011-01-12 | 中国石化集团洛阳石油化工工程公司 | Deacidifying catalyst and preparation method and application thereof |
| CN106582731A (en) * | 2016-12-14 | 2017-04-26 | 钦州学院 | Deacidification catalyst and preparation method thereof |
| CN113736562A (en) * | 2021-09-02 | 2021-12-03 | 重庆大学 | Deacidifying process method for vegetable insulating oil by taking jatropha curcas oil as raw material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5948238A (en) * | 1998-10-06 | 1999-09-07 | Exxon Research And Engineering Co. | Metal compounds as accelerators for petroleum acid esterification |
| WO2000068341A1 (en) * | 1999-05-11 | 2000-11-16 | Exxonmobil Research And Engineering Company | Process for treatment of petroleum acids |
| US6251305B1 (en) * | 1998-10-06 | 2001-06-26 | Exxon Research And Engineering Company | Esterification of acidic crudes |
| WO2002099013A2 (en) * | 2001-06-05 | 2002-12-12 | Bp Exploration Operating Company Limited | Process for deacidifying crude oil |
| CN1456638A (en) * | 2003-06-03 | 2003-11-19 | 石油大学(华东) | Method for deacidification of crude oil and fractional oil by esterification |
-
2004
- 2004-06-29 CN CNB2004100483499A patent/CN1333049C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5948238A (en) * | 1998-10-06 | 1999-09-07 | Exxon Research And Engineering Co. | Metal compounds as accelerators for petroleum acid esterification |
| US6251305B1 (en) * | 1998-10-06 | 2001-06-26 | Exxon Research And Engineering Company | Esterification of acidic crudes |
| WO2000068341A1 (en) * | 1999-05-11 | 2000-11-16 | Exxonmobil Research And Engineering Company | Process for treatment of petroleum acids |
| WO2002099013A2 (en) * | 2001-06-05 | 2002-12-12 | Bp Exploration Operating Company Limited | Process for deacidifying crude oil |
| CN1456638A (en) * | 2003-06-03 | 2003-11-19 | 石油大学(华东) | Method for deacidification of crude oil and fractional oil by esterification |
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