CN100404648C - Method for removing organic carboxylic acid - Google Patents
Method for removing organic carboxylic acid Download PDFInfo
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- CN100404648C CN100404648C CNB2004100689326A CN200410068932A CN100404648C CN 100404648 C CN100404648 C CN 100404648C CN B2004100689326 A CNB2004100689326 A CN B2004100689326A CN 200410068932 A CN200410068932 A CN 200410068932A CN 100404648 C CN100404648 C CN 100404648C
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Abstract
The present invention relates to a method for removing organic carboxylic acid. Raw materials containing acid and a catalyst containing IVA metal ions are mixed and are reacted under the temperature from 260 to 520 DEG C, the pressure from normal pressure to 5.0MPa, and the staying time from 1 to 300 minutes. Reaction products are separated to obtain gas and liquid products. The deacidification rate of the method is higher than 99%.
Description
Technical field
The present invention relates to a kind of method that removes organic carboxyl acid in the material, particularly remove the petroleum acid in crude oil and the distillate thereof.
Background technology
Acidic components in the oil have naphthenic acid, lipid acid, aromatic acid, mercaptan, phenols, other organic acid and mineral acid etc.Wherein naphthenic acid accounts for more than 85%.At first found naphthenic acid by Eichler in 1874, with it as acidic substance; Be defined as having the naphthenic carboxylic acid by people such as W.Markowniroff afterwards and be named.The concentration or the content of acid are represented with total acid value in the petroleum fractions.During total acid value (TAN) is meant and the milligram number of 1 gram crude oil or the needed KOH of all acidic componentses of petroleum fractions, unit is mgKOH/g.Low molecular acids heavy corrosion hardware and pipeline (acid number＞0.5mgKOH/g, 230 ℃～400 ℃ of temperature ranges).Acid oxygenatedchemicals can be separated by methods such as alkali cleanings, and petroleum acid is the difficult separation owing to easy emulsification when alkali cleaning.
Continuous discovery and exploitation along with ground high-acid crude oils such as Venezuela, West Africa, India, China, Russia, the U.S., at present the output of high-acid crude oil accounts for about 5% of global crude oil ultimate production every year on the crude oil market, the world, and annual also with 0.3% speed increment.China's North SinKiang acid value for crude oil reaches 4.5mgKOH/g, and Bohai Sea acid value for crude oil reaches 3.61mgKOH/g, and the LIAOHE CRUDE acid number reaches 2.69mgKOH/g, and Peng Lai acid value for crude oil is up to 6.1mgKOH/g.
The acid value for crude oil height mainly contains the influence that production causes: 1. make production unit and pipeline corrosion serious, because the factors such as complicacy, temperature and hydromeehanics of other component in the kind of acid and the crude oil, naphthenic acid corrosion rule more complicated also has a lot of problems to have little understanding so far; 2. the corresponding raising of the acidity of distillate brings harm to product exquisiteness and quality product; 3. emulsification is serious, and sewage with oil height, environmental pollution are serious.
The braking measure of naphthenic acid corrosion at present mainly comprises: mixing, material upgrading or liner corrosion resistant material, top coat (aluminising, Ni-P electroless plating, supersonic speed thermospray 316L etc.), high-temperature corrosion inhibitor, control velocity flow pattern, separating naphthenic acid or change its form.
It is as follows that crude oil is processed general exemplary flow, and the depickling treatment technology of acid-containing raw oil roughly is divided into the four big starting points.Every place is divided into thorough decomposition carboxylic acid and Separation and Recovery two class thinkings.
The method of crude oil or fraction oil deacidification generally has physical adsorption, solvent extraction, chemical conversion, the most frequently used still chemical conversion process.
USP5,891,325 adopt the petroleum acid in the multistage heat-treating methods reduction crude oil.
USP5,897,769 use aperture hydrogenation catalyst shortening to remove naphthenic acid in the oil.
USP5,914,030 disclose a kind of method that reduces total acid mumber of crude oil.Add the oil soluble of 5wppm at least or can the dispersive metal catalyst in oil in containing acid starting material, metallic element comes from VB, VIB, VIIB or VIII family in the catalyzer.(be heated to 400～800 of certain temperatures (about 204～427 ℃) under about 0.1～6.9MPa) at hydrogen dividing potential drop 15～1000psig.In reaction process, use the inert gas purge reaction system, make water and CO
2The dividing potential drop sum remain on below the 50psig (about 0.3MPa).
USP5,688,395 disclose a kind of heavy oil upgrading process, the used catalyzer of this method comprises first kind of metal and second kind of metal, first kind of group VIII base metal such as iron, cobalt, nickel or its mixture that metal is the periodic table of elements wherein, second kind of metal is basic metal such as potassium, sodium or its mixture.
Acid removal rate was lower when above-mentioned prior art was used to remove crude oil or the acid of its distillate PetroChina Company Limited..
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method that removes crude oil or its distillate PetroChina Company Limited. acid.
Method provided by the invention comprises:
Containing acid starting material and the catalyst mix that contains IVA family metal ion, is that normal pressure reacts to 5.0MPa, the condition of 1～300 minute residence time at 260～520 ℃ of temperature, pressure, and reaction product isolated obtains gas and liquid product.
Method acid removal rate of the present invention is up to more than 99%.
Embodiment
Method provided by the invention comprises:
Containing acid starting material and the catalyst mix that contains IVA family metal ion, is that normal pressure reacts to 5.0MPa, the condition of 1～300 minute residence time at 260～520 ℃ of temperature, pressure, and reaction product isolated obtains gas and liquid product.
The described acid starting material that contains is acidiferous crude oil or various petroleum fractions, and wherein crude oil can be crude oil, crude oil behind the dewatering and desalting without dewatering and desalting or the topped crude that removes moisture and part lighter hydrocarbons by flash distillation; Petroleum fractions is selected from long residuum, vacuum gas oil, deasphalted oil, vacuum residuum etc.This TAN that contains acid starting material is 0.05-100mgKOH/g.
The catalyzer of the described IVA of containing family metal ion also comprises VIIIB family metal ion, IB family metal ion or its mixture.
Described catalyzer comprises IVA family metal ion and VIIIB family metal ion, and wherein the weight ratio of VIIIB family metal ion and IVA family metal ion is 0.05～20: 1.
Described catalyzer comprises IVA family metal ion and IB family metal ion, and wherein the weight ratio of IB family metal ion and IVA family metal ion is 0.05～20: 1.
Described catalyzer comprises IVA family metal ion, VIIIB family metal ion and IB family metal ion, and wherein VIIIB family metal ion, IB family metal ion are 0.05～20 with the weight ratio of IVA family metal ion respectively: 1.
Described IVA family metal ion is selected from germanium ion, tin ion, lead ion or its mixture.
Described VIIIB family metal ion chosen from Fe ion, cobalt ion, nickel ion or its mixture.
Described IB family metal ion is selected from cupric ion, silver ions, gold ion or its mixture.
Described metal ion can be to exist with forms such as vitriol, nitrate, acetate, halogenide, sulfide or oxide compounds.
IVA family metal ion is 50～50000ppm with the weight ratio that contains acid starting material in the described catalyzer, preferred 100～10000ppm.
The preferred reaction conditions of the present invention is: 400～500 ℃ of temperature, pressure 0.1～1.0MPa, 3～150 minutes residence time.
The following examples will give further instruction to present method, but therefore not limit present method.TAN in embodiment and the Comparative Examples is according to the method test of ASTM D664.
Comparative Examples 1
With TAN is that the crude oil without desalination, dehydration of 13mgKOH/g carries out the on-catalytic depickling.Reaction conditions in autoclave is: 430 ℃ of temperature, pressure 3.5MPa, 300 minutes residence time.The TAN of reaction product oil is still up to 5mgKOH/g, and acid removal rate only is 61.5%.The etching problem of product oil in postorder processing is inevitable.
Embodiment 1
With TAN is that the crude oil without desalination, dehydration of 13mgKOH/g carries out catalytic deacidification.Catalyzer is SnCl
45H
2O, wherein the content of tin ion is 10000ppm with respect to raw material.Reaction conditions in autoclave is: 430 ℃ of temperature, pressure 3.5MPa, 300 minutes residence time.The TAN of reaction product oil is 0.12mgKOH/g, and acid removal rate is 99.08%.Avoided the etching problem of product oil in postorder processing effectively.
Embodiment 2
With TAN is that the crude oil without desalination, dehydration of 13mgKOH/g carries out catalytic deacidification.Catalyzer is PbO
2And NiSO
47H
2O, wherein the content of lead ion, nickel ion is 5000ppm, 5000ppm with respect to raw material.Reaction conditions in autoclave is: 500 ℃ of temperature, pressure 0.5MPa, 3 minutes residence time.The TAN of reaction product oil is 0.1mgKOH/g, and acid removal rate is 99.23%.Avoided the etching problem of product oil in postorder processing effectively.
Embodiment 3
With TAN is that the crude oil without desalination, dehydration of 13mgKOH/g carries out catalytic deacidification.Catalyzer is PbCl
4And Cu (CH3COO)
2H
2The content of lead ion, cupric ion is respectively 1000ppm, 500ppm with respect to raw material among the O.Reaction conditions in autoclave is: 390 ℃ of temperature, pressure 2.5MPa, 120 minutes residence time.The TAN of reaction product oil is 0.08mgKOH/g, and acid removal rate is 99.38%.Avoided the etching problem of product oil in postorder processing effectively.
Embodiment 4
With TAN is that the crude oil without desalination, dehydration of 13mgKOH/g carries out catalytic deacidification.Catalyzer is SnS
2, CoCl
26H
2O and AgNO
3, wherein the content of tin ion, cobalt ion, silver ions is respectively 200ppm, 4000ppm, 4000ppm with respect to raw material.Reaction conditions in autoclave is: 370 ℃ of temperature, pressure 5.0MPa, 60 minutes residence time.The TAN of reaction product oil is 0.03mgKOH/g, and acid removal rate is 99.77%.Avoided the etching problem of product oil in postorder processing effectively.
Comparative Examples 2
Compare with embodiment 4, do not have tin ion in the catalyzer, other condition is all identical.
With TAN is that the crude oil without desalination, dehydration of 13mgKOH/g carries out catalytic deacidification.Catalyzer is CoCl
26H
2O and AgNO
3, wherein the content of cobalt ion, silver ions is respectively 4000ppm and 4000ppm with respect to raw material.Reaction conditions in autoclave is: 370 ℃ of temperature, pressure 5.0MPa, 60 minutes residence time.The TAN of reaction product oil is still up to 6.8mgKOH/g, and acid removal rate only is 47.69%.Can't avoid the etching problem of product oil in postorder processing.
Claims (12)
1. method that removes organic carboxyl acid, the catalyst mix that it is characterized in that containing acid starting material and contain IVA family metal ion, at 260～520 ℃ of temperature, pressure is that normal pressure reacts to 5.0MPa, the condition of 1～300 minute residence time, and reaction product isolated obtains gas and liquid product.
2. according to the method for claim 1, it is characterized in that the described acid starting material that contains is acidiferous crude oil or various petroleum fractions, wherein crude oil is crude oil, the crude oil behind the dewatering and desalting or the topped crude without dewatering and desalting; Petroleum fractions is selected from long residuum, vacuum gas oil, deasphalted oil, the vacuum residuum one or more, and this total acid value that contains acid starting material is 0.05-100mgKOH/g.
3. according to the method for claim 1, it is characterized in that the catalyzer of the described IVA of containing family metal ion also comprises VIIIB family metal ion, IB family metal ion or its mixture.
4. according to the method for claim 3, it is characterized in that described catalyzer comprises IVA family metal ion and VIIIB family metal ion, wherein the weight ratio of VIIIB family metal ion and IVA family metal ion is 0.05～20: 1.
5. according to the method for claim 3, it is characterized in that described catalyzer comprises IVA family metal ion and IB family metal ion, wherein the weight ratio of IB family metal ion and IVA family metal ion is 0.05～20: 1.
6. according to the method for claim 3, it is characterized in that described catalyzer comprises IVA family metal ion, VIIIB family metal ion and IB family metal ion, wherein VIIIB family metal ion, IB family metal ion are 0.05～20 with the weight ratio of IVA family metal ion respectively: 1.
7. according to the method for claim 1, it is characterized in that described IVA family metal ion is selected from germanium ion, tin ion, lead ion or its mixture.
8. according to the method for claim 3, it is characterized in that described VIIIB family metal ion chosen from Fe ion, cobalt ion, nickel ion or its mixture.
9. according to the method for claim 3, it is characterized in that described IB family metal ion is selected from cupric ion, silver ions, gold ion or its mixture.
10. according to the method for claim 1, it is characterized in that the IVA family metal ion in the described catalyzer is 50～50000ppm with the weight ratio that contains acid starting material.
11., it is characterized in that the IVA family metal ion in the described catalyzer is 100～10000ppm with the weight ratio that contains acid starting material according to the method for claim 10.
12. according to the method for claim 1, it is characterized in that reaction conditions is: 400～500 ℃ of temperature, pressure 0.1～1.0MPa, 3～150 minutes residence time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100689326A CN100404648C (en) | 2004-07-14 | 2004-07-14 | Method for removing organic carboxylic acid |
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|---|---|---|---|
| CNB2004100689326A CN100404648C (en) | 2004-07-14 | 2004-07-14 | Method for removing organic carboxylic acid |
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|---|---|
| CN1721507A CN1721507A (en) | 2006-01-18 |
| CN100404648C true CN100404648C (en) | 2008-07-23 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5928502A (en) * | 1997-08-29 | 1999-07-27 | Exxon Research And Engineering Co. | Process for reducing total acid number of crude oil |
| CN1334857A (en) * | 1999-02-04 | 2002-02-06 | 英国石油勘探运作有限公司 | Process for deacidifying crude oil system |
-
2004
- 2004-07-14 CN CNB2004100689326A patent/CN100404648C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5928502A (en) * | 1997-08-29 | 1999-07-27 | Exxon Research And Engineering Co. | Process for reducing total acid number of crude oil |
| CN1334857A (en) * | 1999-02-04 | 2002-02-06 | 英国石油勘探运作有限公司 | Process for deacidifying crude oil system |
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| Publication number | Publication date |
|---|---|
| CN1721507A (en) | 2006-01-18 |
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