CN1016354B - Decalcification of hydrocarbonaceous feedstock using extraction - Google Patents
Decalcification of hydrocarbonaceous feedstock using extractionInfo
- Publication number
- CN1016354B CN1016354B CN 89104536 CN89104536A CN1016354B CN 1016354 B CN1016354 B CN 1016354B CN 89104536 CN89104536 CN 89104536 CN 89104536 A CN89104536 A CN 89104536A CN 1016354 B CN1016354 B CN 1016354B
- Authority
- CN
- China
- Prior art keywords
- calcium
- described method
- raw material
- carbonic acid
- extraction agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for removing metal pollutants from a hydrocarbon raw material, particularly to for removing calcium. The method comprises the following steps: mixing the raw material and a metal extraction agent such as carboxylic acid or a salt thereof (particularly ammonium carbonate); then, separating metal containing water solution out of the raw material without metal.
Description
The present invention relates to use carbonic acid or carbonate as extraction agent, from the solvent-deasphalted oils of calcareous crude oil, heavy hydrocarbon residual oil or crude oil and residual oil, remove the method for calcium.Some (but more and more important) petroleum and residual oil all contain calcium in varying degrees, and these raw materials are difficult to conventional method for refining processing.Say that exactly the calcium contamination thing of specific question is the compound of non-porphyrin organo-metallic key form in causing processing.Finding just that recently these compounds are present in the crude oil, particularly in the heavy crude, and is rare comparatively speaking.It is calcium naphthenate and homologue thereof that one class is arranged in the calcium containing compound of having identified.Can not separate these organic calcium compounds with general desalting method from raw material, in the refining process of routine, these compounds can cause the rapid inactivation of hydrotreating catalyst.The example of the raw material that calcium cpd content is high is to originate in California San Jaoquin Valley crude oil.These crude oil generally are the mixtures in the pipeline, refer to San Jaoquin Valley crude oil or residual oil.
Caused problem of calcium in the petroleum and the necessity that removes it are just just coming into one's own recently, also almost do not have specific calcium removal methods in the prior art.Usually adopt the organic compound demetalization, particularly remove those known metallic pollutions such as nickel, vanadium and/or copper, this has introduction in prior art.These compounds generally are the form of porphyrin and other organometallic compound in raw material.
At United States Patent (USP) 3,052,627(Lerner) in, adopt 2-Pyrrolidone one alcohol mixture from petroleum, to remove metal pollutant.At United States Patent (USP) 3,167,500(Payne) in, adopt have C/H preferably than and molecular weight, the condensation polynuclear aromatic compound that generally is referred to as bituminous cement from oil, remove metal pollutant such as metallic porphyrin.At United States Patent (USP) 3,153,623(Eldib etc.) in, by the organic compound of the high dielectric strength that brings Selection In, help electroprecipitation to do in order to remove the metal that has the polarity organic molecule.
Be surprised to find that now, use extraction agent such as carbonic acid and salt thereof to make the calcium cpd combination, can from hydrocarbon raw material, remove the calcic pollutent effectively.
This technology comprises that the aqueous solution that uses extraction agent removes the particularly method of the metal in crude oil or the residual oil of hydrocarbon raw material.Present method is particularly useful for removing calcium, is that non-porphyrin has the switch calcium cpd especially.The preferred metal extraction agent is carbonic acid or its salt, as the aqueous solution of volatile salt.
One preferably in the embodiment, the aqueous solution for the treatment of demetallated raw material and volatile salt closely and mix fully.Metal combines with extraction agent, and water and hydrocarbon phase separation can offer hydrogenation technique with hydrocarbon raw material then.
The residual oil of various automotive gasoline bright stocks and these crude oil contains high calcium containing compound that can not receiving amount.These often make rapid inactivation of hydrogenation catalyst or fouling with organic key bonded calcium cpd, cause tangible processing difficulties in the hydrogenation technique of standard.The present invention includes and adopt known extraction agent, be preferably carbonic acid and its salt, particularly volatile salt, before hydrotreatment crude oil or residual oil, remove the method for calcic pollutent.
The present invention is applicable to any high hydrocarbon raw material that can not receiving amount calcium that contains, comprise crude oil, particularly the crude oil of particular source such as California san Jaoquin Valley crude oil more particularly comprise South Belridge, Huntington Beach, Wilmington, Kern Front, Cymric Heavy, Midwey Sunset or their mixture.In addition, normal pressure or vacuum residuum, or the solvent-deasphalted oils of these crude oil or residual oil more and more by hydrotreatment obtaining more useful product such as gas oil, gasoline, diesel oil etc., but these raw materials also contain calcium high, unacceptable amount.Any other may contain the hydrocarbon raw material of pollutent such as shale oil, liquefaction coal, selected Tar sands etc., and also available the present invention handles, and is also included within the design scope of the present invention.
Basic technological process and uncomplicated, the crude oil that need are handled or the aqueous solution of residual oil and carbonic acid or its salt, and with alkali or sour pH is transferred to more than 2, be preferably 5～9.The calcium complex that forms enters the water of mixture.After water and crude oil or hydrocarbon phase two are separated water is removed.Conventional hydrogen addition technology processing equally be handled and be used to the no calcium hydrocarbon raw material that the result forms can with other hydrocarbon raw material.
Physical sepn is finished with conventional crude oil desalting device usually, and the crude oil desalting device generally is used for the crude oil desalting before the hydrotreatment.Also available any other separation method is finished above-mentioned separation, comprises counter-current extraction.
As everyone knows, carbonate anion has high avidity to calcium and other metal ion.A kind of basic solution is placed high-pressure carbon dioxide, in the aqueous solution, can produce the carbonic acid and the carbanion of high density.
Yet carbonic acid soln is modal to be made a kind of carbonate is soluble in water.A common instance of these salt is volatile salts, (NH
4)
2CO
3, molecular weight is 114.10; Be also referred to as Hartshorn.
The ammonium salts of carbonic acid generally is to form with bicarbonate of ammonia and carbamate solution reaction, also can isolate crystal salt from the aqueous solution in some cases.The general specific ionization sour water of these salt dissolubility is stronger, and acid less and use more conveniently, they contain the water of different quantities, and its general formula contains 30～40%NH
3And 45%CO
2
Volatile salt is generally used for scavenging solution and woolen washing and degreasing.Also in food and drink industry, be used as baking agent and sanitas.Volatile salt also is a kind of in a big class complexing or the complexed metal ionic ligand.The metal ligand complex compound that these compound formation are highly stable, volatile salt itself and Ca
+ 2Ion forms can isolating complex compound.
Carbonic acid and salt thereof also react with other metal ion in the aqueous solution, but to metal pollutant common, that be generally organometallic compound such as nickel and scherbinaite oil porphyrin in the oil, the as if little or not effect at all of effect.Yet iron is had certain effect, and it can be effective that carbonic acid and salt pair thereof remove organoiron compound.
As previously mentioned, calcium and extraction agent are suitable to be combined in order to make, and pH should be higher than 2, is preferably 5～9.Yet a difficult problem that adds the alkali generation is to have emulsion to form, and disturbs effectively and separates.Therefore, best pH is 6, especially for naphthenic acid crude oil.
The extraction agent aqueous solution should be determined its optimum value with the ratio of hydrocarbon raw material, and its determinative is a separation method.For example, commercial demineralizer is generally 10% or be lower than under 10% aqueous solution volume and operate.Also available counter-current extraction partition method.Carried out effective separation of 50% or 50% above aqueous solution volume.
Be important the duration of contact of extraction water solution and hydrocarbon raw material, generally can be several seconds to about 4 hours, and be about 4 seconds to about 60 seconds duration of contact preferably.
The temperature of extraction also is a factor of process efficiency.Extraction can at room temperature be carried out, and the molar equivalent of carbonic acid will be limited in 300 or higher.If extraction is carried out under the temperature that improves, for example 180 °F or more than, the molar equivalent of carbonic acid can be reduced to more than 4.5 or 4.5.Temperature is 180 °F preferably.
Example (volatile salt)
Other carbonic acid class material that can replace volatile salt to use has: and yellow soda ash, soda water and carbonato natural ore deposit (as scale, natrolite (natrite), natron and granular snow stone (nevite).
Be that a certain amount of San Joaquin Valley vacuum residuum (93ppmCa) is dissolved in toluene in laboratory test (result sees following table for details), make it have suitable viscosity, mix with the carbonic acid soln of specified amount then.The preparation of carbonic acid soln is that the volatile salt with specified amount is dissolved in the deionized water to produce the mol ratio of volatile salt and calcium listed in the table, regulates its pH with ammonium hydroxide or strong inorganic acid then.Add demulsifying agent (trade(brand)name treatolite L-1562) to prevent to form emulsification.The mixture of jolting carbonic acid soln and oil, standing separation is preferably placed and is spent the night.Before and after handling residual oil, analyze, measure the decalcification amount.
Example 1
For proof carbonic acid is effective decalcifying agent, at room temperature San Joaquin Valley vacuum residuum has been carried out simultaneous test.Table 1 is pointed out, can remove most calcium with lower carbonic acid (with the volatile salt form) molar equivalent.With refinery desalting water, when bronsted lowry acids and bases bronsted lowry extracts, calcium to remove percentage lower.
Example 2
Improve the temperature carry out laboratory experiment, select to be used for best carbonic acid (with the form of the volatile salt) consumption of calcium extraction.Table 2 shows, the activity of carbonic acid begins to descend when about 5 molar equivalents, and when about 4.0 molar equivalents, active beginning sharply descends.
Example 3
Enumerated result in the table 3, as a means of comparing with conventional desalting soln decalcification.With carbonic acid (with the volatile salt form) contrast, its decalcification amount is lower.
Claims (13)
1, a kind of method of hydrocarbon raw material decalcification, this method comprises:
With the aqueous solution of a said hydrocarbon raw material and a metal extraction agent, extraction agent is selected from carbonic acid, carbonate and its mixture;
From the aqueous solution, isolate the hydrocarbon raw material that has removed calcium substantially.
2, according to the described method of claim 1, calcium wherein is the non-porphyrin compound of organic calcium keyed jointing.
3, according to claim 1 or 2 described methods, wherein said metal extraction agent is selected from volatile salt, yellow soda ash, SODA ASH LIGHT 99.2, scale, natrolite, natron and granular snow stone.
4, according to the described method of claim 3, wherein said metal extraction agent comprises volatile salt.
5, according to claim 3 or 4 described methods, more than the pH regulator to 2 of mixing step wherein.
6, according to claim 3 or 4 described methods, the pH regulator of mixing step wherein is to 5-9.
7, according to the described method of claim 6, temperature wherein is an envrionment temperature.
8, according to the described method of claim 7, wherein carbonic acid is more than 15 or 15 to the molar equivalent ratio of calcium.
9, according to the described method of claim 3, wherein temperature is improved.
10, according to the described method of claim 9, temperature wherein is about more than 180 °F or 180 °F.
11, according to the described method of claim 10, wherein carbonic acid (with the volatile salt form) is about more than 4.5 or 4.5 the molar equivalent ratio of calcium.
12,, wherein separate and carry out with conventional desalination or counter-current extraction according to the described method of claim 3.
13, according to claim 1 or 3 described methods, wherein hydrocarbon raw material is selected from and comprises crude oil, normal pressure or vacuum residuum, shale oil, liquefaction oil and tar sand oils.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US901,342 | 1986-08-28 | ||
| US06/901,341 US4778589A (en) | 1986-08-28 | 1986-08-28 | Decalcification of hydrocarbonaceous feedstocks using citric acid and salts thereof |
| US901,341 | 1986-08-28 | ||
| US06/901,342 US4778591A (en) | 1986-08-28 | 1986-08-28 | Demetalation of hydrocarbonaceous feedstocks using carbonic acid and salts thereof |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87810586.3 Division | 1987-08-28 | ||
| CN 87105863 Division CN1007239B (en) | 1986-08-28 | 1987-08-28 | With sequestrant to the hydrocarbon feed process for demetalizating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040214A CN1040214A (en) | 1990-03-07 |
| CN1016354B true CN1016354B (en) | 1992-04-22 |
Family
ID=27129291
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87105863 Expired CN1007239B (en) | 1986-08-28 | 1987-08-28 | With sequestrant to the hydrocarbon feed process for demetalizating |
| CN 89104536 Expired CN1016354B (en) | 1986-08-28 | 1989-07-04 | Decalcification of hydrocarbonaceous feedstock using extraction |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87105863 Expired CN1007239B (en) | 1986-08-28 | 1987-08-28 | With sequestrant to the hydrocarbon feed process for demetalizating |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1007239B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE299705T1 (en) * | 2002-04-25 | 2005-08-15 | Molteni & C | ANTIBACTERIAL COMPOSITIONS CONTAINING METALLPHTHALOCYANINE ANALOGS |
| US8658030B2 (en) * | 2009-09-30 | 2014-02-25 | General Electric Company | Method for deasphalting and extracting hydrocarbon oils |
| CN102260524B (en) * | 2010-05-24 | 2013-11-06 | 中国石油天然气股份有限公司 | Chemical precipitation method for decalcification of crude oil |
| CN102876352B (en) * | 2012-09-27 | 2014-06-18 | 岳阳宇翔科技有限公司 | Composite additive for reducing metal ion content of vacuum residues and application of composite additive |
| CN103194257B (en) * | 2013-04-18 | 2015-01-28 | 中国人民解放军空军油料研究所 | Method for removing trace metal from coal-based direct liquefied fraction oil |
| US8961780B1 (en) | 2013-12-16 | 2015-02-24 | Saudi Arabian Oil Company | Methods for recovering organic heteroatom compounds from hydrocarbon feedstocks |
| US9688923B2 (en) | 2014-06-10 | 2017-06-27 | Saudi Arabian Oil Company | Integrated methods for separation and extraction of polynuclear aromatic hydrocarbons, heterocyclic compounds, and organometallic compounds from hydrocarbon feedstocks |
| CN105567308A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Method for reducing calcium content in atmospheric pressure residual oil and method for processing atmospheric pressure residual oil |
| CN105733657B (en) * | 2014-12-10 | 2017-10-17 | 中国石油天然气股份有限公司 | Hydrocarbon oil demetallizing agent and hydrocarbon oil demetallizing method |
| US10752842B2 (en) * | 2015-07-02 | 2020-08-25 | Haldor Topsøe A/S | Demetallization of hydrocarbons |
| CN106905490B (en) * | 2017-02-20 | 2019-01-29 | 东南大学 | A kind of environment-friendly type crude oil metal-chelator and preparation method thereof |
-
1987
- 1987-08-28 CN CN 87105863 patent/CN1007239B/en not_active Expired
-
1989
- 1989-07-04 CN CN 89104536 patent/CN1016354B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1007239B (en) | 1990-03-21 |
| CN87105863A (en) | 1988-03-30 |
| CN1040214A (en) | 1990-03-07 |
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