CN1007239B - With sequestrant to the hydrocarbon feed process for demetalizating - Google Patents
With sequestrant to the hydrocarbon feed process for demetalizatingInfo
- Publication number
- CN1007239B CN1007239B CN 87105863 CN87105863A CN1007239B CN 1007239 B CN1007239 B CN 1007239B CN 87105863 CN87105863 CN 87105863 CN 87105863 A CN87105863 A CN 87105863A CN 1007239 B CN1007239 B CN 1007239B
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- China
- Prior art keywords
- described method
- calcium
- citric acid
- metal
- raw material
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Abstract
The present invention relates to remove metal pollutant, particularly remove the method for calcium from hydrocarbon feed.This method comprises the aqueous solution of raw material and metal chelator, particularly hydroxycarboxylic acid (preferably citric acid, its salt or its mixture), then the metallic aqueous solution is separated from the raw material of taking off metal.
Description
The present invention relates to use hydroxycarboxylic acid, particularly citric acid,, from the solvent-deasphalted oils of calcareous crude oil, heavy hydrocarbon residual oil or crude oil and residual oil, remove the method for calcium as sequestrant.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-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 sequestrant such as hydroxycarboxylic acid, preferably citric acid and salt thereof make the calcium cpd combination, can remove the calcic pollutent effectively from hydrocarbon raw material.
This technology comprises that the aqueous solution that uses sequestrant 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 sequestrant is hydroxycarboxylic acid such as citric acid and tartrate, their salt or its mixture.
One preferably in the embodiment, the aqueous solution for the treatment of demetallated raw material and citric acid or its salt or its mixture closely and mix fully.Metal combines with sequestrant, forms water soluble complex at aqueous phase.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 sequestrant, be preferably hydroxycarboxylic acid, particularly citric acid or its 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, Midway 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 this is included in the design scope of the present invention.
Basic craft course is simple relatively: in first embodiment, need the crude oil of processing or the aqueous solution of residual oil and citric acid or its salt or its mixture, and add a kind of alkali, pH is transferred to more than 2, preferably transfer to 5～9.Calcium combines or chelating with the negatively charged ion of acid rapidly.This calcium/citric acid complex is an ionic, and therefore the aqueous phase at mixture has solvability.Water phase separated and crude oil or hydrocarbon phase are removed water.After the aqueous solution that will contain calcium is removed, obtain not calcareous hydrocarbon raw material.Conventional hydrogen addition technology processing equally be handled and be used to this hydrocarbon raw material 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 can finish above separation, comprise counter-current extraction with any other separation method.
As everyone knows, hydroxycarboxylic acid has high avidity to calcium and other metal ion.As sequestrant, an example commonly used of hydroxycarboxylic acid is citric acid-C
6H
8O
7, molecular weight is 192.12.Be also referred to as 2-hydroxyl-1,2,3-tricarballylic acid, or beta-hydroxy tricarballylic acid.
Citric acid is a kind of in a big class complexing or the multiple tooth chelating ligand of complexed metal ionic.The metal ligand complex compound that these compound formation are highly stable.Citric acid is used as sequestrant to remove trace-metal at present, also uses it always as souring agent and sanitas in food and drink technology.
Citric acid and Ca
+ 2Ion forming complex, this complex compound are stable and can be isolating.But citric acid and salt thereof is other metal ion of complexing in the aqueous solution, but to common in the oil, be generally the as if little or basic not effect of effect of organometallic metal pollutant such as nickel and scherbinaite oil porphyrin.Yet iron is but had certain effect, and it may be effective removing organoiron compound.
The salt of citric acid generally can form by any alkali that adds on the spot in the multiple highly basic, also it can be come out as Crystallization Separation from the aqueous solution in some cases.The general specific ionization sour water of these salt dissolubility is stronger, acidity a little less than.
As previously mentioned, calcium and sequestrant 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 sequestrant 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, but the molar equivalent of citric acid will be limited in 10 or higher.If extraction is carried out under the temperature that improves, for example 180 °F or more than, the molar equivalent of citric acid can be reduced to more than 1 or 1.Temperature is 180 °F preferably.
Embodiment (citric acid)
Laboratory test (result sees following table for details) is that San Joaquin Valley vacuum residuum (93ppm Ca) or crude oil are dissolved in toluene, makes it have suitable viscosity, and mixes with the citric acid solution of specified rate.The preparation of citric acid solution is that an amount of citric acid is dissolved in the deionized water to obtain the specific molar ratio of citric acid to calcium, with ammonium hydroxide its pH is transferred to about 9.The demulsifying agent that in indicated example, has added commodity treatolite L-1562 by name.The mixture of citric acid/oil standing separation after jolting is preferably at room temperature spent the night.Residual oil is analyzed before and after processing to measure the amount of removing of calcium.
Example 1
For the proof citric acid is effective decalcifying agent, carried out the controlled trial of San Joaquin Valley crude oil and vacuum residuum.The table I is pointed out, can remove most calcium with lower citric acid molar equivalent.With the contrast extraction of refinery desalting water, bronsted lowry acids and bases bronsted lowry, its decalcification percentage is lower.
Example 2
Carry out laboratory experiment at room temperature selects to be used to extract the optimum amount of the citric acid of calcium.Fig. 1 shows, when about 22 molar equivalents, the activity of citric acid begins to descend; During about 12.5 molar equivalents, active beginning sharply descends.
Example 3
Extraction temperature is risen to 180 °F, and will increase to duration of contact 5 minutes or longer, to increase the activity of citric acid.The table II points out that the activity of citric acid has improved greatly under this temperature, and it is 1 equivalent that its molar equivalent can be reduced to every mole of calcium.
Example 4
For the dependence of best decalcification effect and citric acid solution pH is described, under the condition of the natural pH of citric acid and pH6, extract.The table III indicates, and the decalcification effect of citric acid when higher pH is much higher.
The table I
San Joaquin extraction agent aqueous solution volume equivalent pH decalcification %
The Valley charging
Crude oil citric acid 50% 25 6 97
Vacuum residuum citric acid 51% 22 6 99
Crude oil desalting water 51%-6 19
Vacuum residuum sour water 66%-2 7
Vacuum residuum NH
4OH 75%-9 9
Room temperature
The table II
ID equivalent pH time-temperature decalcification %
180 99 of B7654-37 5 6.0 10 minutes
180 93 of B7654-36 12.5 6.0 5 minutes
180 97 of B7654-39 1.25 6.0 10 minutes
The table III
Citric acid is to the decalcification of SJV vacuum residuum under condition of different pH
Molar equivalent pH decalcification %
2.2 1.1 37
22 1.8 30
156 1.5 99
22 6.1 99
222 6.1 99
Claims (14)
1, a kind of hydrocarbon feed is removed the method for II family metal, this method comprises:
With the aqueous solution of a said hydrocarbon raw material and a metal chelator, sequestrant is selected from and comprises hydroxycarboxylic acid, hydroxycarboxylate and its mixture;
From the aqueous solution, isolate the hydrocarbon raw material that has removed II family metal substantially.
2, according to the described method of claim 1, metal wherein is a calcium.
3, according to the described method of claim 1, metal wherein is the non-porphyrin compound of organo-metallic keyed jointing.
4, according to the described method of claim 3, compound wherein is the compound of calcium.
5, according to the described method of claim 1, wherein said metal chelator comprises citric acid, Citrate trianion or their mixture.
6, according to claim 1 or 5 described methods, wherein more than the pH regulator to 2 of mixing step or 2.
7, according to claim 1 or 5 described methods, wherein more than the pH regulator to 5 of mixing step or 5.
8, according to the described method of claim 7, temperature wherein is an envrionment temperature.
9, described according to Claim 8 method, wherein citric acid is more than 10 or 10 to the molar weight of calcium.
10, according to the described method of claim 7, temperature wherein is about more than 180 °F or 180 °F.
11, according to the described method of claim 7, temperature wherein is about 300 °F.
12, according to the described method of claim 11, wherein citric acid is more than 1 or 1 to the molar equivalent of calcium.
13, according to the described method of claim 1, its separation is to carry out with conventional demineralising process or with counter-current extraction.
14, according to the described method of claim 1, wherein hydrocarbon feed is selected from crude oil, normal pressure or vacuum residuum, shale oil, liquefaction coal and tar sand oils.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/901,341 US4778589A (en) | 1986-08-28 | 1986-08-28 | Decalcification of hydrocarbonaceous feedstocks using citric acid and salts thereof |
| US06/901,342 US4778591A (en) | 1986-08-28 | 1986-08-28 | Demetalation of hydrocarbonaceous feedstocks using carbonic acid and salts thereof |
| US901,341 | 1986-08-28 | ||
| US901,342 | 1986-08-28 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89104536 Division CN1016354B (en) | 1986-08-28 | 1989-07-04 | Decalcification of hydrocarbonaceous feedstock using extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87105863A CN87105863A (en) | 1988-03-30 |
| CN1007239B true CN1007239B (en) | 1990-03-21 |
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 After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89104536 Expired CN1016354B (en) | 1986-08-28 | 1989-07-04 | Decalcification of hydrocarbonaceous feedstock using extraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1007239B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1356813B1 (en) * | 2002-04-25 | 2005-07-20 | L. MOLTENI & C. DEI FRATELLI ALITTI SOCIETA' DI ESERCIZIO SOCIETA' PER AZIONI | Antibacterial compositions comprising metal phthalocyanine analogues |
| 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 removing calcium from 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 | A kind of demetallated method of hydrocarbon oil metal removal agent and hydrocarbon ils |
| EP3317381A1 (en) * | 2015-07-02 | 2018-05-09 | 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 |
|---|---|
| CN1040214A (en) | 1990-03-07 |
| CN1016354B (en) | 1992-04-22 |
| CN87105863A (en) | 1988-03-30 |
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