CN101314728A - Deferrization method for hydrocarbons raw oil - Google Patents
Deferrization method for hydrocarbons raw oil Download PDFInfo
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- CN101314728A CN101314728A CNA2007100998588A CN200710099858A CN101314728A CN 101314728 A CN101314728 A CN 101314728A CN A2007100998588 A CNA2007100998588 A CN A2007100998588A CN 200710099858 A CN200710099858 A CN 200710099858A CN 101314728 A CN101314728 A CN 101314728A
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Abstract
The invention provides a method for removing iron from hydrocarbon feed oil, which comprises the following steps: (1) fully mixing iron-containing hydrocarbon feed oil with iron removing agent solution and reacting; and (2) separating oil-water mixture to remove the majority of iron in hydrocarbon feed oil. The iron removing agent contains a component A and a component B, wherein the component A is selected from one or more of C2 to C6 polycarboxylic acids, C2 to C8 hydroxycarboxylic acids and water-soluble maleic acid and acrylic acid polymer; and the component B is selected from one or more of ammonia, inorganic or organic ammonium compound, C2 to C8 linear alkyl-amines, cycloalkyl amines or alcohol amines, and polyethylene-polyamines with molecular weight of 100 to 5,000. The iron removing agent prepared from nitrogen-containing compound and organic acid by mixing has higher iron ion chelating ability and can achieve better iron removal effect in shorter reaction time and at lower reaction temperature.
Description
Technical field
The present invention relates to from hydrocarbons raw oil, remove the method for iron.
Background technology
In recent years, along with the continuous increase of sulphur-bearing crude and high-acid crude oil and residual oil amount of finish, the iron poisoning of catalytic cracking catalyst more and more is subject to people's attention.Pollute iron on the catalytic cracking equilibrium catalyst and increase the decline that shows catalyst activity reduction and slag oil cracking ability that has a strong impact on that produces, the SOx discharging increases and the regenerated catalyst carbon residue raises (for partial regeneration) degradation under the catalyzer apparent bulk density.In residual hydrogenation process and fraction oil hydrogenation refining process, the iron ion in distillate and the residual oil causes catalyst activity to reduce even inactivation.
Iron both existed with suspension inorganics form in oil and cut thereof, can exist with the form of oil soluble salt (as iron naphthenate) and complex compound (as iron porphyrin) again, pollute iron and generally can be divided into two classes, a class mainly is the inorganic iron that derives from pipeline, storage tank and other hardware devices; Another kind of mainly is the organic iron that derives from charging or generated by other corrosive component corrosion in naphthenic acid and the charging.The iron that is present in the crude oil is called original iron, and a considerable amount of iron is corrosion owing to the pipeline that contacts with oil, storage tank and processing units import be called process iron.Content that it is generally acknowledged process iron is greater than original iron.The method of conventional electric desalting washing can remove inorganic iron, must make it be converted into water-soluble iron by interpolation chemical agent method for the oil soluble iron rule and remove then.
To removing of iron in the crude oil, existing many reports in patent and the document mainly are to use various carboxylic acids and salt thereof both at home and abroad.Beautiful US4853109, US4988433 introduced respectively adopt di-carboxylic acid ,-first carboxylic acid removes the non-porphyrin class calcium of organic constraint in the hydro carbons, the method for iron.CN1036981 has introduced and has adopted di-carboxylic acid to remove the non-porphyrin class iron of organic constraint in the hydrocarbon feed, the method for calcium.CN1521236, CN1521237 have introduced respectively and have adopted vinylformic acid sulfonic acid copolymer, acrylic acrylate multipolymer to remove the method for metal in the hydrocarbon feed.CN1611571, CN1693424 have introduced the method that removes metal in the hydrocarbon feed with hydroxyquinoline, methyl ethyl diketone respectively.These methods have certain deferrization effect simultaneously based on decalcification.US4778592 and US4789463 utilize aminocarboxylic acid and hydroxycarboxylic acid to remove iron in the hydrocarbon ils respectively; US5078858 has introduced a kind of chelating acid such as oxalic acid, citric acid are dissolved in and has added the method that hydrocarbon ils reacts deferrization in the organic solvent again; US5080779 has introduced a kind of employing and has carried out the processing method that two-stage removes iron in the hydro carbons by sequestrants such as EDTA.
Summary of the invention
The invention provides the method for iron in a kind of effective elimination hydrocarbons raw oil.
Method provided by the invention may further comprise the steps:
(1) with ferruginous hydrocarbons raw oil and deferrization agent aqueous solution thorough mixing and reaction,
(2) oil-water mixture is separated, the most of iron in the hydrocarbons raw oil is removed.
Described deferrization agent comprises A, B two class materials, and wherein, category-A is an organic acid, is selected from the polycarboxylic acid of carbon number 2～6, one or more in the hydroxycarboxylic acid of carbon number 2～8 and water-soluble toxilic acid, the acrylate copolymer.Wherein polycarboxylic acid can be a saturated acid, also can be unsaturated acid, can be di-carboxylic acid or tribasic carboxylic acid, preferred toxilic acid, fumaric acid, oxalic acid, propanedioic acid, Succinic Acid etc.; The hydroxyl value of hydroxycarboxylic acid can be 1～6, and carboxyl number can be 1～3, preferred glyconic acid, citric acid, oxysuccinic acid, tartrate, heptonic acid etc.; Water-soluble toxilic acid, acrylate copolymer can be homopolymer or multipolymer, the polyacrylic acid of preferred molecular weight 1000～50000.The category-B material is a nitrogenous compound, is selected from ammonia, inorganic or organic ammonium compounds, the straight chain alkyl amine of carbon number 2～8, Cycloalkyl amine or hydramine, and in the polyethylene polyamine of molecular weight 100～5000 one or more.Wherein, one or more mixture wherein such as ammonium compounds preferably ammonium hydroxide, volatile salt, bicarbonate of ammonia, ammonium hydroxide, butyl ammonium hydroxide.The preferred quadrol of straight chain alkyl amine, propylene diamine, butanediamine, pentamethylene diamine, diethyl ethylenediamine; Cycloalkyl amine preferably encircles amine; The preferred Monoethanolamine MEA BASF of hydramine, diethanolamine and trolamine; The preferred diethylenetriamine of polyethylene polyamine, triethylene tetramine and tetraethylene pentamine.
The mol ratio of category-A material and category-B material is 0.1～9 in the described deferrization agent, preferred 0.5～5.
Described deferrization agent pH value of aqueous solution is 2～10, preferred 2～9.Under suitable pH value, acid ion and ammonium radical ion can reach best dissociated state, fully act on iron ion.And under suitable pH value, oil water interfacial tension is less, and the iron ion in the oil phase is easier to touch the acid ion of aqueous phase and complexing or chelating with it rapidly.
The concentration of the deferrization agent aqueous solution is not particularly limited, and general nothing is separated and gets final product.
Hydrocarbons raw oil can be crude oil, atmospheric residue, vacuum residuum, atmospheric distillate, vacuum distillate, deasphalted oil, shale oil, liquefaction coal and oil-sand cut, often contains a certain amount of iron in these stock oils.Usually iron level is generally lower in the distillate, but when the distillate acid number is higher when causing corrosion, also can make the iron level rising, entering before the hydrogenation unit, iron need be removed to avoid that catalyzer is caused disadvantageous effect.Iron level is 1ppm when above in hydrocarbon feed oil, and the method for the invention can reach good deferrization effect.
When hydrocarbons raw oil and the reaction of deferrization agent aqueous solution,, can fully react with interior at 1min usually because the effect of deferrization agent and iron ion is very strong.Reaction times can be set at 0.1s to 2h, and optimum reacting time is 5s～5min.The method of the invention can be issued to good deferrization effect in lower temperature of reaction, but the high more profit two-phase mixing of temperature is abundant more, speed of response is fast more.Therefore temperature of reaction can be set at 25～150 ℃, is preferably 50～120 ℃.
The hybrid mode of the hydrocarbons raw oil and the deferrization agent aqueous solution has multiple choices, and industrial normal use static mixer also can be other suitable hybrid mode.
After the reaction, make hydrocarbon feed oil and aqueous phase separation, industrial normal use standing sedimentation or electric desalting method also can be used methods such as centrifugation, counter-current extraction.Suitable oil-water separation method can make W/O content meet the requirement of further processing.
The present invention adopts the deferrization agent that nitrogenous compound and organic acid mixed preparing are formed, and has stronger iron ion sequestering power, can be issued to better deferrization effect in the reaction times and the lower temperature of reaction of lacking.
Embodiment
Deferrization agent (the described deferrization agent of this patent is an organic acid and to add in the entry mixed dissolution formulated for the nitrogenous compound) aqueous solution of getting q.s mixes with the iron-bearing material oil that is preheating to 60～120 ℃, mixed 30 seconds with electric mixer, adopt static electric field that profit is fully separated.Analyze iron level in the final oil by ICP (inductively coupled plasma atomic emission spectrum).
Embodiment 1:
Be made into deferrization agent (carboxylic acid and ammonia mol ratio are 1: 1) with mixing acid (toxilic acid, citric acid, EDTA preparation in 1: 1: 1 in molar ratio) with ammoniacal liquor, stock oil is the crude oil of iron content 41ppm, and the result is as shown in table 1.
Comparative Examples 1～3:
Compare three kinds of deferrization effects that carboxylic acid is citric acid, EDTA, toxilic acid, stock oil is the crude oil of iron content 41ppm, and the result is as shown in table 1.
The deferrization effect of the different deferrization agents of table 1 relatively
Embodiment 2～4:
Be hybridly prepared into deferrization agent in 2: 1 in molar ratio with three kinds of different organic acids (polyacrylic acid, citric acid and oxalic acid) and quadrol, investigate the deferrization effect, stock oil is the crude oil of iron content 32ppm, and the result is as shown in table 2.
Comparative Examples 4～6:
Compare the deferrization effect of three kinds of different organic acids (polyacrylic acid, citric acid and oxalic acid), stock oil is the crude oil of iron content 32ppm, and the result is as shown in table 2.
Table 2 different organic acids and quadrol mixing solutions deferrization effect
Embodiment 5～7:
The deferrization agent deferrization effect of 3: 1 in molar ratio mixed preparing of citric acid and tetraethylene pentamine under the more different temperature of reaction, stock oil is the coker gas oil of iron content 29ppm, the result is as shown in table 3.
Under the table 3 differential responses temperature to the deferrization effect of coker gas oil
Embodiment 8～10:
Compare the deferrization agent deferrization effect of citric acid and 3: 1 in molar ratio mixed preparing of dissimilar nitrogenous compound, stock oil is the crude oil of iron content 50ppm, and the result is as shown in table 4.
Table 4 citric acid and dissimilar nitrogenous compound blended deferrization effect
Claims (15)
1. the method for a hydrocarbons raw oil deferrization may further comprise the steps:
(1) with ferruginous hydrocarbons raw oil and deferrization agent aqueous solution thorough mixing and reaction;
(2) oil-water mixture is separated, the most of iron in the hydrocarbons raw oil is removed;
Described deferrization agent comprises A, B two class materials, and wherein, the category-A material is selected from the polycarboxylic acid of carbon number 2～6, one or more in the hydroxycarboxylic acid of carbon number 2～8 and water-soluble toxilic acid, the acrylate copolymer; The category-B material is selected from ammonia, inorganic or organic ammonium compounds, one or more in the polyethylene polyamine of the straight chain alkyl amine of carbon number 2～8, Cycloalkyl amine or hydramine and molecular weight 100～5000.
2. in accordance with the method for claim 1, it is characterized in that polycarboxylic acid is saturated or undersaturated di-carboxylic acid or tribasic carboxylic acid.
3. according to claim 1 or 2 described methods, it is characterized in that polycarboxylic acid is selected from one or more in toxilic acid, fumaric acid, oxalic acid, propanedioic acid and the Succinic Acid.
4. in accordance with the method for claim 1, it is characterized in that the hydroxyl value of hydroxycarboxylic acid is 1～6, carboxyl number is 1～3.
5. according to claim 1 or 4 described methods, it is characterized in that hydroxycarboxylic acid is selected from one or more in glyconic acid, citric acid, oxysuccinic acid, tartrate and the heptonic acid.
6. in accordance with the method for claim 1, it is characterized in that the molecular weight of water-soluble acrylic polymer is 1000～50000.
7. in accordance with the method for claim 1, it is characterized in that the ammonium compounds is selected from one or more in ammonium hydroxide, volatile salt, bicarbonate of ammonia, ammonium hydroxide and the butyl ammonium hydroxide.
8. in accordance with the method for claim 1, it is characterized in that straight chain alkyl amine is selected from one or more in quadrol, propylene diamine, butanediamine, pentamethylene diamine and the diethyl ethylenediamine.
9. in accordance with the method for claim 1, it is characterized in that Cycloalkyl amine preferably encircles amine.
10. in accordance with the method for claim 1, it is characterized in that hydramine is selected from one or more in Monoethanolamine MEA BASF, diethanolamine, the trolamine.
11. in accordance with the method for claim 1, it is characterized in that polyethylene polyamine is selected from one or more in diethylenetriamine, triethylene tetramine and the tetraethylene pentamine.
12. in accordance with the method for claim 1, it is characterized in that the mol ratio of category-A material and category-B material is 0.1～9 in the described deferrization agent.
13. in accordance with the method for claim 1, it is characterized in that the mol ratio of category-A material and category-B material is 0.5～5 in the described deferrization agent.
14. in accordance with the method for claim 1, it is characterized in that temperature of reaction is 25～150 ℃.
15. in accordance with the method for claim 1, it is characterized in that temperature of reaction is 50～120 ℃.
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| CN2007100998588A CN101314728B (en) | 2007-05-31 | 2007-05-31 | Deferrization method for hydrocarbons raw oil |
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| CN2007100998588A CN101314728B (en) | 2007-05-31 | 2007-05-31 | Deferrization method for hydrocarbons raw oil |
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| CN101314728B CN101314728B (en) | 2012-08-01 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399580A (en) * | 2010-09-15 | 2012-04-04 | 中国石油天然气股份有限公司 | Demetalization method by hydrocarbon oil |
| CN102753657A (en) * | 2009-09-21 | 2012-10-24 | 纳尔科公司 | Improved method for removing metals and amines from crude oil |
| CN103031202A (en) * | 2011-09-29 | 2013-04-10 | 南昌洋浦天然香料香精有限公司 | Method for deironing and purifying oil of litsea cubeba |
| CN103031201A (en) * | 2011-09-29 | 2013-04-10 | 南昌洋浦天然香料香精有限公司 | Method for iron removal and purification of citionella oil |
| CN103571523A (en) * | 2012-08-02 | 2014-02-12 | 中国石油天然气股份有限公司 | Crude oil complex decalcifying agent composition and application thereof |
| CN106398750A (en) * | 2016-10-25 | 2017-02-15 | 徐文忠 | Crude oil desalting agent and preparation method thereof |
| CN109294551A (en) * | 2018-10-18 | 2019-02-01 | 顺泰能源科技发展有限公司 | A kind of cleaning low damage agent of molecular cluster and its application |
| CN111662746A (en) * | 2019-03-07 | 2020-09-15 | 中国科学院过程工程研究所 | Method for synchronously demetallizing, desalting and dehydrating coal tar |
| CN114433205A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of bulk phase hydrocracking catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1191326C (en) * | 2002-01-10 | 2005-03-02 | 中国石油化工股份有限公司 | Demetallization agent for hy drocarbon oil and its operation method |
| CN1323138C (en) * | 2004-10-13 | 2007-06-27 | 中国石油化工股份有限公司 | Method for removing metal from hydrocarbon oils through use of homopolymer of carboxylic acid |
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- 2007-05-31 CN CN2007100998588A patent/CN101314728B/en active Active
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102753657A (en) * | 2009-09-21 | 2012-10-24 | 纳尔科公司 | Improved method for removing metals and amines from crude oil |
| CN102399580B (en) * | 2010-09-15 | 2014-06-04 | 中国石油天然气股份有限公司 | Demetalization method by hydrocarbon oil |
| CN102399580A (en) * | 2010-09-15 | 2012-04-04 | 中国石油天然气股份有限公司 | Demetalization method by hydrocarbon oil |
| CN103031202B (en) * | 2011-09-29 | 2015-05-13 | 南昌洋浦天然香料香精有限公司 | Method for deironing and purifying oil of litsea cubeba |
| CN103031201A (en) * | 2011-09-29 | 2013-04-10 | 南昌洋浦天然香料香精有限公司 | Method for iron removal and purification of citionella oil |
| CN103031202A (en) * | 2011-09-29 | 2013-04-10 | 南昌洋浦天然香料香精有限公司 | Method for deironing and purifying oil of litsea cubeba |
| CN103571523A (en) * | 2012-08-02 | 2014-02-12 | 中国石油天然气股份有限公司 | Crude oil complex decalcifying agent composition and application thereof |
| CN103571523B (en) * | 2012-08-02 | 2015-06-03 | 中国石油天然气股份有限公司 | Crude oil complex decalcifying agent composition and application thereof |
| CN106398750A (en) * | 2016-10-25 | 2017-02-15 | 徐文忠 | Crude oil desalting agent and preparation method thereof |
| CN106398750B (en) * | 2016-10-25 | 2018-10-02 | 徐文忠 | A kind of crude oil desalting agent and preparation method thereof |
| CN109294551A (en) * | 2018-10-18 | 2019-02-01 | 顺泰能源科技发展有限公司 | A kind of cleaning low damage agent of molecular cluster and its application |
| CN111662746A (en) * | 2019-03-07 | 2020-09-15 | 中国科学院过程工程研究所 | Method for synchronously demetallizing, desalting and dehydrating coal tar |
| CN114433205A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of bulk phase hydrocracking catalyst |
| CN114433205B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | Preparation method of bulk phase hydrocracking catalyst |
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| CN101314728B (en) | 2012-08-01 |
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