CN101314728B - Deferrization method for hydrocarbons raw oil - Google Patents
Deferrization method for hydrocarbons raw oil Download PDFInfo
- Publication number
- CN101314728B CN101314728B CN2007100998588A CN200710099858A CN101314728B CN 101314728 B CN101314728 B CN 101314728B CN 2007100998588 A CN2007100998588 A CN 2007100998588A CN 200710099858 A CN200710099858 A CN 200710099858A CN 101314728 B CN101314728 B CN 101314728B
- Authority
- CN
- China
- Prior art keywords
- acid
- iron
- deferrization
- oil
- deferrization 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.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 receives people's attention.Polluting iron on the catalytic cracking equilibrium catalyst increases the decline that shows catalyst activity reduction and slag oil cracking ability that has a strong impact on that produces, and the SOx discharging increases and the regenerated catalyst carbon residue raises (as far as 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 (like iron naphthenate) and complex compound (like iron porphyrin) again; Pollute iron and generally can be divided into two types, one type 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 through 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 are main with decalcification, have certain deferrization effect simultaneously.US4778592 and US4789463 utilize aminocarboxylic acid and hydroxycarboxylic acid to remove the iron in the hydrocarbon ils respectively; US5078858 has introduced a kind of chelating property acid such as oxalic acid, Hydrocerol A 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 process method that two-stage removes iron in the hydro carbons through 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.
Said deferrization agent comprises A, two types of materials of B, 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 XPA.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, Hydrocerol A, oxysuccinic acid, tartrate, heptonic acid etc.; Water-soluble toxilic acid, XPA can be homopolymer or multipolymer, the ROHM 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 volatile caustic.The preferred quadrol of straight chain alkyl amine, tn, tetramethylenediamine, pentamethylene diamine, diethyl ethylenediamine; Cycloalkyl amine preferably encircles amine; The preferred Monoethanolamine MEA BASF of hydramine, diethylolamine and trolamine; The preferred diethylenetriamine of polyethylene polyamine, triethylene tetramine and TEPA.
The mol ratio of category-A material and category-B material is 0.1～9 in the said deferrization agent, preferred 0.5～5.
Said 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 not special restriction of the concentration of the deferrization agent aqueous solution, 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 raw oils.Usually iron level is generally lower in the distillate, but when the distillate acid number is higher when causing corrosion, iron level is raise, and before the entering hydrogenation unit, need iron 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 that the high more profit two of temperature mixes mutually is more abundant, 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 the normal static mixer that uses also can be other suitable hybrid mode in the industry.
After the reaction, make hydrocarbon feed oil and aqueous phase separation, normal standing sedimentation or the electric desalting method used also can be used methods such as spinning, counter-current extraction in the industry.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 said 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 through 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, Hydrocerol A, EDTA 1:1:1 preparation in molar ratio) with ammoniacal liquor, raw 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 Hydrocerol A, EDTA, toxilic acid, raw 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:
With three kinds of different organic acids (ROHM, Hydrocerol A and oxalic acid) and quadrol in molar ratio 2:1 be hybridly prepared into deferrization agent, investigate the deferrization effect, raw oil is the crude oil of iron content 32ppm, the result is as shown in table 2.
Comparative Examples 4～6:
Compare the deferrization effect of three kinds of different organic acids (ROHM, Hydrocerol A and oxalic acid), raw 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:
Hydrocerol A and the TEPA deferrization agent deferrization effect of 3:1 mixed preparing in molar ratio under the more different temperature of reaction, raw 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 Hydrocerol A and the dissimilar nitrogenous compound deferrization agent deferrization effect of 3:1 mixed preparing in molar ratio, raw oil is the crude oil of iron content 50ppm, and the result is as shown in table 4.
Table 4 Hydrocerol A and dissimilar nitrogenous compound blended deferrization effect
Claims (9)
1. hydrocarbons raw oil deferrization agent, said deferrization agent comprises A, two types of materials of B, and wherein, the category-A material is selected from the polycarboxylic acid of carbon number 2～6, the hydroxycarboxylic acid of carbon number 2～8 and in the water-soluble acrylic polymer one or more; The category-B material is selected from ammonia; Inorganic or organic ammonium compounds; In the polyethylene polyamine of the straight chain alkyl amine of carbon number 2～8, Cycloalkyl amine or hydramine and molecular weight 100～5000 one or more; The mol ratio of category-A material and category-B material is 0.1～9 in the said deferrization agent; Polycarboxylic acid is saturated or undersaturated di-carboxylic acid or tribasic carboxylic acid, and the hydroxyl value of hydroxycarboxylic acid is 1～6, and carboxyl number is 1～3; The ammonium compounds is selected from one or more in volatile caustic, volatile salt, bicarbonate of ammonia, ammonium hydroxide and the butyl volatile caustic; Straight chain alkyl amine is selected from one or more in quadrol, tn, tetramethylenediamine, pentamethylene diamine and the diethyl ethylenediamine, and hydramine is selected from one or more in Monoethanolamine MEA BASF, diethylolamine, the trolamine, and polyethylene polyamine is selected from one or more in diethylenetriamine, triethylene tetramine and the TEPA.
2. according to the described deferrization agent of claim 1, 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.
3. according to the described deferrization agent of claim 1, it is characterized in that hydroxycarboxylic acid is selected from one or more in glyconic acid, Hydrocerol A, oxysuccinic acid, tartrate and the heptonic acid.
4. according to the described deferrization agent of claim 1, it is characterized in that the molecular weight of water-soluble acrylic polymer is 1000～50000.
5. according to the described deferrization agent of claim 1, it is characterized in that Cycloalkyl amine is a hexahydroaniline.
6. according to the described deferrization agent of claim 1, it is characterized in that the mol ratio of category-A material and category-B material is 0.5～5 in the said deferrization agent.
7. the method for a hydrocarbons raw oil deferrization may further comprise the steps:
(1) with the said deferrization agent aqueous solution of one of ferruginous hydrocarbons raw oil and claim 1～6 thorough mixing and reaction;
(2) oil-water mixture is separated, the most of iron in the hydrocarbons raw oil is removed;
Said deferrization agent pH value of water solution is 2～10.
8. according to the described method of claim 7, it is characterized in that temperature of reaction is 25～150 ℃.
9. according to the described method of claim 7, it is characterized in that temperature of reaction is 50～120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100998588A CN101314728B (en) | 2007-05-31 | 2007-05-31 | Deferrization method for hydrocarbons raw oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100998588A CN101314728B (en) | 2007-05-31 | 2007-05-31 | Deferrization method for hydrocarbons raw oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101314728A CN101314728A (en) | 2008-12-03 |
| CN101314728B true CN101314728B (en) | 2012-08-01 |
Family
ID=40105878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100998588A Active CN101314728B (en) | 2007-05-31 | 2007-05-31 | Deferrization method for hydrocarbons raw oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101314728B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9790438B2 (en) * | 2009-09-21 | 2017-10-17 | Ecolab Usa Inc. | 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 for 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 |
| CN103571523B (en) * | 2012-08-02 | 2015-06-03 | 中国石油天然气股份有限公司 | Crude oil complexing decalcifying agent composition and application 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431277A (en) * | 2002-01-10 | 2003-07-23 | 中国石油化工股份有限公司 | Demetallization agent for hy drocarbon oil and its operation method |
| CN1760340A (en) * | 2004-10-13 | 2006-04-19 | 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 |
-
2007
- 2007-05-31 CN CN2007100998588A patent/CN101314728B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431277A (en) * | 2002-01-10 | 2003-07-23 | 中国石油化工股份有限公司 | Demetallization agent for hy drocarbon oil and its operation method |
| CN1760340A (en) * | 2004-10-13 | 2006-04-19 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101314728A (en) | 2008-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101314728B (en) | Deferrization method for hydrocarbons raw oil | |
| JP5893638B2 (en) | Additive composition and method for removing hydrogen sulfide in hydrocarbon streams | |
| AU2010245644B2 (en) | Method of scavenging hydrogen sulfide from hydrocarbon stream | |
| EP3317383B1 (en) | Hydrogen sulfide scavenging additive compositions, and medium comprising the same | |
| KR101916207B1 (en) | Process for reducing the total acid number in refinery feedstocks | |
| CN101215477A (en) | Heavy metal removing agent for crude oil | |
| WO2013169752A1 (en) | Multi-component scavenging systems | |
| CN109181747B (en) | Eutectic solvent for fuel oil extraction denitrification and use method thereof | |
| WO2017044248A1 (en) | Hydrogen sulfide scavengers | |
| AU2014415242B2 (en) | Process for removing metal naphthenate from crude hydrocarbon mixtures | |
| CN112552952B (en) | Crude oil decalcifying agent and preparation method and application thereof | |
| CN101967389A (en) | Denitrifying agent for directly removing basic nitrogen compound from shale oil | |
| CN103003395A (en) | Improved method of removing hydrogen sulfide | |
| AU2016384296A1 (en) | Hydrogen sulfide scavenging additive composition and method of use thereof | |
| CN103242891A (en) | Decalcifying agent for high-acid heavy crude oil | |
| CN101469279B (en) | Method for removing nickel and vanadium in hydrocarbon raw material | |
| CN1191326C (en) | Demetallization agent for hy drocarbon oil and its operation method | |
| CN101402878B (en) | Method for removing nickel vanadium in crude oil with microwave chemical method | |
| CN103228768B (en) | For making the minimized strong basicity amine of corrosive nature in the system tending to formation corrosive salt | |
| CN102533319A (en) | Method for removing alkaline nitride in oil product | |
| CN110484315B (en) | Gasoline detergent and preparation method thereof | |
| CN111471485B (en) | Method for removing sodium salt from hydrocarbon oil | |
| RU2641910C1 (en) | Process of cleaning hydrocarbon media from h2s and/or mercaptanes | |
| CN102443422A (en) | Method for removing metal in hydrocarbon oil | |
| CN100355863C (en) | Composite emulsion-breaking decalcifying agent for hydrocarbon oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |