CN112322340A - Crude oil iron metal remover and preparation method thereof - Google Patents
Crude oil iron metal remover and preparation method thereof Download PDFInfo
- Publication number
- CN112322340A CN112322340A CN202011118114.8A CN202011118114A CN112322340A CN 112322340 A CN112322340 A CN 112322340A CN 202011118114 A CN202011118114 A CN 202011118114A CN 112322340 A CN112322340 A CN 112322340A
- Authority
- CN
- China
- Prior art keywords
- crude oil
- iron
- iron metal
- agent
- chelating 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/06—Metal salts, or metal salts deposited on a carrier
- C10G29/10—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a crude oil iron metal remover and a preparation method thereof, and relates to the preparation of the crude oil iron metal remover, wherein the crude oil iron metal remover has better removability to iron metal in crude oil and has certain removal effect to metal elements such as nickel, vanadium, calcium and the like; the iron metal remover consists of an iron chelating agent, an organic acid, carboxylate and Schiff base; the iron chelating agent is prepared by synthesizing sulfur dioxide, p-benzoquinone, sodium sulfamate, 2-acrylamido-2-methylpropanesulfonic acid, an amine compound and formamide, and has a structural general formula as follows:
Description
Technical Field
The invention relates to a crude oil iron metal remover and a preparation method thereof, belonging to the field of crude oil iron metal remover preparation.
Background
Crude oil needs to be desalted and pretreated before refining, and at present, the crude oil electric desalting technology can only remove salts, hydrophilic suspended solids and filterable solid particles dissolved in water through crude oil dehydration. Most metals such as calcium, magnesium, iron and the like in the crude oil exist in the forms of naphthenate, phenate and the like, only a small part of metals exist in the forms of water-soluble inorganic salts, and nickel and vanadium exist in the forms of porphyrin compounds or asphaltene mostly. In the heavy oil hydrocracking, iron compounds are deposited on a catalyst bed layer to block a bed layer channel, so that the normal operation of the hydrocracking process is influenced; calcium, magnesium and other elements can also cause the permanent inactivation of the catalytic cracking catalyst, and iron can reduce the selectivity of the catalyst; calcium, magnesium, iron and other elements are also main components of the oil scale of the device and ash in the delayed coking petroleum coke. At present, the technology for removing iron metal from crude oil mainly comprises a membrane separation method, a catalytic hydrogenation method, a chemical method, an ultrasonic removal method, a chelation removal method and the like. The chelation removal method has wide application because of simple process flow, low cost and good removal effect. The existing iron chelating agents mainly comprise inorganic acids, carboxylic acids, organic polybasic phosphonic acids and the like. The chelating ability of the inorganic chelating agent is greatly influenced by temperature and pH value, and is generally suitable for alkaline conditions; the carboxylic acid chelating agent can chelate iron ions under the alkalescent condition, and has weaker chelating capacity in an acidic medium; the preparation process of the organic polybasic phosphonic acid relates to formaldehyde, and the chelating product contains a large amount of phosphorus and is easy to cause great influence on the environment.
Chinese patent CN201410681560.8 provides a ferrous ion treating agent for oil recovery, which mainly comprises an oxidant, a chelating agent, an auxiliary agent and water, and has a good effect of removing ferrous ions, but the chelating effect of the chelating agent under an acidic condition may not be good; chinese patent CN201510445715.2 provides a hydrocarbon oil deferrization agent and a hydrocarbon oil deferrization method, which mainly treat iron sulfide in crude oil, but have poor capability of removing oil-soluble iron compounds. Therefore, the crude oil iron metal remover disclosed by the invention is environment-friendly, good in removing effect, mild in use condition and wide in application range, and meets the development requirements of the petroleum industry.
Disclosure of Invention
The invention provides a crude oil iron metal remover and a preparation method thereof aiming at the defects in the prior art, and aims to solve the problems in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the iron metal chelating agent is synthesized by sulfur dioxide, p-benzoquinone, sodium sulfamate, 2-acrylamido-2-methylpropanesulfonic acid, an amine compound and formamide.
A crude oil iron metal remover is prepared by uniformly mixing an iron chelating agent, an organic acid, carboxylate, Schiff base and deionized water at room temperature; the crude oil iron metal remover consists of the following raw materials in percentage by mass: 45-55% of iron chelating agent, 10-15% of organic acid, 10-15% of carboxylate and 20-30% of Schiff base;
further, the iron chelator has the following structural formula:
wherein the number n of repeating units is 1 to 4.
Further, the preparation steps of the iron chelating agent are as follows:
(1) mixing sulfur dioxide, p-benzoquinone and sodium sulfamate, and then dropwise adding a 2-acrylamide-2-methylpropanesulfonic acid solution into the mixed solution;
(2) after the exothermic reaction is finished, adding an amine compound and metallic sodium and stirring;
(3) adding formamide and aluminum chloride, stirring, and cooling to obtain the iron chelating agent.
Further, the mass ratio of the sulfur dioxide, the p-benzoquinone, the sodium sulfamate, the 2-acrylamido-2-methylpropanesulfonic acid, the amine compound, the metal sodium, the formamide and the aluminum chloride is 1: 0.5-1: 0.5-1: 1.5-2.5: 2-3: 0.2-0.6: 1.2-1.5: 0.1-0.2.
Further, the dropping speed in the step (1) is 1.5-2mL/min, and the reaction temperature of dropping the 2-acrylamido-2-methylpropanesulfonic acid solution is 35-40 ℃.
Further, the stirring time in the step (2) is 1-1.5 h.
Further, the reaction temperature in the step (3) is 70-90 ℃, the reaction pressure is 1.05-1.1MPa, and the reaction time is 3-3.5 h.
Further, in the step (2), the amine compound is any one or more of ethylenediamine, butanediamine, hexanediamine and octanediamine.
Further, the organic acid is any one or more of salicylic acid, glycolic acid and sulfamic acid.
Further, the carboxylate is any one or more of zinc acetate, sodium tartrate and sodium alginate; the Schiff base is one or two of p-amino diphenylimine and 2-hydroxy-1-naphthalene formaldehyde shrinkage o-phenylenediamine.
The iron remover is prepared by compounding organic acid, carboxylate and Schiff base, so that the chelation condition is optimized, functional groups such as carboxyl, amino and the like are further introduced, and the chelation effect is improved.
The carboxylate is adopted to have the following functions: under acidic conditions, the carboxyl group is not dissociated into oxygen anions, so that the complexing ability is weak and the carboxyl group is not suitable for being applied in an acidic medium. The carboxylate solution is alkaline, so that the acidic petroleum deferrization environment can be neutralized, and the complexing capability of the chelating agent is improved; sodium ions and zinc ions are continuously provided, the coordination activity is maintained, and the efficiency reduction of the chelating agent due to the interference of the impurity elements is prevented; the introduced carboxyl oxygen also has certain auxiliary complexation effect on metal ions, and the complexation capability is increased.
The Schiff base has the following functions: after chelating metal iron ions, the Schiff base can form a multi-coordination complex, and the immobilized Schiff base enhances the stability of the complex, increases the stability of the carrier and increases the stability of the iron ion complex.
Carboxyl oxygen atoms have the capacity of forming coordination bonds, have good colloidal performance and dispersion effect, are alkali-resistant but have weak complexing capacity, and therefore the carboxyl oxygen atoms need to be copolymerized or modified to improve the performance; and amides associated with N-H bond bending vibrations after reaction of iron ions with compounds containing amino groups
Tapes and amides
The band intensity decreases, the intensity of the characteristic peak representing the methylene oscillation of the amorphous region increases, and the crystallinity decreases. Thus, the iron ion is in complex coordination with the amino nitrogen atom of the macromolecular chain.
Compared with the prior art, the invention has the following beneficial effects because the technology is adopted:
1. according to the invention, 2-acrylamide-2-methylpropanesulfonic acid is used as a carrier, p-benzoquinone reacts with amino sodium sulfamate to generate Schiff base, sulfydryl is introduced through sulfur dioxide, so that the Schiff base is connected with the carrier to form a chelating agent, after metal iron ions are chelated, a multi-coordination complex can be formed, and the immobilized Schiff base not only can strengthen the stability of the complex and obviously enhance the stability of the carrier, but also can ensure the water solubility of the complex due to the existence of sulfonic acid groups.
2. The iron remover is prepared by compounding organic acid, carboxylate and Schiff base, so that the chelation condition is optimized, functional groups such as carboxyl, amino and the like are further introduced, and the chelation effect is improved.
3. The crude oil metal iron remover can be used for removing elements such as calcium, iron and the like in petroleum crude oil and industrial wastewater, and under the condition of adding 75-125ppm of crude oil metal remover, the removal rate of iron in the petroleum crude oil containing 7-15ppm of iron reaches 88-93%.
Detailed Description
The present invention will be further illustrated with reference to the following specific embodiments.
Example 1:
a crude oil iron metal remover is prepared by the following steps:
uniformly mixing 45g of iron chelating agent, 10g of organic acid, 10g of carboxylate and 20g of Schiff base at room temperature to obtain the crude oil remover.
Wherein the organic acid is salicylic acid; the carboxylate is zinc acetate; the Schiff base is p-aminodiphenylimine.
The performance test results are as follows:
the cramayi crude oil is used as test oil, the iron content of the cramayi crude oil is 8ppm, and when the adding amount of the metal remover of the obtained crude oil is 85ppm, the iron removal rate is 88.4%.
Example 2:
a crude oil iron metal remover is prepared by the following steps:
50g of iron chelating agent, 13g of organic acid, 13g of carboxylate and 25g of Schiff base are uniformly mixed at room temperature to obtain the crude oil remover.
Wherein the organic acid is glycolic acid; the carboxylate is sodium tartrate; the Schiff base is p-aminodiphenylimine.
The performance test results are as follows:
the crude oil of Clarithromi is used as test oil, the iron content is 11ppm, and when the dosage of the metal remover of the obtained crude oil is 100ppm, the iron removal rate is 90.6%.
Example 3:
a crude oil iron metal remover is prepared by the following steps:
and uniformly mixing 55g of iron chelating agent, 15g of organic acid, 15g of carboxylate and 30g of Schiff base at room temperature to obtain the crude oil remover.
Wherein the organic acid is sulfamic acid; the carboxylate is sodium alginate; the Schiff base is 2-hydroxy-1-naphthalene formaldehyde o-phenylenediamine.
The performance test results are as follows:
the crambe crude oil is used as the test oil, the iron content is 14ppm, and the iron removal rate is 92.1% when the adding amount of the metal remover of the obtained crude oil is 115 ppm.
Example 4:
in example 1, the process for preparing the iron chelator is as follows:
mixing 50g of sulfur dioxide, 25g of p-benzoquinone and 30g of sodium sulfamate, adding 80g of 2-acrylamido-2-methylpropanesulfonic acid solution slowly dropwise into a reaction vessel, controlling the mass percent of the solution to be 65wt%, controlling the dropwise adding speed to be 1.5mL/min, cooling and stirring, controlling the stirring temperature to be 40 ℃, adding 100g of ethylenediamine and 30g of metallic sodium after the exothermic reaction is finished, stirring at room temperature for 1h, finally adding 60g of formamide and 5g of aluminum chloride catalyst, heating to 70 ℃, maintaining the pressure to be 1.1MPa, stirring at a constant speed, reacting for 3.5h, and cooling to obtain the iron chelating agent.
The iron chelator has the following structural formula:
wherein the number n of repeating units is 1.
Example 5:
in example 2, the process for preparing the iron chelator is as follows:
mixing 50g of sulfur dioxide, 35g of p-benzoquinone and 40g of sodium sulfamate, adding 90g of 2-acrylamido-2-methylpropanesulfonic acid solution slowly dropwise into a reaction vessel, controlling the mass percent of the solution to be 60wt%, controlling the dropwise adding speed to be 1.5mL/min, cooling and stirring, controlling the stirring temperature to be 40 ℃, after the exothermic reaction is finished, adding 130g of butanediamine and 20g of metal sodium, stirring at room temperature for 1h, finally adding 70g of formamide and 5g of aluminum chloride catalyst, heating to 80 ℃, maintaining the pressure to be 1.1MPa, stirring at constant speed, reacting for 3.5h, and cooling to obtain the iron chelating agent.
The iron chelator has the following structural formula:
wherein the number n of repeating units is 2.
Example 6:
in example 3, the process for preparing the iron chelator is as follows:
mixing 50g of sulfur dioxide, 45g of p-benzoquinone and 50g of sodium sulfamate, adding 100g of 2-acrylamido-2-methylpropanesulfonic acid solution slowly dropwise into a reaction vessel, controlling the mass percent of the solution to be 63wt%, controlling the dropwise adding speed to be 2mL/min, cooling and stirring, controlling the stirring temperature to be 35 ℃, adding 150g of hexamethylenediamine and 30g of metal sodium after the exothermic reaction is finished, stirring at room temperature for 1.5h, finally adding 75g of formamide and 10g of aluminum chloride catalyst, heating to 90 ℃, maintaining the pressure to be 1.1MPa, stirring at a constant speed, reacting for 3.5h, and cooling to obtain the iron chelating agent.
The iron chelator has the following structural formula:
wherein the number n of repeating units is 3.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.
Claims (10)
1. The crude oil iron metal remover is characterized by comprising the following raw materials in percentage by mass: 45-55% of iron chelating agent, 10-15% of organic acid, 10-15% of carboxylate and 20-30% of Schiff base.
2. The crude oil iron metal removal agent of claim 1, wherein the iron chelating agent has the following structural formula:
wherein the number n of repeating units is 1 to 4.
3. The crude oil iron metal remover according to claim 1 or 2, wherein the iron chelating agent is prepared by the following steps:
(1) mixing sulfur dioxide, p-benzoquinone and sodium sulfamate, and then dropwise adding a 2-acrylamide-2-methylpropanesulfonic acid solution into the mixed solution;
(2) after the reaction is finished, adding an amine compound and metallic sodium and stirring;
(3) adding formamide and aluminum chloride, stirring, and cooling to obtain the iron chelating agent.
4. The agent for removing iron metal from crude oil as claimed in claim 3, wherein: the mass ratio of the sulfur dioxide, the p-benzoquinone, the sodium sulfamate, the 2-acrylamido-2-methylpropanesulfonic acid, the amine compound, the metal sodium, the formamide and the aluminum chloride is 1: 0.5-1: 0.5-1: 1.5-2.5: 2-3: 0.2-0.6: 1.2-1.5: 0.1-0.2.
5. The agent for removing iron metal from crude oil as claimed in claim 3, wherein: the dropping speed in the step (1) is 1.5-2mL/min, and the reaction temperature of dropping the 2-acrylamide-2-methylpropanesulfonic acid solution is 35-40 ℃.
6. The agent for removing iron metal from crude oil as claimed in claim 3, wherein: the stirring time in the step (2) is 1-1.5 h.
7. The agent for removing iron metal from crude oil as claimed in claim 3, wherein: the reaction temperature in the step (3) is 70-90 ℃, the reaction pressure is 1.05-1.1MPa, and the reaction time is 3-3.5 h.
8. The agent for removing iron metal from crude oil as claimed in claim 3, wherein: in the step (2), the amine compound is any one or more of ethylenediamine, butanediamine, hexanediamine and octanediamine.
9. The agent for removing iron metal from crude oil as claimed in claim 1, wherein: the organic acid is one or more of salicylic acid, glycolic acid and sulfamic acid.
10. The agent for removing iron metal from crude oil as claimed in claim 1, wherein: the carboxylate is any one or more of zinc acetate, sodium tartrate and sodium alginate; the Schiff base is one or two of p-amino diphenylimine and 2-hydroxy-1-naphthalene formaldehyde shrinkage o-phenylenediamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011118114.8A CN112322340B (en) | 2020-10-19 | 2020-10-19 | Crude oil iron metal remover and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011118114.8A CN112322340B (en) | 2020-10-19 | 2020-10-19 | Crude oil iron metal remover and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112322340A true CN112322340A (en) | 2021-02-05 |
| CN112322340B CN112322340B (en) | 2023-02-24 |
Family
ID=74314159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011118114.8A Active CN112322340B (en) | 2020-10-19 | 2020-10-19 | Crude oil iron metal remover and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112322340B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157869A (en) * | 2007-11-12 | 2008-04-09 | 中国海洋石油总公司 | Crude oil decalcifying agent and preparation method thereof |
| CN105713646A (en) * | 2016-03-21 | 2016-06-29 | 东南大学 | Environment-friendly crude oil decalcifying agent |
| CN107384471A (en) * | 2016-05-17 | 2017-11-24 | 中国石化扬子石油化工有限公司 | A kind of without phosphorus crude oil metal removal agent |
-
2020
- 2020-10-19 CN CN202011118114.8A patent/CN112322340B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157869A (en) * | 2007-11-12 | 2008-04-09 | 中国海洋石油总公司 | Crude oil decalcifying agent and preparation method thereof |
| CN105713646A (en) * | 2016-03-21 | 2016-06-29 | 东南大学 | Environment-friendly crude oil decalcifying agent |
| CN107384471A (en) * | 2016-05-17 | 2017-11-24 | 中国石化扬子石油化工有限公司 | A kind of without phosphorus crude oil metal removal agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112322340B (en) | 2023-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106995221B (en) | Heavy metal ion remover with self-flocculation function and synthesis method thereof | |
| CA3127968C (en) | Amphoteric biomass-based hyperbranched adsorption material to multiple heavy metal ions and preparation method and use thereof | |
| CN110819381A (en) | Demulsifier and preparation method thereof | |
| CN112322340B (en) | Crude oil iron metal remover and preparation method thereof | |
| CN101314728A (en) | Deferrization method for hydrocarbons raw oil | |
| CN105802659A (en) | Environment-friendly composite crude oil decalcifying agent | |
| CN111909296A (en) | Method for preparing instant cationic high molecular weight polyacrylamide by two-step method | |
| CN112624565A (en) | Polyhydroxy organic cation polymer sludge conditioner for deep dehydration of sludge and preparation method thereof | |
| CN112777758A (en) | Environment-friendly corrosion and scale inhibitor and preparation method thereof | |
| CN110743552B (en) | Clay loaded zero-valent metal heavy oil hydrothermal cracking catalyst and its prepn | |
| CN115181211B (en) | Branched high-temperature-resistant polymer filtrate reducer for drilling fluid and preparation method thereof | |
| CN115367808B (en) | Method for passivating pyrite surface | |
| CN109970165B (en) | Heavy metal trapping agent and preparation method thereof | |
| CN111662743A (en) | Metal ion chelating agent and preparation method thereof | |
| CN111068784B (en) | Preparation method and application of lignin ligand hexahedral iron-based catalyst | |
| JPS60118288A (en) | Water treating method | |
| CN111690937A (en) | Corrosion inhibitor for atmospheric and vacuum distillation unit and preparation method thereof | |
| CN113415908B (en) | Modified hydrolyzed polymaleic anhydride water treatment agent and preparation method thereof | |
| CN111453829A (en) | Magnetic heavy metal trapping agent and application thereof | |
| CN104162455A (en) | A water-soluble catalytic cracking multifunctional deactivator and a preparing method thereof | |
| CN110270331A (en) | A kind of suspension bed hydrogenation catalyst and its preparation method and application | |
| CN114605023B (en) | Treatment method of high-concentration phosphorus-containing wastewater of chemical nickel plating | |
| CN109021154B (en) | Method for preparing instant anion high-molecular-weight polyacrylamide by two-step method | |
| CN114291909B (en) | Scale inhibition dispersing agent | |
| CN114684903B (en) | Preparation method of inorganic-organic reinforced dephosphorization flocculant and wastewater treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |