CN112175661A - Low-temperature-resistant crude oil metal chelating agent and preparation method thereof - Google Patents
Low-temperature-resistant crude oil metal chelating agent and preparation method thereof Download PDFInfo
- Publication number
- CN112175661A CN112175661A CN202011301187.0A CN202011301187A CN112175661A CN 112175661 A CN112175661 A CN 112175661A CN 202011301187 A CN202011301187 A CN 202011301187A CN 112175661 A CN112175661 A CN 112175661A
- Authority
- CN
- China
- Prior art keywords
- crude oil
- chelating agent
- metal chelating
- oil metal
- mass
- 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
- C10G29/20—Organic compounds not containing metal atoms
-
- 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
- C10G2300/80—Additives
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a low temperature resistant crude oil metal chelating agent and a preparation method thereof, wherein the chelating agent is prepared by mixing 40-50% of a bisimidazolidinedione complex with a symmetrical structure, 15-25% of an organic polybasic acid, 5-10% of an antifreezing agent and 25-35% of deionized water under a microwave condition for reaction, wherein the bisimidazolidinedione complex with the symmetrical structure is formed by acylation and connection of bisimidazolidinedione.
Description
Technical Field
The invention relates to a low-temperature-resistant crude oil metal chelating agent and a preparation method thereof, belonging to the field of crude oil metal chelating agent preparation.
Background
Along with the rapid development of economy, the oil consumption is larger and larger, the oil resource is deficient day by day, in addition, the quality of the crude oil is reduced, if the crude oil contains some metal ions, the normal use of the crude oil is influenced, a large amount of metal elements in the crude oil can generate adverse effects on the use of the subsequent crude oil, the normal use of the crude oil is limited to a great extent due to the existence of iron, and the performance of a catalyst of a catalytic pyrolysis device is reduced due to the fact that the content of the iron exceeds the. Moreover, as crude oil is used more and more widely, some northern areas have the phenomenon that a deferrization agent is solidified and separated out when crude oil metal is removed, and the metallic iron removal effect of the crude oil is greatly influenced, so that the design of the novel process can keep the crude oil deferrization effect, can ensure that the novel process can be normally used at a low temperature, and cannot generate the phenomenon of solidification and separation is necessary.
In view of the above, the existing iron removing agent cannot meet the requirements of petrochemical industry, and the development of iron removing agent with low temperature resistance and good solubility has been slow.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a low-temperature-resistant crude oil metal chelating agent and a preparation method thereof, 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 low-temperature-resistant crude oil metal chelating agent is composed of the following raw materials in percentage by mass: 40-50% of a bisimidazolidinedione complex with a symmetrical structure, 15-25% of an organic polyacid, 5-10% of an antifreezing agent and 25-35% of deionized water.
Further, the organic polybasic acid is one or more of citric acid, gluconic acid, sulfamic acid and propionic acid. Further, the antifreezing agent is any one or more of methanol, ethanol, ethylene glycol and glycerol.
Further, the preparation method of the bis-imidazolidinedione complex with a symmetrical structure is as follows:
pouring 10-15 parts by mass of diimidazole alkane diketone and 1-3 parts by mass of organic weak base into a three-neck flask in sequence at room temperature, adding 30-50 parts by mass of ethyl acetate, magnetically stirring until the diimidazole alkane diketone and the organic weak base are completely dissolved and the solution is in a uniform state, slowly dropwise adding 0.05-0.1 part by mass of activating agent and 0.1-0.3 part by mass of acylating agent in an ice-water bath at low temperature (0-5 ℃), and reacting for 15-30 min. And after the reaction is finished, removing the low-temperature condition, stirring and reacting for 5-8h at room temperature (20-35 ℃), then condensing and refluxing the obtained solution for 4-8h at 70-90 ℃ to remove the solvent ethyl acetate, finally adding 5-10 parts by mass of ethanol until the solution can be uniformly stirred and transparent, and recrystallizing to obtain the bisimidazolidinedione complex with a symmetrical structure.
Further, the organic weak base is any one of triethylamine, ethylenediamine and dimethylformamide.
Further, the activating agent is one of trifluoroacetic anhydride and methanesulfonic acid, and is preferably trifluoroacetic anhydride.
Further, the acylating agent is any one of monomethyl malonate, 2-phenylbutyric acid and o-bromobenzoic acid.
Further, the preparation method of the low-temperature-resistant crude oil metal chelating agent comprises the following steps:
pouring 40-50 wt% of a bisimidazolidinedione complex with a symmetrical structure, 15-25 wt% of an organic polybasic acid, 5-10 wt% of an antifreezing agent and 25-35 wt% of deionized water into a beaker, continuously stirring the mixture at room temperature for 5-10min until all components are dissolved to form a colorless transparent solution, transferring the colorless transparent solution into a microwave reaction bottle, sealing the microwave reaction bottle, placing the microwave reaction bottle into a microwave synthesizer, reacting at 150 ℃ for 10-20min, and naturally cooling the obtained product to room temperature after the reaction is finished to obtain the crude oil metal chelating agent suitable for low temperature.
Compared with the prior art, the invention has the following beneficial effects because the technology is adopted:
1. the low-temperature resistant crude oil metal chelating agent disclosed by the invention is mainly characterized by comprising the following two aspects:
(1) the structure of the bisimidazolidinedione complex with a symmetrical structure contains a large number of nitrogen atoms and oxygen atoms, and intermolecular hydrogen bonds can be formed with water molecules, so that the solubility of the complex at low temperature is improved, and organic polybasic acid can also form a large number of hydrogen bonds with water, so that the solubility of the chelating agent system at low temperature is ensured, the chelating function of the chelating agent system on metal is exerted at low temperature, in addition, the freezing point of the mixed system can be reduced by adding a certain proportion of antifreezing agent, and the chelating capacity at low temperature is ensured;
(2) based on the fact that oxygen atoms and hydroxyl groups in the complex have strong chelation on metal ions, and organic polybasic acid with good water solubility is added in a certain proportion, the complex has good chelation capacity on water-soluble iron in crude oil water, and the aim of chelating and deferrization is achieved under the combined action of multiple components;
2. after the acylation reaction is carried out, the excessive activating agent and the reaction byproduct components thereof have low boiling points and can be recovered by distillation and reused by further treatment;
3. the existence of a large amount of intermolecular hydrogen bonds and the addition of the antifreezing agent ensure that the metal chelating agent can keep better solubility and chelating ability at 0-10 ℃, and the chelating agent does not contain phosphorus, is more environment-friendly and green.
Detailed Description
The present invention will be further illustrated with reference to the following specific embodiments.
Example 1:
the preparation method of the bisimidazolidinedione complex with a symmetrical structure comprises the following steps:
pouring 10 parts by mass of diimidazole alkane diketone and 1 part by mass of triethylamine into a three-neck flask successively at room temperature, adding 30 parts by mass of ethyl acetate, magnetically stirring until the materials are completely dissolved and the solution is in a uniform state, slowly dropwise adding 0.05 part by mass of trifluoroacetic anhydride and 0.1 part by mass of monomethyl malonate in an ice-water bath at low temperature (0 ℃), and reacting for 15 min. And after the reaction is finished, removing the low-temperature condition, stirring and reacting for 5 hours at room temperature (20 ℃), then condensing and refluxing the obtained solution for 8 hours at 80 ℃ to remove the solvent ethyl acetate, finally adding 5 parts by mass of ethanol until the ethanol and the solution can be uniformly stirred and transparent, and recrystallizing to obtain the high-purity bis-imidazolidinedione complex with the symmetrical structure.
Example 2:
pouring the proportion of 40wt% of the bisimidazolidinedione complex with a symmetrical structure prepared in the example 1, 15wt% of citric acid, 10wt% of methanol and 35wt% of deionized water into a beaker, continuously stirring the mixture at room temperature for 5min until all the components are dissolved to form a colorless transparent solution, transferring the colorless transparent solution into a microwave reaction bottle, sealing the microwave reaction bottle, placing the microwave reaction bottle into a microwave synthesizer, reacting at 150 ℃ for 10min, and naturally cooling the obtained product to room temperature after the reaction is finished to obtain the low-temperature-resistant crude oil metal chelating agent.
The prepared low-temperature-resistant crude oil metal chelating agent has no crystal precipitation when stored in a low-temperature environment (0-10 ℃), and the iron removal rate reaches 87% when the iron content in the crude oil is 15 ppm.
Example 3:
the preparation method of the bisimidazolidinedione complex with a symmetrical structure comprises the following steps:
at room temperature, pouring 12 parts by mass of diimidazole alkane diketone and 2 parts by mass of ethylenediamine into a three-neck flask in sequence, adding 40 parts by mass of ethyl acetate, magnetically stirring until the diimidazole alkane diketone and the ethylenediamine are completely dissolved and the solution is in a uniform state, slowly dropwise adding 0.08 part by mass of methanesulfonic acid and 0.2 part by mass of 2-phenylbutyric acid in an ice-water bath at low temperature (0 ℃), and reacting for 25 min. And after the reaction is finished, removing the low-temperature condition, stirring and reacting for 6 hours at room temperature (35 ℃), then condensing and refluxing the obtained solution for 7 hours at 80 ℃ to remove the solvent ethyl acetate, finally adding 7 parts by mass of ethanol until the solution can be uniformly stirred and transparent, and recrystallizing to obtain the high-purity bis-imidazolidinedione complex with the symmetrical structure.
Example 4:
pouring 50wt% of the bisimidazolidinedione complex with a symmetrical structure prepared in example 3, 15wt% of gluconic acid, 5wt% of glycerol and 30wt% of deionized water into a beaker, continuously stirring the mixture at room temperature for 8min until all the components are dissolved to form a colorless transparent solution, transferring the colorless transparent solution into a microwave reaction bottle, sealing the microwave reaction bottle, placing the microwave reaction bottle into a microwave synthesizer, reacting at 150 ℃ for 15min, and naturally cooling the obtained product to room temperature after the reaction is finished to obtain the low-temperature-resistant crude oil metal chelating agent.
The prepared low-temperature resistant crude oil metal chelating agent has no crystal precipitation when stored in a low-temperature environment (0-10 ℃), and the iron removal rate reaches 82.5 percent when the iron content in the crude oil is 15 ppm.
Example 5:
the preparation method of the bisimidazolidinedione complex with a symmetrical structure comprises the following steps:
pouring 15 parts by mass of diimidazole alkane diketone and 3 parts by mass of dimethylformamide into a three-neck flask successively at room temperature, adding 50 parts by mass of ethyl acetate, magnetically stirring until the materials are completely dissolved and the solution is in a uniform state, slowly dropwise adding 0.1 part by mass of trifluoroacetic anhydride and 0.3 part by mass of o-bromobenzoic acid in an ice-water bath at low temperature (3 ℃), and reacting for 30 min. And after the reaction is finished, removing the low-temperature condition, stirring and reacting for 8 hours at room temperature (25 ℃), then condensing and refluxing the obtained solution for 8 hours at 90 ℃ to remove the solvent ethyl acetate, finally adding 10 parts by mass of ethanol until the ethanol and the solution can be uniformly stirred and transparent, and recrystallizing to obtain the high-purity bis-imidazolidinedione complex with the symmetrical structure.
Example 6:
pouring 45wt% of the bisimidazolidinedione complex with a symmetrical structure prepared in example 5, 20wt% of propionic acid, 10wt% of ethylene glycol and 25wt% of deionized water into a beaker, continuously stirring the mixture at room temperature for 10min until all the components are dissolved to form a colorless transparent solution, transferring the colorless transparent solution into a microwave reaction bottle, sealing the microwave reaction bottle, placing the microwave reaction bottle into a microwave synthesizer, reacting at 150 ℃ for 20min, and naturally cooling the obtained product to room temperature after the reaction is finished to obtain the low-temperature-resistant crude oil metal chelating agent.
The prepared crude oil has no crystal precipitation when stored in a low-temperature environment (0-10 ℃), and the iron removal rate reaches 84% when the iron content in the crude oil is 15 ppm.
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 low-temperature-resistant crude oil metal chelating agent is characterized by comprising the following raw materials in percentage by mass: 40-50% of a bisimidazolidinedione complex with a symmetrical structure, 15-25% of an organic polyacid, 5-10% of an antifreezing agent and 25-35% of deionized water.
2. The low temperature resistant crude oil metal chelating agent of claim 1, wherein: the organic polybasic acid is one or more of citric acid, gluconic acid, sulfamic acid and propionic acid.
3. The low temperature resistant crude oil metal chelating agent of claim 1, wherein: the antifreezing agent is any one or more of methanol, ethanol, ethylene glycol and glycerol.
4. The low temperature resistant crude oil metal chelating agent as defined in claim 1, wherein the bis-imidazolidinedione complex having a symmetrical structure is prepared by the following method:
(1) mixing 10-15 parts by mass of diimidazole alkane diketone, 1-3 parts by mass of organic weak base and 30-50 parts by mass of ethyl acetate;
(2) dropwise adding 0.05-0.1 mass part of activating agent and 0.1-0.3 mass part of acylating agent into the obtained solution for reaction;
(3) stirring the obtained solution at the temperature of 20-35 ℃ for reaction for 5-8h, and then condensing and refluxing the solution at the temperature of 70-90 ℃ for 4-8 h;
(4) and adding 5-10 parts by mass of ethanol into the obtained solution, mixing, and recrystallizing to obtain the bisimidazolidinedione complex with a symmetrical structure.
5. The low temperature resistant crude oil metal chelating agent as defined in claim 4, wherein: in the step (1), the organic weak base is any one of triethylamine, ethylenediamine and dimethylformamide.
6. The low temperature resistant crude oil metal chelating agent as defined in claim 4, wherein: in the step (2), the activating agent is any one of trifluoroacetic anhydride and methanesulfonic acid.
7. The low temperature resistant crude oil metal chelating agent as defined in claim 4, wherein: in the step (2), the acylating agent is any one of monomethyl malonate, 2-phenylbutyric acid and o-bromobenzoic acid.
8. The low temperature resistant crude oil metal chelating agent as defined in claim 4, wherein: the reaction temperature in the step (2) is 0-5 ℃, and the reaction time is 15-30 min.
9. The low temperature resistant crude oil metal chelating agent as set forth in claim 1, wherein the crude oil metal chelating agent is prepared by the following method:
1) respectively weighing 40-50% of bisimidazolidinedione complex with a symmetrical structure, 15-25% of organic polybasic acid, 5-10% of antifreezing agent and 25-35% of deionized water according to mass percentage;
2) mixing and stirring the raw materials weighed in the step 1 for 5-10 min;
3) and (3) putting the obtained solution into a microwave synthesizer for reaction, and cooling to room temperature after the reaction is finished to obtain the crude oil metal chelating agent.
10. The low temperature resistant crude oil metal chelating agent as defined in claim 9, wherein the reaction in step 3) is carried out in a microwave synthesizer at 150 ℃ for 10-20 min.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011301187.0A CN112175661B (en) | 2020-11-19 | 2020-11-19 | Low-temperature-resistant crude oil metal chelating agent and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011301187.0A CN112175661B (en) | 2020-11-19 | 2020-11-19 | Low-temperature-resistant crude oil metal chelating agent and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112175661A true CN112175661A (en) | 2021-01-05 |
CN112175661B CN112175661B (en) | 2023-02-28 |
Family
ID=73918591
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011301187.0A Active CN112175661B (en) | 2020-11-19 | 2020-11-19 | Low-temperature-resistant crude oil metal chelating agent and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112175661B (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1207777A (en) * | 1995-11-03 | 1999-02-10 | 爱达荷研究基金公司 | Process for extracting metals directly from metal oxides |
CN102220170A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工集团公司 | Corrosion inhibitor for hydrogenation unit and preparation method thereof |
CN106867572A (en) * | 2017-03-15 | 2017-06-20 | 东南大学 | A kind of compound without phosphorus crude oil metal-chelator |
CN110643386A (en) * | 2019-09-20 | 2020-01-03 | 南京江宇新材料科技有限公司 | Compound crude oil metal chelating agent |
-
2020
- 2020-11-19 CN CN202011301187.0A patent/CN112175661B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1207777A (en) * | 1995-11-03 | 1999-02-10 | 爱达荷研究基金公司 | Process for extracting metals directly from metal oxides |
CN102220170A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工集团公司 | Corrosion inhibitor for hydrogenation unit and preparation method thereof |
CN106867572A (en) * | 2017-03-15 | 2017-06-20 | 东南大学 | A kind of compound without phosphorus crude oil metal-chelator |
CN110643386A (en) * | 2019-09-20 | 2020-01-03 | 南京江宇新材料科技有限公司 | Compound crude oil metal chelating agent |
Also Published As
Publication number | Publication date |
---|---|
CN112175661B (en) | 2023-02-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112175661B (en) | Low-temperature-resistant crude oil metal chelating agent and preparation method thereof | |
CN109776347B (en) | Thermosetting vegetable oil-based acrylate derivative and preparation method and application thereof | |
CN114292675A (en) | Methanol gasoline additive and preparation method thereof | |
CN113354787A (en) | Environment-friendly furan resin for 3D sand mold printing and preparation method thereof | |
CN101054273A (en) | Method of producing naphthalene series water reducing agent by refined naphthalene residual oil fraction | |
CN104926998A (en) | Unsaturated polyester resin used for bulk molding compound and preparation method thereof | |
CN112322339B (en) | Crude oil metal chelating agent and preparation method thereof | |
CN103467682B (en) | Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method | |
CN114044498B (en) | Wet phosphoric acid purifying method | |
CN101747956A (en) | Novel synthetic liquid fuel and preparation method | |
CN1869000B (en) | Cleaning technology of iso-octly nitrate crude product | |
CN110387549B (en) | Additive and method for inhibiting residual iron powder on surface of steel coil subjected to acid pickling | |
CN1318551C (en) | Additive for producing high-grade gasoline using 90# gasoline and the high grade gasoline | |
CN109504338B (en) | Polyurethane foaming heat-conducting electronic pouring sealant and preparation method thereof | |
CN110415979A (en) | Superhigh temperature LED light capacitor Working electrolyte and preparation method thereof | |
CN114086189B (en) | Environment-friendly stainless steel pickling passivation solution | |
CN109135844B (en) | Preparation method of environment-friendly gasoline | |
CN114920895B (en) | Preparation method of cold-resistant furan resin | |
CN108840826B (en) | Methanol gasoline corrosion-resistant swelling-inhibiting water-resistant additive and preparation method thereof | |
CN114835577B (en) | Aldehyde synthesis method | |
CN111375726B (en) | Low free acid sulfonic acid curing agent and production method thereof | |
CN118599585A (en) | New energy automobile cleaning synergist and preparation method thereof | |
CN115893899B (en) | Antifreezing alkali-free liquid accelerator and preparation method and application thereof | |
CN110655627A (en) | Waste water treatment method in furfuryl alcohol production process | |
CN109355091B (en) | Method for denitrifying fuel oil by using polyether amine-formic acid mixture |
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 |