Crude oil electro-desalting dechlorination agent, and preparation method and use method thereof

Abstract

The application discloses a crude oil electric desalting and dechlorination agent and a preparation method and use method thereof. The crude oil electric desalting and dechlorination agent comprises the following components in percentage by weight: 5wt%-27wt% of an extraction demulsification component, 5wt%-43wt% of a catalytic substitution component, 10wt%-45wt% of an organic acid and alkali neutralization component, and 10wt%-25wt% of a solvent component. Chlorine-containing chemical additives and inorganic chlorides in crude oil can be extracted and dissolved in water through extraction, chlorine elements in organic chlorine complexes in the crude oil are replaced through a catalytic substitution reaction, chlorine-containing corrosion products are neutralized into neutral and dissolved in water through an acid and alkali neutralization effect, and finally, the chlorine-containing corrosion products are removed through an electric desalting and dewatering process, so that the chlorine removal from a crude oil electric desalting source is achieved.

Description

Technical Field

[0001] This invention relates to the field of chemical technology, specifically to a crude oil electro-desalting and dechlorination agent, its preparation method, and its application method. Background Technology

[0002] Due to the increasing scarcity of crude oil resources, in order to increase crude oil production, it is necessary to inject large amounts of chlorination-containing chemical additives during the extraction process, leading to a gradual increase in the chlorine content of crude oil. The chlorine in crude oil not only exacerbates chlorine corrosion in refining units but also causes chloride scale formation in pipelines and equipment, chlorine poisoning of catalysts, and other serious issues, severely impacting the safe operation of refining production. Therefore, crude oil chlorine removal technology is receiving increasing attention.

[0003] Chlorides in crude oil exist in two forms: inorganic chlorine and organic chlorine. Inorganic chlorine originates from the inorganic salts naturally present in the crude oil, primarily alkali metal and alkaline earth metal salts such as NaCl, MgCl2, and CaCl2. These inorganic chlorine salts dissolve in trace amounts of water within the crude oil and, under the influence of chlorination additives during extraction, exist as emulsion colloids or suspended particles. While most of the inorganic chlorine naturally present in the crude oil can be removed through electrochemical desalting, the chlorination additives, due to their unique chemical structure and properties, cannot be removed during this process. Organic chlorine originates from organochlorine complexes present in the crude oil itself. These complexes dissolve in the oil phase and cannot be removed by the physical action of electrochemical desalting.

[0004] Existing desulfurization and dechlorination methods mainly include the following: catalytic hydrogenation, catalytic hydrogen transfer, adsorption, and biological methods.

[0005] Catalytic hydrodesulfurization and chlorination technology is mainly used for the desulfurization and chlorination of sulfur-containing and chlorinated alkanes and alkenes. The principle is that H2 adsorbed on a supported metal catalyst is cracked into H atoms, and then loses one electron to become H. + The product then reacts with sulfur and chlorides adsorbed on the catalyst to produce HCl, H2S, and corresponding hydrocarbons. However, the product from this technology exists in gaseous form, which severely corrodes refining equipment.

[0006] Catalytic hydrogen transfer desulfurization and chlorination are mainly used for the removal of sulfur, chloroaromatics, polysulfides, and chlorobiphenyls from aqueous or organic phases. Generally, a binary metal catalyst system is used as the removal agent, primarily using iron-based metal compounds as the main catalyst, combined with noble metals, and their corresponding ions as auxiliary catalysts. This technology requires modification or the addition of new equipment, and the required catalysts are expensive.

[0007] The principle of adsorption dechlorination mainly utilizes the different adsorption capacities of certain adsorbents for sulfur and chlorine in raw oil to separate them. The main methods include zeolite adsorption, natural bauxite adsorption, and strongly basic anion exchange resin adsorption. Adsorption desulfurization and dechlorination technology has good economic benefits and broad development prospects, but it also has drawbacks such as small adsorption capacity of adsorbents, poor selectivity, and difficulty in regeneration.

[0008] Biodegradation desulfurization and dechlorination technology studies the removal of sulfur and chlorine from benzene, phenol and biphenyl. Biodegradation technology has mild reaction conditions and can be carried out without external energy, but the reaction time is long and the equipment and process requirements are special.

[0009] The above four dechlorination methods either cannot solve the problem of strong corrosion of the dechlorination products; or require the addition of new equipment and the development of expensive catalyst systems; or the adsorbent has a small adsorption capacity and poor selectivity; or the reaction time is long and has special requirements for equipment and processes. Summary of the Invention

[0010] The purpose of this invention is to address the shortcomings of existing technologies by providing a crude oil electro-desalting and dechlorination agent, its preparation method, and its application method. This addresses the problems of existing dechlorination methods, such as the inability to solve the problem of strong corrosion of the dechlorination products, the need to add new equipment, develop expensive catalyst systems, the small adsorption capacity and poor selectivity of the adsorbent, the long reaction time, and the special requirements for equipment and processes.

[0011] This invention provides an oil desalting and dechlorination agent comprising the following components by weight percentage: 5wt%-27wt% extraction and demulsification components, 5wt%-43wt% catalytic substitution components, 10wt%-45wt% organic acid-base neutralization components, and 10wt%-25wt% solvent components.

[0012] Furthermore, the extracted demulsifying component is an amino acid-type amphoteric surfactant.

[0013] Furthermore, the HLB value of the extracted demulsifying component ranges from 4 to 9.

[0014] Furthermore, the extracted demulsifying component is a dodecylaminopropionic acid derivative.

[0015] Furthermore, the catalytic substitution component includes an alkali metal that plays a catalytic role and a substance that plays a substitution role, wherein the alkali metal that plays a catalytic role is an alcohol solution containing potassium, sodium, and aluminum metals.

[0016] Furthermore, the substance that performs the substitution function is an organic basic substance synthesized from oleic acid and polyene polyamines.

[0017] Furthermore, the organic acid-base neutralizing component is methylamine, ethylamine, or propylamine.

[0018] This invention provides a method for preparing the above-mentioned crude oil electrostatic desalting and dechlorination agent, comprising:

[0019] The solvent components are placed in the reaction vessel and stirred. The temperature in the reaction vessel is raised to 40°C and then kept at that temperature for 10 minutes.

[0020] Add the extraction and demulsification components to the reaction vessel, raise the temperature of the reaction vessel to 60°C and keep it at that temperature for 60 minutes;

[0021] A catalytic substitution component is added to the reactor, and the temperature in the reactor is raised to 80°C and held for 50 minutes.

[0022] Stop heating, turn on the cooling circulating water to lower the temperature in the reactor to below 30°C, add the organic acid-base neutralizing components to the reactor and stir for 70 minutes.

[0023] This invention provides a method for using the above-mentioned crude oil electrostatic desalting and dechlorination agent, comprising:

[0024] The crude oil electro-desalting and dechlorination agent is mixed evenly with the crude oil under the action of a mixer;

[0025] The crude oil desalting and dechlorination agent, which is mixed evenly, is fed into the crude oil desalting unit for reaction.

[0026] Furthermore, the reaction pressure is 0MPa-10MPa, the reaction temperature is 40℃-120℃, the amount of crude oil desalting and dechlorination agent added is 50ppm-300ppm, and the reaction time is more than 20 minutes.

[0027] This invention offers the following advantages: The crude oil electro-desalting and dechlorination agent provided by this invention can extract chlorinated chemical additives and inorganic chlorides from crude oil through extraction, dissolving them in water. Through a catalytic substitution reaction, it replaces the chlorine element in the organic chlorine complexes of the crude oil. Then, through acid-base neutralization, the dechlorinated corrosion products are neutralized to a neutral state and dissolved in water. Finally, they are removed through an electro-desalting and dehydration process, achieving the goal of removing chlorine from the source of oil refining electro-desalting. This invention can neutralize the removed harmful substances, rendering them non-corrosive and protecting equipment and pipelines from corrosion. It is convenient to use, requiring no additional auxiliary equipment, and can be used and stopped at any time. It is highly adaptable, has significant effects, and is easy to adjust. It is environmentally friendly, containing no substances harmful to the environment. Unlike solid removal technologies, it is convenient for packaging, transportation, and storage. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This is a flowchart of the crude oil electro-desalting and dechlorination agent preparation method of the present invention. Detailed Implementation

[0030] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be pointed out that the following detailed description is illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0031] The key to crude oil dechlorination technology lies in removing chlorine from the crude oil at the source of electro-desalting, thus effectively preventing the adverse effects of chlorine on the entire refining unit and catalyst. This invention provides a crude oil electro-desalting and dechlorination agent, comprising the following components by weight percentage: 5wt%-27wt% extraction and demulsification components, 5wt%-43wt% catalytic substitution components, 10wt%-45wt% organic acid-base neutralization components, and 10wt%-25wt% solvent components.

[0032] The crude oil electro-desalting and dechlorination agent of this invention is uniformly mixed with crude oil under the action of a mixer and then enters the electro-desalting device together. Through extraction, the chlorinated chemical additives and inorganic chlorides in the crude oil are extracted and dissolved in water. Through catalytic substitution reaction, the chlorine element in the organic chlorine complexes in the crude oil is replaced. Then, through acid-base neutralization, the dechlorinated corrosion products are neutralized to neutral and dissolved in water. Finally, they are removed through the electro-desalting and dehydration process, achieving the purpose of removing chlorine from the source of oil refining electro-desalting.

[0033] The extraction effect of this invention is achieved by an amino acid-type amphoteric surfactant with a specific HLB range. Within this specific HLB range, the lipophilic end of the amino acid-type amphoteric surfactant is adsorbed on the oil phase end of the oil-water emulsion interface, and the hydrophilic end is adsorbed on the aqueous phase end of the oil-water emulsion interface. This effectively reduces the interfacial tension of the oil-water emulsion, allowing salts and inorganic chlorides in the crude oil to be extracted from the crude oil into the aqueous phase.

[0034] Specifically, the extraction and demulsification component of this invention is one of the solutes in the entire system. The selected extraction component underwent multiple experiments, and the salt, metal, chlorine, and sulfur content of the extracted crude oil was analyzed. Ultimately, the effective component with the lowest content of each component in the extracted crude oil was selected. Through theoretical analysis and testing, the selected extraction component was an amino acid-type amphoteric surfactant with a small molecular weight and an HLB value in the range of 4-9, such as dodecylaminopropionic acid.

[0035] The catalytic substitution reaction of the present invention refers to the process by which, under the catalysis of alkali metals, the substitute provides a shared electron pair to the sulfur and chlorine-containing substances in crude oil, thereby breaking the π bonds of the sulfur and chlorine-containing substances in crude oil and forming water-soluble substitution products, without adding new pollutants to the crude oil.

[0036] Specifically, the substance that catalyzes the substitution reaction in this invention is one of the two solutes in the entire system. The alkali metal that plays a catalytic role refers to an alcohol solution containing potassium, sodium, and aluminum metals, and the substance that plays a substitution role is an organic alkaline substance synthesized from oleic acid and polyene polyamines.

[0037] The acid-base neutralization function of this invention uses water-soluble organic alkaline substances to neutralize corrosive substances produced by catalytic substitution reactions and extracted through extraction, thereby turning corrosive products extracted from crude oil into neutral substances and protecting devices and equipment from corrosion.

[0038] The substances involved in the neutralization reaction of organic acids and bases in this invention are methylamine, ethylamine, propylamine, etc.

[0039] The following are several specific embodiments of the crude oil electro-desalting and dechlorination agent of the invention.

[0040] Example 1

[0041] The crude oil electro-desalting and dechlorination agent comprises the following components by weight percentage: 5 wt% extraction and demulsification component, 5 wt% catalytic substitution component, 10 wt% organic acid-base neutralization component, and 10 wt% solvent component.

[0042] Example 2

[0043] The crude oil electro-desalting and dechlorination agent comprises the following components by weight percentage: 15 wt% extraction and demulsification component, 25 wt% catalytic substitution component, 35 wt% organic acid-base neutralization component, and 15 wt% solvent component.

[0044] Example 3

[0045] The crude oil electro-desalting and dechlorination agent comprises the following components by weight percentage: 27 wt% extraction and demulsification components, 43 wt% catalytic substitution components, 5 wt% organic acid-base neutralization components, and 5 wt% solvent components.

[0046] Please see Figure 1 The present invention also provides a method for preparing the above-mentioned oil-to-electric desalting and dechlorination agent, comprising:

[0047] Step 1: Place the solvent components into the reaction vessel and stir. Then, raise the temperature of the reaction vessel to 40°C and maintain the temperature for 10 minutes.

[0048] Step 2: Add the extraction and demulsification components to the reaction vessel, raise the temperature of the reaction vessel to 60°C and keep it at that temperature for 60 minutes.

[0049] Step 3: Add the catalytic substitution component to the reactor, raise the temperature of the reactor to 80°C and keep it at that temperature for 50 minutes.

[0050] Step 4: Stop heating, turn on the cooling circulating water to lower the temperature in the reactor to below 30°C, add the organic acid-base neutralizing components to the reactor and stir for 70 minutes.

[0051] The present invention also provides a method for using the above-mentioned oil-to-oil desalting and dechlorinating agent, comprising: mixing the crude oil desalting and dechlorinating agent with crude oil under the action of a mixer; and feeding the uniformly mixed crude oil desalting and dechlorinating agent and crude oil into an electric desalting device for reaction.

[0052] Specifically, the reaction pressure is 0 MPa–10 MPa, the reaction temperature is 40°C–120°C, the amount of crude oil desalting and dechlorinating agent added is 50 ppm–300 ppm, and the reaction time is more than 20 minutes. The effectiveness of the crude oil desalting and dechlorinating agent of this invention depends on the properties of the crude oil and the desired effect. It is generally recommended to first complete the evaluation in the laboratory to determine the optimal trial dosage, and the recommended addition amount is 200 ppm.

[0053] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the exemplary embodiments according to this application. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0054] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A crude oil electrostatic desalting and dechlorination agent, characterized in that, It includes the following components by weight percentage: extraction and demulsification components 5wt%-27wt%, catalytic substitution components 5wt%-43wt%, organic acid-base neutralization components 10wt%-45wt%, and solvent components 10wt%-25wt%. The extracted demulsifying component is an amino acid-type amphoteric surfactant. The HLB value of the extracted demulsifying component ranges from 4 to 9; The amino acid-type amphoteric surfactant is a dodecylaminopropionic acid derivative. The catalytic substitution component includes an alkali metal that plays a catalytic role and a substance that plays a substitution role, wherein the alkali metal that plays a catalytic role is an alcohol solution containing potassium or sodium metal. The substance that performs the substitution function is an organic basic substance synthesized from oleic acid and polyene polyamine; The organic acid-base neutralizing component is methylamine, ethylamine, or propylamine.

2. A method for preparing the crude oil electro-desalting and dechlorination agent as described in claim 1, characterized in that, include: The solvent components are placed in the reaction vessel and stirred. The temperature in the reaction vessel is raised to 40°C and then kept at that temperature for 10 minutes. Add the extraction and demulsification components to the reaction vessel, raise the temperature of the reaction vessel to 60°C and keep it at that temperature for 60 minutes; A catalytic substitution component is added to the reactor, and the temperature in the reactor is raised to 80°C and held for 50 minutes. Stop heating, turn on the cooling circulating water to lower the temperature in the reactor to below 30°C, add the organic acid-base neutralizing components to the reactor and stir for 70 minutes.

3. A method of using the crude oil electro-desalting and dechlorination agent as described in claim 1, characterized in that, include: The crude oil electro-desalting and dechlorination agent is mixed evenly with the crude oil under the action of a mixer; The crude oil desalting and dechlorination agent, which is mixed evenly, is fed into the crude oil desalting unit for reaction. The reaction pressure is 0MPa-10MPa, the reaction temperature is 40℃-120℃, the amount of crude oil desalting and dechlorination agent added is 50ppm-300ppm, and the reaction time is more than 20 minutes.

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