阅读说明：本技术 一种用于高酸原油及其馏分油脱酸剂的制备 (Preparation of deacidifying agent for high-acid crude oil and distillate oil thereof ) 是由 胡宝清 王栋 余彬 于 2021-01-14 设计创作，主要内容包括：本发明公开了一种用于高酸原油及其馏分油脱酸剂的制备,涉及高酸原油脱酸剂制备技术领域,其包括溶剂组方A和有机胺组方B；所述溶剂组方A由乙醇、异丙醇、水溶性破乳剂、聚季铵盐和水组成,所述有机胺组方B是由沸点高低不同、碱性强弱不同、分子链长不同的有机胺及羟基胺组成,由氨水、羟乙基胺、多乙烯多胺和水组成,并根据高酸原油及其馏分油特性及酸值按一定比例搭配使用。该用于高酸原油及其馏分油脱酸剂的制备,制备的高酸原油及其馏分油脱酸剂,可根据原油及馏分油酸值、粘度等变化采用不同的组合比例进行添加脱酸,适用范围广,脱酸率高。(The invention discloses a preparation method of a deacidification agent for high-acid crude oil and distillate oil thereof, relating to the technical field of preparation of deacidification agents for high-acid crude oil, and comprising a solvent formula A and an organic amine formula B; the solvent formula A consists of ethanol, isopropanol, a water-soluble demulsifier, polyquaternary ammonium salt and water, the organic amine formula B consists of organic amine and hydroxylamine with different boiling points, different alkalinity and different molecular chain lengths, and consists of ammonia water, hydroxyethyl amine, polyethylene polyamine and water, and the organic amine formula B is matched according to a certain proportion according to the characteristics of high-acid crude oil and distillate oil thereof and the acid value. The deacidification agent for the high-acid crude oil and the distillate oil thereof can be used for preparing the deacidification agent for the high-acid crude oil and the distillate oil thereof, can be added and deacidified according to different combination proportions according to the changes of acid values, viscosities and the like of the crude oil and the distillate oil, and has wide application range and high deacidification rate.)

1. The preparation method of the deacidification agent for the high-acid crude oil and the distillate oil thereof comprises a solvent formula A and an organic amine formula B, and is characterized in that: the solvent formula A comprises 17-25% of ethanol, 8-15% of isopropanol, 0.1-0.3% of water-soluble demulsifier, 0.1-0.3% of polyquaternary ammonium salt and the balance of water, the organic amine formula B comprises organic amine and hydroxylamine with different boiling points, different alkalinity and different molecular chain lengths, and comprises ammonia water, hydroxyethylamine, polyethylene polyamine and water, wherein the mass fraction of the ammonia water is 8-10%, the mass fraction of the hydroxyethylamine is 35-40%, the mass fraction of the polyethylene polyamine is 5-8%, and the balance of water.

2. The preparation of deacidification agent for high acid crude oil and distillate oil thereof according to claim 1, characterized in that: the water-soluble demulsifier can be selected from block polyether of ethylenediamine, trihydroxymethane and glycerol, and preferably block polyether of ethylenediamine; the polyquaternary ammonium salt can be copolymer of acrylamide and N, N-dimethyl diallyl ammonium chloride, or condensate of dimethylamine, polyamine and epichlorohydrin, preferably condensate of dimethylamine, polyamine and epichlorohydrin.

3. The preparation of deacidification agent for high acid crude oil and distillate oil thereof according to claim 1, characterized in that: the hydroxyethylamine can be selected from hydroxyethylamine, triethanolamine, and hydroxyethylethylenediamine, preferably hydroxyethylethylenediamine; the polyethylene polyamine in the organic amine formula B can be selected from aminoethyl piperazine, triethylene tetramine and tetraethylenepentamine, preferably triethylene tetramine.

4. The preparation of deacidification agent for high acid crude oil and distillate oil thereof according to claim 1, characterized in that: the solvent formula A and the organic amine formula B are matched according to the high-acid crude oil, the distillate oil characteristics and the acid value of the high-acid crude oil according to a certain proportion, and the addition amount of the organic amine formula B is as the addition amount multiple, namely, the addition amount multiple = the acid value of the oil multiplied by the mass of the oil/(the neutralization value of the deacidification agent multiplied by the mass of the deacidification agent); for diesel oil, the addition amount of the solvent formula A is 0 percent of the mass of the oil, and the addition multiple of the organic amine formula B is 2.0-3.0, preferably 2.5; for wax oil, the addition amount of the solvent formula A is 10-15% of the oil mass, and the addition multiple of the organic amine formula B is 2.5-3.5, preferably 3.0; for high acid crude oil, the addition amount of the solvent formula A is 15-20% of the oil mass, and the addition multiple of the organic amine formula B is 3.5-4.5, preferably 4.0.

Technical Field

The invention relates to the technical field of preparation of deacidification agents for high-acid crude oil, in particular to preparation of deacidification agents for high-acid crude oil and distillate oil thereof.

Background

With the heavy and inferior crude oil, the yield of the crude oil with high acid value is continuously increased, and the processing of the crude oil is more and more emphasized because the high acid value crude oil has low price and can bring rich benefit to refineries. However, the high acid content crude oil is unfavorable for the primary processing of the crude oil, seriously corrodes equipment, influences safe production and also influences the service performance of petroleum products.

The acidic components in petroleum generally refer to naphthenic acids, other carboxylic acids, inorganic acids, phenols, mercaptans, etc., wherein the naphthenic acids and other organic acids can be collectively referred to as petroleum acids, and the mass fraction of naphthenic acids in general acid-containing crude oil accounts for more than 85% of the petroleum acids, so the petroleum acids are conventionally referred to collectively as naphthenic acids. The compositional structure studies of petroleum acids have shown that the acidic components in petroleum are mainly carboxylic acids, including small amounts of fatty acids and dicarboxylic acids in addition to naphthenic acids of various structures. The petroleum carboxylic acid has stronger acidity like saturated carboxylic acid, can carry out amidation, esterification and neutralization reactions, has the strongest acid corrosion to metal and has the greatest harm. The compounds such as phenols and thiols are weak in acidity, small in content and low in corrosiveness.

To reduce the effect of petroleum acid corrosion, the following 4 methods are often adopted by refineries: one is the neutralization of acid components in petroleum with various basic compounds. However, the reaction of petroleum carboxylic acid with alkali to form soap can emulsify viscous crude oil, which causes difficulty in desalting and dewatering crude oil, and increases the salt content in the crude oil after dewatering, thus affecting the subsequent processing of crude oil. And secondly, a large amount of corrosion-resistant metal materials are used in the oil refining equipment. These materials are expensive, increasing the cost of refining, and are impractical to use with new corrosion resistant materials, particularly for existing refineries. And thirdly, the corrosion inhibitor is added into the crude oil, but the refining cost is increased, and particularly, the phosphorus-containing corrosion inhibitor can influence the subsequent device processing process, and the activity and the service life of the catalyst are reduced. And fourthly, the method is the most common method for processing the high-acid-value crude oil and the low-acid-value crude oil by mixing in an oil refinery, but the method is often limited by the supply amount of the low-acid-value crude oil and the storage amount of a crude oil tank in the oil refinery, and particularly for the crude oil with high acid value, the blending amount of the low-acid-value crude oil is required to be large, so that the processing amount of the high-acid-value crude oil is greatly reduced.

A great deal of research work is carried out on crude oil deacidification at home and abroad, and the crude oil deacidification is divided into a physical separation method and a chemical conversion method according to the deacidification process. The physical separation is to separate and recycle the naphthenic acid as a whole, and the chemical conversion is to destructively remove carboxyl in the acid.

The physical separation method is characterized in that the chemical state of naphthenic acid is basically not destroyed and the naphthenic acid is separated from crude oil. The adopted method comprises adsorption separation and solvent extraction. The adsorption separation technology is earlier applied to the separation of naphthenic acid, the process is mature, and the removal of the naphthenic acid is mainly realized by utilizing the difference of the adsorption capacity of petroleum fraction and the adsorption capacity of the naphthenic acid on an adsorbent. The adsorbent used is ion exchange resin, silica gel, silicate, zeolite, or the like. The adsorption separation is adopted to obtain high-quality naphthenic acid products while deacidifying, but corresponding adsorption and desorption devices are also required to be established, so that the operation cost is very high, and the adsorption separation is not suitable for high-viscosity and high-acid crude oil due to the characteristics of the adsorption. The solvent extraction is based on similar compatibility principle, and utilizes the difference of petroleum acid and petroleum component polarity to select proper solvent to extract naphthenic acid from crude oil, and the commonly used solvent includes phenol, aldehyde and alcohol. The solvent extraction can reduce the acidity and corrosivity of the crude oil, and can refine the crude oil to improve the quality of the crude oil. But deacidification by a solvent extraction method has the problems of solvent selection, extraction process optimization, solvent recovery and the like. Especially, the requirements on the proportion of a solvent system are very strict, and the respective solvent system proportion needs to be selected for deacidification of different crude oils, so that the key for searching the solvent system with wide application range, good selectivity and low cost and preventing the deterioration of the recovered solvent is the practicability of the technology. Furthermore, if the naphthenic acids extracted by solvent extraction are not well purified and utilized, the solvent extraction process is economically non-competitive.

The deacidification by chemical conversion method comprises acid-base neutralization method, esterification method, thermal conversion method, hydrogenation method and the like. The acid-base neutralization method is to remove petroleum acid from crude oil by utilizing the chemical property of the petroleum acid, and usually, the weak acid property of the petroleum acid can be utilized to convert the petroleum acid into salts which are easy to remove by neutralization reaction.

Early crude oil deacidification processes primarily utilized bases to neutralize the carboxyl groups in the petroleum acid molecules to effectively control naphthenic acid corrosion. And because of low cost and simple operation, the method is widely adopted by domestic and foreign refineries. However, for crude oil, especially for high acid crude oil, the method can form serious emulsification in the deacidification process, so that the deacidification rate is too low; at the same time, potassium and sodium metals are introduced into the crude oil, which causes downstream catalyst poisoning and influences deep processing. The alkali injection can also cause the equipment to crack slightly under the corrosion of alkali liquor, and can have adverse effects on the quality and the deep processing of the heavy oil. The substitution of ammonia or amines for caustic and the addition of organic solvents is currently one of the most actively studied methods in the deacidification field, essentially converting naphthenic acids into more water-soluble salts, and then separating the salts out using solvents. The method for neutralizing by ammonia or amine has the advantages of good deacidification effect, wide application range and small environmental pollution, but has the problems of large dosage of deacidification agent and solvent, long recovery and purification process and low recovery rate.

The esterification method is to add a certain amount of alcohol and alcohol amine into acid-containing crude oil and convert the acid into ester under certain temperature and pressure and in the presence of a catalyst. The deacidification method has the advantages of less deacidification investment and low operation cost, and the deacidification agent can be recycled, thereby having considerable industrialization prospect, but having the problem of low deacidification rate.

The thermal conversion method is based on the fact that petroleum acid has poor thermal stability at high temperature and can be thermally decomposed and decarboxylated to generate hydrocarbon and CO when heated₂Thermal deacidification is based on this principle. The reaction gaseous products are mainly water vapor and CO₂CO and a small amount of C₁-C₄A hydrocarbon. However, it is noted that when thermal deacidification is carried out at high temperatures, organic acids in crude oil are highly corrosive and a special catalyst must be used to lower the thermal deacidification temperature. At present, the preparation of high-efficiency catalyst, the reduction of catalyst cost and the increase of catalyst cycle times still have a plurality of problems; in addition, during the thermal deacidification reaction, some components in the crude oil may undergo cracking or condensation reactions, thereby causing changes in the physicochemical properties of the crude oil, which may affect the further processing and the quantity and quality of high-quality oil products.

The hydrogenation method can change the structure of the petroleum acid, effectively remove the petroleum acid and improve the quality of the oil product. But the investment and operation cost of hydrogenation is high, and chemical raw material resources such as petroleum acid and the like can be eliminated.

Patent CN101058745A mentions that tetraalkyl quaternary ammonium hydroxide and small molecular alcohol are used to prepare solution as deacidification agent; CN1353746A deacidifies with IIA group metal hydroxide, quaternary ammonium salt phase transfer agent, emulsifier, alcohol ether solvent, and then adds demulsifier to promote oil and solvent phase separation; CN101538477A is deacidified by ammonia water and demulsifier, and is recovered and recycled by organic amine reduction deacidification agent; CN101353592A is used for diesel deacidification by adopting a mixture of ammonia water and small molecular alcohol; CN1810757A is prepared by a compound of micromolecular imidazole and micromolecular alcohol, and then imidazole is recovered by adding acid and distilling for recycling; CN1563283A is composed of ammonia water, micromolecular alcohol amine, inorganic salt flocculant, micromolecular alcohol and demulsifier, and is suitable for deacidifying crude oil and distillate oil; CN1418934A adopts sodium hydroxide (or potassium hydroxide) as neutralizer, sodium naphthenate for solubilizing and demulsifier to compound as deacidification agent; CN105419863A mentions that a mixture of ammonia and ethanol is used as a deacidification agent; CN101016477A mentions that small molecule primary amine, alcohol amine, polyethylene polyamine and alkali metal or alkaline earth metal hydroxide or phosphate are used as deacidification agent; CN106497597A adopts quaternary ammonium salt, sodium hydroxide and sodium carbonate as deacidification agent; in CN104357082A, sodium hydroxide inorganic base is used as a deacidification main agent, and organic base alcohol amine, inorganic salt and an organic active agent (surfactant) are used as deacidification auxiliaries; CN1461795A is deacidified by using monohydric alcohol, dihydric alcohol or trihydric alcohol as solvent and ammonia as deacidifying agent.

In the above-mentioned patent, the emulsifier is used to enhance the dispersion contact of oil and water, but it is easy to increase the emulsibility and increase the difficulty of oil-water separation, and in the neutralization process, it can produce many naphthenate emulsifiers, and the quaternary ammonium salt phase transfer agent is used to raise the neutralization efficiency of naphthenic acid, but the long-chain quaternary ammonium salt is easy to complex with large-molecular naphthenate to form colloid, and then is difficult to enter into water, so that it is easy to be lost, and the tetra-alkyl quaternary ammonium base is strong in alkalinity, and can easily implement neutralization reaction with naphthenic acid to form salt, but when it is recovered, it must use stronger alkali or strong alkali under the anhydrous condition, and when its temperature is higher, it is easy to hydrolyze, and its price is high, and its recovery is difficult, and the naphthenate produced during deacidification by inorganic strong alkali is strong in emulsibility, so that it is not easy to separate oil and water, and can result in that the naphthenate content is, the single ammonia water alcohol solution also has the defects of easy emulsification of oil and water and difficult layering of the oil and the water, and has narrow application range to crude oil and distillate oil with different characteristics and acid values.

Therefore, there is a need for a process for the preparation of deacidification agents for highly acidic crude oils and fractions thereof to solve the above problems.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a preparation method for a deacidification agent for high-acid crude oil and distillate oil thereof, which solves the problems that the emulsifying agent is adopted to enhance the emulsifying property when oil and water are dispersed and contacted, so that the oil and water separation is difficult to increase, a plurality of naphthenate emulsifying agents are generated in the neutralization process, a quaternary ammonium salt phase transfer agent is adopted to improve the neutralization efficiency of naphthenic acid, but long-chain quaternary ammonium salt is easy to be complexed with larger-molecular naphthenate to form glue and is difficult to enter water again, the loss is easy to generate, the basicity of tetraalkyl quaternary ammonium base is strong, the reaction with the naphthenic acid neutralization salt formation is easy to be carried out, but the reaction at higher temperature is easy to hydrolyze, the price is high, the recovery is difficult, the naphthenate generated in the deacidification of inorganic strong alkali is strong, the oil and water are difficult to separate, the naphthenic acid salt content in the crude oil is high, the metal ion, the single ammonia water alcohol solution also has the defects of easy emulsification of oil and water and difficult layering of the oil and the water, and has the problems of narrow application range to crude oil and distillate oil with different characteristics and acid values, and the like.

(II) technical scheme

In order to achieve the above purposes, the technical scheme adopted by the invention is as follows: a deacidifying agent for high-acid crude oil and distillate oil thereof is prepared from solvent formula A and organic amine formula B, the solvent formula A consists of ethanol, isopropanol, a water-soluble demulsifier, polyquaternary ammonium salt and water, wherein the mass fraction of ethanol is 17-25%, the mass fraction of isopropanol is 8-15%, the mass fraction of water-soluble demulsifier is 0.1-0.3%, the mass fraction of polyquaternary ammonium salt is 0.1-0.3%, and the balance is water, the organic amine formula B consists of organic amine and hydroxylamine with different boiling points, different alkalinity and different molecular chain lengths, and consists of ammonia water, hydroxyethyl amine, polyethylene polyamine and water, wherein the mass fraction of the ammonia water is 8-10%, the mass fraction of the hydroxyethylamine is 35-40%, the mass fraction of the polyethylene polyamine is 5-8%, and the balance is water.

Preferably, the water-soluble demulsifier can be selected from block polyether of ethylenediamine, trihydroxymethane and glycerol, and preferably block polyether of ethylenediamine; the polyquaternary ammonium salt can be copolymer of acrylamide and N, N-dimethyl diallyl ammonium chloride, or condensate of dimethylamine, polyamine and epichlorohydrin, preferably condensate of dimethylamine, polyamine and epichlorohydrin.

Preferably, the hydroxyethylamine can be selected from dihydroxyethylamine, triethanolamine or hydroxyethylethylenediamine, preferably hydroxyethylethylenediamine; the polyethylene polyamine in the organic amine formula B can be selected from aminoethyl piperazine, triethylene tetramine or tetraethylene pentamine, and preferably triethylene tetramine.

Preferably, the solvent formula A and the organic amine formula B are matched according to the characteristics and acid values of the high-acid crude oil and distillate oil thereof according to a certain proportion, and the addition amount of the organic amine formula B is the acid value of the oil multiplied by the mass of the oil/(the neutralization value of the deacidification agent multiplied by the mass of the deacidification agent); for diesel oil, the addition amount of the solvent formula A is 0 percent of the mass of the oil, and the addition multiple of the organic amine formula B is 2.0-3.0, preferably 2.5; for wax oil, the addition amount of the solvent formula A is 10-15% of the oil mass, and the addition multiple of the organic amine formula B is 2.5-3.5, preferably 3.0; for high acid crude oil, the addition amount of the solvent formula A is 15-20% of the oil mass, and the addition multiple of the organic amine formula B is 3.5-4.5, preferably 4.0.

(III) advantageous effects

The invention has the beneficial effects that:

1. the deacidification agent for the high-acid crude oil and the distillate oil thereof, which is prepared by the invention, can be added and deacidified in different combination proportions according to the changes of acid values, viscosities and the like of the crude oil and the distillate oil, and has wide application range and high deacidification rate.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a technical scheme that: a preparation method for deacidification agents of high-acid crude oil and distillate oil thereof comprises a solvent formula A and an organic amine formula B, wherein the solvent formula A consists of 17-25% by mass of ethanol, 8-15% by mass of isopropanol, 0.1-0.3% by mass of a water-soluble demulsifier, 0.1-0.3% by mass of a polyquaternium and the balance of water, the water-soluble demulsifier can be selected from block polyethers of ethylenediamine, trihydroxymethane and glycerol, and preferably is the block polyether of ethylenediamine; the polyquaternary ammonium salt can be selected from a copolymer of acrylamide and N, N-dimethyl diallyl ammonium chloride, or a condensate of dimethylamine, polyamine and epichlorohydrin, preferably a condensate of dimethylamine, polyamine and epichlorohydrin, the organic amine component B is composed of organic amine and hydroxylamine with different boiling points, different alkalinity, different molecular chain lengths, and comprises ammonia water, hydroxyethylamine, polyethylene polyamine and water, wherein the mass fraction of the ammonia water is 8-10%, the mass fraction of the hydroxyethylamine is 35-40%, the mass fraction of the polyethylene polyamine is 5-8%, and the balance is water, and the hydroxyethylamine can be selected from hydroxyethylamine, triethanolamine and hydroxyethylethylenediamine, preferably hydroxyethylethylenediamine; the polyethylene polyamine in the organic amine formula B can be selected from aminoethyl piperazine, triethylene tetramine and tetraethylenepentamine, preferably triethylene tetramine, the solvent formula A and the organic amine formula B are matched according to the characteristics and the acid value of the high-acid crude oil and the distillate oil thereof according to a certain proportion, and the addition of the organic amine formula B is the acid value of the oil multiplied by the mass of the oil/(the neutralization value of the deacidification agent multiplied by the mass of the deacidification agent) in terms of the addition multiple; for diesel oil, the addition amount of the solvent formula A is 0 percent of the mass of the oil, and the addition multiple of the organic amine formula B is 2.0-3.0, preferably 2.5; for wax oil, the addition amount of the solvent formula A is 10-15% of the oil mass, and the addition multiple of the organic amine formula B is 2.5-3.5, preferably 3.0; for high acid crude oil, the addition amount of the solvent formula A is 15-20% of the oil mass, and the addition multiple of the organic amine formula B is 3.5-4.5, preferably 4.0.

The method comprises the following operation steps:

s1, preparing a solvent formula A according to the mass percentage: 20% of ethanol, 10% of isopropanol, 0.2% of block polyether of water-soluble demulsifier ethylenediamine, 0.2% of condensation product of dimethylamine, polyamine and epichlorohydrin and 69.6% of water, and uniformly mixing the components according to a proportion to obtain a solvent formula A; the organic amine formula B is prepared by the following components in percentage by mass: 10% of ammonia water, 36% of hydroxyethyl ethylenediamine, 6% of triethylene tetramine and 48% of water, and uniformly mixing the components in proportion to obtain an organic amine component B;

s2, deacidifying the diesel oil cut from the high-acid crude oil, the wax oil cut from the high-acid crude oil and the high-acid crude oil respectively by using a solvent formula A and an organic amine formula B prepared by S1, wherein the deacidification method comprises the following steps: sampling and measuring the acid value of the crude oil or distillate oil to be Y by adopting the method in GB/T264-88₀Weighing 70g of crude oil or distillate oil (the acid value is Y)₀) In the three-neck flask, a condenser pipe is arranged on the three-neck flask, a stirring device is arranged, and then the three-neck flask is placed in a constant temperature water bath tank to be preheated to a preset temperature; calculating the addition amount of a deacidification agent according to the acid value and the addition amount of crude oil, adding a set amount of a solvent formula A and an organic amine formula B into a three-neck flask, heating to a preset deacidification temperature under stirring, stirring at a rotating speed of 350r/min for 2-5min, stopping stirring, and standing in a constant-temperature water bath for 2-12 h; the crude oil or distillate oil is divided into two layers, the upper layer is deacidified oil, the lower layer is solvent phase of organic amine naphthenate, the lower layer is carefully taken out and all the solvent is added into a beaker (the beaker is weighed in advance and is m₀Expressed in above), 50% sulfuric acid is dripped into a beaker filled with a solvent phase under electromagnetic stirring, the pH value of the solvent phase is adjusted to 2.0, the solvent phase in the beaker is divided into two layers at this time, the upper layer is a crude naphthenic acid layer, the lower layer is a water layer, the lower layer aqueous solution is removed by standing, crude naphthenic acid is remained in the beaker, a certain amount of distilled water is added into the beaker, the mixture is stirred and washed, the lower layer water is separated by standing, the mixture is washed for 3 times, then the mixture is dried in vacuum at 110 ℃ for 2 hours for removing water, the mixture is cooled in a drier and weighed, and the mass is m₁Mass m of naphthenic acid is removed₂＝m₁-m₀(ii) a Sampling to measure the acid value of naphthenic acid as Y₁Separating the obtained total naphthenic acid X ═ m₂×Y₁When the deacidification rate is m₂×Y₁/(700×Y₀)×100％；

S3, deacidifying test conditions and results of the crude oil and distillate oil are shown in the following table:

the above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.