阅读说明：本技术 一种船用残渣燃料油稳定分散剂及其制备方法 (Marine residual fuel oil stabilizing dispersant and preparation method thereof ) 是由 赵迎秋 黄占凯 安峰 靳正正 于 2020-12-26 设计创作，主要内容包括：本发明涉及一种船用残渣燃料油稳定分散剂及其制备方法。本发明稳定分散剂以结构式为烷基酚聚醚羧酸为主剂,以一种或几种含有“沥青骨料”结构的低分子量物质为助剂,其制备方法包括先将具有m个环氧基团的烷基酚聚氧乙烯醚碱化后溶于溶剂中,加入氯乙酸取代反应后升温去除溶剂得到浅黄色粘稠状烷基酚聚氧乙烯醚羧酸盐,经酸洗分离得到烷基酚聚氧乙烯醚羧酸与含有“沥青骨料”结构的低分子量物质复配制得。本发明稳定分散剂通过聚醚羧酸与具有“沥青骨料”结构的助剂产生协同吸附作用,可防止沥青质分子的自缔合聚集,起到稳定燃料油体系的良好效果。(The invention relates to a stable residual fuel oil dispersant for ships and a preparation method thereof. The preparation method of the stabilizing dispersant comprises the steps of alkalifying alkylphenol polyoxyethylene ether with m epoxy groups, dissolving the alkylphenol polyoxyethylene ether in a solvent, adding chloroacetic acid for substitution reaction, heating to remove the solvent to obtain light yellow viscous alkylphenol polyoxyethylene ether carboxylate, and performing acid washing separation to obtain alkylphenol polyoxyethylene ether carboxylic acid and the low molecular weight substance with the asphalt aggregate structure for compounding. The stabilizing dispersant can prevent the self-association aggregation of asphaltene molecules by the synergistic adsorption effect of the polyether carboxylic acid and the auxiliary agent with an asphalt aggregate structure, and has good effect of stabilizing a fuel oil system.)

1. A stable dispersant for residual fuel oil for ships is characterized in that alkylphenol polyether carboxylic acid with a structural formula (I) is used as a main agent, and one or more low molecular weight substances containing an asphalt aggregate structure are used as auxiliary agents;

wherein n represents the length of an alkyl chain, n is 2-10, m is the number of epoxy, and m is 2-8;

the low molecular weight substance containing the asphalt aggregate structure is one or more of a pyridyl compound, a quinolyl compound and a tetrahydrofuryl compound.

2. The bunker fuel oil stabilizer dispersant of claim 1, wherein the mass ratio of said main agent to said auxiliary agent is 2.5 to 5.

3. A method of preparing the residual fuel oil stabilizing dispersant for ships of claim 1, comprising the steps of:

1) alkylphenol polyether carboxylic acid

Stirring and alkalizing alkylphenol polyoxyethylene ether with m epoxy groups for 1-3h at 45-50 ℃, adding a solvent, adding chloroacetic acid under the condition of uniform stirring to perform SN2 nucleophilic substitution addition reaction for 4-5 h, heating after the reaction is finished, and evaporating the solvent to obtain light yellow viscous alkylphenol polyoxyethylene ether carboxylate; washing with dilute hydrochloric acid solution, heating to promote separation of organic phase and water phase, collecting organic phase containing alkylphenol polyether carboxylic acid, and washing with distilled water to obtain alkylphenol polyoxyethylene carboxylic acid; the reaction molar ratio of the alkylphenol polyoxyethylene to the chloroacetic acid is 1: 1.5-1: 2.5;

2) compounding the alkylphenol polyoxyethylene ether carboxylic acid obtained in the step 1) and a low molecular weight substance containing an asphalt aggregate structure according to a mass ratio to obtain the residual fuel oil stabilizing dispersant.

4. The method according to claim 1, wherein the solvent is acetone.

Technical Field

The invention relates to the technical field of petroleum refining and processing, in particular to a stable dispersing agent for maintaining the stability of a marine residual fuel oil system in the using and storing processes and a preparation method thereof.

Background

In recent years, the dependence of petroleum resources in China on the outside is serious, the national energy safety situation is increasingly severe, the comprehensive utilization rate of the petroleum resources is improved to reduce the dependence degree of China on imported petroleum, and the method is an important problem which needs to be solved urgently in the petroleum industry of China. The residual oil is a heavy component left after crude oil resources are refined layer by layer, is extremely viscous, has no fluidity and poor combustibility, can only be used as asphalt paving materials or refined coke generally, has extremely low economic value and causes inefficient use of petroleum resources. If the highly viscous residual oil is blended with light oil such as diesel oil to reduce the viscosity and improve the fluidity of the oil, the oil can more fully exert the energy attribute when being made into the marine fuel oil, and the method is one of effective means for improving the comprehensive utilization rate of petroleum resources. However, when the residual oil is mixed with the light diesel oil, the aromatic hydrocarbon atmosphere for stabilizing asphaltene colloid in the residual oil is diluted and replaced by chain alkane in the light oil, and a colloid system with relatively stable asphaltene is destroyed, so that very viscous organic matter precipitates such as colloid and asphaltene are easily separated out, and the mixed oil cannot be normally used.

Disclosure of Invention

Aiming at the problems in the prior art, the invention develops a stable dispersing agent which can stably disperse the asphaltene in the residual oil in the blended oil under the blending conditions of oil materials with different properties to prevent the asphaltene from being separated out so as to ensure the stability and normal use of the residual fuel oil for ships.

According to the problem of easy asphaltene precipitation caused by the difference of properties and compositions among the components of the fuel oil, firstly, an alkylphenol polyether carboxylic acid is designed and synthesized as a stable dispersion main agent, a substance with an asphalt aggregate structure is used as a dispersion auxiliary agent, and the alkylphenol polyether carboxylic acid and the substance are combined into the stable dispersant for the residual fuel oil. The carboxyl of the alkylphenol polyether carboxylic acid and the heteroatom in the asphaltene molecule are adsorbed around the asphaltene molecule through the hydrogen bond effect, meanwhile, m epoxy groups in the polyether carboxylic acid molecule further enhance the polarity of the polyether carboxylic acid molecule, so that the polyether carboxylic acid molecule can generate stronger dipole adsorption effect with the polar asphaltene molecule, the firmer adsorption of the polyether carboxylic acid on the asphaltene molecule is enhanced, meanwhile, the benzene ring on the molecular chain can form delocalized pi bond conjugation with the benzene ring of the asphaltene molecule, the adsorption of the polyether amide molecule on the asphaltene molecule is further enhanced, and the alkyl on the polyether molecule plays a steric hindrance effect to prevent the self-association between the asphaltene molecule. Meanwhile, the dispersing aid with the structure of the asphalt aggregate is similar to the structure of asphaltene molecules, and is adsorbed around the asphaltene molecules through the delocalized large pi bond conjugation, so that the self-association between the asphaltene molecules is further prevented. The specific technical scheme is as follows:

the invention provides a composite stable dispersant for marine residual fuel oil, which takes alkylphenol polyether carboxylic acid with a structural formula (I) as a main agent and one or more low-molecular-weight substances containing an asphalt aggregate structure as an auxiliary agent;

wherein n represents the length of an alkyl chain, n is 2-10, m is the number of epoxy, and m is 2-8;

the low molecular weight substance containing the asphalt aggregate structure is one or more of a pyridyl compound, a quinolyl compound and a tetrahydrofuryl compound.

The mass ratio of the main agent to the auxiliary agent is preferably 2.5-5.

The invention also provides a preparation method of the marine residual fuel oil stabilizing dispersant, which comprises the following steps:

1) alkylphenol polyether carboxylic acid

Stirring and alkalizing alkylphenol polyoxyethylene ether with m epoxy groups for 1-3h at 45-50 ℃, adding a solvent, adding chloroacetic acid under the condition of uniform stirring to perform SN2 nucleophilic substitution addition reaction for 4-5 h, heating after the reaction is finished, and evaporating the solvent to obtain light yellow viscous alkylphenol polyoxyethylene ether carboxylate; washing with dilute hydrochloric acid solution, heating to promote separation of organic phase and water phase, collecting organic phase containing alkylphenol polyether carboxylic acid, and washing with distilled water to obtain alkylphenol polyoxyethylene carboxylic acid; the reaction molar ratio of the alkylphenol polyoxyethylene to the chloroacetic acid is 1: 1.5-1: 2.5;

2) compounding the alkylphenol polyoxyethylene ether carboxylic acid obtained in the step 1) and a low molecular weight substance containing an asphalt aggregate structure according to a mass ratio to obtain the residual fuel oil stabilizing dispersant.

Wherein the solvent is preferably acetone.

The polyether carboxylic acid and the additive with the structure of asphalt aggregate can generate a synergistic adsorption effect, so that the stabilizing dispersant disclosed by the invention can form a polyether carboxylic acid molecule adsorption layer around asphalt molecules, and meanwhile, the additive molecules with the structure of asphalt aggregate are inserted into the gap of the polyether carboxylic acid molecule to adsorb a composite adsorption layer again, thereby effectively preventing the self-association aggregation of the asphalt molecules and playing a good role in stabilizing a fuel oil system.

The specific implementation mode is as follows:

the technical solution and the effects of the present invention will be described in detail with reference to the following examples. However, the content of the present embodiment is illustrative, and the present invention is not limited in any way, and the protection scope of the present invention is not limited thereby.

Example 1: marine residual fuel oil stabilizing dispersant 1^#Preparation of

(1) 30.03g alkylphenol polyether with two epoxy groups is heated to 45 ℃, 14g sodium hydroxide is added to alkalize for 2h, 30g acetone is added, 14.75g chloroacetic acid is added to carry out SN2 nucleophilic substitution addition reaction for 4h at 45 ℃ under the condition of uniform stirring. After the reaction was completed, the temperature was adjusted to 58 ℃ to distill off acetone to obtain alkylphenol polyether carboxylate as a pale yellow viscous substance. The product was acid washed with 2000ml of 0.2M dilute hydrochloric acid solution and appropriately heated to promote separation of the organic and aqueous phases, and the organic phase containing alkylphenol polyether carboxylic acid was collected and washed with distilled water to obtain 31.35g of alkylphenol polyoxyethylene ether carboxylic acid with a yield of 87.83%. And (3) combining the synthesized alkylphenol polyether carboxylic acid and 8.52g of isoquinoline to form a stable dispersant.

Example 2: marine fuel oil stabilizing dispersant 2^#Preparation of

(1) Heating 35.05g alkylphenol polyether with three epoxy groups to 47 ℃, adding 14g of sodium hydroxide for alkalization for 2h, adding 30g of acetone, adding 18.53g of chloroacetic acid at 47 ℃ under the condition of uniform stirring for SN2 nucleophilic substitution addition reaction for 4.5 h. After the reaction was completed, the temperature was adjusted to 58 ℃ to distill off acetone to obtain alkylphenol polyether carboxylate as a pale yellow viscous substance. The product was acid washed with 2000ml of 0.2M dilute hydrochloric acid solution and appropriately heated to promote separation of the organic phase from the aqueous phase, and the organic phase containing alkylphenol polyether carboxylic acid was collected and washed again with distilled water to obtain 35.52g of alkylphenol polyoxyethylene ether carboxylic acid with a yield of 86.95%. And (3) combining the synthesized alkylphenol polyether carboxylic acid and 10.08g of quinoline to form the stable dispersing agent.

Example 3: marine fuel oil stabilizing dispersant 3^#Preparation of

(1) 52.13g of alkylphenol polyether with seven epoxy groups is heated to 50 ℃, 14g of sodium hydroxide is added to be alkalized for 2h, 30g of acetone is added, 20.05g of chloroacetic acid is added to carry out SN2 nucleophilic substitution addition reaction for 5h under the condition of 50 ℃ and uniform stirring. After the reaction was completed, the temperature was adjusted to 58 ℃ to distill off acetone to obtain alkylphenol polyether carboxylate as a pale yellow viscous substance. The product was acid washed with 2000ml of 0.2M dilute hydrochloric acid solution and appropriately heated to promote separation of the organic and aqueous phases, and the organic phase containing alkylphenol polyether carboxylic acid was collected and washed again with distilled water to obtain 51.13g of alkylphenol polyoxyethylene ether carboxylic acid with a yield of 88.24%. And (3) combining the synthesized alkylphenol polyether carboxylic acid and 15.57g of tetrahydrofuran to form a stable dispersing agent.

Example 4: evaluation of the Properties of the three bunker Fuel oil stabilizing dispersants prepared in examples 1 to 3

(1) Experimental materials

The main physicochemical parameters of the bunker fuel oil used in this example, which is the blended fuel oil provided by a certain refinery, are shown in table 1.

TABLE 1 physicochemical Properties of Fuel oils blended in a refinery

Performance index	Numerical value/%)
		Density (20 ℃ C.)/(g. cm)3)	0.998
Kinematic viscosity (50 ℃ C.)/(mm)2·s-1)	1380
		Content of gum/%)	22.95
Asphaltene content/%)	13.31
		Saturated hydrocarbon content/%)	13.56
Content of aromatic hydrocarbons/%)	50.18

(2) Experimental methods

At normal temperature, 5g of alkylphenol polyether amide provided by the invention is dispersed in 5g of specific organic solvent to prepare a fuel oil stabilizer solution with the mass fraction of 50% for standby.

Weighing 25g +/-1 g of uniformly mixed fuel oil sample added with the stabilizer in a conical flask, plugging the sample by using a cork with an air condenser, and then putting the sample into an air sleeve of an aging oil bath at 100 +/-0.5 ℃ for aging for 24h +/-15 min. After the aging was completed, the flask was removed, the air condenser was replaced with a cork and the flask was shaken vigorously to know that all the sludge was suspended, and the bottom and inner wall of the flask were scraped off with a spatula. Total potential precipitate was then determined by thermal filtration according to the test procedure specified in chapter 8 of the SH/T0701-2001 residual fuel oil Total precipitate determination (thermal filtration). The fuel oil samples without stabilizers were also aged for 24h and treated in the same way as blank control samples.

(3) Results of the experiment

The evaluation results of the stability performance of the bunker fuel oil are shown in table 2:

TABLE 2 evaluation effect of stability aid for bunker fuel oil

As can be seen from the data in Table 2, the total deposits of the fuel oil added with the fuel oil stability additive prepared by the invention are all below 0.04 percent and completely meet the index requirements of no more than 0.1 percent in the relevant standards.