阅读说明：本技术 一种树脂聚合液破乳剂及其制备方法 (Demulsifier for resin polymerization liquid and preparation method thereof ) 是由 田民格 曾俊 李爱兵 闫炜 高德超 郏瑞花 曾志农 杨庆军 田沛霖 于 2021-11-25 设计创作，主要内容包括：本发明属于破乳剂生产技术领域,涉及一种树脂聚合液破乳剂,原料包括以下重量百分比组分：30%-40%的改性胺基化淀粉,10%-20%的聚氧乙烯聚氧丙烯嵌段聚醚,1%-3%的无机盐,5%-10%的渗透剂,1%-3%消泡剂和余量水。本发明还公开了一种上述树脂聚合液破乳剂的制备方法。本发明相比现有技术具有以下优点：该破乳主剂是一种高分子量具有亲水亲油两种性能,低表面张力快速打破油水界面膜,与亲水性物质作用,使其中的油被释放,达到优异的油水分离效果。然后,与其他破乳助剂协调作用,达到油、水分别聚集,两相快速分层的目的。基于各组分组成,制定相应的工艺步骤和各组分添加顺序,复配得到体系稳定的树脂聚合液破乳剂。(The invention belongs to the technical field of production of demulsifiers, and relates to a demulsifier for a resin polymerization liquid, which comprises the following raw materials in percentage by weight: 30-40% of modified aminated starch, 10-20% of polyoxyethylene polyoxypropylene block polyether, 1-3% of inorganic salt, 5-10% of penetrating agent, 1-3% of defoaming agent and the balance of water. The invention also discloses a preparation method of the resin polymerization liquid demulsifier. Compared with the prior art, the invention has the following advantages: the demulsifying main agent has two performances of hydrophilicity and lipophilicity, and can quickly break an oil-water interface film by low surface tension to act with hydrophilic substances, so that oil in the oil-water interface film is released, and an excellent oil-water separation effect is achieved. Then, the emulsion breaking agent and other emulsion breaking additives are coordinated to achieve the purposes of respectively gathering oil and water and quickly layering two phases. Based on the composition of each component, corresponding process steps and the adding sequence of each component are formulated, and the resin polymerization liquid demulsifier with stable system is obtained through compounding.)

1. A demulsifier for resin polymerization liquid is characterized in that: the raw materials comprise the following components in percentage by weight: 30-40% of modified aminated starch, 10-20% of polyoxyethylene polyoxypropylene block polyether, 1-3% of inorganic salt, 5-10% of penetrating agent, 1-3% of defoaming agent and the balance of water; the modified aminated starch comprises an initiator, a catalyst and a chain extender, wherein the initiator, the catalyst and an epoxide react to prepare the modified aminated starch.

2. The demulsifier for a resin polymerization fluid of claim 1, wherein: the initiator is amylopectin; the catalyst is a metal catalyst; the chain extender is diethylenetriamine.

3. The demulsifier for resin polymerization fluids according to claim 2, wherein: the preparation method of the modified aminated starch comprises the following steps:

(1) taking amylopectin as raw material, reacting with air under the catalysis of metal catalyst until 3200-3600cm^-1The hydroxyl peak disappears to obtain a first reaction intermediate;

(2) and (2) dropwise adding excessive diethylenetriamine into the first reaction intermediate obtained in the step (1) to perform vacuum reduced pressure distillation, wherein the reaction temperature is 100 ℃ and 150 ℃, and the reaction time is 2-4h, so as to obtain the final product, namely the modified aminated starch.

4. The demulsifier for a resin polymerization fluid of claim 3, wherein: the metal catalyst in the step 1) is a gold catalyst or an iron catalyst or a platinum catalyst.

5. The demulsifier of claim 1, wherein the polyoxyethylene polyoxypropylene block polyether is one or both of fatty alcohol polyoxyethylene polyoxypropylene block polyether and allyl polyoxyethylene polyoxypropylene block polyether.

6. The demulsifier of claim 1, wherein the inorganic salt is one or two of sodium chloride, sodium sulfate, potassium sulfate and ammonium chloride.

7. The demulsifier of claim 1, wherein the penetrant is a fatty alcohol polyoxyethylene ether penetrant.

8. The demulsifier of claim 1, wherein the defoamer is one or both of a silicone defoamer and a polyether defoamer.

9. A method of making the resin polymerization demulsifier of claim 1, comprising the steps of:

s1, preparing modified aminated starch:

(1) taking amylopectin as raw material, reacting with air under the catalysis of metal catalyst until 3200-3600cm^-1The hydroxyl peak disappears to obtain a first reaction intermediate;

(2) dropwise adding excessive diethylenetriamine into the first reaction intermediate obtained in the step (1) to perform vacuum reduced pressure distillation, wherein the reaction temperature is 100 ℃ and 150 ℃, and the reaction time is 2-4h, so as to obtain the final product of modified aminated starch;

s2, weighing a certain mass of deionized water or pure water, putting into a mixing kettle, putting 30-40% of modified aminated starch, 1-3% of inorganic salt, 10-20% of polyoxyethylene polyoxypropylene block polyether and 5-10% of penetrating agent into the mixing kettle in sequence, and stirring for 30-40min until the system is uniform to obtain a mixed solution;

and S3, adding 1-3% of defoaming agent after the mixed liquid in the step S2 is uniform and stable, and stirring for 10min to obtain the resin polymerization liquid demulsifier.

Technical Field

The invention belongs to the technical field of demulsifier production, and particularly relates to a demulsifier for a resin polymerization liquid and a preparation method thereof.

Background

The demulsifier is a chemical assistant with a special structure for dehydration and deoiling, and the product has good lubrication, sufficient flocculation and coalescence capabilities, and can quickly demulsify an emulsification system to achieve the effect of oil-water separation.

The resin polymerization liquid demulsifier is a demulsifier added in an alkaline water washing resin polymerization liquid system, and part of water can be remained in the resin polymerization liquid in the production and cleaning process of the resin polymerization liquid. If the dehydration is not carried out in time, the corrosion and the scaling of the surface of system equipment can be caused, and the resin deep processing of the subsequent process is influenced. The oil contained in the discharged water can also cause the waste of the resin liquid which pollutes the environment. Therefore, the resin liquid needs to be demulsified, dehydrated and deoiled during production.

The existing demulsification method comprises a physical method, a chemical method or a mixed demulsification method of the two methods. More chemical demulsification methods are adopted, namely, the demulsifier is added into a hot resin polymer liquid system for alkali washing, and oil layer dehydration and water layer deoiling are realized in the system.

At present, most of demulsifiers used in China are polyether or modified polyether nonionic demulsifiers. But the solvent is often needed to be dissolved in the production process of the demulsifier, so that the residual organic solvent in a water layer system after demulsification increases the COD of the sewage. The invention patent of patent application CN110643388A discloses a low-temperature demulsifier, on one hand, when the medium-high temperature condition is reached in the process production of resin polymerization liquid, the demulsifier needs to be cooled to use, and the continuity of the process is influenced; on the other hand, the demulsifier contains an organic solvent, which is not beneficial to the development of environmental protection and ecology.

Therefore, the resin polymerization solution demulsifier which has high demulsification speed, does not influence the quality of resin solution and does not increase the COD of alkaline water after resin washing is urgently needed to be developed.

Disclosure of Invention

The demulsifier for the resin polymerization liquid prepared by the invention has high demulsification speed, does not influence the quality of the resin liquid, and does not increase the COD of alkaline water after resin washing.

The technical scheme of the invention is realized as follows:

a demulsifier for resin polymerization liquid is characterized in that: the raw materials comprise the following components in percentage by weight: 30-40% of modified aminated starch, 10-20% of polyoxyethylene polyoxypropylene block polyether, 1-3% of inorganic salt, 5-10% of penetrating agent, 1-3% of defoaming agent and the balance of water; the modified aminated starch comprises an initiator, a catalyst and a chain extender, wherein the initiator, the catalyst and an epoxide react to prepare the modified aminated starch.

Preferably, the initiator is pullulan; the catalyst is a metal catalyst; the chain extender is diethylenetriamine.

Preferably, the chemical structural formula of the modified aminated starch is:

。

preferably, the preparation method of the modified aminated starch comprises the following steps:

(1) taking amylopectin as raw material, reacting with air under the catalysis of metal catalyst until 3200-3600cm^-1The hydroxyl peak disappears to give a first reaction intermediate having the specific reaction formula:

；

(2) dropwise adding excessive diethylenetriamine into the first reaction intermediate obtained in the step (1) for vacuum reduced pressure distillation, wherein the reaction temperature is 100-:

。

preferably, the metal catalyst in the step (1) is a gold catalyst or an iron catalyst or a platinum catalyst.

Preferably, the metal catalyst in step (1) is an iron catalyst, the iron catalyst is preferably selected from one or more of iron chloride, iron sulfate, iron octoate, iron isooctanoate, iron thiocyanide and ferrocene, and more preferably is iron chloride, iron octoate or iron isooctanoate. The source of the iron catalyst in the present invention is not particularly limited, and commercially available products of the above-mentioned iron chloride, iron sulfate, iron octylate, iron isooctanoate, iron thiocyanide and ferrocene, which are well known to those skilled in the art, may be used.

Preferably, the reaction temperature in step (2) is carried out at 120 ℃.

Preferably, the reaction time in step (2) is 3 h.

Preferably, the polyoxyethylene polyoxypropylene block polyether is one or two of fatty alcohol polyoxyethylene polyoxypropylene block polyether and allyl polyoxyethylene polyoxypropylene block polyether.

Preferably, the inorganic salt is one or two of sodium chloride, sodium sulfate, potassium sulfate and ammonium chloride.

Preferably, the penetrant is a fatty alcohol polyoxyethylene ether penetrant.

Preferably, the defoaming agent is one or two of a silicone defoaming agent and a polyether defoaming agent.

The method for preparing the demulsifier of the resin polymerization fluid is characterized by comprising the following steps:

s1, preparing modified aminated starch:

(1) taking amylopectin as raw material, reacting with air under the catalysis of metal catalyst until 3200-3600cm^-1The hydroxyl peak disappears to obtain a first reaction intermediate;

(2) dropwise adding excessive diethylenetriamine into the first reaction intermediate obtained in the step (1) to perform vacuum reduced pressure distillation, wherein the reaction temperature is 100 ℃ and 150 ℃, and the reaction time is 2-4h, so as to obtain the final product of modified aminated starch;

s2, weighing a certain mass of deionized water or pure water, putting the deionized water or the pure water into a mixing kettle, sequentially putting the modified aminated starch, the polyoxyethylene polyoxypropylene block polyether, the inorganic salt and the penetrating agent into the mixing kettle, and stirring for 30-40min until the system is uniform to obtain a mixed solution;

and S3, adding a defoaming agent after the mixed liquid obtained in the step S2 is uniform and stable, and stirring for 10min to obtain the resin polymerization liquid demulsifier.

Compared with the prior art, the invention has the following advantages:

the demulsifier for the resin polymerization liquid is used for carrying out chain extension modification on the amylopectin based on the purpose of demulsification performance optimization. Firstly, an iron-based catalyst is selected to catalyze hydroxyl to generate aldehyde group, and then diethylenetriamine is selected as a chain extender to perform product amination to obtain the demulsification main agent. The demulsifying main agent has two performances of hydrophilicity and lipophilicity, and can quickly break an oil-water interface film by low surface tension to act with hydrophilic substances, so that oil in the oil-water interface film is released, and an excellent oil-water separation effect is achieved. Then, the emulsion breaking agent and other emulsion breaking additives are coordinated to achieve the purposes of respectively gathering oil and water and quickly layering two phases.

The preparation method of the resin polymerization liquid demulsifier provided by the invention is based on the composition of each component, the corresponding process steps and the adding sequence of each component are formulated, and the resin polymerization liquid demulsifier with stable system is obtained by compounding.

The specific implementation mode is as follows:

in order to make the preparation method of the present invention clearer, and the using effect and the product advantages clearer, the technical scheme of the present invention will be described in detail below. Next, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Examples to help explain and define the summary of the invention, other embodiments made by other researchers in the field without making a more prominent creative effort are within the scope of the present invention.

Example 1:

the embodiment discloses a resin polymerization liquid demulsifier, which is prepared from the following components:

35% of modified aminated starch, 15% of fatty alcohol polyoxyethylene polyoxypropylene block polyether, 3% of sodium chloride, 10% of sec-octanol polyoxyethylene ether, 1% of polyether defoaming agent and 36% of water; the modified aminated starch comprises an initiator, a catalyst and a chain extender, wherein the initiator, the catalyst and an epoxide react to prepare the modified aminated starch, and the initiator is amylopectin; the catalyst is an iron catalyst; the chain extender is diethylenetriamine.

In this embodiment, the preparation method of the modified aminated starch includes the following steps:

(1) taking amylopectin as raw material, putting (10 g) amylopectin into a reaction kettle, and reacting with air under the catalysis of (0.01 g) iron catalyst (traditional Chinese medicine reagent, ferric chloride) until 3200-^-1The hydroxyl peak disappears to obtain a first reaction intermediate;

(2) and (3) dropwise adding 3g of diethylenetriamine into the first reaction intermediate obtained in the step (1) to perform vacuum reduced pressure distillation, wherein the reaction temperature is 120 ℃, and the reaction time is 3 hours, so that the final product, namely the modified aminated starch is obtained.

In this embodiment, the method of the resin polymerization demulsifier comprises the steps of:

s1, preparing the modified aminated starch according to the method:

s2, preparing a demulsifier according to the following mixture ratio: putting 36% of deionized water or pure water into a mixing kettle, sequentially putting 35% of modified aminated starch, 15% of fatty alcohol-polyoxyethylene-polyoxypropylene block polyether, 3% of sodium chloride and 10% of sec-octanol polyoxyethylene ether into the mixing kettle, and stirring for 35min until the system is uniform to obtain a mixed solution;

s3, adding 1% glycerol polyether (GP 330, Haian petrochemical plant of Jiangsu province) after the mixed liquid in the step S2 is uniform and stable, and stirring for 10min to obtain the resin polymerization liquid demulsifier.

In a certain C5 petroleum resin refinery, a demulsifier is not added in the process section of alkali washing resin polymerization liquid, the demulsification and dehydration time is usually more than 40min (determined by the demulsification condition), the interfacial demulsification is not obvious, and the problem of emulsion adhesion equipment is caused after long-time operation. The production is stopped frequently, and the equipment is cleaned, so that the problems of slow production speed increase, shortage of driving personnel and parking personnel and the like are caused.

After 300PPM of the demulsifier is added, the demulsification and dehydration time of the system is greatly shortened to about 20-30min, the problem of equipment adhesion is avoided, and the system is only overhauled, stopped and cleaned every year.

Example 2:

the embodiment discloses a resin polymerization liquid demulsifier, which is prepared from the following components:

40% of modified aminated starch, 20% of allyl polyoxyethylene polyoxypropylene block polyether, 3% of ammonia chloride, 10% of isooctanol polyoxyethylene ether, 3% of glycerol polyether and 24% of water; the modified aminated starch comprises an initiator, a catalyst and a chain extender, wherein the initiator, the catalyst and an epoxide react to prepare the modified aminated starch, and the initiator is amylopectin; the catalyst is an iron catalyst; the chain extender is diethylenetriamine.

In this embodiment, the preparation method of the modified aminated starch includes the following steps:

(1) taking amylopectin as raw material, putting (10 g) amylopectin into a reaction kettle, and reacting with air under the catalysis of (0.02 g) ferric sulfate until 3200-^-1The hydroxyl peak disappears to obtain a first reaction intermediate;

(2) and (2) dropwise adding (4 g) diethylenetriamine into the first reaction intermediate obtained in the step (1) to perform vacuum reduced pressure distillation, wherein the reaction temperature is 120 ℃, and the reaction time is 3 hours, so as to obtain the final product, namely the modified aminated starch.

In this embodiment, the method of the resin polymerization demulsifier comprises the steps of:

s1, preparing the modified aminated starch according to the method:

s2, weighing 24% of deionized water or pure water, putting into a mixing kettle, sequentially putting 40% of modified aminated starch, 20% of allyl polyoxyethylene polyoxypropylene block polyether, 3% of ammonia chloride and 10% of isooctanol polyoxyethylene ether into the mixing kettle, and stirring for 35min until the system is uniform to obtain a mixed solution;

s3, adding 3% glycerol polyether (GP 330, Haian petrochemical plant of Jiangsu province) after the mixed liquid in the step S2 is uniform and stable, and stirring for 10min to obtain the resin polymerization liquid demulsifier.

In the alkali washing process of an isoprene production line of a certain oil refinery, a demulsifier is added for demulsification and dehydration, but resin droplets are remained in a water layer system, COD of rear-end sewage is higher by about 600mg/L, and the sewage treatment investment is larger.

After the demulsifier is added, the demulsification and dehydration time is shortened by 200PPM, the COD value of the rear-end sewage is reduced to 400mg/L, and the sewage treatment investment is obviously reduced.

Example 3:

the embodiment discloses a resin polymerization liquid demulsifier, which is prepared from the following components:

30% of modified aminated starch, 15% of allyl polyoxyethylene polyoxypropylene block polyether, 1% of ammonia chloride, 5% of isooctyl alcohol polyoxyethylene ether, 1% of nonionic defoaming agent and 48% of water; the modified aminated starch comprises an initiator, a catalyst and a chain extender, wherein the initiator, the catalyst and an epoxide react to prepare the modified aminated starch, and the initiator is amylopectin; the catalyst is an iron catalyst; the chain extender is diethylenetriamine.

In this embodiment, the preparation method of the modified aminated starch includes the following steps:

(1) taking amylopectin as a raw material, putting (10 g) amylopectin into a reaction kettle, and reacting with air under the catalysis of (0.015 g) iron catalyst until 3200-^-1The hydroxyl peak disappears to obtain a first reaction intermediate;

(2) and (2) dropwise adding 3.5g of diethylenetriamine into the first reaction intermediate obtained in the step (1) to perform vacuum reduced pressure distillation, wherein the reaction temperature is 120 ℃, and the reaction time is 3 hours, so as to obtain the final product, namely the modified aminated starch.

In this embodiment, the method of the resin polymerization demulsifier comprises the steps of:

s1, preparing the modified aminated starch according to the method:

s2, weighing 48% of deionized water or pure water, putting into a mixing kettle, sequentially putting 30% of modified aminated starch, 15% of allyl polyoxyethylene polyoxypropylene block polyether, 1% of ammonium chloride and 5% of isooctanol polyoxyethylene ether into the mixing kettle, and stirring for 35min until the system is uniform to obtain a mixed solution;

s3, adding 1% of nonionic defoaming agent (XS-01, Nantong Hongsheng chemical Co., Ltd.) after the mixed liquid in the step S2 is uniform and stable, and stirring for 10min to obtain the resin polymerization liquid demulsifier.

In the process of alkali cleaning, a certain C9 production line of an oil refinery is added with a demulsifier for demulsification and dehydration, and an emulsion layer adhesion device is usually arranged on a water-oil interface, and the production line is frequently stopped and cleaned every month.

250PPM after the demulsifier is added, the boundary of a water-oil interface is obvious, no emulsification layer is adhered to equipment, and the equipment is shut down and cleaned without additional treatment except major overhaul.

Example 4:

the embodiment discloses a resin polymerization liquid demulsifier, which is prepared from the following components:

40% of modified aminated starch, 10% of allyl polyoxyethylene polyoxypropylene block polyether, 2% of ammonia chloride, 7.5% of isooctanol polyoxyethylene ether, 2% of glycerol polyether and 38.5% of water; the modified aminated starch comprises an initiator, a catalyst and a chain extender, wherein the initiator, the catalyst and an epoxide react to prepare the modified aminated starch, and the initiator is amylopectin; the catalyst is an iron catalyst; the chain extender is diethylenetriamine.

In this embodiment, the preparation method of the modified aminated starch includes the following steps:

(1) taking amylopectin as raw material, putting (10 g) amylopectin into a reaction kettle at (0)02 g) reaction with air under the catalysis of an iron catalyst until 3200-3600cm^-1The hydroxyl peak disappears to obtain a first reaction intermediate;

(2) and (2) dropwise adding (4 g) diethylenetriamine into the first reaction intermediate obtained in the step (1) to perform vacuum reduced pressure distillation, wherein the reaction temperature is 120 ℃, and the reaction time is 3 hours, so as to obtain the final product, namely the modified aminated starch.

In this embodiment, the method of the resin polymerization demulsifier comprises the steps of:

s1, preparing the modified aminated starch according to the method:

s2, weighing 38.5% of deionized water or pure water, putting into a mixing kettle, sequentially putting 40% of modified aminated starch, 10% of allyl polyoxyethylene polyoxypropylene block polyether, 2% of ammonium chloride and 7.5% of isooctanol polyoxyethylene ether into the mixing kettle, and stirring for 35min until the system is uniform to obtain a mixed solution;

s3, after the mixed liquid in the step S2 is uniform and stable, 2% of nonionic defoaming agent (XS-01, Nantong Hongsheng chemical Co., Ltd.) is added and stirred for 10min, and the resin polymerization liquid demulsifier is obtained.

In a certain oil refinery pentadiene production line, a demulsifier is added in the alkali washing process for demulsification and dehydration, but a water layer system has resin liquid drops remaining, the water-oil separation effect is poor, and a resin layer is required to be subjected to steam dehydration subsequently.

After the demulsifier is added into the water, the demulsification and dehydration time is shortened after 400PPM, the water-oil separation is more thorough, and the subsequent dehydration is not needed.

The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; the modifications or the substitutions do not cause the essence of the corresponding technical solutions to depart from the scope of the technical solutions of the embodiments of the present invention, and the technical solutions are all covered in the scope of the claims and the specification of the present invention; it will be apparent to those skilled in the art that any alternative modifications or variations to the embodiments of the present invention may be made within the scope of the present invention.

The present invention is not described in detail, but is known to those skilled in the art.