阅读说明：本技术 一种废水零排放工艺用消泡剂及其制备方法 (Defoaming agent for wastewater zero-discharge process and preparation method thereof ) 是由 胡伟 窦丽英 于 2021-01-14 设计创作，主要内容包括：本发明公开了一种废水零排放工艺用消泡剂及其制备方法,属于消泡剂技术领域。该消泡剂由以下重量份数组分组成：100～200份羟基硅油、75～125份含氢硅油、80～110份烯丙基混聚醚、20～30份聚醚多元醇、5～15份二氧化硅、30～40份单硬脂酸甘油酯、5～15份硬脂酸聚氧乙烯醚。消泡剂制备过程中先制备硅聚醚和硅脂中间体,再与其他组分混合乳化,反应过程条件温和,操作简单,可进行工业化生产应用。消泡剂主要针废水零排放工艺中蒸发结晶过程中的泡沫的消除,在泡沫消除过程中既可以有效的消泡抑泡,而且无副作用。(The invention discloses a defoaming agent for a wastewater zero-discharge process and a preparation method thereof, belonging to the technical field of defoaming agents. The defoaming agent comprises the following components in parts by weight: 100-200 parts of hydroxyl silicone oil, 75-125 parts of hydrogen-containing silicone oil, 80-110 parts of allyl mixed polyether, 20-30 parts of polyether polyol, 5-15 parts of silicon dioxide, 30-40 parts of glyceryl monostearate and 5-15 parts of polyoxyethylene stearate. In the preparation process of the defoaming agent, the silicone polyether and silicone grease intermediate are prepared first and then mixed with other components for emulsification, the reaction process conditions are mild, the operation is simple, and industrial production and application can be carried out. The defoaming agent is mainly used for eliminating foam in the evaporation and crystallization process in the wastewater zero discharge process, can effectively defoam and inhibit foam in the foam elimination process, and has no side effect.)

1. The defoaming agent for the wastewater zero-discharge process is characterized by comprising the following components in parts by weight: 100-200 parts of hydroxyl silicone oil, 75-125 parts of hydrogen-containing silicone oil, 80-110 parts of allyl mixed polyether, 20-30 parts of polyether polyol, 5-15 parts of silicon dioxide, 30-40 parts of glyceryl monostearate and 5-15 parts of stearic acid polyoxyethylene ether; the hydrogen-containing silicone oil is any one of side chain hydrogen-containing silicone oil, terminal hydrogen-containing silicone oil or terminal side mixed hydrogen-containing silicone oil; the hydroxyl silicone oil is linear polydimethylsiloxane with the terminal group being hydroxyl; the molecular weight of the allyl mixed polyether is 200-2000; the initiator of the polyether polyol is any one of ethylene glycol, glycerol, fatty alcohol or fatty acid; the silicon dioxide is fumed silica or precipitated silica.

2. The antifoaming agent for the zero discharge process of wastewater according to claim 1, wherein the viscosity of the hydroxyl silicone oil is 350-60000 mpa-s.

3. The antifoaming agent for zero wastewater discharge process according to claim 1, wherein the hydrogen-containing silicone oil is side chain hydrogen-containing silicone oil, and the hydrogen content is 0.01-0.5%.

4. The antifoaming agent for zero discharge of wastewater process according to claim 1, wherein the hydrogen content of the hydrogen-containing silicone oil is 0.05% to 0.25%.

5. The antifoaming agent for the zero-discharge process of wastewater according to claim 1, wherein the molecular weight of the allyl mixed polyether is 400-1200.

6. The antifoaming agent for the zero-discharge process of wastewater as claimed in claim 1, wherein the initiator of the polyether polyol is glycerol, and the molecular weight is 2000-4000.

7. The antifoaming agent for the zero-discharge wastewater process according to claim 1, wherein the silica is hydrophobic fumed silica, and the specific surface area of the silica is 200m²/g。

8. The preparation method of the defoaming agent for the wastewater zero discharge process as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:

(1) putting allyl polyether into a reaction kettle, heating to 70-90 ℃, adding chloroplatinic acid isopropanol solution, dropwise adding hydrogen-containing silicone oil, controlling the temperature within 140 ℃, and preserving heat for 0.5-1.5 hours when the reaction is transparent to obtain silicon polyether;

(2) putting hydroxyl silicone oil and silicon dioxide into a reaction kettle, heating for reaction, dispersing at a high speed, and cooling after dispersion is finished to obtain silicone grease;

(3) and (3) adding silicon polyether, polyether polyol, glyceryl monostearate and polyoxyethylene stearate into the silicone grease obtained in the step (2), adding water for emulsification, then passing through a colloid mill, and cooling to obtain the defoaming agent.

9. The preparation method of the defoaming agent for the wastewater zero discharge process according to claim 8, wherein in the step (2), the reaction temperature is 150-180 ℃, and the high-speed dispersion is carried out for 0.5-1.5 h.

10. The preparation method of the defoaming agent for the wastewater zero discharge process according to claim 8, wherein the emulsifying temperature is 60-80 ℃ and the time is 1.5-2.5 hours.

Technical Field

The invention belongs to the technical field of defoaming agents, and particularly relates to a defoaming agent for a wastewater zero-discharge process and a preparation method thereof.

Background

The national requirements on environmental protection are getting stricter, so that the research on wastewater treatment is increased in various industries in recent years. The discharge amount of the Chinese pharmaceutical wastewater accounts for 2 percent of the total amount of the wastewater and is one of the main pollutants of the water environment. As long as the wastewater has the characteristics of high COD, high salt, difficult degradation and the like, the wastewater is a recognized Nederland serious pollution source.

For example, the steel industry generally adopts a treatment process of a double-membrane method, ultrafiltration and reverse osmosis, the recovery rate of desalted water of the process is about 70%, the rest 30% of desalted water forms high-salt water which contains various organic and inorganic pollutants and cannot be directly discharged, and if the high-salt water enters a municipal sewage treatment system, the excessive total soluble solids are very unfavorable for the production of activated sludge. The treatment of the high-salinity wastewater is one of the environmental protection emphasis in the steel industry in recent years. And all underground water permeating into the underground mining space in the coal mining process is mine wastewater, so that the zero discharge of the mine wastewater is realized, and the method has important social, environmental and economic effects. And with the stricter and stricter wastewater discharge standards of power plants, coal-fired power plants also go to the power plant zero-discharge engineering successively to treat the desulfurization wastewater. For a power plant with small waste water amount, a 'high-temperature bypass flue gas evaporation' technical route is usually adopted, and a 'crystallization flash evaporation or low-temperature flue gas concentration and high-temperature bypass flue gas evaporation' route is adopted for a power plant with large waste water amount.

The zero discharge process of waste water refers to that industrial water containing a large amount of inorganic salt and organic pollutants is recycled for production (more than 99 percent of the industrial water is recycled) after being treated by proper technology combination, no liquid pollutants are discharged into the environment, and the pollutants are further treated in a concentrated solid state or a crystallized form. There are also many technological methods in the zero-row process, and most of them have multiple-effect evaporation crystallization process. The general production of chemical crystallization procedures, such as the production of chemical commodities such as sodium chloride, sodium sulfate, etc., only needs to process the crystallization of one salt, and the crystallization process of the single-salt brine is easy to master, but like the salt contained in the industrial sewage, the salt is various, and even contains double salt consisting of two salts. Brine with various salts can generate foam and extremely high corrosivity in a crystallizer, and due to the existence of various salts, different boiling points of the brine can be increased. In addition, the industrial wastewater body has organic matters, a large amount of foam is generated in the multi-effect evaporation process, and under the process condition, a defoaming agent is required to be added for chemical foam removal.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide a defoaming agent for a wastewater zero-discharge process, wherein the defoaming agent can effectively defoam and inhibit foams in a foam elimination process and has no side effect. The invention aims to solve another technical problem and provides a preparation method of the defoaming agent for the wastewater zero-discharge process.

In order to solve the problems, the technical scheme adopted by the invention is as follows:

a defoaming agent for a wastewater zero-discharge process is composed of the following components in parts by weight: 100-200 parts of hydroxyl silicone oil, 75-125 parts of hydrogen-containing silicone oil, 80-110 parts of allyl mixed polyether, 20-30 parts of polyether polyol, 5-15 parts of silicon dioxide, 30-40 parts of glyceryl monostearate and 5-15 parts of stearic acid polyoxyethylene ether; the hydrogen-containing silicone oil is any one of side chain hydrogen-containing silicone oil, terminal hydrogen-containing silicone oil or terminal side mixed hydrogen-containing silicone oil; the hydroxyl silicone oil is linear polydimethylsiloxane with the terminal group being hydroxyl; the molecular weight of the allyl mixed polyether is 200-2000; the initiator of the polyether polyol is any one of ethylene glycol, glycerol, fatty alcohol or fatty acid; the silicon dioxide is fumed silica or precipitated silica.

Glyceryl monostearate is an emulsifier and additive for food; cosmetic and pharmaceutical ointment are used as emulsifiers. White waxy flake or bead solids, insoluble in water, are dispersible in water upon vigorous shaking with hot water. In other aspects, as defoaming agents, dispersants, thickeners, wetting agents, and the like.

Stearic acid polyoxyethylene ether, stearic acid is octadecanoic acid, which is slightly soluble in cold water and can be endowed with new characteristics after being connected with ethylene oxide. The stearic acid polyoxyethylene ether is in a diffusion state in water and has good softness and lubricity. Has good emulsification and cleaning effects, is one of chemical fiber spinning oil components in the synthetic fiber industry, can be used as a softening agent for fiber processing, and has good antistatic property and lubricating property. The fabric is used as a softening agent in the weaving process, so that the phenomenon of broken ends is reduced, and the hand feeling of the fabric is improved. The emulsifier is used as an emulsifier in cosmetics, and the dosage is generally 1-3%. As a co-emulsifier for the emulsification of paraffin. Used as emulsifier in the production of lubricating oil. It can be used as emulsifier in cosmetics, unguent, and shoe polish. In the textile industry, emulsifiers and oils used in the finishing of synthetic fibers have softness and antistatic properties. As thickeners and stabilizers in starch coatings for paper. A lubricant for use in multiplexing electrical wires in a raceway.

The defoaming agent is used in the wastewater zero-discharge process, and the viscosity of the hydroxyl silicone oil is 350-60000 mpa & s.

The defoaming agent for the wastewater zero-discharge process is characterized in that the hydrogen-containing silicone oil is side chain hydrogen-containing silicone oil, and the hydrogen content is 0.01-0.5%.

The defoaming agent for the wastewater zero-discharge process is characterized in that the hydrogen content of the hydrogen-containing silicone oil is 0.05-0.25%.

The defoaming agent for the wastewater zero-discharge process is characterized in that the molecular weight of the allyl mixed polyether is 400-1200.

The defoaming agent for the wastewater zero-discharge process is characterized in that an initiator of the polyether polyol is glycerol, and the molecular weight of the initiator is 2000-4000.

The defoaming agent for the wastewater zero-discharge process is characterized in that the silicon dioxide is hydrophobic fumed silica, and the specific surface area of the silicon dioxide is 200m²/g。

The preparation method of the defoaming agent for the wastewater zero-discharge process specifically comprises the following steps:

(1) putting allyl polyether into a reaction kettle, heating to 70-90 ℃, adding chloroplatinic acid isopropanol solution, dropwise adding hydrogen-containing silicone oil, controlling the temperature within 140 ℃, and preserving heat for 0.5-1.5 hours when the reaction is transparent to obtain silicon polyether;

(2) putting hydroxyl silicone oil and silicon dioxide into a reaction kettle, heating for reaction, dispersing at a high speed, and cooling after dispersion is finished to obtain silicone grease;

(3) and (3) adding silicon polyether, polyether polyol, glyceryl monostearate and polyoxyethylene stearate into the silicone grease obtained in the step (2), adding water for emulsification, then passing through a colloid mill, and cooling to obtain the defoaming agent.

The preparation method of the defoaming agent for the wastewater zero-discharge process comprises the step (2), wherein the reaction temperature is 150-180 ℃, and the high-speed dispersion is carried out for 0.5-1.5 h.

The preparation method of the defoaming agent for the wastewater zero-discharge process is characterized in that the emulsifying temperature is 60-80 ℃, and the time is 1.5-2.5 hours.

Has the advantages that: compared with the prior art, the invention has the advantages that:

(1) the defoaming agent is mainly used for eliminating foam in an evaporative crystallization (multi-effect evaporative crystallization or MVR vapor recompression evaporative crystallization) process in a wastewater zero discharge process, can effectively defoam and inhibit foam in the foam eliminating process, and has no side effect.

(2) In the preparation process of the defoaming agent, the silicone polyether and silicone grease intermediate are prepared firstly and then mixed with other components for emulsification, the reaction process has mild conditions and simple operation, and can be applied to industrial production.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.

Example 1

A preparation method of a defoaming agent for a wastewater zero-discharge process specifically comprises the following steps:

(1) putting 96 parts of allyl mixed polyether (with the molecular weight of 800) into a reaction kettle, heating to 80 ℃, adding 200mL of chloroplatinic acid isopropanol solution with the volume fraction of 1%, dropwise adding 100 parts of side chain hydrogen-containing silicone oil (with the hydrogen content of 0.1%), controlling the temperature within 140 ℃, and preserving heat for 1h when the reaction is transparent to obtain silicon polyether;

(2) 200kg of hydroxyl silicone oil with the viscosity of 350mpa & s is added into a reaction kettle, and 10kg of hydroxyl silicone oil with the specific surface area of 200m is added²Heating the fumed silica/g at 180 ℃ for 60min to prepare silicone grease;

(3) then adding 28.5kg of silicon polyether, 25kg of polyether polyol (the initiator is glycerol, the molecular weight is 3000, and the PO accounts for 90%), 33.5kg of glyceryl monostearate and 10.5kg of stearic acid polyoxyethylene ether into the reaction kettle, heating to 80 ℃, stirring for 0.5h, adding water, and emulsifying for 2h at 70 ℃ to obtain 30% of organic silicon emulsion, namely the defoaming agent.

Example 2

A preparation method of a defoaming agent for a wastewater zero-discharge process specifically comprises the following steps:

(1) putting 96 parts of allyl mixed polyether (with the molecular weight of 800) into a reaction kettle, heating to 80 ℃, adding 200mL of chloroplatinic acid isopropanol solution with the volume fraction of 1%, dropwise adding 100 parts of side chain hydrogen-containing silicone oil (with the hydrogen content of 0.1%), controlling the temperature within 140 ℃, and preserving heat for 1h when the reaction is transparent to obtain silicon polyether;

(2) 200kg of hydroxyl silicone oil with the viscosity of 10000mpa & s is added into a reaction kettle, and 10kg of hydroxyl silicone oil with the specific surface area of 200m is added²Heating the white carbon black in the/g meteorological method to 180 ℃ and preserving the temperature for 60min to prepare silicone grease;

(3) then adding 28.5kg of silicon polyether, 25kg of polyether polyol (the initiator is glycerol, the molecular weight is 3000, and the PO accounts for 90%), 33.5kg of glyceryl monostearate and 10.5kg of stearic acid polyoxyethylene ether into the reaction kettle, heating to 80 ℃, stirring for 0.5h, adding water, and emulsifying for 2h at 70 ℃ to obtain 30% of organic silicon emulsion, namely the defoaming agent.

Example 3

A preparation method of a defoaming agent for a wastewater zero-discharge process specifically comprises the following steps:

(1) putting 96 parts of allyl mixed polyether (with the molecular weight of 800) into a reaction kettle, heating to 80 ℃, adding 200mL of 1% chloroplatinic acid isopropanol 1% solution with the volume fraction of 1%, dropwise adding 100 parts of side chain hydrogen-containing silicone oil (with the hydrogen content of 0.1%), controlling the temperature within 140 ℃, and preserving heat for 1h when the reaction is transparent to obtain silicon polyether;

(2) 100kg of hydroxyl silicone oil with the viscosity of 10000mpa & s, 100kg of hydroxyl silicone oil with the viscosity of 350mpa & s and 10kg of hydroxyl silicone oil with the specific surface area of 200m are added into a reaction kettle²Heating the white carbon black in the/g meteorological method to 180 ℃ and preserving the temperature for 60 min;

(3) then adding 28.5kg of silicon polyether, 25kg of polyether polyol (the initiator is glycerol, the molecular weight is 3000, and the PO accounts for 90%), 33.5kg of glyceryl monostearate and 10.5kg of stearic acid polyoxyethylene ether into the reaction kettle, heating to 80 ℃, stirring for 0.5h, adding water, and emulsifying for 2h at 70 ℃ to obtain 30% of organic silicon emulsion, namely the defoaming agent.

Example 4

The defoaming agent prepared in the embodiment 1-3 is applied to a bubble system:

preparing foaming liquid: adding water to 1kg of sodium chloride 20g, potassium chloride 20g, NP-20 (emulsifier with alkylphenol polyoxyethylene ether as effective component) 5g and sodium dodecyl benzene sulfonate 5g, and stirring to obtain foaming solution for use.

Taking 200mL of the foaming solution into a circulating bubbling instrument, and setting the temperature to be 105 ℃; and the defoaming agent is diluted in advance according to the proportion of 1:100 (water, volume ratio) for standby: when the temperature reached 105 ℃, the circulating bubbling was started, when the foam reached 400mL, 0.2mL and 0.4mL of diluted defoaming agent were added to the different defoaming agents, respectively, and the defoaming time and the time for the foam to reach 400mL again were recorded, and the results are shown in table 1. As is clear from Table 1, the defoaming agent of the present invention can effectively defoam and suppress foam in a foaming liquid without causing any side effect.

TABLE 1 Effect of antifoam use