CN111393143B - Desulfurization wastewater debonder and preparation method and application thereof - Google Patents
Desulfurization wastewater debonder and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a desulfurization wastewater debonder and a preparation method and application thereof. The desulfurization wastewater debonder comprises the following components in parts by weight: 30-60 parts of carboxylic acid polymer, 20-45 parts of liquid water glass, 6-18 parts of regulator, 1-5 parts of liquid alkali and 1-10 parts of water. The desulfurization wastewater debonder is prepared by the following method: mixing liquid water glass, liquid alkali, part of regulator and water, and stirring uniformly; and then sequentially adding the carboxylic acid polymer and the rest of the regulator under the stirring state, and uniformly mixing to obtain the desulfurization wastewater dispergator. The desulfurization wastewater debonder has the advantages of wide raw material source, low price and environmental protection, and can be used for recycling desulfurization wastewater to prepare slurry with good viscosity and thixotropy. The invention overcomes the problem that the conventional debonding agent loses efficacy in the desulfurization wastewater, can effectively treat the desulfurization wastewater, and has good economic and environmental benefits and good application prospects.
Description
Technical Field
The invention belongs to the technical field of ceramic industry and fine chemical industry, and particularly relates to a desulfurization wastewater debonder and a preparation method and application thereof.
Background
The desulfurization wastewater contains suspended matters, supersaturated sulfite, sulfate, heavy metals and other impurities, and many of the impurities are the first pollutants which are strictly controlled in the national environmental protection standard. The desulfurization wastewater has complex components and high treatment difficulty, needs to consume equipment, treating agents, energy sources and the like during treatment, occupies large space, has long treatment time and has high comprehensive cost. Common desulfurization wastewater treatment technologies include settling ponds, chemical settling methods, biological treatment, and zero-emission technologies (evaporation ponds, complete circulation, mixing with fly ash, etc.). Wherein, the sedimentation tank has low treatment cost, can remove particles to a certain extent, but can not remove metal salts dissolved in the wastewater, and simultaneously can generate sludge to cause secondary pollution; the chemical sedimentation method can remove most of metals and suspended matters, but has low removal rate of soluble salts such as chloride ions and the like and heavy metals such as selenium and the like, high operation cost and sludge generation; the biological treatment can biodegrade soluble organic pollutants or convert a plurality of insoluble pollutants into floccules, but the system is complex and the cost is high, and toxic organic selenium and organic mercury are easily formed to cause secondary pollution; the evaporation tank method in the zero discharge technology has low treatment cost, but needs anti-seepage treatment, and if the treatment capacity of the waste water is large, the required land area is increased, the treatment cost is increased, and salt pollution to the surrounding environment is caused. Therefore, there is a need to develop an environmentally friendly and economical desulfurization wastewater treatment scheme to accommodate green production.
A large amount of desulfurization waste water needs to be effectively treated for discharge, and ceramic production needs a large amount of water resources. How to change desulfurization waste water into "useless" effectively "is" precious ", with waste water recovery simultaneously being used for ceramic manufacture, have good economy and environmental protection benefit, can alleviate current urgent environmental protection demand and huge market demand.
In patent CN 109400182A, 82-87 parts of water glass, 7-12 parts of sodium polyacrylate and 2-7 parts of sodium hexametaphosphate are used to prepare a ceramic raw material dispergator, and when the usage amount is 0.3-0.6%, the slurry viscosity is 30-70 s. The dispergator has the advantages of improving the fluidity of the ceramic raw material and reducing the water content, and reduces the energy consumption, but the dispergator has higher water glass content, and the thixotropy of the dispergator slurry can be increased rapidly after the dispergator slurry is placed for a long time; and the catalyst is easy to hydrolyze and precipitate in the desulfurization wastewater, thereby reducing the peptization performance. In patent CN 109305817A, 46-66 parts of 50Be sodium silicate, 19-29 parts of 50% caustic soda, 3-7 parts of sodium hexametaphosphate and 12-18 parts of weathered coal are used for preparing the ceramic dispergator. The dispergator has the advantages of low cost and improvement on slurry concentration, stability and suspension property, is mainly composed of inorganic components and low in cost, but is difficult to combine low initial viscosity and small thixotropy when dispergated at a lower dosage. In patent CN110451989A, 85-87 parts of water glass, 5-7 parts of water reducing agent and 6-10 parts of dispersing agent are used to prepare ceramic slurry dispergator, and when the amount of the ceramic slurry dispergator is 1-2%, the slurry viscosity is 58 s. The dispergator has the advantages of low cost and convenient use, but contains carcinogenic naphthalene water reducing agent, and has moderate dispergation effect.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a desulfurization wastewater dispergator.
The invention also aims to provide a preparation method of the desulfurization wastewater dispergator.
The invention further aims to provide application of the desulfurization wastewater dispergator.
The purpose of the invention is realized by the following technical scheme:
the desulfurization wastewater dispergator comprises the following components in parts by weight: 30-60 parts of carboxylic acid polymer, 20-45 parts of liquid water glass, 6-18 parts of regulator, 1-5 parts of liquid alkali and 1-10 parts of water; preferably comprising: 50-60 parts of carboxylic acid polymer, 20-35 parts of liquid water glass, 10-15 parts of regulator, 3-5 parts of liquid alkali and 1-8 parts of water.
The carboxylic acid polymer is preferably any one or a combination of at least two of a hydroxyl (-OH) containing carboxylic acid polymer, a sulfur (S) containing carboxylic acid polymer, and a phosphorus (P) containing carboxylic acid polymer.
The hydroxyl-containing carboxylic acid polymer is preferably prepared by the following method: the ethylene glycol monovinyl polyglycol ether (EPEG for short) containing a group-OH and acrylic acid (AA for short) containing a group-COO are polymerized in a one-pot method according to the molar ratio of 1: 4-7, and the solvent is water. Wherein, the terminal alkenyl groups of the big and small monomers form a molecular main chain through copolymerization, and the polyethylene glycol chain segment of the polyether macromonomer forms a structural side chain.
The molecular weight of the ethylene glycol monovinyl polyglycol ether is preferably 1000-3000, and more preferably 2000-2500.
The molecular weight of the hydroxyl-containing carboxylic acid polymer is preferably 1000-20000, and the hydroxyl content is preferably 0.3-0.9% (mass percentage content).
The sulfur-containing carboxylic acid polymer is preferably prepared by the following method: with acrylic acid containing a group-COO, with acrylic acid containing a group-SO3The sodium Methacrylate (MAS) and the methyl allyl polyoxyethylene ether (TPEG) are polymerized in a one-pot method according to the molar ratio of 5-2: 1:1, and the solvent is water.
The molecular weight of the methyl allyl polyoxyethylene ether is preferably 1000-3000, and more preferably 2000-2500.
The molecular weight of the sulfur-containing carboxylic acid polymer is preferably 1000-20000, and the sulfur content is preferably 0.6-1.6% (mass percentage content).
The phosphorus-containing carboxylic acid polymer is preferably prepared by the following method: mixing methyl allyl polyoxyethylene ether (TPEG) and acrylic acid containing a group-COO according to the molar ratio of 1: 4-7, and adding phosphorus-containing sodium hypophosphite serving as a chain transfer agent to polymerize in a one-pot method to obtain the modified epoxy resin.
The molecular weight of the methyl allyl polyoxyethylene ether is preferably 1000-3000, and more preferably 2000-2500.
The molecular weight of the phosphorus-containing carboxylic acid polymer is preferably 1000-20000, and the phosphorus content is preferably 0.6-1.6% (mass percentage content).
The carboxylic acid polymer is preferably an aqueous solution of a carboxylic acid polymer having a mass concentration of 40 to 50%.
The aqueous carboxylic acid polymer solution is preferably an aqueous carboxylic acid polymer solution having a pH of 4 to 10, and more preferably a pH of 7 to 8.
The chemical formula of the liquid water glass is Na2O·nSiO2Wherein the modulus n is 2.5-3.5; preferably 3.26.
The liquid alkali is preferably sodium hydroxide aqueous solution with the mass concentration of 20-50%.
The regulator is preferably any one or at least two of sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate, sodium humate and sodium metasilicate pentahydrate.
The preparation method of the desulfurization wastewater dispergator comprises the following steps: mixing liquid water glass, liquid alkali, part of regulator and water, and stirring uniformly; and then sequentially adding the carboxylic acid polymer and the rest of the regulator under the stirring state, and uniformly mixing to obtain the desulfurization wastewater dispergator.
The stirring speed is preferably controlled to be 100-200 r/min; more preferably 150 r/min.
The application of the desulfurization wastewater dispergator in desulfurization wastewater recycling is provided.
A method for preparing ceramic slurry by utilizing recovered desulfurization wastewater is characterized by mixing and grinding ceramic soil, the desulfurization wastewater debonder, desulfurization wastewater and industrial water to obtain the ceramic slurry.
The ratio of the desulfurization wastewater to the industrial water is preferably 0.5-1: 9 by mass; more preferably 1: 9.
The dosage of the desulfurization wastewater debonder is preferably 0.4-0.7 wt% of the mass of the ceramic soil; more preferably 0.6 to 0.7 wt%; most preferably 0.7 wt%.
The water content of the ceramic slurry is preferably 32-40%; more preferably 35-39%; most preferably 39%.
The ceramic soil is preferably any one or a mixture of at least two of bentonite, kaolin and ball clay; more preferably ball clay.
The desulfurization wastewater is preferably primary desulfurization wastewater, and the pH is preferably 7-8.
Compared with the prior art, the invention has the following advantages and effects:
1. the dispergator of the invention contains specific functional groups such as-OH, S or P, etc. and has anchoring effect on particles and better adsorption effect; meanwhile, the carboxylic acid polymer has a certain molecular chain length and a branched chain structure, plays a good role in steric hindrance, and enables clay particles to be uniformly and stably dispersed.
2. The dispergator has the advantages of good dispersibility and stability by organic and inorganic compounding, and effectively solves the problems of large initial viscosity and high thixotropy of the common dispergator.
3. Under the condition that the addition amount is the same as that of other conditions, compared with the common dispergator, the ceramic dispergator has the advantage of better dispergation effect, so that the initial viscosity of the slurry is low, the contact is low, and the comprehensive performance is good.
4. The debonder of the invention has the advantages of less addition amount, low cost, simple and convenient use and environmental protection, can effectively treat the desulfurization wastewater, and has good economic and environmental protection benefits.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The raw materials involved in the examples of the present invention and their preparation:
-OH-containing carboxylic acid polymer: the copolymer is obtained by copolymerizing ethylene glycol monovinyl polyglycol ether (molecular weight is 2000) containing group-OH and acrylic acid containing group-COO according to a molar ratio of 1:6 in a one-pot method, wherein the solvent is water, the content of active substances is 41 percent, and then adding a proper amount of liquid alkali to adjust the pH value to 8. The molecular weight of the obtained-OH-containing carboxylic acid polymer was 7500, and the-OH content was 0.36%.
S-containing carboxylic acid polymer: with acrylic acid containing a group-COO, with acrylic acid containing a group-SO3The sodium methacrylate and the methyl allyl polyoxyethylene ether (molecular weight is 2400) are polymerized by a one-pot method according to the molar ratio of 3:1:1, the solvent is water, the content of active substances is 42.5 percent, and then a proper amount of liquid alkali is added to adjust the pH value to 8. The obtained S-containing carboxylic acid polymer had a molecular weight of 3700 and an S content of 0.84%.
P-containing carboxylic acid polymer: mixing methyl allyl polyoxyethylene ether (molecular weight of 2400) and acrylic acid containing a group-COO according to a molar ratio of 1:5, adding sodium hypophosphite containing P as a chain transfer agent, performing one-pot polymerization to obtain the product, adding water as a solvent and an active matter content of 43%, and adding a proper amount of liquid alkali to adjust the pH value to 8. The molecular weight of the obtained P-containing carboxylic acid polymer is 3400, and the P content is 0.9%.
Liquid water glass: molecular formula is Na2O·nSiO2The modulus n is 3.26.
The standard soil used in the embodiments of the present invention is ball soil BC01 of Jiangmen Yike corporation.
The desulfurization wastewater used in the embodiment of the invention is wastewater discharged in the operation of a power plant, and the primary desulfurization wastewater treated by Jiangxi Tanjin company is light green in color and nearly neutral in pH.
The water used in the examples of the present invention was industrial water.
Example 1
The formula (in parts by mass) is as follows:
according to the formula proportion, firstly, mixing liquid water glass, 50% liquid caustic soda (50% sodium hydroxide aqueous solution by mass concentration), sodium pyrophosphate and water, and mechanically stirring at the speed of 150r/min for 10min to be uniform; then slowly adding a carboxylic acid polymer containing-OH, and mechanically stirring at the speed of 150r/min for 10min to be uniform while adding; and finally, slowly adding sodium metasilicate pentahydrate, and mechanically stirring for 10min at the speed of 150r/min to be uniform while adding the sodium metasilicate pentahydrate, thereby preparing the desulfurization wastewater dispergator.
200g of Yingke ball soil BC01 is taken, and added with a desulfurization wastewater dispergator with the mass of 0.6 percent of the ball soil, 12.8g of desulfurization wastewater and 115.1g of water, namely the water content is 39 percent, and the mixture is ground in a planet ball mill for 10min to prepare uniform slurry; then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 37.6 s; after standing for 5min, the viscosity was measured with a paint-4 cup, the slurry viscosity was 71.4s, and the thixotropic index was 1.899. The thixotropy is improved compared with comparative example 1, which follows.
Example 2
The formula (in parts by mass) is as follows:
according to the formula proportion, firstly, mixing liquid water glass, 50% liquid caustic soda, sodium tripolyphosphate and water, and mechanically stirring at the speed of 150r/min for 10min to be uniform; then slowly adding the S-containing carboxylic acid polymer, and mechanically stirring at the speed of 150r/min for 10min to be uniform while adding; and finally slowly adding sodium hexametaphosphate, and mechanically stirring at the speed of 150r/min for 10min to be uniform while adding the sodium hexametaphosphate to obtain the desulfurization wastewater debonding agent.
200g of Yingke ball soil BC01 is taken, and added with a desulfurization wastewater dispergator accounting for 0.5 percent of the mass of the ball soil, 12.8g of desulfurization wastewater and 115.1g of water, namely the water content is 39 percent, and the mixture is ground in a planet ball mill for 10min to prepare uniform slurry. Then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 47.5 s; after standing for 5min, the viscosity was measured with a paint-4 cup, the slurry viscosity was 87.4s, and the thixotropic index was 1.840.
Example 3
The formula (in parts by mass) is as follows:
according to the formula proportion, firstly, mixing liquid water glass, 30% liquid caustic soda, sodium pyrophosphate and water, and mechanically stirring uniformly; then slowly adding the S-containing carboxylic acid polymer while adding; and finally slowly adding sodium hexametaphosphate, and mechanically stirring at the speed of 150r/min for 10min to be uniform while adding the sodium hexametaphosphate to obtain the desulfurization wastewater debonding agent.
200g of Yingke ball soil BC01 is taken, and added with a desulfurization wastewater dispergator accounting for 0.5 percent of the mass of the ball soil, 12.8g of desulfurization wastewater and 115.1g of water, namely the water content is 39 percent, and the mixture is ground in a planet ball mill for 10min to prepare uniform slurry. Then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 48.8 s; after standing for 5min, the viscosity was measured with a paint-4 cup, the slurry viscosity was 87.5s, and the thixotropic index was 1.793.
Example 4
The formula (in parts by mass) is as follows:
according to the formula proportion, firstly, mixing liquid sodium silicate, 30% liquid caustic soda, sodium humate and water, and mechanically stirring at the speed of 150r/min for 10min to be uniform; then slowly adding a carboxylic acid polymer containing P, and mechanically stirring at the speed of 150r/min for 10min to be uniform while adding; and finally, slowly adding sodium metasilicate pentahydrate, and mechanically stirring for 10min at the speed of 150r/min to be uniform while adding the sodium metasilicate pentahydrate, thereby preparing the desulfurization wastewater dispergator.
200g of Yingke ball soil BC01 is taken, and added with a desulfurization wastewater dispergator accounting for 0.6 percent of the mass of the ball soil, 12.8g of desulfurization wastewater and 115.1g of water, namely the water content is 39 percent, and the mixture is ground in a planet ball mill for 10min to prepare uniform slurry. Then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 31.7 s; after standing for 5min, the viscosity was measured with a paint-4 cup, the slurry viscosity was 54.4s, and the thixotropic index was 1.716.
Example 5
The formula (in parts by mass) is as follows:
according to the formula proportion, firstly, mixing water glass, 20% liquid caustic soda, sodium tripolyphosphate and water, and mechanically stirring at the speed of 150r/min for 10min to be uniform; then slowly adding the P-containing carboxylic acid polymer (same as example 4), and mechanically stirring at the speed of 150r/min for 10min until uniform; and finally, slowly adding sodium humate, and mechanically stirring for 10min to be uniform at the speed of 150r/min while adding the sodium humate to obtain the desulfurization wastewater debonding agent.
200g of Yikeke ball soil BC01 is taken, and added with a desulfurization wastewater dispergator accounting for 0.7 percent of the mass of the ball soil, 12.8g of desulfurization wastewater and 115.1g of water, namely the water content is 39 percent, and the mixture is ground in a planet ball mill for 10min to prepare uniform slurry. Then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 23.5 s; after standing for 5min, the viscosity was measured with a paint-4 cup, the slurry viscosity was 38.3s, and the thixotropic index was 1.630.
Example 6
The formula (in parts by mass) is as follows:
according to the formula proportion, firstly, liquid water glass, 30% liquid caustic soda, sodium pyrophosphate and water are mixed and mechanically stirred at the speed of 150r/min for 10min to be uniform, and the mixture is mechanically stirred to be uniform; then slowly adding carboxylic acid polymer containing-OH (same as example 1) and carboxylic acid polymer containing S (same as example 2), and mechanically stirring at 150r/min for 10min to be uniform while adding; and finally slowly adding sodium hexametaphosphate, and mechanically stirring at the speed of 150r/min for 10min to be uniform while adding the sodium hexametaphosphate to obtain the desulfurization wastewater debonding agent.
200g of Yingke ball soil BC01 is taken, and added with a desulfurization wastewater dispergator accounting for 0.5 percent of the mass of the ball soil, 12.8g of desulfurization wastewater and 115.1g of water, namely the water content is 39 percent, and the mixture is ground in a planet ball mill for 10min to prepare uniform slurry. Measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 50.4 s; after standing for 5min, the viscosity was measured with a paint-4 cup, the slurry viscosity was 89.4s, and the thixotropic index was 1.774.
Example 7
The formula (in parts by mass) is as follows:
according to the formula proportion, firstly, mixing liquid water glass, 20% liquid caustic soda, sodium tripolyphosphate and water, and mechanically stirring at the speed of 150r/min for 10min to be uniform; then slowly adding the P-containing carboxylic acid polymer (same as example 4) and the S-containing carboxylic acid polymer (same as example 6), and mechanically stirring at the speed of 150r/min for 10min to be uniform; and finally, slowly adding sodium humate, and mechanically stirring for 10min to be uniform at the speed of 150r/min while adding the sodium humate to obtain the desulfurization wastewater debonding agent.
200g of Yikeke ball soil BC01 is taken, and added with a desulfurization wastewater dispergator accounting for 0.7 percent of the mass of the ball soil, 12.8g of desulfurization wastewater and 115.1g of water, namely the water content is 39 percent, and the mixture is ground in a planet ball mill for 10min to prepare uniform slurry. Then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 25.7 s; after standing for 5min, the viscosity was measured with a paint-4 cup, the slurry viscosity was 42.4s, and the thixotropic index was 1.650.
Comparative example 1
The formula (in parts by mass) is as follows:
the formula (in parts by mass) is as follows:
according to the formula proportion, firstly, mixing liquid water glass, 50% liquid caustic soda, sodium pyrophosphate and water, and mechanically stirring at the speed of 150r/min for 10min to be uniform; then slowly adding the-OH carboxylic acid-containing polymer (same as example 1), and mechanically stirring at the speed of 150r/min for 10min to be uniform while adding; and finally, slowly adding sodium metasilicate pentahydrate, and mechanically stirring for 10min at the speed of 150r/min to be uniform while adding the sodium metasilicate pentahydrate, thereby preparing the desulfurization wastewater dispergator.
200g of Yingke ball soil BC01 is taken, and added with a desulfurization wastewater dispergator with the mass of 0.4 percent of the ball soil, 12.8g of desulfurization wastewater and 115.1g of water, namely the water content is 39 percent, and the mixture is ground in a planet ball mill for 10min to prepare uniform slurry; then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 61.1 s; after standing for 5min, the viscosity was measured by painting 4 cups, and the slurry did not flow out completely, and the thixotropy was large (the value of thixotropy was determined by the ratio of the viscosity of the slurry and the initial viscosity of the slurry after standing for 5 min). Possibly due to the lower amount of debonder used.
Comparative example 2
Taking 200g of Yingke ball clay BC01, adding liquid water glass accounting for 0.5 percent of the mass of the ball clay, 12.8g of desulfurization wastewater and 115.1g of water, namely the water content is 39 percent, and grinding in a planet ball mill for 10min to prepare uniform slurry; then, the viscosity of the slurry is measured by a coating-4 cup, and the slurry is flocculated and has poor dispergation effect. Probably because of the low water glass content.
Comparative example 3
Taking 200g of Yingke ball clay BC01, adding liquid water glass accounting for 0.75 percent of the mass of the ball clay, 12.8g of desulfurization wastewater and 115.1g of water, namely the water content is 39 percent, and grinding in a planet ball mill for 10min to prepare uniform slurry; then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 51.1 s; and standing for 5min, measuring the viscosity by using a coating-4 cup, wherein the slurry cannot flow out completely and the thixotropy is higher. The initial viscosity is reduced compared to comparative example 2, but the thixotropy is still higher, and if the water glass content is higher than 0.5%, the ceramic becomes brittle. Therefore, it is not preferable to add an excessive amount.
Comparative example 4
200g of Yingke ball clay BC01 is taken, ceramic water reducing agent CA100 of Guangzhou chemical Co Ltd (the company) of Chinese academy of China with the mass of 0.7 percent of the ball clay, 12.8g of desulfurization wastewater and 115.1g of water are added, namely the water content is 39 percent, and the mixture is ground in a planetary ball mill for 10min to prepare uniform slurry; then measuring the viscosity of the slurry by using a paint-4 cup, wherein the initial viscosity of the slurry is 23.19 s; after standing for 5min, the viscosity was measured with a paint-4 cup, the slurry viscosity was 38.72s, and the thixotropic index was 1.670. However, the use amount of 0.7% of CA100 is high in comprehensive cost and difficult to popularize. Example 5 comparative desulfurization wastewater debonder the cost of the CA100 debonder of comparative example 4 was reduced by 74.2%. Therefore, the desulfurization wastewater debonder of the present invention has cost advantages.
Comparative example 5
The formula (in parts by mass) is as follows:
according to the formula proportion, firstly, mixing liquid sodium silicate, 30% liquid caustic soda, sodium humate and water, and mechanically stirring at the speed of 150r/min for 10min to be uniform; then slowly adding the P-containing carboxylic acid polymer (same as example 4), and mechanically stirring at the speed of 150r/min for 10min to be uniform while adding; and finally, slowly adding sodium metasilicate pentahydrate, and mechanically stirring for 10min at the speed of 150r/min to be uniform while adding the sodium metasilicate pentahydrate, thereby preparing the desulfurization wastewater dispergator.
200g of Yikeke ball soil BC01 is taken, added with a desulfurization wastewater dispergator accounting for 0.6 percent of the mass of the ball soil, 12.3g of desulfurization wastewater and 110.3g of water, namely the water content is 38 percent (compared with example 4, the water content is reduced from 39 percent to 38 percent), and ground in a planet ball mill for 10min to prepare uniform slurry. Then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 48.5 s; after standing for 5min, the viscosity was measured with a paint-4 cup, the slurry viscosity was 88.32s, and the thixotropic index was 1.821. The viscosity increased significantly compared to example 4.
Comparative example 6
The formula (in parts by mass) is as follows:
according to the formula proportion, firstly, mixing liquid sodium silicate, 30% liquid caustic soda, sodium humate and water, and mechanically stirring at the speed of 150r/min for 10min to be uniform; then slowly adding the P-containing carboxylic acid polymer (same as example 4), and mechanically stirring at the speed of 150r/min for 10min to be uniform while adding; and finally, slowly adding sodium metasilicate pentahydrate, and mechanically stirring for 10min at the speed of 150r/min to be uniform while adding the sodium metasilicate pentahydrate, thereby preparing the desulfurization wastewater dispergator.
200g of Yikeke ball soil BC01 is taken, and added with a desulfurization wastewater dispergator with the mass of 0.6 percent of the ball soil, 25.6g of desulfurization wastewater (compared with example 4, the content of the desulfurization wastewater is increased from 10 percent to 20 percent) and 102.3g of water, namely the water content is 39 percent, and the mixture is ground in a planet ball mill for 10min to prepare uniform slurry. Then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 57.6 s; and standing for 5min, measuring the viscosity by using a coating-4 cup, wherein the slurry cannot completely flow out and has large thixotropy. Compared with example 4, the concentration of the desulfurization waste water is increased from 10% to 20%, and the viscosity of the slurry is obviously increased.
By adopting the same method, the content of the desulfurization wastewater dispergator is only changed and is increased from 0.6 percent to 0.75 percent, and uniform slurry is prepared. Then measuring the viscosity of the slurry by using a coating-4 cup, wherein the initial viscosity of the slurry is 29.9 s; after standing for 5min, the viscosity was measured with a paint-4 cup, the slurry viscosity was 50.5s, and the thixotropic index was 1.689. If the concentration of the desulfurization wastewater is increased to 20%, the dosage of the desulfurization wastewater debonder needs to be increased to 0.75%, and the cost is correspondingly increased. Therefore, in order to reduce the amount of the dispergator and the cost, it is preferable that the concentration of the desulfurization waste water is 10%, that is, the mass ratio of the desulfurization waste water to the industrial water is 1: 9.
Comparative example 7
The formula (in parts by mass) is as follows:
according to the formula proportion, the S-containing carboxylic acid polymer is slowly added into the liquid water glass, and the mechanical stirring is carried out at the speed of 150r/min while the S-containing carboxylic acid polymer is added, so that the dispergator is obviously agglomerated compared with the example 2. Probably because of the high modulus of water glass, which needs to be adjusted.
Comparative example 8
According to the formula proportion, when the dispergator is prepared, liquid water glass and sodium tripolyphosphate are mixed, and compared with example 2, precipitation occurs, probably because the solubility of the sodium tripolyphosphate is not high, the sodium tripolyphosphate is not completely dissolved, and the follow-up dispergator is easy to become turbid.
From comparative example 7 and comparative example 8, it can be seen that the wastewater debonder preparation needs to adopt a certain sequence to mix the water glass, the liquid alkali, part of the regulator and the water and stir uniformly; and then sequentially adding the carboxylic acid polymer and the rest of the regulator under the stirring state, and uniformly mixing to obtain the uniform desulfurization wastewater dispergator.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. The desulfurization wastewater debonder is characterized in that: the adhesive comprises the following components in parts by mass: 30-60 parts of carboxylic acid polymer, 20-45 parts of liquid water glass, 6-18 parts of regulator, 1-5 parts of liquid alkali and 1-10 parts of water;
the carboxylic acid polymer is any one or combination of at least two of hydroxyl-containing carboxylic acid polymer, sulfur-containing carboxylic acid polymer and phosphorus-containing carboxylic acid polymer;
the hydroxyl-containing carboxylic acid polymer is prepared by the following method: the material is obtained by one-pot polymerization of ethylene glycol monovinyl polyglycol ether containing a group-OH and acrylic acid containing a group-COO according to a molar ratio of 1: 4-7, wherein a solvent is water;
the sulfur-containing carboxylic acid polymer is prepared by the following method: with acrylic acid containing a group-COO, with acrylic acid containing a group-SO3The sodium methacrylate and the methyl allyl polyoxyethylene ether are polymerized in a one-pot method according to the molar ratio of 5-2: 1:1, and the solvent is water;
the phosphorus-containing carboxylic acid polymer is prepared by the following method: mixing methyl allyl polyoxyethylene ether and acrylic acid containing a group-COO according to a molar ratio of 1: 4-7, and adding phosphorus-containing sodium hypophosphite serving as a chain transfer agent to polymerize in a one-pot method to obtain the modified acrylic acid, wherein the solvent is water.
2. The desulfurization wastewater debonder of claim 1, wherein: the adhesive comprises the following components in parts by mass: 50-60 parts of carboxylic acid polymer, 20-35 parts of liquid water glass, 10-15 parts of regulator, 3-5 parts of liquid alkali and 1-8 parts of water.
3. The desulfurization wastewater debonder of claim 1, wherein:
the molecular weight of the hydroxyl-containing carboxylic acid polymer is 1000-20000, and the hydroxyl content is 0.3% -0.9%;
the molecular weight of the sulfur-containing carboxylic acid polymer is 1000-20000, and the sulfur content is 0.6-1.6%;
the molecular weight of the phosphorus-containing carboxylic acid polymer is 1000-20000, and the phosphorus content is 0.6% -1.6%;
the molecular weight of the ethylene glycol monovinyl polyglycol ether is 1000-3000;
the molecular weight of the methyl allyl polyoxyethylene ether is 1000-3000.
4. The desulfurization wastewater dispergator according to any one of claims 1 to 3, wherein:
the carboxylic acid polymer is a carboxylic acid polymer aqueous solution with the mass concentration of 40-50%;
the carboxylic acid polymer aqueous solution is a carboxylic acid polymer aqueous solution with pH = 4-10;
the chemical formula of the liquid water glass is Na2O·nSiO2Wherein the modulus n = 2.5-3.5;
the liquid alkali is a sodium hydroxide aqueous solution with the mass concentration of 20-50%;
the regulator is any one or combination of at least two of sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate, sodium humate and sodium metasilicate pentahydrate.
5. The preparation method of the desulfurization wastewater dispergator as set forth in any one of claims 1 to 4, characterized in that: the method comprises the following steps: mixing liquid water glass, liquid alkali, part of regulator and water, and stirring uniformly; and then sequentially adding the carboxylic acid polymer and the rest of the regulator under the stirring state, and uniformly mixing to obtain the desulfurization wastewater dispergator.
6. The method of claim 5, wherein:
the stirring speed is controlled to be 100-200 r/min.
7. The application of the desulfurization wastewater dispergator as defined in any one of claims 1 to 4 in desulfurization wastewater recycling.
8. A method for preparing ceramic slurry by utilizing recovered desulfurization wastewater is characterized by comprising the following steps: the method comprises the following steps: mixing ceramic soil, the desulfurization wastewater debonder according to any one of claims 1 to 4, desulfurization wastewater and industrial water, and grinding to obtain ceramic slurry;
the mass ratio of the desulfurization wastewater to the industrial water is 0.5-1: 9;
the dosage of the desulfurization wastewater debonder is 0.4-0.7 wt% of the mass of the ceramic soil;
the ceramic soil is any one or mixture of at least two of bentonite, kaolin and ball clay;
the water content of the ceramic slurry is 32-40%.
9. The method of claim 8, wherein:
the desulfurization wastewater is primary desulfurization wastewater, and the pH value is 7-8.
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| CN110028178A (en) * | 2019-04-17 | 2019-07-19 | 新疆中泰化学阜康能源有限公司 | The method and device thereof of coagulation chemical oxidation coprecipitation method processing desulfurization wastewater |
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| CN110028178A (en) * | 2019-04-17 | 2019-07-19 | 新疆中泰化学阜康能源有限公司 | The method and device thereof of coagulation chemical oxidation coprecipitation method processing desulfurization wastewater |
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