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Water purifying agent for advanced treatment of pulping, papermaking, printing and dyeing wastewater as well as preparation method of water purifying agent
Description
translated from Chinese
技术领域technical field
本发明涉及一种制浆造纸废水深度处理净水剂的制备方法及其应用，主要用于木材制浆或废纸造纸等制浆造纸企业生产废水。也可广泛用于轻工、纺织、印染、制药和化工等行业废水，主要用于经生化处理后的废水，进一步深度处理脱色和降COD。属于有机、无机高分子复合水处理剂技术。The invention relates to a preparation method and application of a water purifying agent for advanced treatment of pulping and papermaking wastewater, which is mainly used for the production wastewater of pulping and papermaking enterprises such as wood pulping or waste paper making. It can also be widely used in light industry, textile, printing and dyeing, pharmaceutical and chemical industry wastewater, mainly used for biochemically treated wastewater, further advanced treatment for decolorization and COD reduction. It belongs to the technology of organic and inorganic polymer composite water treatment agent.
背景技术Background technique
无机混凝剂包括传统型铝盐和铁盐等无机盐和无机高分子聚合物如聚合硫酸铁、聚合氯化铝及其复合产品等，目前市场上以无机高分子以及复合产品为主。传统型铝盐和铁盐等无机盐，常见的有硫酸铝、氯化铝、硫酸亚铁、氯化亚铁、氯化铁等。铝系混凝剂应用较早，也是当前使用范围最广泛的品种之一，但铝盐处理废水存在不溶物残留、铝离子残留等问题。另一类无机混凝剂就是铁系絮凝剂，具有形成絮体大，沉降速度快等优点。但也存在废水碱度消耗大、投加不当返色等问题。另外将铝系和铁系产品进行复合，得到不能性能的复合产品--聚合铝铁类无机高分子。这类复合混凝剂兼有聚铝和聚铁的优点，既能克服铝盐处理的矾花小、沉降慢的缺点，又能克服铁盐的易“造色”的缺点。实际生产中这类产品多以铝盐为主，铁盐为辅。近些年来，在复合铝铁的基础上，通过聚硅酸阴离子来增强效果的研究越来越多，这类混凝剂由于其优良的性能受到了广泛的关注，发表的论文和公布的专利也较多。诸如中国专利公告号CN200610164427.0，CN200610017141.X，CN200710063749.0，CN200710019268.X，CN200710131436.4等，但现有的净水剂用于深度处理制浆造纸废水时，仍然存在用量大，降COD能力不理想，脱色效果较差，对水质的依赖程度高等缺点，不能满足制浆造纸废水的深度处理需要。Inorganic coagulants include traditional inorganic salts such as aluminum salts and iron salts, and inorganic polymers such as polyferric sulfate, polyaluminum chloride and their composite products. At present, inorganic polymers and composite products are mainly used in the market. Inorganic salts such as traditional aluminum salts and iron salts, common ones include aluminum sulfate, aluminum chloride, ferrous sulfate, ferrous chloride, and ferric chloride. Aluminum-based coagulants have been used earlier and are currently one of the most widely used varieties. However, there are problems such as insoluble residues and aluminum ion residues in wastewater treated with aluminum salts. Another type of inorganic coagulant is iron-based flocculant, which has the advantages of forming large flocs and fast settling speed. However, there are also problems such as high consumption of wastewater alkalinity, improper dosing and color change. In addition, the aluminum-based and iron-based products are compounded to obtain a composite product with no performance-polymerized aluminum-iron-based inorganic polymers. This kind of composite coagulant has the advantages of both polyaluminum and polyiron, which can not only overcome the disadvantages of small alum flowers and slow settlement of aluminum salt treatment, but also overcome the disadvantage of easy "color formation" of iron salt. In actual production, such products are mostly aluminum salts, supplemented by iron salts. In recent years, on the basis of composite aluminum iron, more and more researches have been conducted on the enhancement of the effect by polysilicate anions. This type of coagulant has received extensive attention due to its excellent performance, and published papers and published patents Also more. Such as Chinese Patent Announcement No. CN200610164427.0, CN200610017141.X, CN200710063749.0, CN200710019268.X, CN200710131436.4, etc., but when the existing water purifiers are used for advanced treatment of pulping and papermaking wastewater, there is still a large amount of COD reduction. The ability is not ideal, the decolorization effect is poor, and the dependence on water quality is high, which cannot meet the needs of advanced treatment of pulp and paper wastewater.
发明内容Contents of the invention
为了克服现有技术产品对制浆造纸废水深度处理降COD能力弱、脱色效果不理想的缺点，本发明提供了一种用于处理制浆造纸废水深度处理用的复合净水剂的制备方法。具有制备工艺简单，生产能耗低，各配伍组分协作效果好等特点，特别适合用于造纸废水深度处理，具有比现有市售产品更好的处理效果，一般比PAC脱COD能力提高50%左右，脱色能力提高30%以上。In order to overcome the shortcomings of weak COD reduction ability and unsatisfactory decolorization effect of the prior art products for advanced treatment of pulping and papermaking wastewater, the present invention provides a preparation method of a composite water purifier for advanced treatment of pulping and papermaking wastewater. It has the characteristics of simple preparation process, low production energy consumption, and good synergistic effect of each compatible component. It is especially suitable for advanced treatment of papermaking wastewater. It has a better treatment effect than existing commercially available products, and generally improves the COD removal capacity by 50% compared with PAC. %, the decolorization ability is increased by more than 30%.
本发明的技术方案为：一种用于制浆造纸和印染废水深度处理用净水剂，按质量百分比计组成为：硫酸亚铁35%-60%、硫酸5%-8%、盐酸0.5%～1.5%、氧化剂3%-14%、调理剂1.5%-5%、硅藻精土0.3%～1.8%、再添加占净水剂总质量0.05%-0.15%的高分子聚合物、其余为水；液态产品在20摄氏度时的相对密度为1.20-1.50，氧化铁重量含量：8-14%，固含量≥30%，pH：2-3。The technical solution of the present invention is: a water purifying agent for advanced treatment of pulping, papermaking and printing and dyeing wastewater, composed of: 35%-60% ferrous sulfate, 5%-8% sulfuric acid, 0.5% hydrochloric acid ～1.5%, oxidizing agent 3%-14%, conditioning agent 1.5%-5%, diatomite 0.3%～1.8%, add high molecular polymer accounting for 0.05%-0.15% of the total mass of water purifier, and the rest is Water; the relative density of the liquid product at 20 degrees Celsius is 1.20-1.50, the weight content of iron oxide: 8-14%, the solid content ≥ 30%, pH: 2-3.
更优化方案还可添加占净水剂总质量的0～0.5%的高分子季铵盐或0～0.6%的膨润土。A more optimized solution can also add 0-0.5% of polymer quaternary ammonium salt or 0-0.6% of bentonite, accounting for the total mass of the water purifier.
所述的氧化剂为高锰酸钾，氯酸盐或过硫酸盐中的任意一种或几种。The oxidizing agent is any one or more of potassium permanganate, chlorate or persulfate.
所述的氧化剂为工业级高锰酸钾时添加量为净水剂总质量的6%-12%，氧化剂为氯酸盐时添加量为3%-6%，为双氧水时添加量为8%-14%。When the oxidant is industrial-grade potassium permanganate, the amount added is 6%-12% of the total mass of the water purifier; when the oxidant is chlorate, the amount added is 3%-6%, and when it is hydrogen peroxide, the amount added is 8% -14%.
所述的调理剂为硅酸钠、铝酸钙、氧化镁或氯化镁中的任意一种或几种。The conditioner is any one or more of sodium silicate, calcium aluminate, magnesium oxide or magnesium chloride.
所述的高分子聚合物由丙烯酰胺、苯乙烯磺酸盐和木质磺酸盐共聚而成。The high molecular polymer is formed by copolymerization of acrylamide, styrene sulfonate and lignosulfonate.
所述用于制浆造纸和印染废水深度处理用净水剂的制备方法，具体制备步骤为：The preparation method of the water purifying agent for the advanced treatment of pulping, papermaking and printing and dyeing wastewater, the specific preparation steps are:
a、将固体硫酸亚铁在盐酸和硫酸溶液中溶解混合均匀形成铁盐溶液，加入氧化剂，通入空气反应2～3小时，形成净水剂半成品；a. Dissolve and mix solid ferrous sulfate in hydrochloric acid and sulfuric acid solution to form an iron salt solution, add an oxidant, and let air react for 2 to 3 hours to form a semi-finished water purifier;
b、在a工序制备好的液体中添加调理剂，并加入硅藻精土，最后再加入高分子聚合物反应后，即得本液体产品。b. Add conditioner and diatomite to the liquid prepared in step a, and finally add high molecular polymer to react to obtain the liquid product.
所述的用于制浆造纸和印染废水深度处理用净水剂改进方案的制备方法，具体制备步骤为：The specific preparation steps of the preparation method for the improvement scheme of the water purifying agent for the advanced treatment of pulping, papermaking and printing and dyeing wastewater are as follows:
a、将固体硫酸亚铁在盐酸和硫酸溶液中溶解混合均匀形成铁盐溶液，加入氧化剂，通入空气反应2～3小时，形成净水剂半成品；a. Dissolve and mix solid ferrous sulfate in hydrochloric acid and sulfuric acid solution to form an iron salt solution, add an oxidant, and let air react for 2 to 3 hours to form a semi-finished water purifier;
b、在a工序制备好的液体中添加调理剂，并加入硅藻精土，最后再加入高分子聚合物反应后，再加入高分子季铵盐或膨润土即得本发明的净水剂。b. Add conditioner and diatomite to the liquid prepared in step a, and finally add high molecular polymer after reaction, then add high molecular quaternary ammonium salt or bentonite to obtain the water purifying agent of the present invention.
将所得净水剂干燥后得到固体净水剂。The obtained water purifying agent is dried to obtain a solid water purifying agent.
有益效果Beneficial effect
上述净水剂经干燥后成片状或粉状，即得固体高效多功能净水剂。The above-mentioned water purifying agent is dried into flakes or powders to obtain a solid high-efficiency multifunctional water purifying agent.
本发明首先生产出无机高分子净水剂，然后复合有机高分子，在此基础上再增加具有共聚沉淀作用的多孔类材料如硅藻土等。最终形成集各组分优势增效互补的无机-有机高分子复合产品。In the present invention, the inorganic polymer water purifying agent is firstly produced, and then the organic polymer is compounded, and on this basis, porous materials such as diatomaceous earth and the like with copolymerization and precipitation are added. Finally, an inorganic-organic polymer composite product that integrates the advantages and synergies of each component is formed.
本发明是以工业副产的硫酸亚铁、盐酸和硫酸为原料，工艺过程简单，便于操作，不产生二次污染。生产成本低，处理制浆造纸废水效果明显优于其他市售产品。The invention uses industrial by-products of ferrous sulfate, hydrochloric acid and sulfuric acid as raw materials, has a simple process, is easy to operate, and does not produce secondary pollution. The production cost is low, and the treatment effect of pulping and papermaking wastewater is obviously better than other commercially available products.
具体实施方式：Detailed ways:
下面结合附图和具体实施例作进一步说明：Further description will be made below in conjunction with accompanying drawings and specific embodiments:
本发明所述的高分子聚合物是在搅拌的条件下，将100质量份丙烯酰胺、30质量份苯乙烯磺酸盐和10质量份木质磺酸盐进行混合在引发剂过硫酸钾或硝酸铈铵作用下，进行共聚反应2-3小时，反应结束后形成均匀液体得到。The macromolecular polymer of the present invention is to mix 100 mass parts of acrylamide, 30 mass parts of styrene sulfonate and 10 mass parts of lignosulfonate in the initiator potassium persulfate or cerium nitrate Under the action of ammonium, the copolymerization reaction is carried out for 2-3 hours, and a uniform liquid is formed after the reaction is completed.
本发明的具体制备方法：Concrete preparation method of the present invention:
生产原料有：工业级七水硫酸亚铁，化工厂副产盐酸(20%-30%)或硫酸(50%-90%)，工业级高锰酸钾，工业级氯酸钠，工业级双氧水，铝酸钙粉、硅藻土和高分子聚合物等。Production raw materials are: industrial grade ferrous sulfate heptahydrate, chemical plant by-product hydrochloric acid (20%-30%) or sulfuric acid (50%-90%), industrial grade potassium permanganate, industrial grade sodium chlorate, industrial grade hydrogen peroxide , Calcium aluminate powder, diatomaceous earth and polymers, etc.
制备步骤为：The preparation steps are:
在反应釜中加入适量的水，在搅拌条件下，逐步将工业级硫酸亚铁加入，边搅拌边溶解，固含量控制在20%-30%，然后分批加入一定量浓度20%-30%的盐酸和一定量的50%-90%的硫酸(体积比3：1混合)，控制pH0.5-1.0。之后加入氧化剂，氧化剂可采用高锰酸钾，高氯酸钠、高氯酸钾、氯酸盐、过硫酸盐和双氧水等其中一种或几种，氧化反应会产生大量的热，控制氧化反应温度80-95℃，氧化反应时间控制在45min-90min。反应结束后，再逐步分批加入一定量的调理剂，反应时间控制在1-2h。待冷却后，在搅拌条件下，缓慢加入一定量的高分子聚合物，搅拌反应1-2h，最后加入硅藻精土，搅拌均匀所得混合液即为本产品。Add an appropriate amount of water into the reaction kettle, gradually add industrial grade ferrous sulfate under stirring conditions, dissolve while stirring, control the solid content at 20%-30%, and then add a certain amount of concentration 20%-30% in batches Hydrochloric acid and a certain amount of 50%-90% sulfuric acid (mixed at a volume ratio of 3:1) to control the pH of 0.5-1.0. Add oxidizing agent afterwards, and oxidizing agent can adopt potassium permanganate, sodium perchlorate, potassium perchlorate, chlorate, persulfate and hydrogen peroxide etc. one or more, oxidation reaction can produce a large amount of heat, control oxidation reaction temperature 80 -95°C, the oxidation reaction time is controlled at 45min-90min. After the reaction is completed, a certain amount of conditioning agent is gradually added in batches, and the reaction time is controlled within 1-2 hours. After cooling, under stirring conditions, slowly add a certain amount of high molecular polymer, stir and react for 1-2 hours, finally add diatomite, stir evenly to obtain a mixed solution, which is the product.
实施例1Example 1
1、取100g工业级七水硫酸亚铁(有效含量85%wt以上)，15g硫酸(55%wt)、5g盐酸(30%wt)和水20ml，分批逐步加入到设有搅拌器和保温装置的反应器中，搅拌溶解并混合均匀；1. Take 100g of industrial grade ferrous sulfate heptahydrate (effective content above 85%wt), 15g of sulfuric acid (55%wt), 5g of hydrochloric acid (30%wt) and 20ml of water, and gradually add them in batches to a tank equipped with agitator and heat preservation In the reactor of the device, stir to dissolve and mix evenly;
2、将10g氯酸钠逐步缓慢的加入到反应器中，不断搅拌，控制温度在80℃，反应3h后，静置冷却温度至40℃；2. Add 10g of sodium chlorate gradually and slowly into the reactor, keep stirring, and control the temperature at 80°C. After reacting for 3 hours, let it stand and cool down to 40°C;
3、在搅拌的情况下，加入调理剂铝酸钠3g，调节pH值至2.0-3.0；之后再逐步分批加入2g硅藻精土，搅拌使之均匀分散在液体产品中；3. While stirring, add 3g of conditioning agent sodium aluminate to adjust the pH value to 2.0-3.0; then gradually add 2g of diatomite in batches and stir to disperse it evenly in the liquid product;
4、在缓慢搅拌条件下，在上述液体中加入0.2g高分子聚合物，搅拌反应3h后，所得液体即为本液体产品。4. Under the condition of slow stirring, add 0.2g of high molecular polymer to the above liquid, stir and react for 3 hours, the obtained liquid is the liquid product.
5、将所得的液体产品进行干燥，即得固体产品。5. Dry the obtained liquid product to obtain a solid product.
实施例2Example 2
1、取副产盐酸（有效含量20%）10ml到反应器中，加入20g硫酸（有效含量60%），搅拌均匀，分批加入硫酸亚铁120g，在搅拌条件下混合溶解；1. Take 10ml of by-product hydrochloric acid (effective content 20%) into the reactor, add 20g of sulfuric acid (effective content 60%), stir evenly, add 120g of ferrous sulfate in batches, mix and dissolve under stirring conditions;
2、投加双氧水(27.5%)5ml，反应30min后，逐步加入氯酸钠2.6g，控制反应温度在60℃，反应4h后，静置待温度降至40℃；2. Add 5ml of hydrogen peroxide (27.5%), after 30 minutes of reaction, gradually add 2.6g of sodium chlorate, control the reaction temperature at 60°C, after 4 hours of reaction, let it stand until the temperature drops to 40°C;
3、在30℃-40℃和搅拌的情况下，再缓慢加入6g铝酸钙粉，调节pH值至2.0-3.0。之后再逐步分批加入4g硅藻精土，搅拌使之均匀分散在液体产品中；3. With stirring at 30°C-40°C, slowly add 6g of calcium aluminate powder to adjust the pH value to 2.0-3.0. Then gradually add 4g diatomite in batches and stir to make it evenly dispersed in the liquid product;
4、逐滴加入10ml高分子聚合物，共聚反应4h；4. Add 10ml high molecular polymer drop by drop, and copolymerize for 4 hours;
5、静置存放1-2天，所得液体即为本液体产品。5. After standing for 1-2 days, the resulting liquid is the liquid product.
6、将所得的液态产品进行干燥，即得相应固体产品。6. Dry the obtained liquid product to obtain the corresponding solid product.
实施例3Example 3
1、加入实施例1液态产品80ml到反应器中，缓慢升温到40℃-50℃，在搅拌的条件下，缓慢加入实施例2液态产品20ml；1. Add 80ml of the liquid product of Example 1 into the reactor, slowly raise the temperature to 40°C-50°C, and slowly add 20ml of the liquid product of Example 2 under stirring conditions;
2、低温反应2h后，在搅拌条件下，加入0.5g高分子季铵盐（宜兴市绿科环保药剂有限公司，季铵盐系列03号），反应2h后，出料。放出混合液静置24小时后，得到复合净水剂；2. After reacting at low temperature for 2 hours, add 0.5 g of polymer quaternary ammonium salt (Yixing Lvke Environmental Protection Pharmaceutical Co., Ltd., quaternary ammonium salt series No. 03) under stirring conditions, and discharge after 2 hours of reaction. After releasing the mixed solution and standing for 24 hours, a composite water purifying agent is obtained;
3、将所得的液态复合净水剂进行干燥，即得固体复合净水剂。3. Dry the obtained liquid composite water purifier to obtain a solid composite water purifier.
实施例4Example 4
1、加入实施例2液态产品90ml到反应器中，缓慢升温到40℃-50℃，在搅拌的条件下，缓慢加入实施例1液态产品10ml；1. Add 90ml of the liquid product of Example 2 into the reactor, slowly raise the temperature to 40°C-50°C, and slowly add 10ml of the liquid product of Example 1 under stirring conditions;
2、低温反应2h后，在搅拌条件下加入0.5-1g膨润土，放出混合液静置24小时后，得到复合净水剂；2. After reacting at low temperature for 2 hours, add 0.5-1g of bentonite under stirring condition, release the mixed solution and let it stand for 24 hours to obtain a composite water purifier;
3、将所得的液态复合净水剂进行干燥，即得固体复合净水剂。3. Dry the obtained liquid composite water purifier to obtain a solid composite water purifier.
本实施例中四种净水剂小样，与市场上的有代表性的净水剂如：聚合氯化铝(PAC)、硫酸铝、聚合硫酸铁等，采用某纸厂杨木化机浆生化处理出水进行混凝对比试验，其结果如下表所示。In this example, the four water purifier samples are compared with representative water purifiers on the market such as polyaluminum chloride (PAC), aluminum sulfate, polyferric sulfate, etc., and the effluent of a paper mill is treated with poplar chemical pulp biochemically. The coagulation comparison test was carried out, and the results are shown in the table below.
