CN101015755A - Porous calcium silicate filter material for water treatment - Google Patents
Porous calcium silicate filter material for water treatment Download PDFInfo
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- CN101015755A CN101015755A CN 200610161586 CN200610161586A CN101015755A CN 101015755 A CN101015755 A CN 101015755A CN 200610161586 CN200610161586 CN 200610161586 CN 200610161586 A CN200610161586 A CN 200610161586A CN 101015755 A CN101015755 A CN 101015755A
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- 239000000463 material Substances 0.000 title claims abstract description 26
- 239000000378 calcium silicate Substances 0.000 title claims abstract description 12
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 12
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 7
- 239000010440 gypsum Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000011398 Portland cement Substances 0.000 claims abstract description 5
- 230000015271 coagulation Effects 0.000 claims abstract description 4
- 238000005345 coagulation Methods 0.000 claims abstract description 4
- 238000005187 foaming Methods 0.000 claims abstract description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 17
- 239000000292 calcium oxide Substances 0.000 claims description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims 2
- 238000012423 maintenance Methods 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 7
- 239000004568 cement Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 3
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- Water Treatment By Sorption (AREA)
Abstract
一种经混凝、蒸汽发泡养护、高温高压蒸汽处理后得到的水处理用多孔硅酸钙滤材，其特征在于以国产粉状石英(SiO2)、普通硅酸盐水泥、粉状氧化钙(CaO)、粉状石膏(CaSO4)、和铝(Al)粉为主要原料。成品具有很强的有机物、磷、氮的吸附、分解能力，是小型生活污水处理系统的理想滤材。A porous calcium silicate filter material for water treatment obtained after coagulation, steam foaming curing, and high-temperature and high-pressure steam treatment, which is characterized in that it is made of domestic powdery quartz (SiO 2 ), ordinary Portland cement, powdery Calcium (CaO), powdered gypsum (CaSO 4 ), and aluminum (Al) powder are the main raw materials. The finished product has strong adsorption and decomposition capabilities of organic matter, phosphorus and nitrogen, and is an ideal filter material for small domestic sewage treatment systems.
Description
一、技术领域1. Technical field
本发明属废水、污水处理技术领域中的过滤材料制造技术。The invention belongs to the filter material manufacturing technology in the technical field of waste water and sewage treatment.
二、背景技术2. Background technology
随着工农业生产和人民生活水平的提高，我国的工业污水和生活污水排放量越来越大，且生活污水的排放总量已经超过了工业污水的排放量，根据2005年度的统计，当年的生活污水的排放总量为281.4亿吨，工业污水的排放总量为243.1亿吨。With the improvement of industrial and agricultural production and people's living standards, the discharge of industrial sewage and domestic sewage in my country is increasing, and the total discharge of domestic sewage has exceeded the discharge of industrial sewage. According to the statistics of 2005, the domestic The total discharge of sewage is 28.14 billion tons, and the total discharge of industrial sewage is 24.31 billion tons.
生活污水中的污染源主要为有机物和磷、氮等，已成为河流、湖泊富营养化的主导因素。随着经济的发展，污水量还会增加，如不加以治理，建设优美环境，使河流、湖泊变清的环境治理目标很难实现。借鉴国外发达国家的先进经验，只有从源头开始治理水污染，才可以真正实现理想的污水处理目标，因此，小型生活污水处理系统也已逐渐开始在国内得到推广使用。目前引进的一些小型污水处理系统，主要使用活性滤材完成对生活污水中的污染源进行吸附、分解处理，且滤材必须定期更换。对常用的多孔硅酸钙滤材分析表明，其主要成分为雪硅钙石(Tobermorite)和硬硅钙(Xonotlite)，简称TBX。在电镜中可见很多的小气孔，有很大的外表面积(参见附图1)；在小孔间是片状雪硅钙石结晶体，他们间又有很多微孔，有很大的内表面积(参见附图2)。由于多孔硅酸钙滤材的大孔隙内可以进行有机物质的微生物好气分解，而在微孔隙内可进行厌气分解，可将吸附的有机物分解，延长材料的使用寿命，同时雪硅钙本身对磷又可进行物理化学吸附。因此，多孔硅酸钙滤材具有很强的有机物和磷、氮等的吸附、分解能力，是小型生活污水处理系统的理想滤材。The pollution sources in domestic sewage are mainly organic matter, phosphorus, nitrogen, etc., which have become the leading factors of eutrophication in rivers and lakes. With the development of the economy, the amount of sewage will increase. If it is not treated, it will be difficult to achieve the goal of environmental governance to build a beautiful environment and make rivers and lakes clear. Drawing on the advanced experience of foreign developed countries, only by controlling water pollution from the source can the ideal sewage treatment target be truly realized. Therefore, small-scale domestic sewage treatment systems have gradually begun to be promoted and used in China. Some small-scale sewage treatment systems introduced at present mainly use active filter materials to complete the adsorption and decomposition treatment of pollution sources in domestic sewage, and the filter materials must be replaced regularly. The analysis of the commonly used porous calcium silicate filter material shows that its main components are Tobermorite and Xonotlite, referred to as TBX. A lot of small pores can be seen in the electron microscope, with a large external surface area (see accompanying drawing 1); between the small pores are flaky tobermorite crystals, and there are many micropores between them, with a large internal surface area ( See accompanying drawing 2). Since the aerobic microbial decomposition of organic substances can be carried out in the large pores of the porous calcium silicate filter material, and the anaerobic decomposition can be carried out in the micropores, which can decompose the adsorbed organic substances and prolong the service life of the material. Phosphorus can also undergo physical and chemical adsorption. Therefore, the porous calcium silicate filter material has strong adsorption and decomposition capabilities for organic matter, phosphorus, nitrogen, etc., and is an ideal filter material for small domestic sewage treatment systems.
由于引进设备中使用的多孔硅酸钙滤材配方，目前尚不对外公开，因此设备引进之后，尚需定期向国外厂商订货，不仅耗资大，且大大影响了设备的推广使用。Since the formula of the porous calcium silicate filter material used in the imported equipment is not disclosed to the public at present, after the equipment is introduced, it is still necessary to order regularly from foreign manufacturers, which not only costs a lot, but also greatly affects the promotion and use of the equipment.
三、发明内容3. Contents of the invention
本发明的目的就是根据小型污水处理系统的滤材要求，开发以国产原料为基础的新型多孔硅酸钙高效污水净化矿物滤材。The purpose of the present invention is exactly according to the filter material requirement of small-scale sewage treatment system, develops the novel porous calcium silicate highly efficient sewage purification mineral filter material based on domestic raw material.
本发明的技术解决方案为：以国产粉状石英(SiO2)、普通硅酸盐水泥、粉状氧化钙(CaO)、粉状石膏(CaSO4)、和铝(Al)粉为主要原料，经混凝、蒸汽发泡养护、高温高压蒸汽处理后得到成品水处理用多孔硅酸钙滤材，原料配比如下(以重量份计)：The technical solution of the present invention is: with domestic powdery quartz (SiO 2 ), ordinary Portland cement, powdery calcium oxide (CaO), powdery gypsum (CaSO 4 ), and aluminum (Al) powder as main raw materials, After coagulation, steam foaming curing, and high temperature and high pressure steam treatment, the finished porous calcium silicate filter material for water treatment is obtained. The raw material ratio is as follows (by weight):
粉状石英(SiO2)--50Powdered Quartz (SiO 2 )--50
普通硅酸盐水泥--10～26Ordinary Portland cement--10～26
粉状氧化钙(CaO)--5～26Powdered calcium oxide (CaO)--5～26
粉状石膏(CaSO4)--5Powdered gypsum (CaSO 4 )--5
铝(Al)粉--0.15～0.22Aluminum (Al) powder--0.15～0.22
试验表明，在配方中加入适量晶种可使雪硅钙石(Tobermorite)快速结晶析出，抑制硬硅钙(Xonotlite)的形成，成品过滤性能更好，同时又可废物利用，节约成本。成品锯切边角碎料粉碎后，即可作为晶种使用，加入量为总重的1～5％。Tests have shown that adding an appropriate amount of seed crystals to the formula can quickly crystallize Tobermorite, inhibit the formation of Xonotlite, and improve the filtration performance of the finished product. At the same time, it can be used for waste and save costs. After the finished sawing scraps are crushed, they can be used as crystal seeds, and the addition amount is 1-5% of the total weight.
四、附图说明4. Description of drawings
图1为进口TBX滤材中的大孔隙电镜图；Figure 1 is the electron micrograph of the large pores in the imported TBX filter material;
图2为进口TBX滤材中的板片晶体间微孔电镜图；Figure 2 is an electron microscope image of micropores between plate crystals in the imported TBX filter material;
图3为根据本发明配方制造的TBX滤材中的大孔隙电镜图；Fig. 3 is the large-pore electron microscope figure in the TBX filter material that formula manufactures according to the present invention;
图4为根据本发明配方制造的TBX滤材中的板片晶体间微孔电镜图；Fig. 4 is according to the micropore electron microscope picture between plate crystals in the TBX filter material that formula of the present invention manufactures;
五、具体实施方式5. Specific implementation
实施例1：Example 1:
滤材配方如下(以重量份计)：Filter material formula is as follows (by weight):
粉状石英(SiO2)--50Powdered Quartz (SiO 2 )--50
普通硅酸盐水泥(标号425或425R)--10～26Ordinary Portland cement (label 425 or 425R)--10～26
粉状氧化钙(CaO)--5～26Powdered calcium oxide (CaO)--5～26
粉状石膏(CaSO4)--5Powdered gypsum (CaSO 4 )--5
铝(Al)粉--0.15～0.22Aluminum (Al) powder--0.15～0.22
水--适量water - appropriate amount
配方中的粉状石英(SiO2)可以使用国产粉状鳞英石或风化石英、硅藻土等；氧化钙(CaO)也可以先用水将生石灰化开得到的Ca(OH)2代用。The powdered quartz (SiO 2 ) in the formula can use domestic powdered thymite or weathered quartz, diatomaceous earth, etc.; calcium oxide (CaO) can also be replaced by Ca(OH) 2 obtained by first dissolving quicklime with water.
a.混凝a. Coagulation
先将粉状石英(SiO2)、普通硅酸盐水泥(标号425或425R)、石膏(CaSO4)、氧化钙(CaO)和铝(Al)粉混匀；First mix powdered quartz (SiO 2 ), ordinary Portland cement (label 425 or 425R), gypsum (CaSO 4 ), calcium oxide (CaO) and aluminum (Al) powder;
再加水快速搅拌均匀后注入模具中成型。Add water and stir quickly and then pour it into the mold.
b.蒸汽发泡养护b. Steam foam curing
将模具和半成品移到60℃蒸锅中发泡、固化、养护8小时左右。Move the mold and semi-finished products to a 60°C steamer for foaming, curing, and curing for about 8 hours.
c.高温高压蒸汽处理c. High temperature and high pressure steam treatment
将蒸汽养护的半成品移入高压蒸汽釜中，在180～200℃，10MPa的条件下反应10小时左右，即得成品多孔硅酸钙高效污水净化矿物滤材。Move the steam-cured semi-finished product into a high-pressure steam kettle, and react for about 10 hours under the conditions of 180-200 ° C and 10 MPa to obtain the finished porous calcium silicate high-efficiency sewage purification mineral filter material.
为了保证成品的过滤活性，必须控制成品的pH值在9.5左右，成品的pH值主要与水泥与CaO的配比相关，下表为水泥与CaO对成品pH值的影响：In order to ensure the filtration activity of the finished product, the pH value of the finished product must be controlled at about 9.5. The pH value of the finished product is mainly related to the ratio of cement and CaO. The following table shows the influence of cement and CaO on the pH value of the finished product:
说明：表中数值均以重量份计Note: the values in the table are in parts by weight
从表中可知，水泥含量越低、CaO含量越高，成品的pH值也将越低，但水泥含量过低、CaO含量过高将会影响成品的机械强度。It can be seen from the table that the lower the cement content and the higher the CaO content, the lower the pH value of the finished product will be, but too low cement content and too high CaO content will affect the mechanical strength of the finished product.
成品水处理用多孔硅酸钙滤材的主要物理化学性能如下：The main physical and chemical properties of the porous calcium silicate filter material for finished water treatment are as follows:
密度：0.3～0.6gcm-3 Density: 0.3～0.6gcm -3
pH值：9.3～9.6pH value: 9.3～9.6
抗压强度：4～7N mm-2 Compressive strength: 4～7N mm -2
成品可按水处理设备要求将滤材制成各种形状或锯割成不同型号的尺寸，代替进口滤材使用。The finished product can be made into various shapes or sawed into different sizes according to the requirements of water treatment equipment, which can be used instead of imported filter materials.
实施例2：Example 2:
试验表明，在配方中加入适量晶种可使雪硅钙石(Tobermorite)快速结晶析出，抑制硬硅钙(Xonotlite)的形成，成品过滤性能更好，同时又可废物利用，节约成本，因此，可以在配方中加入重量份为1～5％的晶种。Tests have shown that adding an appropriate amount of seed crystals to the formula can quickly crystallize Tobermorite and inhibit the formation of Xonotlite. The finished product has better filtration performance, and at the same time, it can be used for waste and save costs. Therefore, 1-5% by weight of seed crystals can be added into the formula.
将实施例1中获得的成品锯割边角碎料粉碎后作为晶种使用，配方中加入重量份为1～5％的晶种以后，成品中的雪硅钙石(Tobermorite)增加3～6％。After crushing the finished sawing scraps obtained in Example 1, use them as seed crystals. After adding 1 to 5% by weight of seed crystals in the formula, the tobermorite (Tobermorite) in the finished product increases by 3 to 6 %.
加晶种提高成品中雪硅钙石比例的方法，仅对以鳞英石为原料的配方有效，对以风化石英或硅藻土为原料的配方，效果不明显或基本无效，但仍可达到废物利用，节约成本的目的。The method of adding crystal seeds to increase the proportion of tobermorite in the finished product is only effective for the formula with pyrymite as raw material, and the effect is not obvious or basically ineffective for the formula with weathered quartz or diatomite as raw material, but it can still reach The purpose of waste utilization and cost saving.
本发明与日本进口同类材料相比，微观结构和过滤性能基本相近，完全可以作为同类产品使用。Compared with similar materials imported from Japan, the present invention has basically similar microstructure and filtering performance, and can be used as similar products.
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| CN103058312A (en) * | 2013-01-09 | 2013-04-24 | 内蒙古科技大学 | Treatment method of domestic wastewater |
| CN103435057A (en) * | 2013-08-05 | 2013-12-11 | 陕西科技大学 | Method for preparing aluminum tobermorite sewage treatment material with ordinary portland cement |
| WO2014067444A1 (en) * | 2012-10-29 | 2014-05-08 | 日铁住金环境株式会社 | Noxious substance processing material and preparation method thereof, and noxious substance processing method |
| CN105622028A (en) * | 2015-12-25 | 2016-06-01 | 成都新柯力化工科技有限公司 | Organic-inorganic composite porous sewage treatment material and preparation method thereof |
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- 2006-12-28 CN CNB2006101615865A patent/CN100467095C/en not_active Expired - Fee Related
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| CN103785348A (en) * | 2012-10-29 | 2014-05-14 | 日铁住金环境株式会社 | Harmful-substance processing material, its manufacturing method and harmful-substance processing method |
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| CN103058312A (en) * | 2013-01-09 | 2013-04-24 | 内蒙古科技大学 | Treatment method of domestic wastewater |
| CN103435057A (en) * | 2013-08-05 | 2013-12-11 | 陕西科技大学 | Method for preparing aluminum tobermorite sewage treatment material with ordinary portland cement |
| CN103435057B (en) * | 2013-08-05 | 2015-06-03 | 陕西科技大学 | Method for preparing aluminum tobermorite sewage treatment material with ordinary portland cement |
| CN105622028A (en) * | 2015-12-25 | 2016-06-01 | 成都新柯力化工科技有限公司 | Organic-inorganic composite porous sewage treatment material and preparation method thereof |
| CN109761641A (en) * | 2017-11-09 | 2019-05-17 | 卢松 | Aerated bricks and its processing technology containing desulfurized gypsum |
| CN109704446A (en) * | 2019-01-10 | 2019-05-03 | 四川大学 | A method for efficiently removing phosphorus in eutrophic water |
| CN109704446B (en) * | 2019-01-10 | 2022-01-14 | 四川大学 | Method for efficiently removing phosphorus in eutrophic water body |
| CN112064423A (en) * | 2020-08-17 | 2020-12-11 | 浙江农林大学 | Preparation method of hydrated calcium silicate nanosheet, nanocomposite paper and preparation method thereof |
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