WO2015021797A1 - Magnetic kieselguhr-based adsorbent, preparation method therefor and application thereof - Google Patents
Magnetic kieselguhr-based adsorbent, preparation method therefor and application thereof Download PDFInfo
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- WO2015021797A1 WO2015021797A1 PCT/CN2014/077638 CN2014077638W WO2015021797A1 WO 2015021797 A1 WO2015021797 A1 WO 2015021797A1 CN 2014077638 W CN2014077638 W CN 2014077638W WO 2015021797 A1 WO2015021797 A1 WO 2015021797A1
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- magnetic
- diatomite
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003463 adsorbent Substances 0.000 title claims description 25
- 238000012986 modification Methods 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 22
- 238000001179 sorption measurement Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 241000195493 Cryptophyta Species 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- -1 hydroxide ions Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052754 neon Inorganic materials 0.000 claims 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000000967 suction filtration Methods 0.000 abstract description 3
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000002250 absorbent Substances 0.000 abstract 2
- 230000002745 absorbent Effects 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000005389 magnetism Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000005909 Kieselgur Substances 0.000 description 40
- 238000005516 engineering process Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000012847 fine chemical Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000011949 advanced processing technology Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3021—Milling, crushing or grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/481—Treatment of water, waste water, or sewage with magnetic or electric fields using permanent magnets
Definitions
- the invention relates to a magnetic diatomaceous earth-based adsorbent, a preparation method and application thereof. Background technique
- the fine chemical wastewater is pre-treated and biochemically treated, and its biochemical tailwater pollutants are still very complex. Faced with the environmental pressure of industry standardization and water reuse, there is an urgent need for cost-effective advanced processing technology.
- the water reuse rate of fine chemical wastewater in China is low, and the technical level of deep treatment and water quality maintenance is not high.
- the current advanced treatment technologies mainly include oxidation technology, membrane separation technology and adsorption technology.
- Diatomaceous earth is a non-metallic mineral that is formed by diatom residues grown in the ocean or lake and deposited on the bottom of the water and formed by the natural environment. China's diatomaceous earth is rich in resources. So far, the country has proven reserves of 320 million tons, and the prospective reserves can exceed 1 billion tons, ranking the world's forefront. The remarkable characteristics of diatomite are light, porous, high liquid adsorption capacity, large specific surface area, and excellent physical and chemical properties such as chemical inertness and insoluble in general acids. Therefore, diatomaceous earth is widely used for the preparation of filter aids and adsorption. Agent, catalytic carrier and functional filler.
- Diatomaceous earth is light, porous, and has a large specific surface area, and is expected to be one of the cheap adsorbents for replacing activated carbon.
- the unmodified diatomaceous earth raw material has poor adsorption performance and may contain accompanying impurities, which affects its application in dye wastewater treatment. Therefore, it needs to be purified and modified to remove the large diatomaceous earth.
- Ministry The specification is divided into impurities and active materials to obtain a richer internal pore structure, increase the specific surface area, further improve the adsorptivity, and further enhance the application in the field of water treatment. Summary of the invention
- An object of the present invention is to provide a method for preparing a magnetic diatomaceous earth-based adsorbent in view of the above-mentioned drawbacks of the prior art.
- Another object of the present invention is to provide a magnetic diatomaceous earth-based adsorbent prepared by the method.
- a method for preparing a magnetic diatomaceous earth-based adsorbent comprising the steps of: (a) pretreating diatomaceous earth with an acid solution; (b) physically pre-modifying with a plasma; (c) using ferrous iron After the ions are immersed and modified by diatomaceous earth, the pH is adjusted by alkali to form a magnetic precursor; (d) the magnetic diatomaceous earth-based adsorbent is obtained by drying, roasting and grinding.
- the acid solution described in the step (a) is preferably a hydrochloric acid solution having a mass fraction of 1 to 10%, and the solid-liquid ratio of the diatomaceous earth to the acid solution is preferably 1:10 (g/ml) to 1:20 (g/ Ml) ; the pretreatment conditions are preferably 80 ⁇ 100 ° C heat treatment l ⁇ 2h.
- the diatomaceous earth after the pretreatment is preferably subjected to suction filtration, drying, and grinding to carry out the next pre-modification.
- the physical pre-modification described in the step preferably uses a dual dielectric barrier plasma generating device, and the pre-treatment sample is placed between the electrodes and argon or helium gas is introduced for plasma modification, and the modified voltage is 10-20 kV. , modification time is 3 ⁇ 10min.
- Step (c) the physically pre-modified diatomaceous earth is mixed with the FeS0 7 7H 2 0 or FeCI 2 solution in a nitrogen-protected environment, so that the diatomaceous earth sufficiently adsorbs the ferrous ions, and then is adjusted with NaOH or KOH solution. pH to pH8 ⁇ ll; wherein the concentration of FeS0 4 .7H 2 0 or a solution of FeS0 4 FeCI 2 FeCl 2 or is 1% to 3%, and the mass ratio of solid modified liquid volume of diatomaceous earth is 1:10 (g/ml) ⁇ l: 20 (g/ml), adsorption time is 5 ⁇ 12h.
- the concentration of hydroxide ions in the NaOH or KOH solution is preferably 5% to 10%.
- the drying temperature in the step (d) is preferably 80 to: 110 ° C, the drying time is preferably 3 to 5 h, the calcination temperature is preferably 500 to 800 ° C, the calcination time is preferably 1 to 3 h, and the magnetic diatomaceous soil adsorption after the grinding is performed.
- the average particle size of the agent is preferably from 100 to 200.
- the use of the magnetic diatomaceous earth-based adsorbent according to the present invention in water treatment is preferably used in the adsorption of phosphorus in aromatic substances, heavy metal ions or eutrophic water bodies which are commonly found in sewage.
- the aromatic substance is preferably nitrobenzene or aniline.
- the present invention has the following advantages:
- the magnetic diatomaceous earth-based adsorbent prepared by the method of the invention has magnetic properties, is convenient for solid-liquid separation, and is easy to recover and reuse.
- the diatomaceous earth modification method of the present invention has a low calcination temperature, does not damage the structure of the diatomaceous earth, and ensures the adsorption performance thereof; on the other hand, the magnetic property reduces the loss of the lost powdery diatomaceous earth.
- Example 2 Example 2:
- the solid-liquid ratio of soil mass to volume of HCI solution is 1:20 (g/ml). After heating at 80 °C for 2 hours, it is filtered, dried in an oven, and ground to an average size of 150-200 diatomaceous earth. Head. (2) 20 g of the pretreated sample was subjected to plasma physical modification in a double dielectric barrier plasma generating apparatus, the modified voltage was 20 kV, and the inert gas was introduced into helium gas, and the modification time was 10 min.
- Example 3
Abstract
Disclosed is a magnetic kieselguhr-based absorbent, a preparation method therefor and the application thereof. The kieselguhr is subjected to firstly a pre-treatment with a 1 to 10 percent hydrochloric acid solution, suction filtration and drying, a physical pre-modification by a plasma, soaking with a ferrous ion solution for modification, alkali addition for adjusting the pH value so as to generate a magnetic precursor, and then the magnetic kieselguhr-based absorbent is prepared after suction filtration, stoving, baking and grinding. The kieselguhr modified by the present invention not only has a remarkably improved adsorbability and a favourable adsorbability to substances difficult to degrade, but also has a greater magnetism, facilitating the solid-liquid separation after wastewater treatment and the reutilization of the kieselguhr.
Description
说明书 Instruction manual
一种磁性硅藻土基吸附剂及其制备方法和应用 技术领域 Magnetic diatom earth-based adsorbent, preparation method and application thereof
本发明涉及一种磁性硅藻土基吸附剂及其制备方法和应用。 背景技术 The invention relates to a magnetic diatomaceous earth-based adsorbent, a preparation method and application thereof. Background technique
化工是我国的重要支柱产业，其中精细化工企业约占 90%， 对我国国民经济 的发展起着举足轻重的作用。 同时， 精细化工行业也是重污染的行业， 年废水排 放量上百亿吨， 不仅量大， 而且水质复杂， 成为废水污染治理的重点和难点。 Chemical industry is an important pillar industry in China, among which fine chemical enterprises account for about 90%, which plays an important role in the development of China's national economy. At the same time, the fine chemical industry is also a heavily polluting industry. The annual discharge of wastewater is over 10 billion tons. Not only is the volume large, but the water quality is complex, which has become the focus and difficulty of wastewater pollution control.
精细化工废水经过前预处理和生化处理，其生化尾水污染物成分仍然十分复 杂。面对行业提标改造、 中水回用的环保压力， 迫切需求经济有效的深度处理技 术。我国精细化工废水中水回用率低下， 深度处理、 回用水水质保持技术水平不 高。 目前的深度处理技术主要有氧化技术、膜分离技术和吸附技术。深度氧化技 术种类较多， 能在一定程度上降低尾水 COD，但由于经过物化预处理和生化处理 后尾水的 COD较低， 反应的有效性和处理效率都较低， 处理成本偏高； 膜分离 技术是一种相对成熟的尾水深度处理与回用技术， 但单单依靠膜设备， 不仅投资 大、 运行成本高， 同时， 膜浓缩液易造成二次污染； 吸附技术可适应大多数有机 工业废水深度处理与回用的要求， 以活性炭为例， 其吸附效果较好， 吸附稳定性 好， 但存在处理成本高、 可再生性差、 碳损比较严重等问题， 这使得废水的处理 相应带来的经济负担较重。 The fine chemical wastewater is pre-treated and biochemically treated, and its biochemical tailwater pollutants are still very complex. Faced with the environmental pressure of industry standardization and water reuse, there is an urgent need for cost-effective advanced processing technology. The water reuse rate of fine chemical wastewater in China is low, and the technical level of deep treatment and water quality maintenance is not high. The current advanced treatment technologies mainly include oxidation technology, membrane separation technology and adsorption technology. There are many types of deep oxidation technology, which can reduce the COD of tail water to a certain extent. However, due to the low COD of tail water after physicochemical pretreatment and biochemical treatment, the effectiveness and treatment efficiency of the reaction are low, and the treatment cost is high; Membrane separation technology is a relatively mature technology for advanced treatment and reuse of tail water, but relying solely on membrane equipment, it not only has large investment and high operating cost, but also membrane concentrate is easy to cause secondary pollution; adsorption technology can adapt to most organic The requirements for advanced treatment and reuse of industrial wastewater, with activated carbon as an example, have better adsorption effect and good adsorption stability, but there are problems such as high treatment cost, poor reproducibility and serious carbon loss, which makes the treatment of wastewater The economic burden is heavy.
硅藻土是海洋或湖泊中生长的硅藻类残骸在水底沉积，经自然环境作用逐渐 形成的一种非金属矿物。 我国硅藻土资源丰富， 迄今为止， 全国已探明的储量 3.2亿吨， 远景储量可超过 10亿吨， 位居世界前列。 硅藻土的显著特性是轻质、 多孔、 高液体吸附能力、 比表面积大、 以及化学惰性和不溶于一般酸等优异的物 理化学性质， 因此硅藻土被广泛用于制备助滤剂、 吸附剂、催化载体以及功能填 料。 Diatomaceous earth is a non-metallic mineral that is formed by diatom residues grown in the ocean or lake and deposited on the bottom of the water and formed by the natural environment. China's diatomaceous earth is rich in resources. So far, the country has proven reserves of 320 million tons, and the prospective reserves can exceed 1 billion tons, ranking the world's forefront. The remarkable characteristics of diatomite are light, porous, high liquid adsorption capacity, large specific surface area, and excellent physical and chemical properties such as chemical inertness and insoluble in general acids. Therefore, diatomaceous earth is widely used for the preparation of filter aids and adsorption. Agent, catalytic carrier and functional filler.
硅藻土轻质、 多孔、 比表面积大， 有望成为代替活性炭的廉价吸附剂之一。 然而， 未经改性的硅藻土原料吸附性能较差， 而且可能含有伴生杂质， 影响它在 染料废水处理中的应用， 因此， 需要通过提纯、 改性， 以去除硅藻土所含的大部
说明书 分杂质及活性物质， 得到更加丰富的内部孔状结构， 增大其比表面积， 使吸附性 进一步提高， 进而在水处理领域的应用性更强。 发明内容 Diatomaceous earth is light, porous, and has a large specific surface area, and is expected to be one of the cheap adsorbents for replacing activated carbon. However, the unmodified diatomaceous earth raw material has poor adsorption performance and may contain accompanying impurities, which affects its application in dye wastewater treatment. Therefore, it needs to be purified and modified to remove the large diatomaceous earth. Ministry The specification is divided into impurities and active materials to obtain a richer internal pore structure, increase the specific surface area, further improve the adsorptivity, and further enhance the application in the field of water treatment. Summary of the invention
本发明的目的是针对现有技术的上述缺陷，提供一种磁性硅藻土基吸附剂的 制备方法。 SUMMARY OF THE INVENTION An object of the present invention is to provide a method for preparing a magnetic diatomaceous earth-based adsorbent in view of the above-mentioned drawbacks of the prior art.
本发明的另一目的是提供该方法制备的磁性硅藻土基吸附剂。 Another object of the present invention is to provide a magnetic diatomaceous earth-based adsorbent prepared by the method.
本发明的又一目的是提供该磁性硅藻土基吸附剂的应用。 It is yet another object of the present invention to provide the use of the magnetic diatomaceous earth based adsorbent.
本发明的目的可以通过如下技术方案实现： The object of the present invention can be achieved by the following technical solutions:
一个磁性硅藻土基吸附剂的制备方法， 该方法包含如下步骤： （a )将硅藻土 用酸溶液进行预处理； （b ) 用等离子体进行物理预改性； （c) 用亚铁离子对硅 藻土进行浸渍改性后， 加碱调节 pH 生成磁性前驱体； （d ) 经烘干、 焙烧、 研 磨即得到所述的磁性硅藻土基吸附剂。 A method for preparing a magnetic diatomaceous earth-based adsorbent, the method comprising the steps of: (a) pretreating diatomaceous earth with an acid solution; (b) physically pre-modifying with a plasma; (c) using ferrous iron After the ions are immersed and modified by diatomaceous earth, the pH is adjusted by alkali to form a magnetic precursor; (d) the magnetic diatomaceous earth-based adsorbent is obtained by drying, roasting and grinding.
( a ) 步骤所述的酸溶液优选质量分数为 1〜10%的盐酸溶液， 所述的硅藻土 与酸溶液的固液比优选 1: 10(g/ml)〜l: 20(g/ml); 所述的预处理条件优选 80〜 100°C加热处理 l〜2h。 The acid solution described in the step (a) is preferably a hydrochloric acid solution having a mass fraction of 1 to 10%, and the solid-liquid ratio of the diatomaceous earth to the acid solution is preferably 1:10 (g/ml) to 1:20 (g/ Ml) ; the pretreatment conditions are preferably 80~100 ° C heat treatment l~2h.
( a ) 步骤预处理后的硅藻土优选经抽滤、 烘干、 研磨后进行下一步预改性。 (a) The diatomaceous earth after the pretreatment is preferably subjected to suction filtration, drying, and grinding to carry out the next pre-modification.
( b)步骤所述的物理预改性优选使用双介质阻挡等离子体发生装置，将预处 理样品放入电极之间通入氩气或者氖气进行等离子体改性， 改性电压为 10~20kV, 改性时间为 3~10min。 (b) The physical pre-modification described in the step preferably uses a dual dielectric barrier plasma generating device, and the pre-treatment sample is placed between the electrodes and argon or helium gas is introduced for plasma modification, and the modified voltage is 10-20 kV. , modification time is 3~10min.
步骤 （c) 优选在氮气保护的环境下， 经物理预改性的硅藻土与 FeS047H20 或者 FeCI2溶液混合， 使得硅藻土充分吸附亚铁离子， 然后用 NaOH或者 KOH溶 液调节 pH至 pH8~ll; 其中 FeS04.7H20或者 FeCI2溶液中 FeS04或 FeCI2的质量 浓度是 1%~3%， 硅藻土质量与改性液体积的固液比为 1: 10(g/ml)~l: 20(g/ml), 吸附时间为 5~12h。 Step (c) Preferably, the physically pre-modified diatomaceous earth is mixed with the FeS0 7 7H 2 0 or FeCI 2 solution in a nitrogen-protected environment, so that the diatomaceous earth sufficiently adsorbs the ferrous ions, and then is adjusted with NaOH or KOH solution. pH to pH8 ~ ll; wherein the concentration of FeS0 4 .7H 2 0 or a solution of FeS0 4 FeCI 2 FeCl 2 or is 1% to 3%, and the mass ratio of solid modified liquid volume of diatomaceous earth is 1:10 (g/ml) ~l: 20 (g/ml), adsorption time is 5~12h.
所述的 NaOH或者 KOH溶液中氢氧根离子的浓度优选 5%~10%。 The concentration of hydroxide ions in the NaOH or KOH solution is preferably 5% to 10%.
步骤 （d ) 所述的烘干温度优选 80〜： 110°C， 烘干时间优选 3〜5h， 焙烧温度 优选 500~800°C，焙烧时间优选 l~3h，研磨后磁性硅藻土基吸附剂的平均粒度优 选 100—200巨。
说明书 按照本发明所述的方法制备的磁性硅藻土基吸附剂。 The drying temperature in the step (d) is preferably 80 to: 110 ° C, the drying time is preferably 3 to 5 h, the calcination temperature is preferably 500 to 800 ° C, the calcination time is preferably 1 to 3 h, and the magnetic diatomaceous soil adsorption after the grinding is performed. The average particle size of the agent is preferably from 100 to 200. A magnetic diatomaceous earth based adsorbent prepared according to the method of the present invention.
本发明所述的磁性硅藻土基吸附剂在水处理中的应用， 优选在吸附污水中常 见的芳香族物质、 重金属离子或富营养化水体中的磷中的应用。 The use of the magnetic diatomaceous earth-based adsorbent according to the present invention in water treatment is preferably used in the adsorption of phosphorus in aromatic substances, heavy metal ions or eutrophic water bodies which are commonly found in sewage.
所述的芳香族物质优选硝基苯或苯胺。 The aromatic substance is preferably nitrobenzene or aniline.
与现有技术相比， 本发明具有以下优点： Compared with the prior art, the present invention has the following advantages:
( 1 ) 本发明方法制备的磁性硅藻土基吸附剂有磁性， 便于固液分离， 易于 回收和再利用。 (1) The magnetic diatomaceous earth-based adsorbent prepared by the method of the invention has magnetic properties, is convenient for solid-liquid separation, and is easy to recover and reuse.
( 2 ) 本发明硅藻土改性方法焙烧温度低， 不会破坏硅藻土的结构， 确保了 其吸附性能； 另一方面加上磁性后， 会减少流失粉末状硅藻土的流失。 (2) The diatomaceous earth modification method of the present invention has a low calcination temperature, does not damage the structure of the diatomaceous earth, and ensures the adsorption performance thereof; on the other hand, the magnetic property reduces the loss of the lost powdery diatomaceous earth.
( 3 ) 经本发明方法改性后的磁性硅藻土基吸附剂吸附能力较之未改性的硅 藻土有显著提高。 具体实施方式 (3) The adsorption capacity of the magnetic diatomaceous earth-based adsorbent modified by the method of the present invention is significantly improved compared with the unmodified diatomaceous earth. detailed description
实施例 1 Example 1
制备： （ 1)取 40g硅藻土原土分别与 400ml的 5%的 HCI溶液混合（硅藻土 质量与 HCI溶液体积的固液比为 1:10 (g/ml ) ) ， 在温度 10CTC下加热处理 lh 后过滤， 置于烘箱中烘干， 研磨至硅藻土平均粒度为 100~200目。 （2 ) 取预处 理的样品 20g在双介质阻挡等离子体发生装置中进行等离子体物理改性，改性电 压 10kV， 通入惰性气体为氩气， 放电时间为 3min。 （3 ) 取 FeS04'7H20 5.49g， 配成 100ml, 3%的 FeS04溶液， 加硅藻土 10g (硅藻土质量与改性溶液体积的固 液比为 1: 10 (g/ml ) )浸渍 5h后加 5%的 NaOH调节 pH为 8， 生成磁性前驱体， 过滤； （4)磁性前驱体在 80°C， 烘干 3h， 以 500°C焙烧 lh， 经研磨后得到平均 粒度为 100目的磁性硅藻土基吸附剂。 Preparation: (1) 40 g of diatomaceous earth original soil was mixed with 400 ml of 5% HCI solution (the solid-liquid ratio of diatomite mass to HCI solution volume was 1:10 (g/ml)), at a temperature of 10 CTC After heating for 1 h, the mixture was filtered, dried in an oven, and ground to a diatomaceous earth with an average particle size of 100 to 200 mesh. (2) 20 g of the pretreated sample was subjected to plasma physical modification in a double dielectric barrier plasma generating apparatus, the modified voltage was 10 kV, the inert gas was introduced into argon gas, and the discharge time was 3 min. (3) Take FeS0 4 '7H 2 0 5.49g, prepare 100ml, 3% FeS0 4 solution, add diatomaceous earth 10g (the solid-liquid ratio of diatomite mass to modified solution volume is 1: 10 (g/ Ml)) After immersion for 5h, add 5% NaOH to adjust the pH to 8, to form a magnetic precursor, and filter; (4) Magnetic precursor at 80 ° C, dry for 3 h, calcined at 500 ° C for 1 h, after grinding to obtain an average A magnetic diatomaceous earth based adsorbent having a particle size of 100 mesh.
吸附性能： 在 25°C， pH=7, 吸附速率 145r/min， 振荡时间 12h， 磁性硅藻 土基吸附剂用量 lg/200mL, 硝基苯溶液浓度为 200mg/L， 硝基苯去除率： 87.5%。 相同条件， 未经改性的硅藻土对硝基苯的去除率仅 48.1%。 实施例 2: Adsorption performance: at 25 ° C, pH = 7, adsorption rate 145r / min, shaking time 12h, magnetic diatomaceous earth based adsorbent dosage lg / 200mL, nitrobenzene solution concentration 200mg / L, nitrobenzene removal rate: 87.5%. Under the same conditions, the removal rate of nitrobenzene by unmodified diatomaceous earth was only 48.1%. Example 2:
制备： （1) 取 40g硅藻土原土分别与 800ml的 10%的 HCI溶液混合 （硅藻
说明书 Preparation: (1) Take 40g of diatomaceous earth original mixed with 800ml of 10% HCI solution (diatom Instruction manual
土质量与 HCI溶液体积的固液比为 1:20 (g/ml ) ) ， 在温度 80°C下加热 2h后过 滤， 置于烘箱中烘干， 研磨至硅藻土平均粒度为 150~200目。 （2 ) 取预处理的 样品 20g 在双介质阻挡等离子体发生装置中进行等离子体物理改性， 改性电压 20kV，通入惰性气体为氖气， 改性时间为 10min。 ( 3 )取 2g的 FeCI2配成 100ml, 2%的 FeCI2溶液， 加硅藻土 10g (硅藻土质量与改性溶液体积的固液比为 1: 10 (g/ml ) )浸渍 12h后加 10%KOH调节 pH为 11， 生成磁性前驱体， 过滤； （3 ) 磁性前驱体在 110°C， 烘干 5h， 以 800°C焙烧 3h， 经研磨后得到平均粒度为 200 目的磁性硅藻土基吸附剂。 The solid-liquid ratio of soil mass to volume of HCI solution is 1:20 (g/ml). After heating at 80 °C for 2 hours, it is filtered, dried in an oven, and ground to an average size of 150-200 diatomaceous earth. Head. (2) 20 g of the pretreated sample was subjected to plasma physical modification in a double dielectric barrier plasma generating apparatus, the modified voltage was 20 kV, and the inert gas was introduced into helium gas, and the modification time was 10 min. (3) Take 2g of FeCI 2 into 100ml, 2% FeCI 2 solution, add diatomaceous earth 10g (the solid-liquid ratio of diatomaceous earth mass and modified solution volume is 1:10 (g/ml)) for 12h After adding 10% KOH to adjust the pH to 11, the magnetic precursor is formed and filtered; (3) The magnetic precursor is baked at 110 ° C for 5 h, calcined at 800 ° C for 3 h, and after grinding, the magnetic silicon having an average particle size of 200 mesh is obtained. Algae-based adsorbent.
吸附性能： 在 25°C， pH=7, 吸附速率 145r/min， 振荡时间 12h， 磁性硅藻 土基吸附剂用量 lg/200mL, 硝基苯溶液浓度为 200mg/L， 硝基苯去除率： 78%。 相同条件， 未经改性的硅藻土对硝基苯的去除率仅 48.1%。 实施例 3: Adsorption performance: at 25 ° C, pH = 7, adsorption rate 145r / min, shaking time 12h, magnetic diatomaceous earth based adsorbent dosage lg / 200mL, nitrobenzene solution concentration 200mg / L, nitrobenzene removal rate: 78%. Under the same conditions, the removal rate of nitrobenzene by unmodified diatomaceous earth was only 48.1%. Example 3:
制备： （ 1)取 40g硅藻土原土分别与 400ml的 6%的 HCI溶液混合（硅藻土 质量与 HCI溶液体积的固液比为 1:10 (g/ml ) ) ， 在温度 90°C下加热 1.5h后过 滤， 置于烘箱中烘干， 研磨至硅藻土平均粒度为 100~150目。 （2 ) 取预处理的 样品 20g 在双介质阻挡等离子体发生装置中进行等离子体物理改性， 改性电压 15 kV, 通入惰性气体为氩气， 改性时间为 5min。 （3 ) 力 B FeS04-7H201.83g, 配 成 100ml ， 1%的 FeS04溶液， 加硅藻土 10g (硅藻土质量与改性溶液体积的固液 比为 1: 10 (g/ml ) ) 浸渍 9h后加 8%的 NaOH调节 pH为 9， 生成磁性前驱体， 过滤； （4) 磁性前驱体在 100°C， 烘干 4h， 以 600°C焙烧 2h， 经研磨后得到平 均粒度为 100目的磁性硅藻土基吸附剂。 Preparation: (1) 40 g of diatomaceous earth original soil was mixed with 400 ml of 6% HCI solution (the solid-liquid ratio of diatomite mass to HCI solution volume was 1:10 (g/ml)), at a temperature of 90 ° After heating for 1.5 hours under C, it was filtered, dried in an oven, and ground to a diatomaceous earth with an average particle size of 100 to 150 mesh. (2) 20 g of the pretreated sample was subjected to plasma physical modification in a double dielectric barrier plasma generating apparatus, the modified voltage was 15 kV, and the inert gas was introduced into argon gas, and the modification time was 5 min. (3) Force B FeS0 4 -7H 2 01.83g, formulated into 100ml, 1% FeS0 4 solution, plus diatomaceous earth 10g (the solid-liquid ratio of diatomaceous earth mass to modified solution volume is 1: 10 (g/ Ml)) After immersion for 9h, add 8% NaOH to adjust the pH to 9, to form a magnetic precursor, and filter; (4) Magnetic precursor at 100 ° C, dry for 4 h, calcined at 600 ° C for 2 h, after grinding to obtain an average A magnetic diatomaceous earth based adsorbent having a particle size of 100 mesh.
吸附性能： 在 25°C， pH=7, 吸附速率 145r/min， 振荡时间 12h， 磁性硅藻土基 吸附剂用量 lg/200mL, 硝基苯溶液浓度为 200mg/L， 硝基苯去除率： 74.2%。 相 同条件， 未经改性的硅藻土对硝基苯的去除率仅 48.1%。
Adsorption performance: at 25 ° C, pH = 7, adsorption rate 145r / min, shaking time 12h, magnetic diatomaceous earth based adsorbent dosage lg / 200mL, nitrobenzene solution concentration 200mg / L, nitrobenzene removal rate: 74.2%. Under the same conditions, the removal rate of nitrobenzene by unmodified diatomaceous earth was only 48.1%.
Claims
1、 一种磁性硅藻土基吸附剂的制备方法， 其特征在于该方法包含如下步骤： ( a )将硅藻土用酸溶液进行预处理； （b)用等离子体进行物理预改性； （c)用 亚铁离子对硅藻土进行浸渍改性后， 加碱调节 pH 生成磁性前驱体； （d ) 经烘 干、 焙烧、 研磨即得到所述的磁性硅藻土基吸附剂。 1. A method for preparing magnetic diatomite-based adsorbent, characterized in that the method includes the following steps: (a) pretreating diatomite with an acid solution; (b) physically pre-modifying with plasma; (c) After impregnating and modifying diatomite with ferrous ions, adding alkali to adjust the pH to generate a magnetic precursor; (d) Obtaining the magnetic diatomite-based adsorbent after drying, roasting and grinding.
2、 根据权利要求 1所述的制备方法， 其特征在于 （a ) 步骤所述的酸溶液为质 量分数为 1〜10%的盐酸溶液， 所述的硅藻土与酸溶液的固液比为 1: 10(g/ml)〜 1： 20(g/ml); 所述的预处理条件为 80〜： 100°C加热处理 l〜2h。 2. The preparation method according to claim 1, characterized in that the acid solution in step (a) is a hydrochloric acid solution with a mass fraction of 1 to 10%, and the solid-liquid ratio of the diatomite and the acid solution is 1: 10 (g/ml) ~ 1: 20 (g/ml) ; the pretreatment conditions are 80 ~: 100°C and heat treatment for 1 ~ 2h.
3、 根据权利要求 1所述的制备方法， 其特征在于 （a ) 步骤预处理后的硅藻土 经抽滤、 烘干、 研磨后进行下一步预改性。 3. The preparation method according to claim 1, characterized in that the diatomite pretreated in step (a) is subjected to the next step of pre-modification after being filtered, dried and ground.
4、 根据权利要求 1所述的制备方法， 其特征在于 （b)步骤所述的物理预改性 使用双介质阻挡等离子体发生装置，将预处理样品放入电极之间通入氩气或者氖 气进行等离子体改性， 改性电压 10~20kV， 改性时间 3~10min。 4. The preparation method according to claim 1, characterized in that the physical pre-modification in step (b) uses a dual dielectric barrier plasma generating device, and the pre-treated sample is placed between the electrodes and argon or neon is passed therein Gas is used for plasma modification, the modification voltage is 10~20kV, and the modification time is 3~10min.
5、 根据权利要求 1所述的制备方法， 其特征在于步骤 （c) 在氮气保护的环境 下， 经物理预改性的硅藻土与 FeS04，7H20或者 FeCI2溶液混合， 使得硅藻土充分 吸附亚铁离子， 然后用 NaOH或者 KOH溶液调节 pH至 pH8~ll; 其中「6504或 FeCI2溶液质量浓度是 1%~3%， 硅藻土质量与改性液体积的固液比为 1： 10(g/ml)~l: 20(g/ml)， 吸附时间为 5~12h。 5. The preparation method according to claim 1, characterized in that step (c) in a nitrogen-protected environment, physically pre-modified diatomite is mixed with FeSO 4 , 7H 2 0 or FeCI 2 solution, so that silicon Algae fully absorb ferrous ions, and then use NaOH or KOH solution to adjust the pH to pH 8~11; where the mass concentration of 650 4 or FeCl 2 solution is 1%~3%, and the mass of diatomite and the solid-liquid volume of the modified liquid are The ratio is 1: 10(g/ml)~1: 20(g/ml), and the adsorption time is 5~12h.
6、 根据权利要求 5所述的制备方法， 其特征在于所述的 NaOH或者 KOH溶液 中氢氧根离子的浓度是 5%~10%。 6. The preparation method according to claim 5, characterized in that the concentration of hydroxide ions in the NaOH or KOH solution is 5% to 10%.
7、 根据权利要求 1所述的制备方法， 其特征在于步骤（d )所述的烘干温度为 80〜： 110°C， 烘干时间为 3〜5h， 焙烧温度为 500~800°C， 焙烧时间为 l~3h， 研 磨后磁性硅藻土基吸附剂的平均粒度为 100〜200目。 7. The preparation method according to claim 1, characterized in that the drying temperature in step (d) is 80~110°C, the drying time is 3~5h, and the roasting temperature is 500~800°C. The roasting time is 1~3h, and the average particle size of the magnetic diatomite-based adsorbent after grinding is 100~200 mesh.
8、 按照权利要求 1~7中任一项所述的方法制备的磁性硅藻土基吸附剂。 8. The magnetic diatomite-based adsorbent prepared according to the method of any one of claims 1 to 7.
9、 权利要求 8所述的磁性硅藻土基吸附剂在水处理中的应用。 9. Application of the magnetic diatomite-based adsorbent of claim 8 in water treatment.
10、 根据权利要求 9所述的应用， 其特征在于所述的磁性硅藻土基吸附剂在吸 附污水中常见的芳香族物质、重金属离子或富营养化水体中的磷中的应用； 所述 的芳香族物质优选为硝基苯或苯胺。
10. Application according to claim 9, characterized in that the magnetic diatomite-based adsorbent is used to adsorb aromatic substances, heavy metal ions commonly found in sewage, or phosphorus in eutrophic water bodies; The aromatic substance is preferably nitrobenzene or aniline.
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| Publication number | Publication date |
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| CN103432986A (en) | 2013-12-11 |
| CN103432986B (en) | 2016-05-25 |
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