TWI267399B - Adsorptive filter media - Google Patents

Abstract

A new adsorptive filter media is invented to treat the with arsenic contaminated water. The GaAs manufacturers, for example, use mostly AsH3 gas as reactant in the surface organic synthesis process. The exhaust gas is treated in a washing tower using hyper chlorite from which the small quantity of waste water with high arsenic concentration is produced. Precipitation/coagulation is the most used method to remove arsenic from water. The arsenic containing sledges have to be transported and treated with high costs. Some new technologies were also developed to solve the arsenic problems in waste water, however with disadvantages such as slow kinetics and high costs. In order to substitute the conventional methods, the inventors have developed a new type of adsorptive filter by modifying the sintered diatomite surface using iron hydroxide. The modification can be achieved by mean of adding diatomite into aqueous solution of ferric chloride followed by the treatment in sodium hydroxide solution. This new type of adsorbent is characterized through its high kinetics and low costs.

Description

1267399

The invention relates to a method for preparing an adsorbent filter material, which is mainly prepared by using a wet surface treatment to form an active layer of iron hydroxide having an adsorption month b force on the surface by using a wet surface treatment. The adsorbent Shixiazao soil filter material is specially used for treating arsenic-containing wastewater or drinking water and mineral water for purifying and purifying, and can avoid the production of a large amount of arsenic-containing sludge. [Prior Art] In recent years, the optoelectronic industry has been a major development industry in most regions. In the case of optoelectronic semiconductor components, "GaAs" has higher frequency, less noise, radiation resistance, small size, and high temperature resistance compared with conventional germanium components, so it has a broader development space, arsenic. Since gallium (GaAs) has many advantages at the same time, it is widely used in the communication equipment and electronic equipment industry, and gradually replaces the traditional tantalum component diode. Based on this, only two companies have invested a large amount of capital to carry out research and development, and according to statistics, the production capacity of Chenghua Record has reached 50-800 million. The production technology of arsenic and gallium optoelectronic components are currently in use. It is also made of organic gold by hydrogenation (Ash3) gas; its (M0CVD) technology is most widely used; and its production is two, 曰曰-like: using sodium hypochlorite to add to the washing tower, the trivalent hair: processing facilities five prices Arsenate, and then discharge high concentration: Ma Shen is turned into water-soluble wastewater treatment. ❿The above-mentioned wastewater, in the technology of re-continuation, mainly by chemical coagulation precipitation method, ie, 'geographic arsenic-containing wastewater coagulant and molecular molecular coagulant to make the pentavalent shape _ / The ageing agent and the mixing amount are only in the environment during the treatment. But this law is not

Page 8 ------- A member, and will produce 1267399 Case No. 93Π8026 Amendment 曰5, invention description (2) A large amount of arsenic-containing sludge, the average treatment of one ton of wastewater produces about 丨〇〇 kg of sewage Mud, and the subsequent cleaning costs of this arsenic-containing sludge have remained high, at a rate of NT$1,200 per ton. The treatment of arsenic sludge is currently only cured, and a feasible technology is not only attached. The cost is high, and it is impossible to solve the problem of waste and ask for a waste of resources. In order to make up for the shortcomings of chemical coagulation and sedimentation methods, experts and scholars from various countries have recently developed various new technologies to replace this technology, including the method of separation from the father, activated sludge and adsorption: Α·in ion exchange technology In the present, several kinds of anion exchange have been developed to remove the water in the water, and then quantitatively analyzed in sodium hydroxide lye, the tree; 2: with the 2 method, although it has the advantages of high removal rate, good adsorption power and 荨ι regeneration, However, it still cannot overcome the shortcomings of high cost. Β·The other 'activated sludge is co-extracted by the bacteria isolated from the culture: After planting 2 gas, sinking the temple, dehydration can obtain high concentration of side-effect activity ί 2 1 : Ϊ t : Geographical cost is good, The activated sludge biological treatment technology: 7 treatment is relatively mature; but this technology also has the biggest shortcomings of biological ^: low reaction rate and the production of a large amount of sludge containing sludge. At present, this technology is still in the laboratory stage, and the final destination of sludge has not been set, so its industrial availability still needs to be considered.

Page 9 C. In addition, there are arsenic removal methods using various metal oxides as adsorbents, including adsorbents based on emulsified manganese ((i)n02) and iron hydroxide (such as furnace edge, steel slab, etc.) For example, German-made GEH uses beta-iron oxide (/5 FeOOH, also known as Akaganei te) as the main adsorbent component; currently, such commercial adsorbents have: large specific surface area, low f crystal, surface _ Features such as high activity and large amount of equilibrium adsorption, can be used to go to 1267399. Case No. 5. Invention Description (3) There is no practical experience in removing trace amounts of water in water, and there is no practical experience in water or desalinated seawater. However, after desorption, it can be desorbed. Inventors with reduced system in view of the attached diatomaceous earth filter i, on the other hand 93110026 metal, adsorption in the removal of the sputum, if the recovery of the stone application costs, special materials, a large-scale high-cost arsenic removal The present invention is based on the combination of materials to produce a high-performance low-cost system by soaking and adjusting the acid in the iron salt solution, so that the pH is adjusted to 2 ± 0.1, the surface 'fine to obtain a material 0 correction one Clever phosphorus Advanced treatments such as organic nitrogen; but by force u, it has only been used in advanced applications such as drinking water and underground kun. It has good desorption characteristics for the treatment of high-concentration wastewater. It can be saturated and refined. It is used in the process, that is, it can reduce the double advantages of producing the combination, and it can be used to reduce the production cost and increase the adsorption efficiency at a certain level. Adsorb the power to take the technology. : Method of attaching ferric hydroxide and high permeability diatomaceous earth filter. The alkali of the invention is carried out in two stages; firstly, the diatomaceous earth is immersed: the iron salt solution is added, and then the sodium hydroxide alkali solution is added to directly coat the cerium oxide iron feathers on the broken soil surface to adsorb the arsenic in the adsorbed water. Diatomaceous earth filter: = gold '" metal, can be +5, +3, 0 and -3 and other oxygen: number i exists, generally there are two sources of arsenic in water, natural and artificial pollution; in industrial pollution In addition to the aforementioned optoelectronic industry,

The adsorbent filter material obtained by the present inventors, in particular, is directed to arsenic in water and has excellent adsorption efficiency. The arsenic element itself is 1267399 — case 5 tiger 93118026 V. Invention description (4) Drinking water also endangers our living environment. Therefore, the inventor combined with the research and development spirit and efforts of the team, through continuous experiment and trial work, The invention combines the adsorbed iron oxychloride with the highly permeable diatomaceous earth filter material to prepare a high-efficiency and low-cost god-adsorbing diatomaceous earth filter material. 4. The above-mentioned beta iron hydroxide (Wan-FeOOH) adsorbent, which exhibits the surface characteristics of the amphoteric surface due to the protonation and deprotonation of the surface hydroxide ions in the aqueous phase, can simultaneously Organic and inorganic substances produce an adsorbent that is developed on the basis of this material (such as German GEΗ). Its main components are low crystallinity-FeOOH and Fe(OH)3 (55% by weight) , the particle size distribution is between 〇· 32-2 mm, and has a high specific surface area ^: 2曰50-30 0 m2 / g), high surface activity and other characteristics; can be used to remove traces of heavy metals, organic phosphorus and organic nitrogen in water For advanced treatment, the actual use of 3:: also in the water, drinking water and desalinated seawater in addition to arsenic and organic matter ί Ϊ tube, but the production process of this sorbent is complicated, must be centrifuged and = 垦 procedure to make the stone - Fe〇〇H is granulated, and the cost of the drug is not low. The price of the product is NT$32, and the adsorption equilibrium time is as long as i 5〇: The second ί adsorbent is currently only for use. Drinking water and groundwater purification; f, operating technology is fixed bed filtration The equipment is mainly. ♦ Ancient ^ Ϊ, in terms of adsorbent composition, iron hydroxide is the active ingredient of stone removal Φ in water. If the manufacturing cost comes from ', the application of iron into the sputum adsorption is a waste; according to the adsorption theory, the milk is limited to the sorbent particle extension; & 丄咐 丄咐 仅 本 本 本 本 本 本 本 本 本 本 本γ, pen..., Bellow. It is ^^ ^ that uses the roof-type technology to coat iron hydroxide on the support and develop innovative technology for producing adsorption filter. . Physically, in terms of body, in addition to cost and filming,

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Case No. 9311802R V. Invention Description (5) Need to test "Loading water permeability and specific surface area" to facilitate filtration. In the past, there were stones used in the past: ◊;, body, film coating technology, but due to the filming property not #, The quality of the finished product is unstable, and the adsorption efficiency is limited and cannot be promoted. Soil == Condition 'This invention is based on Shixiazao soil. Shishizao & II: μ, the material is buried underground, collapsed After the solution, the large hollow particles from the remaining ^ ^ 乂 edge, the average particle size is about 1 5 / 4 m up and down (1 0 η Γ porous with acid salts can be seen by two electron microscope ^ Q see Annex I), due to The diatomaceous earth has a high porosity, a porosity of up to 80% or more, and an adsorption force. It is a filter material and can be used as a source of human trace elements. Shiyuezao soil i food grade and industry..., mainly depends on the other oxygen dioxide = 1曰2, the crystallinity of the grade-grade algae soil must be below 3%, and it is not used as the production I. For food and feed, it can be good: the pesticide and beverage industry has been assisted by the process, and the effect is very good, and the scorpion soil has a higher crystallinity, mainly because of the crust. The action of the squeezing mountain causes recrystallization, and its use is as a filling $, a turbidity remover/deodorant, and an explosive. The suction = ^ study pointed out that the diatomaceous earth has a certain degree of organic matter and inorganic matter = f, the absorption and adsorption of proteins, sugars, fats and microbial cells can be filtered in the beverage industry. It has been confirmed; in the case of inorganic substances such as gold L, some studies have pointed out that diatomaceous earth has certain adsorption effects on some heavy metals, such as cations and chromium. In the arsenic-containing waste liquid, Shi Xisheng + ^ points is the arsenate ion (AS〇4 3_), so the surface modified by the surface can achieve better results of arsenic removal. Lu's algae soil can be divided into ground diatomaceous earth powder according to the processing procedure.

General + 1267399 Amendment number 93118026 V. Invention description (6) ^ Two kinds of 矽 矽 矽 algae soil 为 矽 algae soil powder is a ground powder, its specific area is about 50 m2 / g, the bulk density is about 〇· 5 g/cm3 ; 煆 矽 矽 呈 呈 呈 呈 呈 呈 呈 呈 呈 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽The particle size distribution on 6 g/cm3 is shown in the first figure. In order to avoid excessive loss of force when used in the filtration technique, in the present invention, the calcined algae having a larger particle size is used as the adsorbent carrier. Therefore, the present inventors have concluded the characteristics of ferric hydroxide and diatomaceous earth by using a wet surface treatment to produce a diatomaceous earth filter material which adsorbs arsenic. The invention mainly adopts an iron hydroxide active layer which is formed on the surface by using simmered diatomaceous earth as an adsorbent carrier, and is suitable for arsenic-containing waste water to avoid arsenic-containing waste water. Mud production 'and can greatly increase the cost of adsorbent (estimated production cost is less than NT$3 per kilogram, ^ commercial GEH is comparable to 132 yuan per kilogram of new station, saving 8〇 [Embodiment] The expected effect and purpose, the embodiment is described in detail as follows: · 1 1 First, the kiss refers to the flow shown in the second figure, the present invention provides a method for preparing the diatomaceous earth filter material mainly including modulation Iron salt solution, mixing with slag coating, adjusting pH, standing and curing, and dehydration drying: () Preparation of iron salt solution · This step uses gasified iron salt as solute, dissolved in water to form iron, and light , calcium, 々, right 〆 〆 ^ ^ human milk now / combined, iron salt solution preparation system will be 8 j. 丨 number of iron dissolved in 50 0 rn ^ l water towel; because the gasification of iron dissolved in water In order to release the heat, the emulsified iron salt should be dissolved into the water first. 5至Μ ;

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\1) Pretreatment of diatomaceous earth: In this step, the industrial grade simmering: shale is first sieved and sorted, and the granules in the range of 30 to 7 〇 are used as the main raw material, and the β washing is performed to ensure the removal of pores. Intrinsic impurities, the invention adopts ultrasonic oscillating cleaning technology; ^3) immersing diatomaceous earth: this step is to mix the pulverized seaweed pretreated by step (2) into the iron salt solution prepared in step (1); The average contact between the particles of Shixi soil and the solution, and the air in the pores is driven out, the soaking process needs to be mixed with slow stirring, the stirring rate is 7, and the soaking time is preferably two hours; (4) adding sodium hydroxide solution Adjust the pH ● Add 20% sodium hydroxide lye to the solution, adjust the pH to 1.5 to 3.0, and the pH value is 2 ± 〇 · ι. The reaction is optimal; Avoid dissolving the iron hydroxide film. Add sodium hydroxide lye and apply slow stirring at 70 rpm. The reaction time is preferably 4 hours. (5) Static curing: the reaction to be stirred After completion, let the diatomaceous earth in the step ( The liquid in the liquid f 'make the iron hydroxide adsorption layer stable and mature, the standing time is preferably 12 hours; (6) solid-liquid separation and cleaning: due to the sedimentation speed of the granular smoldering stone Ferric hydroxide #羽' Therefore, it needs to be gently stirred before separation, so that the excess iron hydroxide plume is suspended in the liquid, after waiting for 30 seconds, after the sedimentation of the crushed algae, the decantation method is carried out. One solid-liquid separation, and the solid-liquid separation cleaning liquid is returned to the step (1) for reuse, and the collected diatomaceous earth needs to be further cleaned to remove the last remaining unattached iron hydroxide rubber feather and other impurities. ;

1267399 _ Case No. 93118026_年月日日 Revision_ V. Invention description (8) (7) Drying: The subsequent drying procedure temperature should not be too high to prevent dehydration of ferric hydroxide to produce a qualitative change, with a maximum of 50 ± 2 °C Preferably, it takes about 12 hours to dry to a water content of less than 5% (it can also be dried naturally at room temperature, but it takes a long time to be less economical). According to the above steps, the diatomaceous earth covered with iron salt on the surface is treated with iron content of more than 16% (the composition of the composition is shown in the following list 1), and the adsorption of the iron hydroxide film is produced. The diatomaceous earth filter material is especially suitable for removing arsenic in water, has excellent adsorption effect, and the coating layer is stable, and the iron dissolution phenomenon caused by being tested in a water environment is less than 2 ppm.

Table 1: Composition of diatomaceous earth after surface treatment with iron hydroxide Element Weight % [%] 矽Si 26.82 Oxygen 〇 45.52 Aluminum A1 7.59 Iron Fe 16.48 Potassium K 1.15 Na Na 2.43

[Treatment effect] The adsorbent diatomaceous earth filter material prepared by the inventor of the present invention performs different adsorption tests, and the adsorption test is divided into a pH-dependent influence experiment and a constant temperature adsorption.

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Test the two parts. First, the solution of low arsenic t 珅 is 1 〇, and the second solution: the relationship with pH. In the soil-containing filter material, after the shock i ^ β,, | this 〇 · 4 g of the adsorbent diatoms as shown in the third figure 1 = the change in the amount of adsorption to the pH value, the result of the treatment of the algae soil; The fourth figure in the comparison is shown in the figure, which is the result of no adsorption on the surface soil; and the different dreams have no significant effect. Τ By the brother, the four figures of the right · Zhao Ke j | soil to the five-price stone Shen (arsenate II:: the surface of the hole treated by alginic acid or alkaline conditions 1),,,,,,, Efficacy, regardless of the surface treatment of Shi Xi Book I are above 3 mg As々; in contrast, the table is with the general commercial ΐ attached;:: quantity with. Increase in H value and decrease... and appendix 1 · Under p Η 2 · 5 acidic conditions, 逵 曰 iso 曰 μ η 2 · under neutral conditions, "maximum adsorption 篁 40 mg As / g ; 3 f The time required to maintain the adsorption of t, i ' at 20 mg As " is 38 hours, which is much lower than the 15 hours required for the German commercial and the GEH adsorption equilibrium. In the dish adsorption test, the initial solution adsorption of the different concentrations of the sulphate was used to investigate the temperature profile of the adsorbed zephyrite soil. The enthalpy concentration was divided into 3·6, 8·2, 16·3, 44· 5, 75.4, 155 and the initial 2 6 4ppm. As shown in the fifth figure, (10) of γ-axis represents the concentration of lanthanum in the solid after adsorption (Shixiabian soil), the unit is (4) As/g diatomaceous earth, and the Q of χ_axis represents the concentration in the liquid after 24 hours. Under neutral conditions (pH7), after 24 hours of adsorption time, the arsenic concentration of the adsorbed diatomaceous earth and the constant temperature adsorption curve of arsenic in water are roughly in accordance with the F nd id temperature adsorption mode, and the initial concentration of strontium is 250 ppm. At the time of the highest adsorption amount of up to 63 mg As / g, in Shishi Shen

1267399 five

L. Description of the invention (10) One ~^--Ξ----- In the case of indifference (7ppm), too attached to the ability. The adsorptive diatomaceous earth can maintain the absorption of 5mg As/g from I-^^3118026^, and the above-mentioned adsorption-adsorbed diatomaceous earth, the result of the corpse V, can be provided by the invention. The arsenic removal of dreams has a good effect, and the arsenic removal of the spring water contains industrial arsenic-containing wastewater, and the drinking water and mineral system show the purpose and efficacy of JL. To achieve the desired adsorption benefit, ^Ming's prepared adsorptive diatomaceous earth filter material, industry or other industrial producers can be used to process gallium arsenide optoelectronic components: the innovative preparation of this case J f Water, hydrazine and mineral water in addition to arsenic purification:: Economic benefits: ^, and provide industrial use of the 曰 曰 提出 提出 提出 提出 提出 提出 提出 = = = = = = = = = 。 发明 发明 。 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明The application of s month ‘I would like to ask for review, and early

苐17 pages 1267399 _ Case number 93118026_年月日日__ Simple description of the drawing [Simple description of the diagram] The first figure shows the weight accumulation <33 distribution map of the industrial grade 煆 矽 矽 土 粒径 。 The second figure shows the preparation flow chart of the present invention. The third figure shows the relationship between the adsorption amount of arsenic in the adsorbed diatomaceous earth and the pH value. The fourth figure shows the relationship between the arsenic adsorption amount of untreated diatomaceous earth and the pH value.

The fifth figure shows the adsorption curve of the adsorbent diatomaceous earth of the present invention at pH 7 and 24 hours; wherein the horizontal axis represents the equilibrium concentration of arsenic in the aqueous solution and the vertical axis represents the equilibrium adsorption amount of arsenic. [Annex 1] Algae soil observed under an electron microscope ·· A. Untreated algae powder. B. The algae soil after the simmering treatment.

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Claims (1)

1267399 M3t 9311S09R Λ_Μ 曰 Amendment 6. Patent application scope 1. The present invention is a method for preparing an adsorbent filter material, the preparation step is the first step (1) modulating the iron salt solution; (1) sifting the calcined stone Sorting and cleaning; (3) immersing the diatomaceous earth in the iron salt solution; (4) adding sodium hydroxide solution to adjust the pH: Λ sodium hydroxide, solution, adjust the value of ρΗ to “~3〇 , emulsified sodium should be added to make iron hydroxide; '幵,, stirring, reverse (5), standing still: the diatomaceous earth is allowed to stand in the sodium hydroxide solution, so that the ferric hydroxide produced by the > (6) Solid-liquid separation: Separation of the mature diatomaceous earth from the solution by filtration and precipitation, and Qinghaoshi Xiluo soil μ wt other impurities; Χ β冼矽 genus Attached to the bismuth iron powder and (7) Drying · Drying the diatomaceous earth at a temperature of 48t~52t, that is, the final product. 2. An absorbent filter material according to the scope of the patent application. Preparation method, wherein step one is combined with iron salt solution The method for preparing an adsorbent filter material according to the above-mentioned item is as follows: after the heat is dissolved in 50 〇ml of water to be completely dissolved and exothermic, and then diluted with water to a degree of 0.5 Μ. In the second step, the industrial grade simmered diatomaceous earth is used, and the granules having a particle size of 30 to 70 mesh are used as raw materials. 4, and the preparation method of the adsorbent filter material according to the first item of the patent scope of Shenqing, wherein Step 2: The diatomaceous earth cleaning program is strongly stirred and ultrasonic. Page 19 1267399 Case No. 93118026 yj /,: Applying for a patent ^ ' ' ' --- The complex positive method does wash out the fine powder impurities hidden in the pores. 5. An adsorption method according to claim 1, wherein the step three diatomaceous earth is immersed in the iron salt solution to prepare a slow stirring at a speed of 70 rpm. Seek to need to be transferred. 6. An adsorption method as described in claim 5, wherein the diatomaceous earth is immersed in the iron salt solution for 2 hours =. Injury, 7. The preparation method of an adsorbent filter according to the scope of the patent application, wherein the concentration of sodium hydroxide lye added in step 4 is 2%, and the pH is adjusted to 1.9~2.1. . 8. A method of preparing an adsorptive filter material according to claim 7, wherein the step 4 is carried out by adding a slow stirring at a rotation speed of 70 rpm while adding the bismuth oxide lye. 9. A method for preparing an adsorbent filter according to claim 7, wherein the step 4 is carried out while adding sodium hydroxide lye for a period of 4 hours. I 0 The preparation method of an adsorptive filter material according to the first aspect of the invention is in which the standing time of the step 5 is 12 hours. II. The preparation method of an adsorbent filter material according to the first aspect of the patent application, wherein the solid-liquid separation in step 6 utilizes the difference in the sedimentation speed of the stone and the plume, and the solution is slightly stirred and then decanted. Separation. 1 2 The method for preparing an adsorbent material according to the first aspect of the invention, wherein the liquid after the solid-liquid separation in the step 6 can be refluxed to the step of reuse. Page 20 1267399