TWI506096B - Gel coated with straw powders composition and method for preparation of the same - Google Patents
Gel coated with straw powders composition and method for preparation of the same Download PDFInfo
- Publication number
- TWI506096B TWI506096B TW102117048A TW102117048A TWI506096B TW I506096 B TWI506096 B TW I506096B TW 102117048 A TW102117048 A TW 102117048A TW 102117048 A TW102117048 A TW 102117048A TW I506096 B TWI506096 B TW I506096B
- Authority
- TW
- Taiwan
- Prior art keywords
- straw
- seaweed
- water
- composition
- adsorption
- Prior art date
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本發明係有關於一種能提升吸附去除帶正電之水中生物代謝廢物氨氮之效果的海藻膠類包覆稻草粉末之組成物及其製備方法。 The present invention relates to a composition of a seaweed-based coated straw powder capable of improving the effect of adsorbing and removing positively charged biological metabolic waste ammonia nitrogen and a preparation method thereof.
台灣許多地區為養豬重鎮，該地區之臭味逸散嚴重，常造成附近居民不悅及抗議，其中氨為畜牧場最主要的臭味源，它常伴隨其他化學物質生成，也可能造成二次氣膠、土壤酸化或地表水優養化等問題。 Many areas in Taiwan are pig-raising towns. The smell of this area is severely dissipated, often causing dissatisfaction and protests among nearby residents. Among them, ammonia is the main source of odors in livestock farms. It is often accompanied by other chemical substances, which may also cause two Problems such as secondary gas gel, soil acidification or surface water salinization.
而近年來畜牧業為降低廢水的處理成本及廢水量，於是建立一種完全無排放水之一貫式墊料禽舍，其常用的墊料為稻殼及木屑；然而，稻殼在高溼度下，因吸濕容量小，因此容易造成濕透現象，而墊料如含水量過高，會增強細菌活動力以及 含氨量，容易造成豬隻與雞隻的疾病，除此之外，木屑粉塵也容易造成動物吸入，引發呼吸道問題及皮膚沾黏。 In recent years, in order to reduce the treatment cost and the amount of wastewater, the animal husbandry has established a consistent litter house with no discharge water. The commonly used litter is rice husk and wood chips; however, the rice husk is under high humidity. Because of the small moisture absorption capacity, it is easy to cause wetness, and if the moisture content is too high, it will enhance the bacterial activity and The ammonia content is easy to cause diseases of pigs and chickens. In addition, wood dust is also likely to cause animal inhalation, causing respiratory problems and skin stickiness.
又，台灣稻草年產量260萬公噸，且稻草具有質輕軟且韌性強、通氣又保溫、透水又保濕及生物可分解之特色，尤其曝曬後的稻草含水率為12~14%，如以露天燃燒方式處理，會產生PM10、CO、NOx等污染物，不只降低空氣品質也浪費資源。如能透過接枝，改變質材的表面結構，改善其物理性使之有助於對氨氮的吸附性能，將可應用於墊料及吸附養殖、畜牧業廢水處理上使用。 In addition, the annual output of straw in Taiwan is 2.6 million metric tons, and the straw has the characteristics of light and soft and tough, ventilated and heat-insulated, permeable and moisturizing, and biodegradable. Especially, the moisture content of straw after exposure is 12-14%, such as in the open air. Combustion treatment will produce pollutants such as PM10, CO, NOx, etc., not only reducing air quality but also wasting resources. If the surface structure of the material can be changed by grafting, and the physical properties of the material can be improved to contribute to the adsorption performance of ammonia nitrogen, it can be used in the treatment of litter and adsorption culture and animal husbandry wastewater.
另外，海藻膠又稱海藻酸、藻酸、褐藻酸，是存在於褐藻細胞壁中的一種天然多醣，容易與陽離子形成凝膠，如海藻酸鈉、海藻酸鎂與海藻酸鈣等，又被稱為褐藻膠或藻膠。海藻酸鈉是一種天然的高分子陰離子電解質，其分子鏈上具有官能基-羧基，海藻酸鈉可以和二價離子，如二價的Ca2+、Sr2++和Ba2+進行離子***聯形成錯化合物，為一三維網狀結構，即一般所稱的”egg-box”緊密結構。 In addition, seaweed gum, also known as alginic acid, alginic acid, alginic acid, is a natural polysaccharide present in the cell wall of brown algae, which easily forms gels with cations, such as sodium alginate, magnesium alginate and calcium alginate. It is alginate or algin. Sodium alginate is a natural polymer anionic electrolyte with a functional group-carboxyl group in its molecular chain. Sodium alginate can be ionically crossed with divalent ions such as divalent Ca 2+ , Sr 2++ and Ba 2+ . The complex compound is formed into a three-dimensional network structure, which is generally referred to as an "egg-box" compact structure.
今，本發明即是透過海藻膠交聯反應微粒包覆改質稻草粉末，合成海藻膠(Gel)/改質稻草(MS)交聯共聚合物(Gel-MS)，經純化、烘乾製成環保吸附劑，進行吸附帶正電之廢水中的氨氮，除能提升稻草在環境工程上之應用與價值之外，更能進一步改善廢水中氨、氮的含量。 Nowadays, the present invention is a method for synthesizing a seaweed gum (Gel)/modified straw (MS) crosslinked copolymer (Gel-MS) through a seaweed cross-linking reaction particle coated modified rice straw powder, which is purified and dried. It is an environmentally friendly adsorbent for the adsorption of ammonia nitrogen in the positively charged wastewater. In addition to improving the application and value of straw in environmental engineering, it can further improve the ammonia and nitrogen content in wastewater.
本發明之主要目的，係提供一種海藻膠類包覆稻草粉末之組成物及其製備方法，其主要是藉海藻膠類包覆改質後之稻草粉末形成交聯共聚合物(Gel-MS)，使由該交聯共聚合物之組成物形成的吸附劑，能提升吸附去除帶正電之水中生物代謝廢物氨氮之效果，以及稻草在環境工程上之應用與價值。 The main object of the present invention is to provide a composition of a seaweed-based coated straw powder and a preparation method thereof, which mainly comprises forming a crosslinked copolymer (Gel-MS) by modifying the modified straw powder with seaweed gum. The adsorbent formed by the composition of the crosslinked copolymer can enhance the effect of adsorbing and removing the ammonia nitrogen of the biologically metabolized waste in the positively charged water, and the application and value of the straw in environmental engineering.
本發明之主要目的與功效，是由以下具體技術手段達成：一種海藻膠類包覆稻草粉末之組成物，係包含經鹼洗處理、清洗、接枝聚合反應之改質後的稻草粉末與海藻膠類，於氯化鈣水溶液中交聯共聚合反應形成親陽離子性微粒包覆層之交聯共聚合組成物。 The main object and effect of the present invention are achieved by the following specific technical means: a composition of seaweed-based coated straw powder, which comprises modified straw powder and seaweed after alkali washing, washing and graft polymerization. A gum, which is crosslinked and copolymerized in an aqueous calcium chloride solution to form a crosslinked copolymer composition of an cation-containing fine particle coating layer.
如上所述之海藻膠類包覆稻草粉末之組成物，其中，海藻膠類係選用自海藻膠或海藻酸鈉其中之一種。 The composition of the seaweed gum-coated straw powder as described above, wherein the seaweed gum is selected from one of seaweed gum or sodium alginate.
一種海藻膠類包覆稻草粉末之組成物的製備方法，包含：(a)稻草接枝改質：(a1)鹼洗處理，將純稻草倒入氫氧化鈉(NaOH)水溶液中，攪拌數分鐘進行鹼洗處理，攪拌完後靜置； (a2)清洗，經一段時間後，將經鹼洗之稻草以水清洗，直到稻草的pH值為中性，再用丙酮洗數次，洗完後放入烘箱烘乾；(a3)完成接枝改質，將烘乾過的稻草置入包括甲基丙烯酸、過氧化氫〔俗稱雙氧水〕、去離子水及硫酸亞鐵銨的反應溶液中，在定溫下進行攪拌，於反應結束後取出反應溶液，將材料過濾後用水再次清洗，最後以丙酮攪拌清洗即完成稻草的接枝改質；(b)製備A材料：(b1)取用所需份量之打碎後的改質稻草粉末與海藻膠類；(b2)將海藻膠類與溫水加在一起攪拌並震盪一段時間形成海藻膠類溶液；(b3)將海藻膠類溶液加入上述之改質稻草粉末，攪拌並震盪一段時間，完成A材料之製備；(c)製備B材料：將氯化鈣(CaCl2)加入水，攪拌溶解形成氯化鈣水溶液；(d)交聯共聚合反應：將A材料注入B材料中，並在停止注入後靜置一段時間；(e)清洗：將步驟(d)完成的材料撈起並清洗；(f)乾燥：將清洗後之材料乾燥； 經由上述步驟，即完成海藻膠類包覆稻草粉末之組成物的製備。 A method for preparing a composition of seaweed gum-coated straw powder, comprising: (a) straw grafting modification: (a1) alkali washing treatment, pouring pure straw into an aqueous solution of sodium hydroxide (NaOH), stirring for several minutes After alkali washing, it is allowed to stand after stirring; (a2) Washing, after a period of time, the alkali washed straw is washed with water until the pH of the straw is neutral, and then washed several times with acetone, after washing Put it into the oven for drying; (a3) complete the graft modification, and put the dried straw into a reaction solution including methacrylic acid, hydrogen peroxide (commonly known as hydrogen peroxide), deionized water and ammonium ferrous sulfate. Stirring is carried out at a constant temperature. After the reaction is completed, the reaction solution is taken out, the material is filtered, and then washed again with water. Finally, the grafting and upgrading of the straw is completed by stirring with acetone; (b) Preparation of material A: (b1) required for use a portion of the crushed modified straw powder and seaweed gum; (b2) adding the seaweed gum and warm water together and shaking for a period of time to form a seaweed gum solution; (b3) adding the seaweed gum solution to the above Change the straw powder, stir and shake for a while to complete the A material Preparation B material (C); Preparation of: Calcium chloride (CaCl 2) was added water, dissolved under stirring forming an aqueous solution of calcium chloride; (d) a crosslinking copolymerization reaction: A material into the B material, and stopping injection After standing for a period of time; (e) cleaning: picking up and cleaning the material completed in step (d); (f) drying: drying the cleaned material; through the above steps, completing the seaweed-coated straw powder Preparation of the composition.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，在(a1)步驟中，該氫氧化鈉(NaOH)水溶液濃度為0.01~6.0M。 The method for producing a composition of a seaweed-based coated straw powder of the present invention as described above, wherein in the step (a1), the concentration of the aqueous solution of sodium hydroxide (NaOH) is 0.01 to 6.0 M.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，在(a2)步驟中，該稻草以丙酮清洗後進行烘乾之溫度為25~80℃。 The method for producing a composition of a seaweed-based coated straw powder of the present invention as described above, wherein in the step (a2), the straw is washed with acetone and then dried at a temperature of 25 to 80 °C.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，在(a3)步驟中，該稻草與該反應溶液中各成分之使用量為：1~100g的稻草及以0.2~900g甲基丙烯酸、0.02~80g過氧化氫(濃度8~40%)、5~5000g去離子水、0.0005~10g硫酸亞鐵銨。 The method for preparing a composition of a seaweed-based coated straw powder according to the present invention, wherein, in the step (a3), the straw and the components of the reaction solution are used in an amount of from 1 to 100 g of straw and 0.2~900g methacrylic acid, 0.02~80g hydrogen peroxide (concentration 8~40%), 5~5000g deionized water, 0.0005~10g ferrous ammonium sulfate.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，在(a3)步驟中，在定溫下進行攪拌，是指反應溶液在恆溫循環水槽25~95℃定溫下以攪拌馬達攪拌，攪拌馬達轉速控制在每分鐘100~1000轉。 The method for preparing a composition of a seaweed-based coated straw powder of the present invention as described above, wherein in the step (a3), stirring at a constant temperature means that the reaction solution is kept at a constant temperature circulating water tank at a temperature of 25 to 95 ° C. Stirring with a stirring motor, the speed of the stirring motor is controlled at 100~1000 rpm.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，稻草粉末與海藻膠類選用之比例為9：1~2：8。 The preparation method of the composition of the seaweed-based coated straw powder of the present invention as described above, wherein the ratio of the straw powder to the seaweed gum is selected from 9:1 to 2:8.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，海藻膠類與水之比例為1%：99%~10%：90%。 The method for producing a composition of a seaweed-based coated straw powder of the present invention as described above, wherein the ratio of the seaweed gum to water is 1%: 99% to 10%: 90%.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，加入海藻膠類之水的水溫介於40~90℃攪拌。 The method for producing a composition of a seaweed-based coated straw powder of the present invention as described above, wherein the water temperature of the water to which the seaweed gum is added is stirred at 40 to 90 °C.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，海藻膠類溶液加入稻草粉末後以超音波震盪攪拌10分鐘。 The method for producing a composition of a seaweed-based coated straw powder of the present invention as described above, wherein the seaweed gum solution is added to the straw powder and stirred by ultrasonic vibration for 10 minutes.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，B材料是由氯化鈣(CaCl2)與水之比例為0.2%：99.8%~15%：85%，攪拌溶解而得。 a method for preparing a composition of a seaweed-based coated straw powder of the present invention, wherein the B material is a ratio of calcium chloride (CaCl 2 ) to water of 0.2%: 99.8% to 15%: 85%, Stirred and dissolved.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，A材料是以針筒注射方式注入B材料中。 The method for producing a composition of a seaweed-based coated straw powder of the present invention as described above, wherein the A material is injected into the B material by syringe injection.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，在步驟(f)中，烘乾之溫度介於25~75℃。 The method for producing a composition of a seaweed-based coated straw powder of the present invention as described above, wherein in the step (f), the drying temperature is between 25 and 75 °C.
如上所述本發明之海藻膠類包覆稻草粉末之組成物的製備方法，其中，該海藻膠類係選用自海藻膠或海藻酸鈉其中之一種。 The method for producing a composition of a seaweed-based coated straw powder of the present invention as described above, wherein the seaweed gum is selected from the group consisting of seaweed gum or sodium alginate.
第一圖：本發明之製備流程圖 First Figure: Flow chart of preparation of the present invention
第二圖：32℃下，MS粉末吸附氨氮之LM與FD等溫吸附線之比較圖 Second figure: Comparison of LM and FD isotherm adsorption lines of MS powder adsorbed by MS powder at 32 °C
第三圖：32℃下，Gel-MS(6：4)吸附氨氮之LM與FD等溫吸附線之比較圖 Figure 3: Comparison of LM and FD isotherm adsorption lines for adsorption of ammonia nitrogen by Gel-MS (6:4) at 32 °C
第四圖：32℃下，Gel-MS(8：2)吸附氨氮之LM與FD等溫吸附線之比較圖 Figure 4: Comparison of LM and FD isotherm adsorption lines for adsorption of ammonia nitrogen by Gel-MS (8:2) at 32 °C
第五圖：稻草放大1000倍之SEM圖形 Figure 5: SEM graphics with 1000x magnification of straw
第六圖：稻草放大3000倍之SEM圖形 Figure 6: SEM image of straw magnified 3000 times
第七圖：改質稻草放大3000倍之SEM圖形 Figure 7: SEM image of 3000 times magnification of modified straw
第八圖：Gel-MS(8：2)放大3000倍及5200倍之SEM圖形 Figure 8: SEM graphics magnified 3000 times and 5200 times by Gel-MS (8:2)
第九圖：Gel-MS(8：2)在32℃及氨氮初濃度150ppm吸附2hr，放大3000倍之SEM圖形 Figure 9: Gel-MS (8:2) adsorbed at 32 ° C and ammonia nitrogen concentration of 150 ppm for 2 hr, magnified 3000 times SEM graphics
為令本發明所運用之技術內容、發明目的及其達成之功效有更完整且清楚的揭露，茲於下詳細說明之，並請一併參閱所揭之圖式及圖號：請參看第一圖所示，其係本發明之製備流程圖。 For a more complete and clear disclosure of the technical content, the purpose of the invention and the effects thereof achieved by the present invention, the following is a detailed description, and please refer to the illustrated drawings and drawings: please refer to the first The figure shows a flow chart of the preparation of the present invention.
一種海藻膠類包覆稻草粉末之組成物的製備方法，係包含：(a)稻草接枝改質：(a1)鹼洗處理，將純稻草倒入氫氧化鈉(NaOH)水溶液中，攪拌數分鐘進行鹼洗處理，攪拌完後靜置； (a2)清洗，經一段時間後，將經鹼洗之稻草以水清洗，直到稻草的pH值為中性，再用丙酮洗數次，洗完後放入烘箱烘乾；(a3)完成接枝改質，將烘乾過的稻草置入包括甲基丙烯酸、過氧化氫〔俗稱雙氧水〕、去離子水及硫酸亞鐵銨的反應溶液中，在定溫下進行攪拌，於反應結束後取出反應溶液，將材料過濾後用水再次清洗，最後以丙酮攪拌清洗即完成稻草的接枝改質；(b)製備A材料：(b1)取用所需份量之海藻膠類與打碎後的改質稻草粉末；(b2)將海藻膠類與溫水加在一起攪拌並震盪一段時間形成海藻膠類溶液，而加入海藻膠類之水的水溫介於40~90℃攪拌；(b3)將海藻膠類溶液加入上述之改質稻草，攪拌並震盪一段時間，完成A材料之製備；(c)製備B材料：將氯化鈣(CaCl2)加入水，攪拌溶解形成氯化鈣水溶液，B材料是由氯化鈣(CaCl2)與水之比例為0.2%：99.8%~15%：85%，攪拌溶解而得；(d)交聯共聚合反應：將A材料注入B材料中，並在停止注入後靜置一段時間；(e)清洗：將步驟(d)完成的材料撈起並清洗； (f)乾燥：將清洗後之材料乾燥；經由上述步驟，即完成一種包含經鹼洗處理、清洗、接枝聚合反應之改質後的稻草粉末與海藻膠類，而於氯化鈣水溶液中交聯共聚合反應形成親陽離子性微粒包覆層之交聯共聚合的海藻膠類包覆稻草粉末之組成物。而所完成的海藻膠類包覆稻草粉末之組成物可被用來作為吸附劑，尤其是可以應用在水質淨化上。 The invention relates to a method for preparing a composition of seaweed gum-coated straw powder, which comprises: (a) straw grafting modification: (a1) alkali washing treatment, pouring pure straw into sodium hydroxide (NaOH) aqueous solution, stirring number In the minute, the alkali washing treatment is carried out, and after stirring, it is allowed to stand; (a2) washing, after a period of time, the alkali-washed straw is washed with water until the pH of the straw is neutral, and then washed several times with acetone, and washed. After drying in an oven; (a3) complete the graft modification, and put the dried straw into a reaction solution including methacrylic acid, hydrogen peroxide (commonly known as hydrogen peroxide), deionized water and ammonium ferrous sulfate. Stirring is carried out at a constant temperature. After the reaction is completed, the reaction solution is taken out, the material is filtered, and then washed again with water. Finally, the grafting and upgrading of the straw is completed by stirring with acetone; (b) Preparation of material A: (b1) The amount of seaweed gum and the modified straw powder after crushing; (b2) stirring the seaweed gum together with warm water and shaking for a period of time to form a seaweed solution, and adding the water temperature of the seaweed water Stirring between 40 and 90 ° C; (b3) adding a seaweed solution to the above Quality straw, stirred and shaken for some time, preparation of material A is completed; (c) Preparation of Material B: Calcium chloride (CaCl 2) was added water, dissolved under stirring an aqueous solution of calcium chloride is formed, the material B is calcium chloride (CaCl 2 ) The ratio of water to water is 0.2%: 99.8%~15%: 85%, obtained by stirring and dissolving; (d) cross-linking copolymerization: injecting A material into B material and letting it stand for a while after stopping the injection (e) cleaning: picking up and cleaning the material completed in step (d); (f) drying: drying the cleaned material; through the above steps, completing a process comprising alkali washing, washing, graft polymerization The modified straw powder and the seaweed gum are cross-linked and copolymerized in an aqueous calcium chloride solution to form a cross-linked copolymerized seaweed-coated straw powder composition of the cation-containing microparticle coating layer. The composition of the finished seaweed-coated straw powder can be used as an adsorbent, especially for water purification.
以下再進一步根據實際數據說明本發明海藻膠類包覆稻草粉末之組成物的製備步驟，其中，該海藻膠類可選自海藻膠或海藻酸鈉其中之一，於下面之具體實施例中是採用海藻膠作為實施說明。 The preparation step of the composition of the seaweed-based coated straw powder of the present invention is further described below based on actual data, wherein the seaweed gum may be selected from one of seaweed gum or sodium alginate, in the following specific examples. Seaweed gum was used as an implementation note.
(a)稻草接枝改質：(a1)鹼洗處理，將純稻草倒入0.01~6.0M氫氧化鈉(NaOH)水溶液中，攪拌30分鐘進行鹼洗處理，攪拌完後靜置隔夜；(a2)清洗，第二天將稻草以水清洗直到pH值為中性，再用丙酮洗2次，洗完後放入烘箱(約25~80℃)烘乾至隔天；(a3)完成接枝改質，第三天將鹼洗烘乾過1~100g的稻草及以0.2~900g甲基丙烯酸、0.02~80g過氧化氫(濃度8~40%)【俗稱雙氧水】、5~5000g去離子水、0.0005~10g硫酸亞鐵銨的反應溶液在恆溫循環水槽25~95℃定溫下攪拌1.5小時、攪拌馬達轉速控制在每分鐘100~1000轉上下，反 應結束後，取出反應溶液，之後把材料過濾後先用水洗二次，在用丙酮攪拌下洗過3次就可完成稻草的接枝改質；(b)製備A材料：(b1)將改質稻草以粉碎機打碎成粉末狀，再將改質稻草粉末與海藻膠依照其比例(9：1~2：8)製備所需材料份量(14.4g：1.6g~0.4g：1.6g)；(b2)將海藻膠類與60℃溫水按1.6g：14.4g~1.6g：158.4g比例加在一起攪拌，並於超音波震盪機攪拌10分鐘，形成海藻膠類溶液，其中所需海藻膠佔全部的1~10%；(b3)將海藻膠類溶液加入上述之改質稻草粉末，並於超音波震盪機攪拌10分鐘，完成A材料之製備；(c)製備B材料：將1~75g氯化鈣(CaCl2)加入425~499ml水，攪拌溶解形成氯化鈣水溶液；(d)交聯共聚合反應：將A材料用針筒注入B材料中，計時10分鐘當時間到即停止注射並靜置5分鐘；(e)清洗：將步驟(d)完成的材料撈起並用二段水清洗2~3次；(f)乾燥：將清洗後之材料放入烘乾溫度於25~75℃之烘箱內 (a) Straw grafting modification: (a1) alkaline washing treatment, pour pure straw into 0.01~6.0M sodium hydroxide (NaOH) aqueous solution, stir for 30 minutes for alkali washing, and then stand overnight after stirring; A2) Washing, the straw is washed with water until the pH is neutral on the next day, and then washed twice with acetone. After washing, put it in an oven (about 25~80 °C) and dry until the next day; (a3) The branch is modified. On the third day, the alkali is washed and dried with 1~100g of straw and 0.2~900g of methacrylic acid, 0.02~80g of hydrogen peroxide (concentration of 8~40%) [commonly known as hydrogen peroxide], 5~5000g deionization. The reaction solution of water, 0.0005~10g ammonium ferrous sulfate is stirred at a constant temperature circulating water tank at a constant temperature of 25~95 °C for 1.5 hours, and the stirring motor speed is controlled at 100~1000 rpm. After the reaction is finished, the reaction solution is taken out, and then After the material is filtered, it is washed twice with water, and the grafting modification of straw is completed after washing 3 times with acetone; (b) Preparation of material A: (b1) The modified straw is broken into powder by a pulverizer Then, the modified rice straw powder and seaweed gum are prepared according to the ratio (9:1~2:8) to prepare the required material amount (14.4g: 1.6g~0.4g: 1.6g); (b2) the seaweed gum and 60 Warm water is stirred in a ratio of 1.6g: 14.4g~1.6g: 158.4g, and stirred in a ultrasonic oscillator for 10 minutes to form a seaweed solution, wherein the required seaweed gel accounts for 1~10% of the total; B3) adding the seaweed gum solution to the above modified straw powder, and stirring in an ultrasonic oscillating machine for 10 minutes to complete the preparation of the A material; (c) preparing the B material: adding 1 to 75 g of calcium chloride (CaCl 2 ) 425~499ml water, stirred and dissolved to form an aqueous solution of calcium chloride; (d) cross-linking copolymerization: inject A material into B material with a syringe, and wait 10 minutes to stop the injection and let stand for 5 minutes; Cleaning: pick up the material completed in step (d) and wash it with two waters for 2~3 times; (f) dry: put the cleaned material into the oven at 25~75 °C
經由上述步驟，即完成海藻膠包覆稻草粉末之吸附劑的製備。 Through the above steps, the preparation of the adsorbent for the seaweed-coated straw powder is completed.
為說明本發明稻草改質交聯共聚合物之吸附劑的吸附能力，故進行以本發明之海藻膠包覆稻草改質之交聯共聚合物(Gel-MS)自製吸附劑及傳統改質稻草對不同氨氮(NH4 --N)起始濃度之吸附實驗：起始濃度分別為50、100、150、200，及250ppm等，吸附時間約為兩個小時。另外以吸附等溫線作為佐證，吸附等溫線乃是表示平衡恆溫關係曲線，在研製吸附劑時，吸附等溫線是不可缺少的資料，在吸附分離的方法上，等溫線更提供選擇的依據。最常使用之固、液相間的吸附等溫線有Langmuir、Freundlich等型之等溫線。而其吸附量與液體濃度之關係為：qe=(Vb/W)(C0-Ce) In order to illustrate the adsorption capacity of the adsorbent of the straw-modified cross-linked copolymer of the present invention, the cross-linked copolymer (Gel-MS) self-adsorbing agent modified by the seaweed coating of the present invention and the conventional modification are carried out. Adsorption experiments of straw on different initial concentrations of ammonia nitrogen (NH 4 - -N): initial concentrations were 50, 100, 150, 200, and 250 ppm, respectively, and the adsorption time was about two hours. In addition, the adsorption isotherm is used as evidence. The adsorption isotherm is the equilibrium constant temperature curve. When developing the adsorbent, the adsorption isotherm is indispensable. In the method of adsorption separation, the isotherm provides more choice. Basis. The most commonly used adsorption isotherms between solid and liquid phases are the isotherms of Langmuir and Freundlich. The relationship between the amount of adsorption and the concentration of liquid is: q e =(V b /W)(C 0 -C e )
其中，qe表示溶液中溶質減少的量(mg/g-吸附劑)；Vb表示溶液體積(L)；W表示吸附劑的重量(g)；C0表示初濃度(ppm)；Ce表示水溶液中之溶質平衡濃度(ppm)。 Where q e represents the amount of solute reduction in the solution (mg/g-adsorbent); V b represents the solution volume (L); W represents the weight of the adsorbent (g); C 0 represents the initial concentration (ppm); C e Indicates the equilibrium concentration (ppm) of the solute in the aqueous solution.
Langmuir吸附等溫線 Langmuir adsorption isotherm
qe=β Ce/(1+α Ce)=qm α Ce/(1+α Ce) q e =β C e /(1+α C e )=q m α C e /(1+α C e )
其中，α、β為Langmuir等溫吸附方程式係數；qm為單層飽和吸附量。於Langmuir模式中，如以ψ代表1/(1+α C0)則ψ>1為不利吸附；ψ=1為線性吸附；0<ψ<1為有利吸附；ψ=0為不可逆吸附。 Among them, α and β are the coefficients of the Langmuir isotherm adsorption equation; q m is the single-layer saturated adsorption amount. In Langmuir mode, if ψ represents 1/(1+α C 0 ) then ψ>1 is unfavorable adsorption; ψ=1 is linear adsorption; 0<ψ<1 is favorable adsorption; ψ=0 is irreversible adsorption.
Freundlich吸附等溫線 Freundlich adsorption isotherm
qe=k×Ce 1/n q e =k×C e 1/n
其中，k、n均為Freundlich常數。 Where k and n are Freundlich constants.
於Freundlich模式中，如以熱力學的方法所推導求得之n值。當1/n>1為不利吸附；1/n=1為線性吸附；1/n<1為有利吸附。 In the Freundlich mode, the value of n is derived as a thermodynamic method. When 1/n>1 is unfavorable adsorption; 1/n=1 is linear adsorption; 1/n<1 is favorable adsorption.
以下請參表1，藉以說明傳統改質稻草與稻殼接枝百分比之比較：接枝率公式：(接枝後總重-原本材料重)/原本材料重*100% Please refer to Table 1 below to illustrate the comparison of the percentage of traditional modified straw and rice hull grafting: the formula of grafting ratio: (total weight after grafting - weight of original material) / original material weight * 100%
由表1知改質稻草之接枝百分比為82.3%，比改質稻殼最高接枝百分比68.7%，還高出13.6%，顯示改質稻草接枝狀況相當不錯。 It is known from Table 1 that the grafting percentage of the modified straw is 82.3%, which is 68.7% higher than that of the modified rice husk, and 13.6% higher than that of the modified rice straw, indicating that the grafting status of the modified straw is quite good.
再進一步透過實際之試驗證明本發明製成稻草改質交聯共聚合物之吸附劑所產生之效果，高於目前單純使用沸石之效果。 Further, through actual experiments, it is proved that the effect of the adsorbent which is made into the straw-modified crosslinked copolymer of the present invention is higher than the effect of using zeolite alone.
一、配製氨氮檢測試劑： First, the preparation of ammonia nitrogen detection reagents:
1、無氨水：可用一般純水通過強酸性陽離子交換樹脂或加硫酸和高錳酸鉀後，重蒸餾得到。 1. No ammonia water: It can be obtained by re-distilling with normal pure water through strong acid cation exchange resin or adding sulfuric acid and potassium permanganate.
2、納氏試劑：秤取160g氫氧化鈉，溶於500mL水中，充分冷卻至室溫。另秤取70g碘化鉀和100g碘化汞(HgI2)溶於水，然後將此溶液在攪拌下緩慢注入氫氧化鈉溶液中。用水稀釋至1L，貯於聚乙烯瓶中，封塞保存。 2. Nessler's reagent: Weigh 160g of sodium hydroxide, dissolve it in 500mL of water, and cool to room temperature. Another 70 g of potassium iodide and 100 g of mercury iodide (HgI 2 ) were weighed and dissolved in water, and then this solution was slowly poured into a sodium hydroxide solution with stirring. Dilute to 1 L with water, store in a polyethylene bottle, and store in a sealed place.
3、銨標準儲備溶液：稱取3.819g經100℃乾燥過的氯化銨(NH4Cl)溶於水中，移入1L容量瓶中，稀釋至標線。此溶液每毫升含1.00mg氨氮≒1000ppm氨氮。 3. Ammonium standard stock solution: Weigh 3.819g of ammonium chloride (NH 4 Cl) dried at 100 ° C, dissolve it in water, transfer it to a 1L volumetric flask, and dilute to the mark. This solution contains 1.00 mg of ammonia nitrogen and 1000 ppm of ammonia nitrogen per ml.
4、銨標準使用溶液：移取10.00mL銨標準儲備液於1L容量瓶中，用水稀釋至標線。此溶液每毫升含0.010mg氨氮≒10ppm氨氮。 4. Ammonium standard use solution: Pipette 10.00mL of ammonium standard stock solution into a 1L volumetric flask and dilute to the mark with water. This solution contained 0.010 mg of ammonia nitrogen 10 ppm ammonia nitrogen per ml.
二、氨氮吸附準備： Second, ammonia nitrogen adsorption preparation:
1、水樣預處理：無色澄清的水樣可直接測定；色度、渾濁度較高和含干擾物質較多的水樣，需經過蒸餾或混凝沉澱等預處理步驟。 1. Water sample pretreatment: colorless clarified water samples can be directly measured; water samples with high chroma and turbidity and more interfering substances need to be subjected to pretreatment steps such as distillation or coagulation sedimentation.
2、標準檢量線的繪製：吸取0(空白試驗)、0.10、0.30、0.50、0.70和1.0ppm氨氮標準使用液於20mL試管中(若為池水須加入2滴之ZnSO4及EDTA溶液)；分別加入吸取10、9.90、9.70、9.50、9.30和10.0mL的純水；再分別加入0.4mL納氏試劑計時，混合均勻。放置20min後，在波長425nm處，用光程1cm之比色管，以零濃度空白管為參考，測定吸光度，繪製以氨氮含量(ppm，範圍0.10~1.0ppm)對吸光度A的標準檢量線。 2. Drawing of standard calibration curve: draw 0 (blank test), 0.10, 0.30, 0.50, 0.70 and 1.0ppm ammonia nitrogen standard solution in 20mL test tube (if it is water, add 2 drops of ZnSO 4 and EDTA solution); Add 10, 9.90, 9.70, 9.50, 9.30, and 10.0 mL of pure water, respectively; add 0.4 mL of Nessler's reagent separately and mix well. After standing for 20 min, the absorbance was measured at a wavelength of 425 nm using a colorimetric tube of 1 cm with a zero-concentration blank tube, and a standard calibration curve for the absorbance A of ammonia nitrogen content (ppm, range 0.10 to 1.0 ppm) was plotted. .
3、水樣的測定：分別取0.1mL的水樣(使氨氮含量不超過1.0ppm)及9.90mL的純水，於20mL試管中，加0.4mL的納氏試劑，混合均勻，放置20min，測定吸光度。 3. Determination of water sample: Take 0.1mL water sample (so that the ammonia nitrogen content does not exceed 1.0ppm) and 9.90mL of pure water, add 0.4mL of Nessler reagent in 20mL test tube, mix well, place for 20min, determine Absorbance.
三、氨氮吸附的測定實驗 Third, the determination of ammonia nitrogen adsorption experiment
將本發明完成海藻膠包覆改質稻草交聯共聚合物之吸附劑之吸附劑Gel-MS(選用改質稻草與海藻膠比例為8：2及6：4兩例說明)及單純的改質稻草對不同氨氮(NH4 +-N)起始濃度進行吸附實驗，起始濃度分別為50、100、150、200，及250ppm，吸附時間約為兩個小時。 The present invention completes the adsorbent Gel-MS of the adsorbent which is coated with the seaweed gel modified straw cross-linked copolymer (the description of the modified straw and seaweed gum ratios of 8:2 and 6:4) and the simple modification The straw was subjected to adsorption experiments on different initial concentrations of ammonia nitrogen (NH 4 + -N) at initial concentrations of 50, 100, 150, 200, and 250 ppm, respectively, and the adsorption time was about two hours.
1、32℃改質稻草(MS)氨氮吸附等溫線：在32℃時，改質稻草(MS)對氨氮濃度平衡吸附量的關係，如表2以及第二圖所示。由表2知，在32℃及氨氮初濃度為250ppm時，MS對氨氮之實際吸附量可達18.64mg/g，吸附量不錯。表3為在32℃時，MS粉末吸附氨氮之Langmuir及Freundlich等溫吸附線的比較。由表3知，Freundlich(r=99.92%)比Langmuir(r=99.82%)等溫吸附線更能適合描述改質稻草對氨氮吸附之情形(亦如第二圖所示)。且其單層飽和吸附量也具有38.9mg/g之潛力，吸附量相當不錯。 1. 32 °C modified straw (MS) ammonia nitrogen adsorption isotherm: at 32 ° C, the relationship between modified straw (MS) and ammonia nitrogen concentration equilibrium adsorption, as shown in Table 2 and Figure 2. It is known from Table 2 that at 32 ° C and the initial concentration of ammonia nitrogen is 250 ppm, the actual adsorption amount of MS to ammonia nitrogen can reach 18.64 mg / g, and the adsorption amount is good. Table 3 is a comparison of the Langmuir and Freundlich isotherm adsorption lines for the adsorption of ammonia nitrogen by MS powder at 32 °C. It is known from Table 3 that Freundlich (r=99.92%) is more suitable for describing the adsorption of ammonia to nitrogen by modified straw than the Langmuir (r=99.82%) isotherm adsorption line (also shown in the second figure). And its single-layer saturated adsorption capacity also has a potential of 38.9mg/g, and the adsorption amount is quite good.
表2、在32℃時，接枝稻草與氨氮濃度吸附量之關係
*r：線性最小平方法之相關係數 * r: correlation coefficient of linear least squares method
2、32℃ Gel-MS(6：4)氨氮吸附等溫線：在32℃時，Gel-MS(6：4)對氨氮濃度平衡吸附量的關係，如表4以及第三圖所示。由表4知，在32℃及氨氮初濃度為250ppm時，Gel-MS(6：4)對氨氮之實際吸附量可達21.23mg/g，吸附量比32℃改質稻草(18.64mg/g)為高，其可能原因乃在32℃時Gel-MS(6：4)之海藻膠親水性或親陽離子性微粒包覆層，可以促進氨氮陽離子在Gel-MS(6：4)顆粒中的擴散速率，也增加了包覆層中改質稻草對氨氮離子的實際吸附量。表5為在32℃時，改質稻草吸附氨氮之Langmuir及Freundlich等溫吸附線的比較。由表5知，Langmuir(r=99.999%)比Freundlich(r=99.54%)等溫吸附線更適合描述活性碳粉末對氨氮吸附之情形(亦如第三圖所示)。而且其單層飽和吸附量為35.2mg/g，吸附量比改質稻 草(38.9mg/g)稍低。主要原因可能是：在32℃下Gel-MS(6：4)微粒包覆層中之改質稻草粉末實際可用於吸附氨氮離子之質量小於純改質稻草顆粒的緣故。另外，由第二圖也可知在32℃及氨氮低初濃度(C0<50ppm)時，Gel-MS(6：4)對氨氮之實際吸附量可達7.75mg/g，其吸附量比32℃改質稻草(5.61mg/g)為高，低氨氮初濃度之曲線斜率也相對較大，此亦表示Gel-MS(6：4)比MS顆粒有利於低濃度氨氮的吸附去除。 2, 32 ° C Gel-MS (6:4) ammonia nitrogen adsorption isotherm: At 32 ° C, the relationship between Gel-MS (6:4) on the equilibrium adsorption capacity of ammonia nitrogen concentration, as shown in Table 4 and Figure 3. It is known from Table 4 that the actual adsorption amount of Gel-MS (6:4) to ammonia nitrogen can reach 21.23 mg/g at 32 ° C and the initial concentration of ammonia nitrogen is 250 ppm, and the adsorption amount is 32.64 mg/g. High), the possible reason is that the gelatinic hydrophilic or cationic particulate coating of Gel-MS (6:4) at 32 °C can promote the ammonia nitrogen cation in the Gel-MS (6:4) particles. The diffusion rate also increases the actual adsorption of ammonia nitrogen ions by the modified straw in the coating. Table 5 is a comparison of the Langmuir and Freundlich isotherm adsorption lines of modified rice straw adsorbing ammonia nitrogen at 32 °C. It is known from Table 5 that Langmuir (r = 99.999%) is more suitable for describing the adsorption of ammonia carbon by activated carbon powder than the Freundlich (r = 99.54%) isotherm adsorption line (also shown in the third figure). Moreover, the single layer saturated adsorption amount was 35.2 mg/g, and the adsorption amount was slightly lower than that of the modified straw (38.9 mg/g). The main reason may be that the modified straw powder in the Gel-MS (6:4) particle coating at 32 ° C can actually be used to adsorb ammonia nitrogen ions with less mass than pure modified straw particles. In addition, it can be seen from the second figure that the actual adsorption amount of Gel-MS (6:4) to ammonia nitrogen can reach 7.75 mg/g at 32 ° C and low initial concentration of ammonia nitrogen (C 0 <50 ppm), and the adsorption ratio is 32. °C modified straw (5.61mg/g) is high, and the slope of the initial concentration of low ammonia nitrogen is relatively large, which also indicates that Gel-MS (6:4) is better than MS particles for the adsorption removal of low concentration ammonia nitrogen.
r：線性最小平方法之相關係數 r: correlation coefficient of linear least squares method
3、32℃ Gel-MS(8：2)氨氮吸附等溫線：在32℃時，Gel-MS(8：2)對氨氮濃度平衡吸附量的關係，如表6以及第四圖所示。由表6知，在22℃及氨氮初濃度為250ppm時，Gel-AC(8：2)對氨氮之實際吸附量可 達24.49mg/g，吸附量均比32℃之MS(18.64mg/g)及32℃ Gel-MS(6：4)之21.23mg/g為大。其原因可能為：在32℃下，氨氮離子在Gel-MS(8：2)顆粒親正離子及親水性之膠體中的擴散速率，比其在同溫度下之MS及Gel-MS(6：4)顆粒孔隙中者，相對的較大；所以，32℃時Gel-MS(8：2)的吸附量均比相同溫度之MS及Gel-MS(6：4)為大。 3, 32 °C Gel-MS (8:2) ammonia nitrogen adsorption isotherm: At 32 ° C, the relationship between Gel-MS (8:2) and ammonia nitrogen concentration equilibrium adsorption amount, as shown in Table 6 and Figure 4. It is known from Table 6 that the actual adsorption amount of Gel-AC (8:2) to ammonia nitrogen can be obtained at 22 ° C and the initial concentration of ammonia nitrogen is 250 ppm. The amount of adsorption was 24.49 mg/g, and the adsorption amount was larger than the MS of 32 ° C (18.64 mg / g) and 21.23 mg / g of 32 ° C Gel-MS (6: 4). The reason may be: at 32 ° C, the diffusion rate of ammonia nitrogen ions in Gel-MS (8:2) particle positive ions and hydrophilic colloids, compared to MS and Gel-MS at the same temperature (6: 4) The particle pores are relatively large; therefore, the adsorption amount of Gel-MS (8:2) at 32 °C is larger than that of MS and Gel-MS (6:4) at the same temperature.
表7為在32℃時，Gel-MS(8：2)顆粒吸附氨氮之Langmuir及Freundlich等溫吸附線的比較。由表7知，Langmuir(r=99.58%)比Freundlich(r=99.54%)等溫吸附線更能適合描述Gel-MS(8：2)對氨氮吸附之情形(亦如第四圖所示)。其單層飽和吸附量為30.13mg/g，均較在同溫度下之MS(38.9mg/g)及Gel-MS(6：4)之35.2mg/g為小。其可能原因為： Table 7 is a comparison of the Langmuir and Freundlich isotherm adsorption lines for the adsorption of ammonia nitrogen by Gel-MS (8:2) particles at 32 °C. It is known from Table 7 that Langmuir (r=99.58%) is more suitable for describing the adsorption of ammonia nitrogen by Gel-MS (8:2) than the Freundlich (r=99.54%) isotherm adsorption line (also as shown in the fourth figure). . The single layer saturated adsorption amount was 30.13 mg/g, which was smaller than 35.2 mg/g of MS (38.9 mg/g) and Gel-MS (6:4) at the same temperature. The possible reasons are:
(1)微粒包覆層中之改質稻草粉末實際可用於吸附氨氮離子之總質量稍小於純改質稻草顆粒。 (1) The modified straw powder in the microparticle coating layer can actually be used to adsorb ammonia nitrogen ions with a total mass slightly smaller than pure modified straw particles.
(2)在較高氨氮起始濃度的情況下Gel-MS(8：2)顆粒中改質稻草粉末之吸附潛力，較之Gel-MS(6：4)為稍小，可能與顆粒中膠體交聯的情況較緊密有關。 (2) The adsorption potential of modified straw powder in Gel-MS (8:2) granules at a higher initial concentration of ammonia nitrogen is slightly smaller than that of Gel-MS (6:4), possibly with colloid in granules The situation of cross-linking is more closely related.
表6、在32℃時，海藻膠包覆稻草接枝粉末(8：2)與氨氮吸附量之關係
r：線性最小平方法之相關係數 r: correlation coefficient of linear least squares method
4、吸附劑的SEM圖形 4. SEM image of adsorbent
第五圖~第六圖為稻草放大1000、3000倍之SEM圖形；由第五圖中可看出稻草呈現規則的植物細胞。而第六圖則為改質稻草放大3000倍之SEM圖形，由於甲基聚丙烯酸接枝於稻草上，使得稻草植物細胞規則的形狀顯得較不明顯。第七圖為Gel-MS(8：2)放大3000倍及5200倍之SEM圖形。第七圖顯示海藻膠包覆改質稻草的的情況良好。而第八圖、第九圖為Gel-MS(8：2)及Gel-MS(6：4)在32℃及氨氮初濃度150ppm吸附2hr，放大3000倍之SEM圖形。第七圖及第九圖均顯示海藻膠的包覆改質稻草的的情況仍然良好。 The fifth to sixth figures show the SEM patterns of straw magnified 1000 and 3000 times; from the fifth figure, it can be seen that the straw presents regular plant cells. The sixth figure is a SEM image magnified 3000 times by the modified straw. Since the methyl polyacrylic acid is grafted on the straw, the regular shape of the straw plant cells is less obvious. The seventh picture shows the SEM image of 3000-fold and 5200-fold magnification of Gel-MS (8:2). The seventh figure shows that the algae gel coated the modified straw is in good condition. The eighth and ninth graphs are SEM images of Gel-MS (8:2) and Gel-MS (6:4) adsorbed at 32 ° C and an initial concentration of ammonia nitrogen of 150 ppm for 2 hr, magnified 3000 times. Both the seventh and ninth figures show that the case of coated algae coated with modified straw is still good.
本發明可應用於化學吸附(陽離子交換)功能在土壤改良、土壤解毒、水質淨化(飲用水、工廠廢水、生活廢水、河 川湖泊)、中水處理、人工土壤、培地及水耕栽培用安定培地等多方面皆能有效運用。 The invention can be applied to chemical adsorption (cation exchange) function in soil improvement, soil detoxification, water purification (drinking water, factory wastewater, domestic wastewater, river Sichuan Lake), water treatment, artificial soil, cultivated land and hydroponic cultivation can be effectively used in many aspects.
以上所舉者僅係本發明之部份實施例，並非用以限制本發明，致依本發明之創意精神及特徵，稍加變化修飾而成者，亦應包括在本專利範圍之內。 The above is only a part of the embodiments of the present invention, and is not intended to limit the present invention. It is intended to be included in the scope of the present invention.
綜上所述，本發明實施例確能達到所預期之使用功效，又其所揭露之具體技術手段，不僅未曾見諸於同類產品中，亦未曾公開於申請前，誠已完全符合專利法之規定與要求，爰依法提出發明專利之申請，懇請惠予審查，並賜准專利，則實感德便。 In summary, the embodiments of the present invention can achieve the expected use efficiency, and the specific technical means disclosed therein have not been seen in similar products, nor have they been disclosed before the application, and have completely complied with the patent law. The regulations and requirements, the application for invention patents in accordance with the law, and the application for review, and the grant of patents, are truly sensible.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW102117048A TWI506096B (en) | 2013-05-14 | 2013-05-14 | Gel coated with straw powders composition and method for preparation of the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW102117048A TWI506096B (en) | 2013-05-14 | 2013-05-14 | Gel coated with straw powders composition and method for preparation of the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201443163A TW201443163A (en) | 2014-11-16 |
| TWI506096B true TWI506096B (en) | 2015-11-01 |
Family
ID=52423239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102117048A TWI506096B (en) | 2013-05-14 | 2013-05-14 | Gel coated with straw powders composition and method for preparation of the same |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI506096B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967698A (en) * | 2010-10-02 | 2011-02-09 | 山东海龙股份有限公司 | Method for preparing alginate/cellulose composite fibers |
| CN102674561A (en) * | 2012-05-30 | 2012-09-19 | 中国海洋大学 | Preparation method for immobilized spherules for mariculture waste water treatment |
-
2013
- 2013-05-14 TW TW102117048A patent/TWI506096B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967698A (en) * | 2010-10-02 | 2011-02-09 | 山东海龙股份有限公司 | Method for preparing alginate/cellulose composite fibers |
| CN102674561A (en) * | 2012-05-30 | 2012-09-19 | 中国海洋大学 | Preparation method for immobilized spherules for mariculture waste water treatment |
Non-Patent Citations (1)
| Title |
|---|
| 施宇峰，大量製造甲基丙烯酸改質稻殼吸附劑及吸附巴拉刈之研究，學生專題，崑山科技大學高分子材料系，2009 * |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201443163A (en) | 2014-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Use of carboxylated cellulose nanofibrils-filled magnetic chitosan hydrogel beads as adsorbents for Pb (II) | |
| CN103041787B (en) | Preparation method of crosslinked chitosan-manganese dioxide composite adsorbing material | |
| Liakos et al. | 3D printed composites from heat extruded polycaprolactone/sodium alginate filaments and their heavy metal adsorption properties | |
| Liu et al. | Adsorption of Reactive Blue 19 from aqueous solution by chitin nanofiber-/nanowhisker-based hydrogels | |
| Mohammed et al. | Calcium alginate thin films derived from Sargassum natans for the selective adsorption of Cd2+, Cu2+, and Pb2+ ions | |
| CN106732425A (en) | The modified bentonite adsorption material of Quaternary Ammonium Salt of Chitosan and its preparation and the application in Adsorbing Lead Ion in Polluted Water | |
| Zhou et al. | Design of amphoteric bionic fibers by imitating spider silk for rapid and complete removal of low-level multiple heavy metal ions | |
| CN101757892A (en) | Preparation method of bagasse active carbon/ferric oxide | |
| CN109179616A (en) | Natural degradable high-efficiency flocculant and preparation method and application thereof | |
| Zhang et al. | Modification and characterization of hydrogel beads and its used as environmentally friendly adsorbent for the removal of reactive dyes | |
| Lin et al. | Development of an innovative capsule with three-dimension honeycomb architecture via one-step titration-gel method for the removal of methylene blue | |
| Hu et al. | Eco-friendly poly (dopamine)-modified glass microspheres as a novel self-floating adsorbent for enhanced adsorption of tetracycline | |
| CN109942874A (en) | A kind of heavy metal-polluted water process composite sponge and preparation method thereof | |
| CN106238005B (en) | A kind of chitosan-oyster shell complex microsphere and preparation method thereof | |
| CN107583620A (en) | A kind of chitosan-based metal ion adsorbent and preparation method thereof | |
| CN107159157A (en) | Contain heavy metal ion blotting cross-linked chitosan nano fibrous membrane and preparation method thereof | |
| TWI506096B (en) | Gel coated with straw powders composition and method for preparation of the same | |
| CN104289200B (en) | A kind of preparation method and application of magnetic HACC/ oxidation multi-walled carbon nano-tubes adsorbent | |
| JPS61171537A (en) | Gel-like adsorbent | |
| CN109054076A (en) | The preparation method and products obtained therefrom of a kind of three-dimensional porous modified starch and application | |
| CN102060365B (en) | Disposable defluorinating bag for removing fluorine from drinking water | |
| CN101647422A (en) | Composition for improving pond substrate and preparation method thereof | |
| Itodo et al. | Chitosan-starch polymeric blend hydrogels as scavengers of antibiotics from simulated effluent: sorbent characterization and sorption kinetic studies | |
| TW201425226A (en) | Composition comprising microencapsulation of zeolite in alginate and preparation thereof | |
| CN100522345C (en) | Method for embedding adsorbent of poly m-phenylene diamine by using polyvinyl alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |