CN102153665A - Method for preparing high water absorbing gel by using apple residues as raw materials - Google Patents
Method for preparing high water absorbing gel by using apple residues as raw materials Download PDFInfo
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- CN102153665A CN102153665A CN 201110059377 CN201110059377A CN102153665A CN 102153665 A CN102153665 A CN 102153665A CN 201110059377 CN201110059377 CN 201110059377 CN 201110059377 A CN201110059377 A CN 201110059377A CN 102153665 A CN102153665 A CN 102153665A
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Abstract
The invention discloses a method for preparing high water absorbing gel by using apple residues as raw materials. The method comprises the following preparation processes of: drying the apple residues, crushing and screening, soaking the apple residues in a mixed solution of ethanol and NaOH, performing ultrasonic alkalization and microwave irradiation alkalization, adding an etherifying agent, performing ultrasonic etherification and microwave irradiation etherification, adding a cross-linker, performing ultrasonic cross-linking and microwave irradiation cross-linking, regulating a pH value, washing with water, washing with ethanol, filtering and drying to obtain the high water absorbing gel. The water absorbing rate of the high water absorbing gel prepared by using the method can reach 30-100g/g. According to the method for preparing the high water absorbing gel, the apple residues do not need to be thinned and can be used as the raw materials by directly crushing, and the water holding rate of the prepared gel is high compared with a water absorbing material prepared from cellulose.
Description
Technical field
The present invention relates to a kind of method for preparing water absorbent gel, being specifically related to a kind of is the method for feedstock production water absorbent gel with the apple residue.
Background of invention
The a large amount of apple residue of the annual generation of China is except that being applied to the deep processing most abandoneds on a small quantity.According to investigations, Shaanxi Province makes the 15%-20% that accounts for of fertilizer, fuel at present with apple residue, used as fodder be about 10%, when refuse treatment account for 70%, the apple residue of annual nearly 100,000-150,000 t not only wastes, and goes back serious environment pollution.After measured, robust fibre and nitrogen-free extract content are respectively 18.6% and 58.1% in the dry fruit slag, and mainly are starch component in the nitrogen-free extract.At present, cellulose-based, starch is the preparation of class high-absorbent material and the growing interest that performance study has been subjected to domestic and international investigator.
High-absorbent material is widely used in aspects such as chemical industry, agricultural, and is instantly serious day by day in the global environment problem, and high-absorbent material is widely used in aspects such as planting tree in arid area afforestation, farm crop drought resisting especially.For example, China's forest-covered area is little, and the desertification of land area increases, need afforestation, plant careless vegetation, plant trees grow seedlings, soil conservation, need a large amount of high-absorbent materials, and the throughput of China is very low at present, less than 1% of the world.
Summary of the invention
The object of the present invention is to provide a kind of is the method for feedstock production water absorbent gel with the apple residue, crosslinked method prepared water absorbent gel after this method was utilized traditional first etherificate, and in conjunction with utilize the irradiation technique of microwave and ultrasonic wave in medium efficiently propagation characteristic prepare water absorbent gel, than traditional method save time and gellifying property better relatively, for traditional high-absorbent material that utilizes preparation of cellulose, its water retention height.
For achieving the above object, the technical solution used in the present invention is:
1) with the apple residue oven dry, crushing screening, standby;
2) apple residue after will sieving places ethanolic soln to make it form homogeneous system, leaves standstill 5～8h and gets mixed solution to wherein adding sodium hydroxide solution, adding a cover again;
3) with mixed solution behind ultrasonic alkalization 15～30min under the ultrasonic frequency of 60kHz, be microwave intermitant irradiation alkalization 1～2min under the 2450MHz in microwave frequency again;
4) adding the Mono Chloro Acetic Acid etherifying agent in the mixed solution after alkalization, behind ultrasonic etherificate 10～25min under the ultrasonic frequency of 60kHz, is microwave intermitant irradiation etherificate 1～3min under the 2450MHz in microwave frequency again;
5) adding N-N-methylene-bisacrylamide linking agent in the mixed solution after etherificate, behind ultrasonic etherificate 15-30min under the ultrasonic frequency of 60kHz, is microwave intermitant irradiation etherificate 1-4min under the 2450MHz in microwave frequency again;
6) after reaction finished, transferring pH value with Glacial acetic acid was 7;
7) centrifugation reaction product under the rotating speed of 1500r/s discards supernatant liquid, and throw out is washed with water, and is centrifugal again, repeats repeatedly;
8) last, throw out is removed salinity with washing with alcohol, suction filtration with the filter cake oven dry, is pulverized, is sieved, and obtains water absorbent gel.
Described step 2) solid-liquid ratio of apple residue and ethanolic soln is 1: 5～1: 8 (g/ml), and the volume fraction of ethanolic soln is 75～85%, and the solid-liquid ratio of apple residue and sodium hydroxide is 1: 12～1: 18 (g/ml), and the massfraction of sodium hydroxide is 25～35%.
Described hyperacoustic power is 140～200W, and microwave power is 119～200W.
The mass ratio of described Mono Chloro Acetic Acid etherifying agent and sodium hydroxide is 1: 2-3.
The mass ratio of described N-N-methylene-bisacrylamide linking agent and apple residue is 0.03-0.06: 1.
Crossing grit number in the described step 8) is 80～120 orders.
Compared with the prior art the present invention has following advantage:
At first, selected raw material need not to carry out thinning processing, and directly oven dry is pulverized and can be utilized, and reduces cost greatly.And, apple residue is prepared into the comprehensive utilization that water absorbent gel has realized improving its added value.Secondly, crosslinked method prepared high-absorbent material after tradition utilized Mierocrystalline cellulose or starch to adopt first etherificate, adopted usually and stirred the also reaction conditions of controlled temperature.In recent years, also there is the investigator to adopt the microwave exposure method to prepare.And the present invention, microwave and ultrasonic wave coupling are prepared each performance that water absorbent gel not only saves time and also improved product, the water absorbent gel Billy who prepares is the water retention height that feedstock production obtains water-absorbing material with Mierocrystalline cellulose, and the water absorbent rate of the water absorbent gel of the present invention's preparation can reach 30～100g/g.
Description of drawings
The water absorbent gel that Fig. 1 prepares for the present invention, the photo of its gel under various states: (a) water absorbent gel (non-over dry state) not; (b) be in gel under the solvent swelling state after the suction.
Embodiment
Embodiment 1:
1) with the apple residue oven dry, crushing screening, standby;
2) apple residue after will sieving places ethanolic soln to make it form homogeneous system, leaves standstill 5h and gets mixed solution to wherein adding sodium hydroxide solution, adding a cover again; Wherein the solid-liquid ratio of apple residue and ethanolic soln is 1: 8 (g/ml), and the volume fraction of ethanolic soln is 75%, and the solid-liquid ratio of apple residue and sodium hydroxide is 1: 18 (g/ml), and the massfraction of sodium hydroxide is 25%;
3) being that 60kHz, ultrasonic power are under 140～200W behind ultrasonic alkalization 15～30min with mixed solution in ultrasonic frequency, is that 2450MHz, microwave power are microwave intermitant irradiation alkalization 1～2min under 119～200W in microwave frequency again;
4) mass ratio by Mono Chloro Acetic Acid etherifying agent and sodium hydroxide is 1: 3 adding Mono Chloro Acetic Acid etherifying agent in the mixed solution after alkalization, in ultrasonic frequency is that 60kHz, ultrasonic power are under 140～200W behind ultrasonic etherificate 10～25min, is that 2450MHz, microwave power are microwave intermitant irradiation etherificate 1～3min under 119～200W in microwave frequency again;
5) mass ratio by N-N-methylene-bisacrylamide linking agent and apple residue is 0.06: 1 adding N-N-methylene-bisacrylamide linking agent in the mixed solution after etherificate, in ultrasonic frequency is that 60kHz, ultrasonic power are under 140～200W behind the ultrasonic etherificate 15-30min, is that 2450MHz, microwave power are microwave intermitant irradiation etherificate 1-4min under 119～200W in microwave frequency again;
6) after reaction finished, transferring pH value with Glacial acetic acid was 7;
7) centrifugation reaction product under the rotating speed of 1500r/s discards supernatant liquid, and throw out is washed with water, and is centrifugal again, repeats repeatedly;
8) last, throw out is removed salinity with washing with alcohol, suction filtration, with the filter cake oven dry, pulverize, cross 80～120 mesh sieves, obtain water absorbent gel, its water absorbent rate is 78g/g, as seen from Figure 1 the water absorbent gel (a) of the present invention preparation water absorbent gel (non-over dry state) not; (b) be in the water retention height of the gel under the solvent swelling state after the suction.
Embodiment 2:
1) with the apple residue oven dry, crushing screening, standby;
2) apple residue after will sieving places ethanolic soln to make it form homogeneous system, leaves standstill 8h and gets mixed solution to wherein adding sodium hydroxide solution, adding a cover again; Wherein the solid-liquid ratio of apple residue and ethanolic soln is 1: 5 (g/ml), and the volume fraction of ethanolic soln is 85%, and the solid-liquid ratio of apple residue and sodium hydroxide is 1: 12 (g/ml), and the massfraction of sodium hydroxide is 35%;
3) being that 60kHz, ultrasonic power are under 140～200W behind ultrasonic alkalization 15～30min with mixed solution in ultrasonic frequency, is that 2450MHz, microwave power are microwave intermitant irradiation alkalization 1～2min under 119～200W in microwave frequency again;
4) mass ratio by Mono Chloro Acetic Acid etherifying agent and sodium hydroxide is 1: 2 adding Mono Chloro Acetic Acid etherifying agent in the mixed solution after alkalization, in ultrasonic frequency is that 60kHz, ultrasonic power are under 140～200W behind ultrasonic etherificate 10～25min, is that 2450MHz, microwave power are microwave intermitant irradiation etherificate 1～3min under 119～200W in microwave frequency again;
5) mass ratio by N-N-methylene-bisacrylamide linking agent and apple residue is 0.03: 1 adding N-N-methylene-bisacrylamide linking agent in the mixed solution after etherificate, in ultrasonic frequency is that 60kHz, ultrasonic power are under 140～200W behind the ultrasonic etherificate 15-30min, is that 2450MHz, microwave power are microwave intermitant irradiation etherificate 1-4min under 119～200W in microwave frequency again;
6) after reaction finished, transferring pH value with Glacial acetic acid was 7;
7) centrifugation reaction product under the rotating speed of 1500r/s discards supernatant liquid, and throw out is washed with water, and is centrifugal again, repeats repeatedly;
8) last, throw out is removed salinity with washing with alcohol, suction filtration with the filter cake oven dry, is pulverized, is crossed 80～120 mesh sieves, obtains water absorbent gel, and its water absorbent rate is 98g/g.
Embodiment 3:
1) with the apple residue oven dry, crushing screening, standby;
2) apple residue after will sieving places ethanolic soln to make it form homogeneous system, leaves standstill 7h and gets mixed solution to wherein adding sodium hydroxide solution, adding a cover again; Wherein the solid-liquid ratio of apple residue and ethanolic soln is 1: 6 (g/ml), and the volume fraction of ethanolic soln is 83%, and the solid-liquid ratio of apple residue and sodium hydroxide is 1: 14 (g/ml), and the massfraction of sodium hydroxide is 32%;
3) being that 60kHz, ultrasonic power are under 140～200W behind ultrasonic alkalization 15～30min with mixed solution in ultrasonic frequency, is that 2450MHz, microwave power are microwave intermitant irradiation alkalization 1～2min under 119～200W in microwave frequency again;
4) mass ratio by Mono Chloro Acetic Acid etherifying agent and sodium hydroxide is 1: 2.3 adding Mono Chloro Acetic Acid etherifying agent in the mixed solution after alkalization, in ultrasonic frequency is that 60kHz, ultrasonic power are under 140～200W behind ultrasonic etherificate 10～25min, is that 2450MHz, microwave power are microwave intermitant irradiation etherificate 1～3min under 119～200W in microwave frequency again;
5) mass ratio by N-N-methylene-bisacrylamide linking agent and apple residue is 0.05: 1 adding N-N-methylene-bisacrylamide linking agent in the mixed solution after etherificate, in ultrasonic frequency is that 60kHz, ultrasonic power are under 140～200W behind the ultrasonic etherificate 15-30min, is that 2450MHz, microwave power are microwave intermitant irradiation etherificate 1-4min under 119～200W in microwave frequency again;
6) after reaction finished, transferring pH value with Glacial acetic acid was 7;
7) centrifugation reaction product under the rotating speed of 1500r/s discards supernatant liquid, and throw out is washed with water, and is centrifugal again, repeats repeatedly;
8) last, throw out is removed salinity with washing with alcohol, suction filtration with the filter cake oven dry, is pulverized, is crossed 80～120 mesh sieves, obtains water absorbent gel, and its water absorbent rate is 56g/g.
Embodiment 4:
1) with the apple residue oven dry, crushing screening, standby;
2) apple residue after will sieving places ethanolic soln to make it form homogeneous system, leaves standstill 6h and gets mixed solution to wherein adding sodium hydroxide solution, adding a cover again; Wherein the solid-liquid ratio of apple residue and ethanolic soln is 1: 7 (g/ml), and the volume fraction of ethanolic soln is 78%, and the solid-liquid ratio of apple residue and sodium hydroxide is 1: 16 (g/ml), and the massfraction of sodium hydroxide is 28%;
3) being that 60kHz, ultrasonic power are under 140～200W behind ultrasonic alkalization 15～30min with mixed solution in ultrasonic frequency, is that 2450MHz, microwave power are microwave intermitant irradiation alkalization 1～2min under 119～200W in microwave frequency again;
4) mass ratio by Mono Chloro Acetic Acid etherifying agent and sodium hydroxide is 1: 2.7 adding Mono Chloro Acetic Acid etherifying agent in the mixed solution after alkalization, in ultrasonic frequency is that 60kHz, ultrasonic power are under 140～200W behind ultrasonic etherificate 10～25min, is that 2450MHz, microwave power are microwave intermitant irradiation etherificate 1～3min under 119～200W in microwave frequency again;
5) mass ratio by N-N-methylene-bisacrylamide linking agent and apple residue is 0.04: 1 adding N-N-methylene-bisacrylamide linking agent in the mixed solution after etherificate, in ultrasonic frequency is that 60kHz, ultrasonic power are under 140～200W behind the ultrasonic etherificate 15-30min, is that 2450MHz, microwave power are microwave intermitant irradiation etherificate 1-4min under 119～200W in microwave frequency again;
6) after reaction finished, transferring pH value with Glacial acetic acid was 7;
7) centrifugation reaction product under the rotating speed of 1500r/s discards supernatant liquid, and throw out is washed with water, and is centrifugal again, repeats repeatedly;
8) last, throw out is removed salinity with washing with alcohol, suction filtration with the filter cake oven dry, is pulverized, is crossed 80～120 mesh sieves, obtains water absorbent gel, and its water absorbent rate is 82g/g.
Claims (6)
1. one kind is the method for feedstock production water absorbent gel with the apple residue, it is characterized in that:
1) with the apple residue oven dry, crushing screening, standby;
2) apple residue after will sieving places ethanolic soln to make it form homogeneous system, leaves standstill 5～8h and gets mixed solution to wherein adding sodium hydroxide solution, adding a cover again;
3) with mixed solution behind ultrasonic alkalization 15～30min under the ultrasonic frequency of 60kHz, be microwave intermitant irradiation alkalization 1～2min under the 2450MHz in microwave frequency again;
4) adding the Mono Chloro Acetic Acid etherifying agent in the mixed solution after alkalization, behind ultrasonic etherificate 10～25min under the ultrasonic frequency of 60kHz, is microwave intermitant irradiation etherificate 1～3min under the 2450MHz in microwave frequency again;
5) adding N-N-methylene-bisacrylamide linking agent in the mixed solution after etherificate, behind ultrasonic etherificate 15-30min under the ultrasonic frequency of 60kHz, is microwave intermitant irradiation etherificate 1-4min under the 2450MHz in microwave frequency again;
6) after reaction finished, transferring pH value with Glacial acetic acid was 7;
7) centrifugation reaction product under the rotating speed of 1500r/s discards supernatant liquid, and throw out is washed with water, and is centrifugal again, repeats repeatedly;
8) last, throw out is removed salinity with washing with alcohol, suction filtration with the filter cake oven dry, is pulverized, is sieved, and obtains water absorbent gel.
2. according to claim a kind is the method for feedstock production water absorbent gel with the apple residue, it is characterized in that: described step 2) solid-liquid ratio of apple residue and ethanolic soln is 1: 5～1: 8 (g/ml), the volume fraction of ethanolic soln is 75～85%, the solid-liquid ratio of apple residue and sodium hydroxide is 1: 12～1: 18 (g/ml), and the massfraction of sodium hydroxide is 25～35%.
3. according to claim a kind is the method for feedstock production water absorbent gel with the apple residue, and it is characterized in that: described hyperacoustic power is 140～200W, and microwave power is 119～200W.
4. according to claim a kind is the method for feedstock production water absorbent gel with the apple residue, and it is characterized in that: the mass ratio of described Mono Chloro Acetic Acid etherifying agent and sodium hydroxide is 1: 2-3.
5. according to claim a kind is the method for feedstock production water absorbent gel with the apple residue, and it is characterized in that: the mass ratio of described N-N-methylene-bisacrylamide linking agent and apple residue is 0.03-0.06: 1.
6. according to claim a kind is the method for feedstock production water absorbent gel with the apple residue, it is characterized in that: crossing grit number in the described step 8) is 80～120 orders.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553784A (en) * | 2018-12-06 | 2019-04-02 | 陕西科技大学 | A kind of apple pomace cellulose-oxycellulose composite hydrogel and preparation method thereof |
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| CN1554692A (en) * | 2003-12-23 | 2004-12-15 | 哈尔滨工业大学 | Process for microwave radiation synthesizing cellulose base high water absorption resin |
| US20080227944A1 (en) * | 2004-12-29 | 2008-09-18 | Luigi Ambrosio | Biodegradable, Super Absorbent Polymer Hydrogels and a Method For Their Preparation |
| CN101367878A (en) * | 2008-07-24 | 2009-02-18 | 吴茂玉 | Method for preparing high-viscosity sodium carboxymethylcellulose with apple residue |
| CN101735396A (en) * | 2009-12-31 | 2010-06-16 | 陕西科技大学 | Method for preparing super absorbent resin by using wheat straw |
| CN101768241A (en) * | 2010-03-18 | 2010-07-07 | 绥化学院 | Method for preparing high-water-absorptivity resin by using ultrasonic irradiation |
| CN101871189A (en) * | 2009-04-25 | 2010-10-27 | 刘利军 | Nutritive absorbent resin seedling raising paper and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554692A (en) * | 2003-12-23 | 2004-12-15 | 哈尔滨工业大学 | Process for microwave radiation synthesizing cellulose base high water absorption resin |
| US20080227944A1 (en) * | 2004-12-29 | 2008-09-18 | Luigi Ambrosio | Biodegradable, Super Absorbent Polymer Hydrogels and a Method For Their Preparation |
| CN101367878A (en) * | 2008-07-24 | 2009-02-18 | 吴茂玉 | Method for preparing high-viscosity sodium carboxymethylcellulose with apple residue |
| CN101871189A (en) * | 2009-04-25 | 2010-10-27 | 刘利军 | Nutritive absorbent resin seedling raising paper and preparation method thereof |
| CN101735396A (en) * | 2009-12-31 | 2010-06-16 | 陕西科技大学 | Method for preparing super absorbent resin by using wheat straw |
| CN101768241A (en) * | 2010-03-18 | 2010-07-07 | 绥化学院 | Method for preparing high-water-absorptivity resin by using ultrasonic irradiation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553784A (en) * | 2018-12-06 | 2019-04-02 | 陕西科技大学 | A kind of apple pomace cellulose-oxycellulose composite hydrogel and preparation method thereof |
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