CN115093508A - Corn stalk cellulose sludge-based biochar-based composite super absorbent resin - Google Patents
Corn stalk cellulose sludge-based biochar-based composite super absorbent resin Download PDFInfo
- Publication number
- CN115093508A CN115093508A CN202210825357.8A CN202210825357A CN115093508A CN 115093508 A CN115093508 A CN 115093508A CN 202210825357 A CN202210825357 A CN 202210825357A CN 115093508 A CN115093508 A CN 115093508A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- biochar
- absorbent resin
- super absorbent
- corn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 240000008042 Zea mays Species 0.000 title claims abstract description 63
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 title claims abstract description 63
- 235000002017 Zea mays subsp mays Nutrition 0.000 title claims abstract description 63
- 235000005822 corn Nutrition 0.000 title claims abstract description 63
- 239000001913 cellulose Substances 0.000 title claims abstract description 62
- 229920002678 cellulose Polymers 0.000 title claims abstract description 61
- 239000011347 resin Substances 0.000 title claims abstract description 41
- 229920005989 resin Polymers 0.000 title claims abstract description 41
- 239000002250 absorbent Substances 0.000 title claims abstract description 33
- 230000002745 absorbent Effects 0.000 title claims abstract description 33
- 239000010802 sludge Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010902 straw Substances 0.000 claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 229920002488 Hemicellulose Polymers 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 9
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 8
- 229960002218 sodium chlorite Drugs 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000010559 graft polymerization reaction Methods 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000013021 overheating Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 238000004132 cross linking Methods 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003898 horticulture Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical class OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the technical field of high polymer materials and agricultural biology, in particular to a corn straw cellulose sludge-based biochar-based composite super absorbent resin, which comprises the following steps: s1, extracting corn stalk cellulose, S2, preparing modified porous biochar, S3 and carrying out polymerization reaction, wherein the corn stalk cellulose sludge-based biochar-based composite super absorbent resin is prepared by taking corn stalks as raw materials, so that waste corn stalks can be quickly treated, a large number of crystallization areas in the corn stalk cellulose are damaged, the cellulose is easier to modify in the subsequent process, the liquid absorption rate is accelerated, and the gel strength and the water absorption rate of the resin after water absorption are improved; the cross-linked resin has more cross-linked positions, so that the structure of a cross-linked network is changed, the method is different from the conventional inorganic additive doping, the system viscosity is low in the polymerization process, the monomers and the polymer are uniformly mixed, the heat transfer is easy, the temperature is controllable, and the local overheating is avoided.
Description
Technical Field
The invention relates to the technical field of high polymer materials and agricultural biology, in particular to a corn straw cellulose sludge-based biochar-based composite super absorbent resin.
Background
The super absorbent resin as a high polymer material with a three-dimensional reticular aperture structure has high water absorption and water retention performance, is widely applied to the fields of agriculture, forestry and horticulture, medical sanitation, petrochemical industry, building materials, intelligent manufacturing and the like, and is mainly used for fertilizer slow release, medicine slow release, water absorption and retention, breeding and seedling culture and the like in agriculture, forestry and horticulture. However, at present, the backbone structure of the super absorbent resin is mostly made of petroleum resources, has weak degradability, and is also an unrenewable resource from the sustainable development perspective, and therefore, the development of natural cellulose-based super absorbent resin draws much attention.
The preparation method of the natural cellulose-based super absorbent resin generally selects a polymerizable monomer containing hydrophilic groups such as sulfonic acid group, carboxyl group, hydroxyl group, cyano group and amide to graft and modify natural cellulose. A great deal of literature reports that various natural polysaccharides including cellulose are grafted and modified to prepare super absorbent resin, and the main functions of the super absorbent resin are water absorption and water retention. The super absorbent resin is prepared by grafting and modifying most of the plant tree cellulose or carboxymethyl cellulose such as flax, bagasse cellulose, tea leaves, wheat straws, rice straws, banana barks, peanut shells, palms and the like by hydrophilic monomers such as acrylic acid, acrylamide, polyvinyl alcohol, allyl sulfonic acid derivatives and the like, has the functions of drying, water absorption, water retention, slow release, fire prevention and the like, has a wide application prospect, and has important scientific significance and strategic significance for sustainable development.
At present, the method for preparing the corn straw cellulose sludge-based biochar-based composite super absorbent resin by taking corn straws as raw materials is lacked, so that the discarded corn straws are quickly treated, a large number of crystallization areas in the corn straw cellulose are damaged, the cellulose is easier to modify in the follow-up process, the liquid absorption rate is accelerated, and the gel strength and the water absorption rate of the resin after water absorption are improved; the crosslinking resin has more crosslinking positions, so that the structure of a crosslinking network is changed, the problem of the doping of the traditional inorganic additive is distinguished, and on the premise of ensuring low system viscosity in the polymerization process, the monomer and the polymer are mixed uniformly, the heat transfer is easy, and the temperature is controllable, so that the problem of local overheating is solved.
In conclusion, the problems are solved by designing the corn straw cellulose sludge-based biochar-based composite super absorbent resin.
Disclosure of Invention
The invention aims to provide a corn straw cellulose sludge-based biochar-based composite super absorbent resin to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a corn stalk cellulose sludge-based biochar-based composite super absorbent resin comprises the following steps:
s1, extracting the cornstalk cellulose, wherein the extraction of the cornstalk cellulose comprises the following specific steps:
1) alkali treatment: crushing a corn straw crusher, sieving with a 60-mesh sieve, weighing corn straw residues sieved with the 60-mesh sieve, adding 8-10% by mass of a sodium hydroxide solution into the corn straw residues, carrying out water bath at 60-80 ℃, extracting for 90-150 min, stirring at the speed of 300-500 r/min, carrying out suction filtration and washing until the pH is =7, adding deionized water, removing residual sugar in the water bath at 80 ℃, and finally drying and storing to obtain hemicellulose;
2) acid treatment: weighing 5g of corn straw residue without hemicellulose, 100mL of deionized water, 1.0-2.0 g of sodium chlorite and 5-20 mL of acetic acid, reacting in an ultrasonic catalytic extractor, wherein the ultrasonic power is set to 220-250W, the extraction temperature is 60-80 ℃, reacting for 60-90 min, the stirring speed is 300-800 r/min, washing with deionized water until the pH value is =7, and drying at 60 ℃ to obtain cellulose;
s2, preparing modified porous biochar: putting the sludge-based biochar solid into a ball mill, adding triethanolamine and ethanolamine, ball milling for 30-60 min, washing with deionized water, and drying at 50-60 ℃ to obtain porous biochar; weighing the dried porous biochar, adding 5% methyltrimethoxysilane aqueous solution, stirring with a stirrer at the rotation speed of 500rpm for 30min, standing at room temperature for 24h, washing with deionized water for 5 times, centrifugally dewatering at 100 ℃, drying, grinding into powder particles, and sieving with a 120-mesh sieve to obtain the modified porous biochar
S3, polymerization: weighing corn straw cellulose and modified porous biochar, adding deionized water, introducing N2 as protective gas, gelatinizing in a water bath at 68 ℃, adding an initiator ammonium persulfate, a cross-linking agent N, N' -methylene bisacrylamide, acrylic acid AA and acrylamide, performing a graft polymerization reaction in a nitrogen atmosphere in the water bath at 55-75 ℃ to obtain the corn straw cellulose/modified porous biochar-based super absorbent resin; the mass ratio of corn straw cellulose to acrylic acid is 1: 3-1: 5, the neutralization degree of acrylic acid is 65-80%, the mass ratio of cellulose to acrylamide is 1: 2-1: 4, the mass of ammonium persulfate is 1% -3% of the total mass of acrylic acid and acrylamide, the mass of N, N' -methylene-bis-acrylamide is 0.2% -1.2% of the total mass of acrylic acid and acrylamide, and the mass ratio of corn straw cellulose to modified porous charcoal is 1: 0.1-1: 1.
In a preferable scheme of the invention, the hemicellulose removal and extraction time in the S1 is 120min, the stirring speed is 500r/min, and the extraction temperature is 60 ℃.
In a preferred embodiment of the present invention, the sodium chlorite in S1 is 1.5g, the acetic acid is 10mL, the extraction temperature is 70 ℃, the reaction time is 60min, and the stirring speed is 500 r/min.
In a preferred embodiment of the present invention, the mass ratio of the corn straw stalk cellulose to the acrylamide in S3 is 1: 2.
In a preferred embodiment of the present invention, the mass of ammonium persulfate in S3 is 1.2% of the total mass of acrylic acid and acrylamide.
In a preferred embodiment of the present invention, the mass of N, N' -methylenebisacrylamide in S3 is 0.5% of the total mass of acrylic acid and acrylamide.
In a preferable scheme of the invention, the neutralization degree of AA acrylic acid and sodium hydroxide solution in S3 is adjusted to 65-80%.
Compared with the prior art, the invention has the beneficial effects that:
1. in the invention, rich corn straws are used as raw materials to extract cellulose, so that a channel is opened up for utilizing farmland waste corn straws, and the sustainable development of rural economy is promoted; the corn stalks are treated by using the ultrasonic-assisted acidic sodium chlorite, so that the method is quick and efficient, the hemicellulose and lignin in the corn stalks can be removed in a short time, and a large number of crystallization areas in the corn stalk cellulose are damaged, so that the cellulose is easier to modify in the subsequent process.
2. According to the invention, by utilizing the characteristics of excellent pore structure, larger specific surface area, strong adsorption capacity, natural activity and low price of the sludge-based biochar, from the perspective of molecular structure design, the high water absorption composite material with the sludge-based activated carbon/corn straw cellulose-based organic/inorganic interpenetrating network structure and the porous structure is prepared, so that the liquid absorption rate is accelerated, the gel strength and the water absorption rate of the resin after water absorption are improved, and the research result has important significance for promoting economic sustainable development.
3. In the invention, the addition of the modified sludge-based activated carbon enables the crosslinked resin to have more crosslinking positions, and the adjustment of the consumption of the sludge-based activated carbon can change the structure of a crosslinking network, combine with acrylic acid and the like in a chemical bond manner, and is different from the conventional inorganic additive doping.
4. In the invention, the aqueous solution graft polymerization is carried out within the operation range, the viscosity of the system is low in the polymerization process, the monomers and the polymers are uniformly mixed, the heat transfer is easy, the temperature is controllable, the local overheating can be avoided, and the large-scale production can be realized.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments, and based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
The invention provides a technical scheme that:
a corn stalk cellulose sludge-based biochar-based composite super absorbent resin comprises the following steps:
(1) extracting corn stalk cellulose:
step one, alkali treatment: crushing a corn straw crusher, sieving with a 60-mesh sieve, weighing corn straw residues sieved with the 60-mesh sieve, adding 8-10% by mass of a sodium hydroxide solution into the corn straw residues, carrying out water bath at 60-80 ℃, extracting for 90-150 min, stirring at the speed of 300-500 r/min, carrying out suction filtration and washing until the pH is =7, adding deionized water, removing residual sugar in the water bath at 80 ℃, and finally drying and storing to obtain hemicellulose;
step (2) diacid treatment: weighing 5g of corn straw residue without hemicellulose, 100mL of deionized water, 1.0-2.0 g of sodium chlorite and 5-20 mL of acetic acid, reacting in an ultrasonic catalytic extractor, wherein the ultrasonic power is set to 220-250W, the extraction temperature is 60-80 ℃, reacting for 60-90 min, the stirring speed is 300-800 r/min, washing with deionized water until the pH value is =7, and drying at 60 ℃ to obtain cellulose;
(2) preparing modified porous biochar: putting the sludge-based biochar solid into a ball mill, adding triethanolamine and ethanolamine, ball milling for 30-60 min, washing with deionized water, and drying at 50-60 ℃ to obtain porous biochar; weighing the dried porous biochar, adding a 5% methyltrimethoxysilane aqueous solution, stirring by using a stirrer at the rotating speed of 500rpm for 30min, standing at room temperature for 24h, washing for 5 times by using deionized water, centrifugally dewatering, drying at 100 ℃, grinding into powdery particles, and sieving by using a 120-mesh sieve to obtain the modified porous biochar;
(3) polymerization reaction: weighing corn straw cellulose and modified porous biochar, adding deionized water, introducing N2 as protective gas, gelatinizing in a water bath at 68 ℃, then adding an initiator ammonium persulfate, a cross-linking agent N, N' -methylene bisacrylamide, acrylic acid AA (the neutralization degree is adjusted to 65-80 percent by a sodium hydroxide solution) and acrylamide, performing a graft polymerization reaction in a water bath at 55-75 ℃ under the nitrogen atmosphere to obtain the corn straw cellulose/modified porous biochar-based super absorbent resin; the mass ratio of corn straw cellulose to acrylic acid is 1: 3-1: 5, the neutralization degree of acrylic acid is 65-80%, the mass ratio of cellulose to acrylamide is 1: 2-1: 4, the mass of ammonium persulfate is 1% -3% of the total mass of acrylic acid and acrylamide, the mass of N, N' -methylene-bis-acrylamide is 0.2% -1.2% of the total mass of acrylic acid and acrylamide, and the mass ratio of corn straw cellulose to modified porous charcoal is 1: 0.1-1: 1.
The specific implementation mode is as follows: in the preparation method of the composite super absorbent resin, the extraction time for removing the hemicellulose in the step (1) is 120min, the stirring speed is 500r/min, and the extraction temperature is 60 ℃.
Further, in the preparation method of the composite super absorbent resin, in the step (1), the amount of sodium chlorite removed by lignin is 1.5g, the amount of acetic acid is 10mL, the extraction temperature is 70 ℃, the reaction is carried out for 60min, and the stirring speed is 500 r/min.
Further, in the preparation method of the composite super absorbent resin, the mass ratio of the corn straw cellulose to the acrylamide in the step (3) is 1: 2.
Further, in the above method for producing a composite super absorbent resin, the mass of ammonium persulfate in the step (3) is 1.2% of the total mass of acrylic acid and acrylamide.
Further, in the above method for producing a composite super absorbent resin, the mass of N, N' -methylenebisacrylamide in step (3) is 0.5% of the total mass of acrylic acid and acrylamide.
Therefore, the composite super absorbent resin product produced according to the steps has the water absorption multiplying power of over 860g/g and the salt (0.9 wt.% NaCl) absorption multiplying power of over 135g/g, and achieves the following effects:
1) the scheme takes rich corn straws as raw materials to extract cellulose, opens up a channel for utilizing farmland waste corn straws, and promotes the sustainable development of rural economy; the corn straws are treated by using the ultrasonic-assisted acidic sodium chlorite, so that the method is quick and efficient, the hemicellulose and the lignin in the corn straws can be removed in a short time, and a large number of crystallization areas in the corn straw cellulose are damaged, so that the cellulose is easier to modify in the follow-up process;
2) according to the scheme, the characteristics of excellent pore structure, larger specific surface area, strong adsorption capacity, natural activity and low price of the sludge-based biochar are utilized, and from the perspective of molecular structure design, the high water absorption composite material with the sludge-based activated carbon/corn straw cellulose-based organic/inorganic interpenetrating network structure and the porous structure is prepared, so that the liquid absorption rate is increased, the gel strength and the water absorption rate of the resin after water absorption are improved, and the research result has important significance for promoting economic sustainable development;
3) in the scheme, the addition of the modified sludge-based activated carbon is utilized, so that the crosslinked resin has more crosslinking positions, the structure of a crosslinking network can be changed by adjusting the using amount of the sludge-based activated carbon, and the modified sludge-based activated carbon is combined with acrylic acid and the like in a chemical bond manner, so that the modified sludge-based activated carbon is different from the conventional inorganic additive doping;
4) the aqueous solution graft polymerization of the scheme is in an operation range, the viscosity of a system is low in the polymerization process, the monomers and the polymers are uniformly mixed, the heat transfer is easy, the temperature is controllable, the local overheating can be avoided, and the large-scale production can be realized.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A corn stalk cellulose sludge-based biochar-based composite super absorbent resin comprises the following steps:
s1, extracting the cornstalk cellulose, wherein the extraction of the cornstalk cellulose comprises the following specific steps:
1) alkali treatment: crushing a corn straw crusher, sieving with a 60-mesh sieve, weighing corn straw residues after sieving with the 60-mesh sieve, adding 8-10% by mass of a sodium hydroxide solution, carrying out water bath at 60-80 ℃, extracting for 90-150 min, stirring at the speed of 300-500 r/min, carrying out suction filtration washing until the pH is =7, adding deionized water, removing residual sugar in the water bath at 80 ℃, and finally drying and storing to obtain hemicellulose;
2) acid treatment: weighing 5g of corn straw residue without hemicellulose, 100mL of deionized water, 1.0-2.0 g of sodium chlorite and 5-20 mL of acetic acid, reacting in an ultrasonic catalytic extractor, wherein the ultrasonic power is set to be 220-250W, the extraction temperature is 60-80 ℃, the reaction time is 60-90 min, the stirring speed is 300-800 r/min, washing is carried out by adopting deionized water until the pH value is =7, and drying is carried out at 60 ℃ to obtain cellulose;
s2, preparing the modified porous biochar: putting the sludge-based biochar solid into a ball mill, adding triethanolamine and ethanolamine, ball milling for 30-60 min, washing with deionized water, and drying at 50-60 ℃ to obtain porous biochar; weighing the dried porous biochar, adding 5% methyltrimethoxysilane aqueous solution, stirring with a stirrer at the rotation speed of 500rpm for 30min, standing at room temperature for 24h, washing with deionized water for 5 times, centrifugally dewatering at 100 ℃, drying, grinding into powder particles, and sieving with a 120-mesh sieve to obtain the modified porous biochar
S3, polymerization: weighing corn straw cellulose and modified porous biochar, adding deionized water, introducing N2 as protective gas, gelatinizing in a water bath at 68 ℃, adding an initiator ammonium persulfate, a cross-linking agent N, N' -methylene bisacrylamide, acrylic acid AA and acrylamide, performing a graft polymerization reaction in a nitrogen atmosphere in the water bath at 55-75 ℃ to obtain the corn straw cellulose/modified porous biochar-based super absorbent resin; the mass ratio of corn straw cellulose to acrylic acid is 1: 3-1: 5, the neutralization degree of acrylic acid is 65-80%, the mass ratio of cellulose to acrylamide is 1: 2-1: 4, the mass of ammonium persulfate is 1-3% of the total mass of acrylic acid and acrylamide, the mass of N, N' -methylene bisacrylamide is 0.2-1.2% of the total mass of acrylic acid and acrylamide, and the mass ratio of corn straw cellulose to modified porous biochar is 1: 0.1-1: 1.
2. The corn stalk cellulose sludge-based biochar-based composite super absorbent resin as claimed in claim 1, wherein the hemicellulose removal and extraction time in S1 is 120min, the stirring speed is 500r/min, and the extraction temperature is 60 ℃.
3. The corn stalk cellulose sludge-based biochar-based composite super absorbent resin as claimed in claim 1, wherein the amount of sodium chlorite used in S1 is 1.5g, the amount of acetic acid used is 10mL, the extraction temperature is 70 ℃, the reaction time is 60min, and the stirring speed is 500 r/min.
4. The corn stalk cellulose sludge-based biochar-based composite super absorbent resin as claimed in claim 1, wherein the mass ratio of corn stalk cellulose to acrylamide in S3 is 1: 2.
5. The corn stalk cellulose sludge-based biochar-based composite super absorbent resin as claimed in claim 1, wherein the mass of ammonium persulfate in S3 is 1.2% of the total mass of acrylic acid and acrylamide.
6. The corn stalk cellulose sludge-based biochar-based composite super absorbent resin as claimed in claim 1, wherein the mass of N, N' -methylene bisacrylamide in S3 is 0.5% of the total mass of acrylic acid and acrylamide.
7. The corn stalk cellulose sludge-based biochar-based composite super absorbent resin as claimed in claim 1, wherein neutralization degree of AA acrylic acid and sodium hydroxide solution in S3 is adjusted to 65-80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210825357.8A CN115093508A (en) | 2022-07-14 | 2022-07-14 | Corn stalk cellulose sludge-based biochar-based composite super absorbent resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210825357.8A CN115093508A (en) | 2022-07-14 | 2022-07-14 | Corn stalk cellulose sludge-based biochar-based composite super absorbent resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115093508A true CN115093508A (en) | 2022-09-23 |
Family
ID=83297555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210825357.8A Pending CN115093508A (en) | 2022-07-14 | 2022-07-14 | Corn stalk cellulose sludge-based biochar-based composite super absorbent resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115093508A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117229101A (en) * | 2023-09-06 | 2023-12-15 | 齐齐哈尔大学 | Preparation method of modified corn stalk cellulose gel slow release fertilizer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1063237A (en) * | 1964-04-02 | 1967-03-30 | Gen Aniline & Film Corp | Improvements in or relating to photopolymerization of vinylidene and vinyl monomers |
| JP2009185216A (en) * | 2008-02-07 | 2009-08-20 | San-Dia Polymer Ltd | Absorbent resin particle and method of producing the same |
| CN104109221A (en) * | 2014-07-08 | 2014-10-22 | 中国农业科学院农业环境与可持续发展研究所 | Synthetic method of cellulose grafted cyclodextrin high molecular water-absorbent resin |
| CN112500530A (en) * | 2020-10-30 | 2021-03-16 | 广西大学 | Calcium carbonate/bagasse cellulose-based super absorbent resin and preparation method thereof |
-
2022
- 2022-07-14 CN CN202210825357.8A patent/CN115093508A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1063237A (en) * | 1964-04-02 | 1967-03-30 | Gen Aniline & Film Corp | Improvements in or relating to photopolymerization of vinylidene and vinyl monomers |
| JP2009185216A (en) * | 2008-02-07 | 2009-08-20 | San-Dia Polymer Ltd | Absorbent resin particle and method of producing the same |
| CN104109221A (en) * | 2014-07-08 | 2014-10-22 | 中国农业科学院农业环境与可持续发展研究所 | Synthetic method of cellulose grafted cyclodextrin high molecular water-absorbent resin |
| CN112500530A (en) * | 2020-10-30 | 2021-03-16 | 广西大学 | Calcium carbonate/bagasse cellulose-based super absorbent resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117229101A (en) * | 2023-09-06 | 2023-12-15 | 齐齐哈尔大学 | Preparation method of modified corn stalk cellulose gel slow release fertilizer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112500530B (en) | Calcium carbonate/bagasse cellulose-based super absorbent resin and preparation method thereof | |
| CN102961777B (en) | Method for preparing porous compound type high permeability absorption hemostasis coating with modified nano-crystalline cellulose | |
| CN102417548B (en) | Method for extracting active polysaccharides from brown algae | |
| CN108976440B (en) | Method for preparing hydrogel from bagasse hemicellulose | |
| CN101519476A (en) | Method for preparing high-hydroscopicity resin in homogeneous aqueous medium by using straw as raw material | |
| CN103224635A (en) | Preparation method of compound-type starch modification super absorbent resin | |
| CN102344532A (en) | Method for synthesizing super absorbent resin by using invasive plant | |
| CN104788619A (en) | Star-netted organic-inorganic composite super absorbent and preparation method thereof | |
| CN101670276A (en) | Amorphophallus glucomannan drying agent and preparation method thereof | |
| WO2021184566A1 (en) | Chitin polyester master batch and preparation process therefor | |
| CN101691416B (en) | Method for preparing super absorbent resin with cross-linked structure from potato starch phosphate graft co-polymeric acrylic acid and sodium salt thereof | |
| CN107337764A (en) | The preparation method and application of the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group | |
| CN103183742A (en) | Sodium alginate containing high molecular weight polyguluronic acid and application thereof | |
| CN113480694A (en) | Enzyme catalysis graft modified cotton pulp cellulose and method for preparing regenerated bioplastic by using same | |
| CN108329403A (en) | A kind of efficient pectous extracting method | |
| CN110028624A (en) | Preparation method and application based on hemicellulose compound temperature-sensitive gel | |
| CN107759735A (en) | A kind of water-insoluble hemicellulose grafted polyacrylamide and its preparation and application | |
| CN115093508A (en) | Corn stalk cellulose sludge-based biochar-based composite super absorbent resin | |
| Yang et al. | Categories and application fields and manufacturing process and action mechanism of water retaining agent | |
| CN115109377A (en) | Wheat straw cellulose sludge-based biochar-based super absorbent resin | |
| CN110734553A (en) | Preparation method of degradable super absorbent resins | |
| CN105622869A (en) | Preparation method of wood fiber temperature sensitive type semi-interpenetrating network gel material | |
| CN102178691B (en) | Starch stypticum and preparation method thereof | |
| CN114045316A (en) | Modified cereal dietary fiber and preparation method thereof | |
| CN102649833B (en) | Method for preparing superabsorbent resin based on waste woody plant branches |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220923 |
|
| RJ01 | Rejection of invention patent application after publication |