CN114920606B - Preparation method of adsorption type degradable soil moisture conservation slow release fertilizer based on modified wheat straw - Google Patents
Preparation method of adsorption type degradable soil moisture conservation slow release fertilizer based on modified wheat straw Download PDFInfo
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- CN114920606B CN114920606B CN202210452288.0A CN202210452288A CN114920606B CN 114920606 B CN114920606 B CN 114920606B CN 202210452288 A CN202210452288 A CN 202210452288A CN 114920606 B CN114920606 B CN 114920606B
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- 239000010902 straw Substances 0.000 title claims abstract description 112
- 239000003337 fertilizer Substances 0.000 title claims abstract description 52
- 241000209140 Triticum Species 0.000 title claims abstract description 49
- 235000021307 Triticum Nutrition 0.000 title claims abstract description 49
- 239000002689 soil Substances 0.000 title claims abstract description 39
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920005610 lignin Polymers 0.000 claims abstract description 41
- 229920002678 cellulose Polymers 0.000 claims abstract description 38
- 239000001913 cellulose Substances 0.000 claims abstract description 38
- 239000003463 adsorbent Substances 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 235000015097 nutrients Nutrition 0.000 claims abstract description 8
- 238000007385 chemical modification Methods 0.000 claims abstract description 4
- 239000002154 agricultural waste Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 102
- 239000000243 solution Substances 0.000 claims description 89
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000000017 hydrogel Substances 0.000 claims description 36
- 229920002125 Sokalan® Polymers 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 229910052625 palygorskite Inorganic materials 0.000 claims description 35
- 239000002114 nanocomposite Substances 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 26
- 239000004584 polyacrylic acid Substances 0.000 claims description 25
- 229920001732 Lignosulfonate Polymers 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 235000019357 lignosulphonate Nutrition 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- 229920001661 Chitosan Polymers 0.000 claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 229920002488 Hemicellulose Polymers 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- ALNUPAIRBMNLLB-UHFFFAOYSA-M dodecyl-dimethyl-(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1CO1 ALNUPAIRBMNLLB-UHFFFAOYSA-M 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 4
- 229940106681 chloroacetic acid Drugs 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 229920001277 pectin Polymers 0.000 claims description 4
- 239000001814 pectin Substances 0.000 claims description 4
- 235000010987 pectin Nutrition 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 4
- 229960002218 sodium chlorite Drugs 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 238000005481 NMR spectroscopy Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- -1 dodecyl dimethyl tertiary amine Chemical class 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000007781 pre-processing Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- 206010016807 Fluid retention Diseases 0.000 description 5
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/003—Pulping cellulose-containing materials with organic 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
-
- 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
- D21C3/06—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides sulfur dioxide; sulfurous acid; bisulfites sulfites
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Soil Sciences (AREA)
- Sustainable Development (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method of an adsorption type degradable soil moisture conservation slow release fertilizer based on modified wheat straw. The preparation method of the adsorption type degradable soil moisture conservation slow release fertilizer based on the modified wheat straw comprises the steps of firstly, preprocessing the wheat straw, separating and extracting to obtain cellulose and lignin, and preparing the amphoteric straw adsorbent by a chemical modification method; the adsorbent is utilized to adsorb and remove NH4+ and H2P 04-from the aqueous solution, the adsorbent containing nitrogen and phosphorus nutrients is recovered, and finally the adsorbent is used as a multifunctional soil moisture conservation slow release compound fertilizer. According to the invention, the wheat straw is modified to serve as a multifunctional slow-release compound fertilizer carrier, so that the production cost of the fertilizer can be greatly reduced, the fertilizer has the characteristics of degradability, no pollution and environmental friendliness, the fertilizer is endowed with a soil improvement function, and conditions are provided for comprehensive utilization of agricultural waste resources.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method of an adsorption type degradable soil moisture conservation slow release fertilizer based on modified wheat straw.
Background
At present, various methods are available for removing NH contained in wastewater 4 + And H 2 P0 4 - Including chemical precipitation, supercritical water oxidation, reverse osmosis, electrochemical, biological treatment, flocculation, adsorption, and the like. Among these methods, adsorption is considered to be the most reliable and effective method for removing nitrogen and phosphorus contaminants from wastewater because of the advantages of high treatment efficiency, simple operation, low cost, and avoidance of secondary pollution caused by chemical sludge or the like.
Adsorption by biological adsorbents is currently the removal of NH from wastewater 4 + And H 2 P0 4 - One of the effective methods of contamination. At present, biomass materials, particularly agricultural byproducts, are widely used for preparing adsorbents in water treatment due to wide sources, low cost and environmental friendliness. The wheat straw is a renewable biomass material, has rich resources and low cost, and has wide application in water treatment. The main components of the wheat straw are cellulose, hemicellulose and lignin. There are various functional groups on these constituent components, such as carboxyl groups, hydroxyl groups, ether groups, amino groups, phosphate groups, and the like. The presence of these functional groups makes wheat straw a great advantage in the preparation of wastewater treatment adsorbents. Moreover, when the fertilizer is used as a fertilizer, the recycling of crop wastes can be realized, and meanwhile, rich nutrient elements and organic matters are provided in the aspect of improving the soil fertility.
However, the direct use of wheat straw as an adsorbent may have a series of problems such as low adsorption capacity and adsorption efficiency, easy release of soluble organic matters present in the material, and the like. Therefore, the wheat straw is necessary to be pretreated and modified before being used as an adsorbent.
Disclosure of Invention
The invention aims to provide a hydrogel adsorbent based on modified wheat straw and a preparation method of a degradable multifunctional soil moisture conservation slow release fertilizer, so as to solve the problems that the adsorption capacity and adsorption efficiency are low when the wheat straw is used as an adsorbent in the existing water treatment method, and soluble organic matters in the material are easy to release.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the adsorption type degradable soil moisture conservation slow release fertilizer based on the modified wheat straw comprises the steps of firstly, preprocessing the wheat straw, separating and extracting to obtain cellulose and lignin, and preparing the amphoteric straw adsorbent by a chemical modification method; adsorption removal of NH from aqueous solutions using the adsorbent 4 + And H 2 P0 4 - And (3) recovering the adsorbent containing nitrogen and phosphorus nutrients, and finally taking the adsorbent as a degradable soil moisture conservation slow release fertilizer.
The preparation method of the adsorption type degradable multifunctional soil moisture conservation slow release fertilizer based on the modified wheat straw comprises the following steps:
s1, cutting wheat straw into small pieces (about 5mm long), washing with distilled water, and separating and extracting to obtain cellulose and lignin;
s2, obtaining sulfonated lignin by distillation, acidification, PH adjustment and filtration and drying of the lignin obtained in the step S1;
s3, preparing an intermediate (2, 3-epoxypropyl) -dodecyl dimethyl ammonium chloride (DMAC), and then adding the sulfonated lignin prepared in the step S2 into an intermediate solution to prepare amphoteric lignin;
s4, adding NaOH into the cellulose obtained in the step S1 for precooling, then dissolving the precooled solution by using urea solution, finally neutralizing and filtering precipitate by using acetic acid solution, repeatedly washing to be neutral by using distilled water, and finally drying to obtain amphoteric straw cellulose for later use;
s5, adding the nano composite hydrogel adsorbent into the NH-containing material 4 + And H 2 PO 4 - And standing the ionic solution, filtering, and drying the obtained sample to obtain the multifunctional slow-release ammonium fertilizer.
Further, the method for separating and extracting cellulose and lignin comprises the steps of,
s1.1, firstly, placing the processed wheat straw in water at 90 ℃ for extraction for 6 hours, then adding 1.3% sodium chlorite solution, adjusting the pH value to 3.5-5.0 by using 10% acetic acid solution, reacting for 2 hours at 80 ℃ to separate lignin in the straw, filtering, and drying for later use;
s1.1, adding 10wt% NaOH solution into the filter residue remained in the step S1.1, adjusting the temperature to 75 ℃ for reaction for 3 hours, removing residual lignin and pectin, and then placing the product into 2% (V/V) H with the solid-to-liquid ratio of 1:25 at the pH of 10.0 2 O 2 Reacting with 2% (W/V) NaOH in the mixed solution at room temperature for 2 hours to remove hemicellulose in the straw; finally, filtering a hemicellulose sample, washing for a plurality of times by using distilled water and 95% ethanol solution until the washing liquid is neutral, and drying for 12 hours at 70 ℃ to obtain white powder straw cellulose.
Further, the preparation method of the sulfonated lignin in the step S2 comprises the steps of weighing 10g of the lignin obtained in the step S1.1, putting the lignin into a three-neck flask, adding 150ml of distilled water, heating to 50 ℃, stirring at constant temperature for 30min, adding 1.5ml/L sulfuric acid into the solution, adjusting pH to be 1-3, adding hydrogen peroxide solution, heating to 65 ℃, reacting at constant temperature for 3 hours, heating to 95 ℃, adjusting pH to be 10 by 0.1mol/L sodium hydroxide solution, adding a certain amount of formaldehyde and sodium sulfite under stirring, refluxing and stirring for reacting for 6 hours, filtering to remove insoluble matters, adjusting pH of the filtrate to be 2, precipitating the sulfonated lignin, filtering, and drying at constant temperature to obtain brown powder sulfonated lignin.
Further, the preparation method of the amphoteric lignin in the step S3 comprises the steps of adding 10mL of epoxy chloropropane into a 500mL three-neck flask, adding hydrochloric acid, heating to 50 ℃, adding 0.2mol of dodecyl dimethyl tertiary amine, heating to 60 ℃ after heat preservation for 30min, continuously and slowly dropwise adding 0.10mol/L sodium hydroxide aqueous solution in a stirring state to regulate a reaction system to be alkalescent, and reacting for 2 hours to obtain a (2, 3-epoxypropyl) -dodecyl dimethyl ammonium chloride (DMAC) intermediate; then weighing 15g of sulfonated lignin, adding the sulfonated lignin into a 500mL three-neck flask, adding an acetone solvent, heating to 55 ℃, adjusting the pH=10 of a reaction system by using a 0.10mol/L sodium hydroxide aqueous solution, preserving heat for 20min, fully dissolving the sulfonated lignin, heating to 65 ℃, slowly dropwise adding an intermediate DMAC, stirring for reaction for 3h, then distilling and recovering acetone, carrying out suction filtration, washing until the pH of a filtrate is about 7, and then drying in a constant-temperature blast drying box to obtain the amphoteric lignin.
Further, the preparation method of the amphoteric straw cellulose in the step S4 comprises the steps of adding 1.0g of straw cellulose extracted from wheat straw into 30mL of a 14wt% NaOH solution, and precooling to-12 ℃; then adding a certain amount of 24wt% urea solution precooled to-12 ℃, stirring and mixing until straw cellulose is completely dissolved, reacting at 70 ℃, slowly dropwise adding 15ml of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, and stirring and reacting at the temperature for 2 hours; finally, 6.69g of chloroacetic acid is added to continue the reaction for 1 hour, and the reaction is stopped; neutralizing the reaction solution with 10% acetic acid solution, filtering the precipitate, repeatedly washing with distilled water to neutrality, and vacuum drying the product at 60deg.C for 24 hr to obtain amphoteric straw cellulose for use.
Further, the nano-composite hydrogel adsorbent in the step S5 comprises amphoteric straw cellulose-g-polyacrylic acid/palygorskite (ASC-g-PAA/PGS) nano-composite hydrogel adsorbent and amphoteric straw lignin-g-polyacrylic acid/palygorskite (ASL-g-PAA/PGS) nano-composite hydrogel adsorbent.
Further, the method for synthesizing the amphoteric straw cellulose-g-polyacrylic acid/palygorskite (ASC-g-PAA/PGS) nanocomposite hydrogel adsorbent comprises the steps of dissolving 0.5g of amphoteric straw cellulose in 50mL of distilled water, and placing the mixture in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet pipe; after passing nitrogen for 30min, 0.1g (NH) 4 )SO 4 ·FeSO 4 And 3% H 2 O 2 5mL of the solution was mixed and slowly added to a four-necked flask from a constant pressure funnel; then, 2.8g of acrylic acid (with 5mL of 7mol L -1 NaOH neutralization), 0.03g of n-maleylated chitosan and 1.0g of palygorskite, wherein the reactant mixture was reacted at room temperature under nitrogen atmosphere for 3 hours; finally, the product is dried and sieved for standby.
Further, the amphoteric straw lignin-g-The method for synthesizing the polyacrylic acid/palygorskite (ASL-g-PAA/PGS) nano composite hydrogel comprises the following steps: 0.5g of amphoteric straw lignin was dissolved in 50mL of distilled water, placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, and after 30 minutes of nitrogen was introduced, 0.1g (NH) 4 )SO 4 ·FeSO 4 And 3% H 2 O 2 5mL of the solution was mixed and slowly added to the above solution from a constant pressure funnel; then, 2.8g of acrylic acid (neutralized with 5mL of 7mol L-1 NaOH), 0.03g of N-maleylated chitosan and 1.0g of palygorskite were added successively; the reactant mixed solution reacts for 3 hours at room temperature under nitrogen atmosphere; finally, the product is dried and sieved for standby.
Further, the synthesis method of the N-maleated chitosan cross-linking agent comprises the steps of dissolving 0.5g of chitosan in 40mL of 2wt% acetic acid solution; adding an acetone solution dissolved with 0.25g of N-maleic anhydride into the mixed solution, and stirring and reacting for 8 hours at room temperature; precipitating in acetone after the reaction is finished to obtain a product, washing the product for three times by using acetone, and then drying in vacuum for later use; the degree of substitution of the product was determined by nuclear magnetic resonance analysis to be 14.5%.
Further, in the step S5, 0.2g of nanocomposite hydrogel adsorbent particles (0.090 to 0.110mm diameter) was added to 300mL of 200mgL -1 Containing NH 4 + And H 2 PO 4 - Placing the solution of ions at 25 ℃ for 2 hours; after filtration, the obtained sample is dried to constant weight at 40 ℃ for standby; measurement of NH4 adsorption + And H 2 PO 4 - The ionic amphoteric straw cellulose adsorbent dry particles have 9.81 percent of nitrogen and 0.8469mgg percent of phosphorus -1 。
In summary, by adopting the technical scheme, the invention has the beneficial technical effects that:
the multifunctional slow-release compound fertilizer obtained by the method not only can improve the utilization rate of the fertilizer, but also can effectively improve the water retention capacity of soil. The wheat straw is modified to be used as a multifunctional slow-release compound fertilizer carrier, so that the production cost of the fertilizer can be greatly reduced, the fertilizer has the characteristics of degradability, no pollution and environmental friendliness, the fertilizer is endowed with a soil improvement function, and a new way is provided for the comprehensive utilization of agricultural waste resources.
Drawings
FIG. 1 is a graph showing the nitrogen (N) slow release effect of two types of nano-composite hydrogel adsorbed slow release fertilizers under the conditions that the soil humidity is 30% and the room temperature, wherein the graph shows the nitrogen release behavior of the two types of nano-composite hydrogel adsorbed slow release fertilizers in the soil, and a is an amphoteric straw cellulose-g-polyacrylic acid/palygorskite adsorbed slow release fertilizer; b is an amphoteric straw lignin-g-polyacrylic acid/palygorskite nano composite hydrogel adsorption slow release fertilizer;
FIG. 2 shows the phosphorus (P) content of two types of nano-composite hydrogel adsorption slow release fertilizers under the conditions of soil humidity of 30% and room temperature 2 O 5 ) A slow release effect curve which shows the phosphorus release behavior of two types of nano composite hydrogel adsorption slow release fertilizers in soil, wherein a is amphoteric straw cellulose-g-polyacrylic acid/palygorskite adsorption slow release fertilizer; b is an amphoteric straw lignin-g-polyacrylic acid/palygorskite nano composite hydrogel adsorption slow release fertilizer;
FIG. 3 is a graph showing the nitrogen (N) slow release effect of the pretreated wheat straw-g-polyacrylic acid/palygorskite adsorption slow release fertilizer under the condition of the soil humidity of 30 percent and the room temperature.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
1) Wheat straw pretreatment
Wheat straw was cut into small pieces (about 5mm long) and washed with distilled water. Extracting in water at 90 deg.c for 6 hr, adding 1.3% concentration sodium chlorite solution, regulating pH value with 10% concentration acetic acid solution to 3.5-5.0, and reaction at 80 deg.c for 2 hr to separate and filter lignin from stalk. Adding 10wt% NaOH solution into the filter residue, adjusting the temperature to 75 ℃ for reaction for 3 hours, and further removing residual lignin and pectin. Finally, the product was subjected to a solid-to-liquid ratio of 1:25 at pH10.02％(V/V)H 2 O 2 And 2% (W/V) NaOH, and reacting for 2 hours at room temperature to remove hemicellulose in the straw. Filtering, washing the sample with distilled water and 95% ethanol solution for several times until the washing liquid is neutral, and drying at 70 ℃ for 12 hours to obtain white powder straw cellulose.
2) Preparation of sulfonated lignin
Weighing 10g lignin, placing into a three-neck flask, adding 150ml distilled water, heating to 50deg.C, stirring at constant temperature for 30min,
then adding 1.5ml/L sulfuric acid into the solution, adjusting the pH to be 1-3, adding hydrogen peroxide solution, heating to 65 ℃, reacting for 3 hours at constant temperature, heating to 95 ℃, adjusting the pH to be 10 by 0.1mol/L sodium hydroxide solution, adding a certain amount of formaldehyde and sodium sulfite under stirring, refluxing and stirring for reacting for 6 hours, filtering to remove insoluble matters, adjusting the pH of the filtrate to be 2, precipitating sulfonated lignin, filtering and drying at constant temperature to obtain brown powder sulfonated lignin.
3) Preparation of amphoteric straw lignin
Adding 10mL of epichlorohydrin into a 500mL three-neck flask, adding hydrochloric acid, heating to 50 ℃, adding 0.2mol of dodecyl dimethyl tertiary amine, heating to 60 ℃ after heat preservation for 30min, continuously and slowly dropwise adding 0.10mol/L of sodium hydroxide aqueous solution under stirring to regulate a reaction system to be alkalescent, and reacting for 2h to obtain a (2, 3-epoxypropyl) -dodecyl dimethyl ammonium chloride (DMAC) intermediate; then weighing 15g of sulfonated lignin, adding the sulfonated lignin into a 500mL three-neck flask, adding an acetone solvent, heating to 55 ℃, adjusting the pH=10 of a reaction system by using a 0.10mol/L sodium hydroxide aqueous solution, preserving heat for 20min, fully dissolving the sulfonated lignin, heating to 65 ℃, slowly dropwise adding an intermediate DMAC, stirring for reaction for 3h, then distilling and recovering acetone, carrying out suction filtration, washing until the pH of a filtrate is 7, and then drying in a constant-temperature blast drying oven to obtain the amphoteric lignin.
(4) Preparation of amphoteric straw cellulose
1.0g of straw cellulose extracted from wheat straw is added into 30mL of 14wt% NaOH solution, and precooled to-12 ℃. Then adding a certain amount of 24wt% urea solution precooled to-12 ℃, stirring and mixing until straw cellulose is completely dissolved, reacting at 70 ℃, slowly dropwise adding 15ml of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, and stirring and reacting at the temperature for 2 hours. Finally, 6.69g of chloroacetic acid was added to continue the reaction for 1 hour, and the reaction was stopped. The reaction solution was neutralized with 10% acetic acid solution, the precipitate was filtered, repeatedly washed with distilled water to neutrality, and the product was dried in vacuo at 60 ℃ for 24h, ready for use.
(5) Synthesis of N-maleylated chitosan crosslinker
N-maleylated chitosan was synthesized according to methods reported in the literature. 0.5g of maleylated chitosan was dissolved in 40mL of 2wt% acetic acid solution. An acetone solution in which 0.25g of maleic anhydride was dissolved was added to the above mixed solution, and the reaction was stirred at room temperature for 8 hours. And precipitating in acetone after the reaction is finished to obtain a product, washing the product with acetone for three times, and then drying in vacuum for later use. The degree of substitution of the product was determined by nuclear magnetic resonance analysis to be 14.5%.
(6) Preparation of amphoteric straw cellulose-g-polyacrylic acid/palygorskite (ASC-g-PAA/PGS) nanocomposite hydrogel
The nano composite hydrogel ASC-g-PAA/PGS is synthesized according to the following method: 0.5g of amphoteric straw cellulose was dissolved in 50mL of distilled water and placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. After 30min of nitrogen, 0.1g (NH) 4 )SO 4 ·FeSO 4 And 3% H 2 O 2 5mL of the solution was mixed and slowly added to the above solution from a constant pressure funnel. Then, 2.8g of acrylic acid (with 5mL of 7mol L -1 NaOH neutralization), 0.03g of n-maleated chitosan and 1.0g of palygorskite. The reaction mixture was reacted at room temperature under nitrogen atmosphere for 3 hours. Finally, the product is dried and sieved for standby.
(7) Preparation of amphoteric straw lignin-g-polyacrylic acid/palygorskite (ASL-g-PAA/PGS) nanocomposite hydrogel
The nano composite hydrogel ASL-g-PAA/PGS is synthesized according to the following method: 0.5g of amphoteric straw lignin was dissolved in 50mL of distilled water and placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. After 30min of nitrogen, 0.1g (NH) 4 )SO 4 ·FeSO 4 And 3% H 2 O 2 5mL of the solution was mixed and slowly added to the above solution from a constant pressure funnel. Then, 2.8g of acrylic acid (with 5mL of 7mol L -1 NaOH neutralization), 0.03g of n-maleated chitosan and 1.0g of palygorskite. The reaction mixture was reacted at room temperature under nitrogen atmosphere for 3 hours. Finally, the product is dried and sieved for standby.
(8) Preparation of multifunctional slow-release compound fertilizer (ASCF)
The preparation process of the multifunctional slow-release ammonium fertilizer comprises the following steps: 0.2g of nano composite hydrogel adsorbent particles (0.090-0.110 mm diameter) was added to 300mL of 200mg L -1 Containing NH4 + And H 2 PO 4 - In solution of ions, the solution was left at 25℃for 2h. After filtration, the resulting sample was dried to constant weight at 40 ℃ for use. Measurement of NH adsorption 4 + And H 2 PO 4 - The ionic amphoteric straw cellulose adsorbent dry particles have 9.81 percent of nitrogen and 0.8469mgg percent of phosphorus -1 。
(9) Sustained release behavior of ASCF in soil
Packaging 0.2g ASCF in a non-woven fabric bag, placing in a beaker containing 200g dry soil (below 26 meshes), placing at 6cm below the soil surface layer, and measuring the slow release performance of ASCF at room temperature. The water retention rate of the soil is kept at about 30% in the whole experimental process. The soil used in the experiment was taken from lan in semiarid area of china as sandy loam type. Under the same experimental conditions, 8 groups of experiments were performed in total. After 1, 3, 5, 7, 10, 15, 20 and 30 days respectively, the mesh bags were taken out, after drying at room temperature, fertilizer samples were taken out from the nylon mesh bags, and residual nitrogen (N) and phosphorus (P) were measured by elemental analysis and ammonium vanadium molybdate colorimetry, respectively 2 O 5 ) Is contained in the composition.
(10) Study of Water Retention of ASCF in soil
Mixing 200g (less than 26 mesh) of soil sample with a certain amount of ASCF fertilizer particles (0%, 0.5%,1.0% and 2.0%), loading into 4.5cm polyvinyl chloride plastic tube, sealing the bottom of the tube with 100 mesh non-woven fabric, weighing, and recording as W 0 . Slow from the top of the sample tubeAdding tap water until water drops at the bottom begin to exude, standing for 10min, weighing the sample tube, and recording as W 1 . The sample tube was weighed daily at room temperature and noted as W i For 30 days of continuous measurement, the soil water retention (WR%) was calculated according to the following formula:
example 1
Wheat straw was cut into small pieces (about 5mm long) and washed with distilled water. 100 parts of the straw is taken and placed in 90 ℃ water for extraction for 6 hours, then 20 parts of 1.3% sodium chlorite solution is added, 10% acetic acid solution is used for adjusting the pH value to 3.5-5.0, the temperature is 80 ℃ for reaction for 2 hours to separate and filter, and the pH value of the filtrate is adjusted to be acidic, so that lignin in the straw is obtained. 15 parts of 10wt% NaOH solution is added into the filter residue, the temperature is adjusted to 75 ℃ for reaction for 3 hours, and the residual lignin and pectin are further removed. Finally, the product is subjected to 260 parts of 2% (V/V) H at a pH of 10.0 2 O 2 And 2% (W/V) NaOH, reacting for 2 hours at room temperature, removing hemicellulose in the straw, and filtering to obtain straw cellulose. And (3) respectively washing the extracted straw lignin and cellulose with distilled water and 95% ethanol solution for several times until the washing liquid is neutral, and then drying at 70 ℃ for 12 hours to obtain brown powder lignin and white powder straw cellulose.
Weighing 30 parts of lignin, putting the lignin into a three-neck flask, adding 150 parts of distilled water, heating to 50 ℃, stirring at constant temperature for 30min, adding 1.5ml/L sulfuric acid into the solution, adjusting pH=1-3, adding hydrogen peroxide solution, heating to 65 ℃, reacting at constant temperature for 3h, heating to 95 ℃, adjusting pH=10 with 0.1mol/L sodium hydroxide solution, adding 5 parts of formaldehyde and 25 parts of sodium sulfite under stirring, refluxing and stirring for reacting for 6h, filtering to remove insoluble matters, adjusting pH=2 of the filtrate to precipitate sulfonated lignin, filtering, and drying at constant temperature to obtain brown powder sulfonated lignin.
150 parts of sodium lignin sulfonate aqueous solution with the pH value of 12.0 and the mass fraction of 25% are prepared, added into a 500mL three-neck flask, heated to 90 ℃ and kept at constant temperature, 20 parts of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride aqueous solution with the mass fraction of 30wt% are dropwise added into the flask by a dropping funnel, 10 parts of NaOH solution with the mass fraction of 20wt% are added, the reaction is stopped after 3 hours, the pH value of the solution is regulated to 5.0, and then the amphoteric straw lignin is obtained through filtering, washing and drying.
10 parts of wheat straw cellulose is added into 200 parts of 14wt% NaOH solution, and precooled to-12 ℃. Then 50 parts of urea solution with the weight percent of 24 percent of precooled to-12 ℃ is added, stirred and mixed until straw cellulose is completely dissolved, the reaction is carried out at the temperature of 70 ℃, 15 parts of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution with the weight percent of 30 percent is slowly added dropwise, and the reaction is carried out for 2 hours at the temperature under stirring. Finally, 60 parts of chloroacetic acid is added for continuous reaction for 1 hour, and the reaction is stopped. Neutralizing the reaction solution with 10% acetic acid solution, filtering the precipitate, repeatedly washing with distilled water to neutrality, and vacuum drying the product at 60deg.C for 24 hr to obtain amphoteric straw cellulose.
The amphoteric straw cellulose-g-polyacrylic acid/palygorskite (ASC-g-PAA/PGS) nano composite hydrogel is synthesized according to the following method: 15 parts of amphoteric straw cellulose were dissolved in 50 parts of distilled water and placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. After passing nitrogen for 30min, 1 part (NH 4 )SO 4 ·FeSO 4 And 3 parts of 3% H 2 O 2 Solution mixing was slowly added to the solution from a constant pressure funnel. Then, 30 parts of acrylic acid (5 parts of 7mol L -1 NaOH solution), 0.03 parts of N-maleated chitosan and 10 parts of palygorskite. The reaction mixture was reacted at room temperature under nitrogen atmosphere for 3 hours. Finally, the product is dried and sieved for standby.
The amphoteric straw lignin-g-polyacrylic acid/palygorskite (ASL-g-PAA/PGS) nano composite hydrogel is synthesized according to the following method: 20 parts of amphoteric straw lignin was dissolved in 50 parts of distilled water and placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. After passing nitrogen for 30min, 1 part (NH 4 )SO 4 ·FeSO 4 And 3 parts of 3% H 2 O 2 Solution mixing was slowly added to the above solution from a constant pressure funnel. Then, 25 parts of acrylic acid (5 parts of 7mol L -1 NaOH solution), 0.03 parts of N-maleated chitosan and 10 parts of palygorskite. The reaction mixture was reacted at room temperature under nitrogen atmosphere for 3 hours. Finally, the product is dried and sieved for standby.
The preparation process of the multifunctional slow-release compound fertilizer comprises the following steps: 20 parts of amphoteric straw cellulose-g-polyacrylic acid/palygorskite or amphoteric straw lignin-g-polyacrylic acid/palygorskite nano composite hydrogel (diameter of 0.160-0.425 mm) is added into 500 parts of 200mg L -1 Containing NH 4 + And H 2 PO 4 - In solution of ions, the solution was left at 25℃for 2h. After filtration, the resulting sample was dried to constant weight at 40 ℃ for use. Measurement of NH adsorption 4 + And H 2 PO 4 - Ionic amphoteric straw cellulose-g-polyacrylic acid/palygorskite nano composite hydrogel adsorbent dry particles, wherein the nitrogen content is 13.81%, and the phosphorus content is 1.1469mgg -1 . Measurement of NH adsorption 4 + And H 2 PO 4 - Ionic amphoteric straw lignin-g-polyacrylic acid/palygorskite nano composite hydrogel adsorbent dry particles, wherein the nitrogen content is 13.25%, and the phosphorus content is 1.2158mgg -1 。
The biomass wheat straw is used as a raw material, after pretreatment, the biomass wheat straw is prepared into novel amphoteric straw and lignin through chemical modification, and the novel nano composite hydrogel is prepared through in-situ graft polymerization reaction, and the prepared palygorskite nano composite hydrogel can be used as an efficient adsorbent. Adsorption removal of NH from aqueous solutions 4 + And H 2 PO 4 - . In addition, the recovered carrier material rich in nitrogen (N) and phosphorus (P) nutrients can be reused as a multifunctional slow-release compound fertilizer for slowing down the release rate of fertilizer nutrients and improving the water retention capacity of soil. The multifunctional slow release fertilizer not only can slow down the release rate of fertilizer nutrients and prolong the fertilizer efficiency period, but also can improve the water holding capacity and the water holding capacity of soil.
Comparative example 1
Pretreatment of wheat straw: small sizePulverizing wheat straw, drying, sieving, collecting 0.18-0.35mm part, weighing 20 parts of the pretreated wheat straw, adding into 500 parts of distilled water, adding into 1000mL three-neck flask, placing the suspension into water bath at 60deg.C, distilling for 12 hr, filtering, adding the filtrate into three-neck flask, and adding 80 parts (24 wt% KOH) + 1 wt％NaBH 4 ) The solution was mixed and reacted at room temperature with mechanical stirring for 3 hours. The suspension was filtered and the filtrate was washed with ethanol to neutrality and dried at 105 ℃ for use.
The preparation of the pretreated wheat straw-g-polyacrylic acid/palygorskite composite hydrogel is synthesized according to the following method: into a three-necked flask, 25 parts of acrylic acid and 5 parts of 7mol L were charged -1 And (5) neutralizing by NaOH solution. Subsequently, 20 parts of pretreated wheat straw was added, 1 part (NH 4 )SO 4 ·FeSO 4 And 3 parts of 3% H 2 O 2 Solution mixing was slowly added to the solution from a constant pressure funnel. Then, 0.03 part of N, N-methylene bisacrylamide and 10 parts of palygorskite are sequentially added, and the mixture is reacted for 3 hours at the constant temperature of 70 ℃ under the protection of nitrogen. Finally, the product is dried and sieved for standby.
The preparation process of the multifunctional slow-release compound fertilizer comprises the following steps: 20 parts of pretreated wheat straw-g-polyacrylic acid/palygorskite composite hydrogel (with the diameter of 0.160-0.425 mm) is added into 500 parts of the pretreated wheat straw-g-polyacrylic acid/palygorskite composite hydrogel with the concentration of 200mgL -1 Containing NH 4 + And H 2 PO 4 - The solution of ions was left at 25℃for 2h. After filtration, the resulting sample was dried to constant weight at 40 ℃ for use. Measurement of NH adsorption 4 + And H 2 PO 4 - Ion pretreatment wheat straw-g-polyacrylic acid/palygorskite composite hydrogel adsorbent dry particles, wherein the nitrogen content is 5.61%, and the phosphorus content is 0mgg -1 。
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. Adsorption type degradable wheat strawThe preparation method of the soil moisture conservation slow release fertilizer is characterized in that wheat straw is pretreated, cellulose and lignin are obtained through separation and extraction, and an amphoteric straw adsorbent is prepared through a chemical modification method; adsorption removal of NH from aqueous solutions using amphoteric straw adsorbents 4 + And H 2 P0 4 - Recovering the adsorbent containing nitrogen and phosphorus nutrients, and finally taking the adsorbent containing nitrogen and phosphorus nutrients as an adsorption type degradable soil moisture conservation slow release fertilizer;
the method comprises the following steps:
s1, cutting wheat straw into small pieces, washing with distilled water, and separating and extracting to obtain cellulose and lignin;
s2, obtaining sulfonated lignin by distillation, acidification, PH adjustment and filtration and drying of the lignin obtained in the step S1;
s3, preparing an intermediate (2, 3-epoxypropyl) -dodecyl dimethyl ammonium chloride, and then adding the sulfonated lignin prepared in the step S2 into an intermediate solution to prepare amphoteric straw lignin;
s4, adding NaOH into the cellulose obtained in the step S1 for precooling, then dissolving the precooled solution by using urea solution, finally neutralizing and filtering precipitate by using acetic acid solution, repeatedly washing to be neutral by using distilled water, and finally drying to obtain amphoteric straw cellulose for later use;
s5, adding the nano composite hydrogel adsorbent into the NH-containing material 4 + And H 2 PO 4 - Standing in an ionic solution, filtering, and drying the obtained sample to obtain the adsorption type degradable soil moisture slow release fertilizer of the modified wheat straw;
the nano composite hydrogel adsorbent in the step S5 is amphoteric straw cellulose-g-polyacrylic acid/palygorskite nano composite hydrogel adsorbent or amphoteric straw lignin-g-polyacrylic acid/palygorskite nano composite hydrogel adsorbent;
the synthesis method of the amphoteric straw cellulose-g-polyacrylic acid/palygorskite nano composite hydrogel adsorbent comprises the steps of dissolving 0.5g of amphoteric straw cellulose obtained in step S4 in 50mL of distilled water, and placing the mixture in a stirring deviceThe device, the reflux condenser tube, the thermometer and the nitrogen inlet tube are arranged in a four-necked bottle; after passing nitrogen for 30min, 0.1g (NH) 4 )SO 4 ·FeSO 4 And 5mL of 3% H 2 O 2 Solution mixing was slowly added from a constant pressure funnel to a four-necked flask; then, 2.8g of acrylic acid, 0.03g of N-maleated chitosan and 1.0g of palygorskite are sequentially added, wherein the reactant mixed solution reacts for 3 hours at room temperature under nitrogen atmosphere; finally, drying and sieving the product;
wherein, the acrylic acid is 5mL of 7mol.L -1 Neutralizing with NaOH;
the method for synthesizing the amphoteric straw lignin-g-polyacrylic acid/palygorskite nano composite hydrogel comprises the following steps: dissolving 0.5g of the amphoteric straw lignin obtained in the step S3 in 50mL of distilled water, placing in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet pipe, introducing nitrogen for 30min, and then adding 0.1g (NH) 4 )SO 4 ·FeSO 4 And 5mL of 3% H 2 O 2 Slowly adding the solution mixture from a constant pressure funnel into the solution; then, 2.8g of acrylic acid, 0.03g of N-maleylated chitosan and 1.0g of palygorskite were added in this order; the reactant mixed solution reacts for 3 hours at room temperature under nitrogen atmosphere; finally, drying and sieving the product;
wherein 5mL of 7mol.L of acrylic acid is used -1 And (5) neutralizing by NaOH.
2. The method for preparing the modified wheat straw-based adsorption-type degradable soil moisture conservation slow release fertilizer according to claim 1, wherein the method for separating and extracting cellulose and lignin in the step S1 comprises the following steps:
s1.1, firstly, placing the processed wheat straw in water at 90 ℃ for extraction for 6 hours, then adding 1.3% sodium chlorite solution, adjusting the pH value to 3.5-5.0 by using 10% acetic acid solution, reacting for 2 hours at 80 ℃ to separate lignin in the straw, filtering, and drying for later use;
s1.2, adding 10wt% NaOH solution into the filter residue remained in the step S1.1, adjusting the temperature to 75 ℃ for reaction for 3 hours, removing residual lignin and pectin, and then placing the product into 2% (V/V) H with the solid-to-liquid ratio of 1:25 at the pH of 10.0 2 O 2 Reacting with 2% (W/V) NaOH in the mixed solution at room temperature for 2 hours to remove hemicellulose in the straw; finally, filtering a hemicellulose sample, washing for a plurality of times by using distilled water and 95% ethanol solution until the washing liquid is neutral, and drying for 12 hours at 70 ℃ to obtain white powder straw cellulose.
3. The preparation method of the modified wheat straw-based adsorption type degradable soil moisture conservation slow release fertilizer is characterized in that the preparation method of the sulfonated lignin in the step S2 comprises the steps of weighing 10g of lignin obtained in the step S1.1, putting the lignin into a three-neck flask, adding 150ml of distilled water, heating to 50 ℃, stirring at constant temperature for 30min, adding 1.5ml/L sulfuric acid into the solution, adjusting pH=1-3, adding hydrogen peroxide solution, heating to 65 ℃, reacting at constant temperature for 3h, then heating to 95 ℃, adjusting pH=10 with 0.1mol/L sodium hydroxide solution, adding a certain amount of formaldehyde and sodium sulfite under stirring, refluxing and stirring for 6h, filtering to remove insoluble matters, adjusting pH=2 of filtrate to precipitate the sulfonated lignin, filtering, and drying at constant temperature to obtain brown powder sulfonated lignin.
4. The preparation method of the modified wheat straw-based adsorption type degradable soil moisture conservation slow release fertilizer is characterized in that the preparation method of the amphoteric straw lignin in the step S3 comprises the steps of adding 10mL of epoxy chloropropane into a 500mL three-neck flask, adding hydrochloric acid, heating to 50 ℃, adding 0.2mol of dodecyl dimethyl tertiary amine, heating to 60 ℃ after heat preservation for 30min, continuously and slowly dropwise adding 0.10mol/L of sodium hydroxide aqueous solution in a stirring state to regulate a reaction system to be alkalescent, and reacting for 2h to obtain the (2, 3-epoxypropyl) -dodecyl dimethyl ammonium chloride intermediate; then weighing 15g of sulfonated lignin, adding the sulfonated lignin into a 500mL three-neck flask, adding an acetone solvent, heating to 55 ℃, adjusting the pH=10 of a reaction system by using a 0.10mol/L sodium hydroxide aqueous solution, preserving heat for 20min, fully dissolving the sulfonated lignin, heating to 65 ℃, slowly dripping the intermediate, stirring for reaction for 3h, then distilling and recovering acetone, carrying out suction filtration, washing until the pH of a filtrate is 7, and then drying in a constant-temperature blast drying box to obtain the amphoteric straw lignin.
5. The method for preparing the modified wheat straw-based adsorption-type degradable soil moisture conservation slow release fertilizer according to claim 1, wherein the preparation method of the amphoteric straw cellulose in the step S4 comprises the steps of adding 1.0g of straw cellulose extracted from wheat straw into 30mL of a 14wt% NaOH solution, and precooling to-12 ℃; then adding a certain amount of 24wt% urea solution precooled to-12 ℃, stirring and mixing until straw cellulose is completely dissolved, reacting at 70 ℃, slowly dropwise adding 15ml of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, and stirring and reacting at the temperature for 2 hours; finally, 6.69g of chloroacetic acid is added to continue the reaction for 1 hour, and the reaction is stopped; neutralizing the reaction solution with 10% acetic acid solution, filtering the precipitate, repeatedly washing with distilled water to neutrality, and vacuum drying the product at 60deg.C for 24 hr to obtain amphoteric straw cellulose.
6. The preparation method of the modified wheat straw-based adsorption type degradable soil moisture conservation slow release fertilizer is characterized in that the synthesis method of the N-maleylation chitosan cross-linking agent comprises the steps of dissolving 0.5g chitosan in 40mL of 2wt% acetic acid solution; adding an acetone solution with 0.25g of maleic anhydride dissolved therein into the mixed solution, and stirring at room temperature for reaction for 8 hours; precipitating in acetone after the reaction is finished to obtain a product, washing the product for three times by using acetone, and then drying in vacuum for later use; the degree of substitution of the product was determined by nuclear magnetic resonance analysis to be 14.5%.
7. The application of the adsorption type degradable soil moisture conservation slow release fertilizer obtained by the preparation method based on the modified wheat straw in improving soil and comprehensively utilizing agricultural waste resources.
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