CN106588459A - Preparation method of chicken feather crosslinked cellulose multifunctional zinc fertilizer - Google Patents
Preparation method of chicken feather crosslinked cellulose multifunctional zinc fertilizer Download PDFInfo
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- CN106588459A CN106588459A CN201611103202.4A CN201611103202A CN106588459A CN 106588459 A CN106588459 A CN 106588459A CN 201611103202 A CN201611103202 A CN 201611103202A CN 106588459 A CN106588459 A CN 106588459A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
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- 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
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- 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
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Abstract
The invention discloses a preparation method of a chicken feather crosslinked cellulose multifunctional zinc fertilizer. According to the preparation method, chicken feather and paper pulp serve as raw materials, a potassium hydroxide/water/urea system serves as a composite solvent, the influence of proportion of the composite solvent system and the experimental condition on the hydrolysis rate of the chicken feather and the dissolution rate of the cellulose is discussed, and the result indicates that each millimeter of composite solvent can hydrolyze 0.1 g of chicken feather when reacting at 75 DEG C for 120 minutes; the chicken feather hydrolysate is precooled to -12 DEG C, 0.06 g of cellulose is added into each millimeter of chicken feather hydrolysate to form a gelatinized mixture; and then the gel is prepared into chicken feather crosslinked cellulose gel containing nitrogen with a concentration of 150.6 mg/g, potassium with a concentration of 136.7 mg/g and zinc with a concentration of 13.9 mg/g and also containing nutritional elements such as sulfur, polypeptide and amino acid. The results of a soil cultivation experiment and a corn potting experiment indicate that the chicken feather crosslinked cellulose multifunctional zinc fertilizer has high Cell-CF bio-availability and can serve as a long-acting zinc fertilizer.
Description
Technical field
The invention belongs to agricultural technology field, specifically, is related to a kind of system of the multi-functional zinc fertilizer of chicken feather cross-linked cellulose
Preparation Method.
Background technology
Cellulose is nature the first mcroorganism matter resource, and is widely used multiple in papermaking, weaving, new material etc.
Field.Used as a kind of native protein resource, its protein content is 85-99% to feather, and the feather yield in the annual whole world is reachable
8500000000 tons, in addition the native protein such as hoof tips of substantial amounts of hair and animal resource do not utilized well, cause serious
The wasting of resources and environmental pollution.Because intermolecular and intramolecular hydrogen bond is strong, the dissolubility of cellulose is poor, in addition solvent and
Reactant is difficult to enter the crystal region of cellulose, reacts the development and utilization of cellulose of accessibility lower limit.Feather keratin
It is a kind of rigid albumen, its structure has very high steady by intermolecular disulfide bond, hydrogen bond, salt type bond and other crosslinked actions
It is qualitative, water solublity and biological degradability it is poor.Therefore the lytic agent for developing excellent cellulose and feather keratin be improve this two
Premise and basis of the Nature development of resources with value.In recent years Zhang Lina seminars exploitation alkali/urea system it is new
One fiber element double solventss, there is cheap environmental protection.More research shows, produces after feather hydrolysis
The small-molecule substance such as polypeptide and aminoacid functional group come out with preferable hydrophilic and complexing of metal ion ability and
Biological effectiveness is improved.Inorganic micro- fertilizer such as ferrum, zinc etc. are easily subject to pH and soil mineral and ring after being manured into soil
The impact in border and be rapidly converted into invalid state nutrient, with Organic substance chelating can improve it is micro- fertilizer soil effectiveness.It is sharp in addition
The hydrogel of function admirable can be made with the interspersed crosslinking between hydrophilic high mol, can be with the substantial amounts of moisture of sticking and in fertilizer
Slow release aspect has broad application prospects.For example utilize gel made by the crosslinked action of carboxymethyl cellulose and metal ion
Fertilizer, can significantly improve utilization rate of fertilizer.
At present, a kind of multi-functional zinc fertilizer of with low cost, eco-friendly chicken feather cross-linked cellulose is badly in need of in prior art
Preparation method.
The content of the invention
It is an object of the invention to provide a kind of multi-functional zinc fertilizer of with low cost, eco-friendly chicken feather cross-linked cellulose
Preparation method.Using potassium hydroxide/water/carbamide (KOH/H2O/CO(NH2)2) double solventss, alkaline hydrolysis, Ran Houjia are carried out to feather
Enter paper cellulose, it is 6.5 addition zinc sulfate to adjust pH with dilute sulfuric acid, is prepared for a kind of gel rubber sustained-release of polypeptide cross-linked cellulose
Zinc fertilizer (Cell-CF), have studied the biological effectiveness of structure, water absorbing properties, sustained release performance and the zinc fertilizer of the gel fertilizer.
Its concrete technical scheme is：
A kind of preparation method of the multi-functional zinc fertilizer of chicken feather cross-linked cellulose, comprises the following steps：
Step 1, feather are through potassium hydroxide/water/carbamide KOH/H2O/CO(NH2)2The alkaline hydrolysis of double solventss, its process is broken
The bad hydrogen bond for maintaining keratin space structure, disconnects disulfide bond and hydrolysising peptide key so that it is little that feather keratin becomes molecular weight, water
The good protein peptide of dissolubility and aminoacid, obtain chicken feather hydrolyzed solution；
Step 2, in chicken feather hydrolyzed solution cellulose is added, this process cellulose is because absorbing chicken feather hydrolyzed solution and swelling, companion
With there is a protein peptide, the inside of aminoacid infiltration and carbamide to cellulose, the crystal region of cellulose is broken with the hydrogen bond of noncrystalline domain
Bad, degree of crystallinity declines, and reacts accessibility raising, and this process cellulose chain and protein peptide chain carry out the interspersed folding of height, shape
Into pluralgel；
Step 3, by the pH regulator of pluralgel it is faintly acid 6.5 with dilute sulfuric acid, sulphuric acid has neutralized pluralgel fertilizer
Alkalescence, alkali disappears to the swelling effect of cellulose, a large amount of hydrogen bonds are formed between protein peptide chain and cellulose chain, so as to both tightly
It is bound together, cellulose chain is modified becomes the compound chain of the higher cellulose polypeptide of hydrophilic and complexing of metal ion ability,
And fold lightly crosslinked with interchain of chain constitutes tridimensional network；
Step 4, in pluralgel metal trace element is added, using the functional group in gel and metal ion network is carried out
Close, this is tested and Zinc vitriol is added in gel, continue to stir 1h, pour gel fertilizer into mould in 60 DEG C of dryings
Drying forming in case.
Preferably, KOH concentration is 1.5mol/L, CO (NH in step 12)2Content is 0.12g/mL, every milliliter of double solventss
120min is reacted under the conditions of 75 DEG C, 0.1g chicken feathers are hydrolyzed.
Preferably, chicken feather hydrolyzed solution described in step 2 is cooled in advance -12 DEG C, and every milliliter of chicken feather hydrolyzed solution adds 0.06g fibers
Element.
Preferably, the mould described in step 4 is provided with the lattice of 1cm × 1cm × 1cm.
Compared with prior art, beneficial effects of the present invention：
The present invention is successfully prepared a kind of hydrogel matrix Cell-CF, its preparation process take full advantage of potassium hydroxide and
The chemical property of carbamide simultaneously can make gel rich in nitrogen and potassium element, the preparation process economy of Cell-CF and environmental friendliness.Research knot
Really show, process Cell through double solventss and destroy complete with the crystalline texture of CF raw materials, without the need for any chemical cross-linking agent, by dividing
Intert folding, intermolecular hydrogen bonding CF and Cell between son to combine closely.Cellulose is combined rear hydrophilicity and is carried with polypeptide and aminoacid
Height, Cell-CF shows preferable water absorption and swelling.Cell-CF is that a kind of substrate rich in functional group can be entered with zinc ion
Row complex reaction, played important function on long-acting zinc fertilizer making, and can maintain effectiveness of the zinc in soil with the long period,
It is a kind of long-acting zinc fertilizer.Semen Maydiss potted plant experiment shows that the biological effectiveness of Cell-CF zinc fertilizers is higher.The chicken feather of this experiment synthesis
Grafted cellulose based aquagel material acts not only as long-acting zinc fertilizer, make long-acting copper fertilizer, fertiliser containing magnesium, iron fertilizer, calcareous fertilisers, cobalt and
Nickel etc. it is micro- fertilizer on have very big potential using value, in addition this gel fertilizer water conservation and improve Soil structure functionally have compared with
Big development space.
Description of the drawings
Fig. 1 is chicken feather alkaline hydrolysis condition, and wherein Fig. 1 a are KOH concentration, and Fig. 1 b are reaction temperature (T), and Fig. 1 c are hydrolysis times
T (), Fig. 1 d are chicken feather and alkali liquor ratio (S/L)；
Fig. 2 is impact of the carbamide to cellulose dissolution rate；
Fig. 3 is the synthesis step of Cell-CF；
Fig. 4 is the infrared spectrum of sample, and wherein Fig. 4 a are the infrared spectrums of CF and U-CF, and Fig. 4 b are Cell and U-Cell
Infrared spectrum, Fig. 4 c are the infrared spectrums of U-Cell；
Fig. 5 is the XRD spectrum of sample, and wherein Fig. 5 a are the XRD spectrums of CF and U-CF, and Fig. 5 b are Cell and U-Cell
XRD spectrum, Fig. 5 c are the XRD spectrums of Cell-CF；
Fig. 6 is the XPS collection of illustrative plates of Cell-CF, and wherein Fig. 6 a are the XPS width collection of illustrative plates of Cell-CF；Fig. 6 b- Fig. 6 d are respectively
Cell-CF C1s, N1s and Zn2p 3/2, XPS high resolution collection of illustrative plates；
Fig. 7 A, C and E be U-CF, U-Cell and Cell-CF water immersion after bright field image；B, D and F are U-CF, U-Cell
With the fluoroscopic image after the immersion of Cell-CF water；
Fig. 8 (a-c) Cell-CF enters 0min, 5min, 10min after water；(A-C) U-Cell enter 0min after water, 5min,
10min；
Fig. 9 is the hydrostatic release profiles of K and Zn in Cell-CF；
Figure 10 is the nutrient content for testing soil and milpa, CKO in figure:Blank；CK1:ZnSO4,CO
(NH2)2,K2SO4,(NH4)2HPO4；CK2:Zn-EDTA,CO(NH2)2,K2SO4,(NH4)2HPO4；Cell-CF:Cell-CF,
(NH4)2HPO4；- 20%:- 20%Cell-CF, (NH4)2HPO4, wherein Figure 10 a total nitrogen content of soil, Figure 10 b available potassium in soils
Content, Figure 10 c Available Zn content in soil, the Zn content of Figure 10 d maize seedlings.
Specific embodiment
Technical scheme is described in more detail with reference to specific embodiment.
1 experimental section
1.1 materials and reagent
Cellulose (Cell)：The broad-leaved wood paper pulp of crushing；Chicken feather (CF)：Poultry dressing farm is collected, and is removed impurity and is used again
Tap water is rinsed and dried afterwards for several times；Potassium hydroxide, carbamide, sulphuric acid, Zinc vitriol, potassium sulfate, Diammonium phosphate (DAP) is commercially available
Analytical reagent.
The preparation of 1.2 slow release zinc fertilizers
1.2.1 the hydrolysis of chicken feather
Using control monofactor quantity method, the concentration of KOH, reaction temperature (T), hydrolysis time (t), chicken feather and alkali are explored
Impact of four factors of liquor ratio rate (S/L) to chicken feather water-solubility protein yield (PDI).Method is as follows, according to setting four because
Sub (1)-(4) are tested under varying level, add alkali liquor 5mL, the whole magnetic agitation of reaction in 50mL centrifuge tubes every time.Chicken
The pH of alkaline hydrolysis mixed liquor is adjusted to neutrality after the completion of hair alkaline hydrolysis, in the case where rotating speed is 3500rpm centrifugation ten minutes is carried out, it is heavy to isolate
Shallow lake part, the drying in 60 DEG C of baking ovens determines insoluble matter quality (m1).The protein calculated according to formula one under different condition is molten
Xie Du (PDI).Each process level is averaged in triplicate.
PDI=(m-m1) × 100/m formula one
M in formula1：Sediment fraction quality (mass of residue), m：Quality (the mass of chicken of chicken feather
feather)。
(1) impact of the KOH concentration to PDI
Plus 0.5g chicken feathers, reaction temperature is 50 DEG C, under the conditions of response time 60min.The concentration for probing into KOH is respectively 0,
0.3rd, 0.6,0.9,1.2,1.5, impacts of the 1.8mol/L to chicken feather protein solubility.
(2) impact of the reaction temperature (T) to PDI
Plus 0.5g chicken feathers, KOH concentration is 0.9mol/L, under the conditions of response time 60min.Exploratory response temperature is respectively
35th, 55,75,95,115 DEG C of impacts to chicken feather protein solubility.
(3) impact of the response time (t) to PDI
Plus 0.5g chicken feathers, KOH concentration is 0.9mol/L, under the conditions of 75 DEG C of reaction temperature.The exploratory response time is respectively 20,
60th, 100,120,140, impacts of the 180min to chicken feather protein solubility.
(4) impact of the solid-to-liquid ratio (S/L) to PDI
KOH concentration is 0.9mol/L, and 75 DEG C of reaction temperature, the response time is under the conditions of 60min.Probe into chicken feather consumption difference
For 0.1,0.3,0.5,0.7,0.9,1.2, impacts of the 1.4g to chicken feather protein solubility.
1.2.2 cellulose is dissolved
In experiment 1.2.1 under the conditions of resulting most suitable chicken feather alkaline hydrolysis KOH concentration (1.5moL/L), further research
- 12 DEG C of (hydrogen bond of the double solventss near freezing point easily between destruction cellulosic molecule) double solventss urea content to fibre
The impact of the plain dissolubility of dimension.It is configured to every 100mL KOH (1.5mol/L) solution and contains carbamide 0,2,4,6,8,10,12,14g respectively
Composite solvent system.50mL double solventss are taken in 100mL centrifuge tubes, and in cryogenic thermostat stirring reactive bath (DHJF-
4002) paper cellulose 1.45g is added after being cooled to -12 DEG C in advance in, after stirring reaction half an hour, 10 points is centrifuged under 3500rpm
Clock, upper strata is cellulose solution, and lower floor is cellulose insoluble matter, lower floor insoluble matter pH is washed with deionized for neutrality, in 60
Drying in DEG C baking oven determines insoluble matter quality and calculates dissolubility of the composite solution to cellulose (experiment is averaged in triplicate
Value).To determine the optimal compatibility of double solventss, with the double solventss of optimal compatibility come alkaline hydrolysis chicken feather (U-CF) and dissolving cellulose
(U-Cell)。
1.2.3 determine that cellulose composite solution occurs the amount of cellulose required for gelation
The sol gel transformation of polymer solution is determined using falling ball method, per 50mL potassium hydroxide/water/carbamide (KOH/
H2O/CO(NH2)2) composite solution in cryogenic thermostat stirring reactive bath pre-cooling be subzero 12 DEG C, be then gradually increased paper pulp fiber
The addition of element, is put into the rustless steel small ball that radius (r) is 2mm, when small ball can after the stirring reaction being interrupted
The colloidal sol that cellulose is thought when in being still in gel there occurs gelation transition, and record the addition of cellulose. this fiber
The addition of element is used to prepare gel fertilizer (Cell-CF).Synthesis path is as shown in Figure 3.
The X-ray diffraction analysis (XRD) and infrared analysiss (FTIR) of 1.3 gel fertilizer
Chicken feather raw material (CF), the sample (U-CF) after the drying of double solventss chicken feather alkali solution liquid, cellulosic material (Cell) is fine
The gel fertilizer (Cell-CF) of sample (U-Cell) and synthesis after the composite solution drying of dimension element carries out XRD and FTIR
Test.XRD method of testings：Sample mill poling fine-powdered, is placed on specimen holder, is tested after steady-state conditionss.Test strip
Part：Cu target Ka rays, Ni pieces filtering eliminates CuKa radiation, λ=0.154nm, tube voltage 40kV, tube current 30mA, scanning speed
2 °/min, 5～40 ° of sweep limitss.FTIR is tested：Sample is adopted so red with the type Fourier of Nicolet 750 together with KBr after tabletting
External spectrum instrument is in 400-4000cm-1In the range of scan and record.
The X-ray photoelectron spectroscopic analysis (XPS) of 1.4 gel fertilizer (Cell-CF)
Using gel fertilizer of ESCALAB 250Xi (Thermo Fisher companies of the U.S.) the type photoelectron spectrographs to synthesis
Material (Cell-CF) is composed scanning analysis entirely, and light source is monochrome Al Ka (hv=1486.6eV).(XPS is tested by Tsing-Hua University
Materials Academy laboratory is completed)
1.5 use respectively the bonding state of fluorescence microscope and stereomicroscope observation gel fertilizer (Cell-CF) in water
And swelling behavior
Respectively by U-CF, a little powder of U-Cell and Cell-CF is placed on microscope slide, and respectively drips deionized water, is protected
Hold sample and be constantly in drop package status up to more than 8h, period notes keeping the skin wet.Then covered adopts LEICA
DM2500 types fluorescence microscope gathers respectively the bright field image and fluoroscopic image of sample.Cut block U-Cell and Cell-CF is each
About 0.5g, in being put into the surface plate for having added 200mL tap waters in advance, with stereomicroscope state of two kinds of samples in water is gathered
Modified-image.
The measure of the 24h dissolution rates of the hydrostatic released nutrient curve of Zn and K and N in 1.6 Cell-CF
The measure of the hydrostatic released nutrient curve of Zn and K designs as follows on the basis of with reference to HG/T 3997-2008：Claim
Block Cell-CF 0.5g are taken, is fitted in the pouch that 100 mesh nylon gauzes are made and is sealed, subsequently pouch is placed in into 250mL tools
In plug triangular flask, and 100mL deionized waters are accurately added, jumped a queue closed, be subsequently placed at the thermostat water bath for being preheated to 38 DEG C
In, triangular flask is taken out every 2h, triangular flask turning upside down three times gently makes solution concentration in bottle uniformly, pipette 1mL solution
In 50mL volumetric flasks and constant volume.Respectively with atomic absorption instrument (Z-2000) and flame photometer (FP6410) carries out zinc and potassium is dense
The measure of degree.In addition remaining liq in triangular flask is carried out into dry filtration after 24h, draw 50mL, steamed in 60 DEG C of baking ovens
Send out and be concentrated into 10mL, then according to the regulation in GB/T 8572 carries out the measure of 24h total nitrogen stripping quantities.
1.7 the zinc fertilizer evaluation experimental of Cell-CF
Zinc fertilizer fertilizer efficiency evaluation of programme arranges five process：Blank (CKO), Zinc vitriol fertilizer (CK1), EDTA chelas
Close zinc fertilizer (CK2), chicken feather cross-linked cellulose gel fertilizer (Cell-CF) and subtract Cell-CF process (- 20%) for applying 20%.
The nutrient composition of Cell-CF is shown in Table 2.Other process in addition to blank and -20% are processed are the fertilising of equivalent nutrient.Per kilogram
The concrete dose of wind desiceted soil is as follows, CK0：Labile soil organic carbon is listed in table 3；CK1：Carbamide 0.3227g, Diammonium phosphate (DAP) 0.20g, sulfur
Sour potassium 0.3046g, Zinc vitriol 0.0610g；CK2：Carbamide 0.3227g, Diammonium phosphate (DAP) 0.20g, potassium sulfate 0.3046g,
EDTA fertilizer of chelated zinc 53.1mL (EDTA of 0.01moL/L and zinc ion 1:1 chelating)；Cell-CF：Gel fertilizer 1.00g, phosphoric acid
Diammonium 0.20g；- 20%：Gel fertilizer 0.80g, Diammonium phosphate (DAP) 0.16g.
1.7.1 soil incubation experiment
Require that seedling-growing container (190 × 135 will be loaded after 2.5Kg Soil and Fertilizer mix homogeneously according to the fertilising of each experiment process
× 170mm), aperture is left in bottom, is positioned over outdoor area without shade, respectively pours 200mL tap waters twice sooner or later per basin daily.Soil
Culture experiment originates in July 21, respectively 5,15,25,35,45,55 after day, and fetch earth about 50g per basin, air-dries laggard
Row Soil Available Zinc, available potassium in soils, the measure of total soil nitrogen.(effective zinc：DTPA extraction Atomic Absorption flame luminosities are measured
It is fixed, effective potassium：Cold 2MHNO3Extraction-flame spectrophotometric determination, full nitrogen：Triumphant formula nitriding is determined).
1.7.2 Semen Maydiss potted plant experiment probes into the biological effectiveness of zinc fertilizer
Semen Maydiss potted plant experiment is consistent with soil incubation experiment dose and the same period is carried out, and 2.5Kg clay fertilizers mixture is filled into basin,
Four cave Semen Maydiss, every bunch planting kind corn seed two are sowed per basin. outdoor area without shade is positioned over, 7 days laggard Seedlings in the ranks of emerging, per basin
Retain the consistent maize seedling four of growth.Early stage respectively pours twice daily 200mL tap waters sooner or later per basin, grows to maize seedling
5 leaf phase transpirations are strong, and irrigation quantity is increased every time to 250mL.After maize seedling grows 55 days, under ground portion and ground are harvested respectively
Upper part, is completed, drying, is crushed, and after ashing is processed, determines Zn content.
2 results and discussion
The synthesis of 2.1 gel fertilizer
2.1.1 the determination of gel fertilizer synthesis condition
Chicken feather alkali solution liquid is not added with advance carbamide, using monofactor control variate method, KOH concentration, reaction is explored respectively
Temperature (T), hydrolysis time (t), four factors of chicken feather and alkali liquor ratio (S/L), the shadow to chicken feather water-solubility protein yield (PDI)
Ring.Understand concentration of potassium hydroxide within 1.5moL/L with the raising of alkali concn, the increase of PDI values, the hydrogen of 1.5moL/L by Fig. 1 a
Potassium oxide can make PDI stable in a higher value.Alkaline hydrolysis temperature is in the rising PDI values of temperature in the range of 35-75 DEG C
The trend for ramping, is tended towards stability by Fig. 1 b reaction temperatures higher than PDI after 75 DEG C.The alkaline hydrolysis time in 120min, with the time
Prolongation PDI values gradually increase, by Fig. 1 c understand 120min after PDI basically reach maximum.Material ratio also has larger shadow to PDI
Ring, increase with the input amount of chicken feather, PDI is gradually reduced, but when the addition of chicken feather is less than 0.5g in every 5mL potassium hydroxide solutions
The slope that PDI declines is less, under the premise of ensureing that chicken feather preferably decomposes, to make chicken feather alkali solution liquid in polypeptide and aminoacid have
Higher concentration, it is more satisfactory from 0.1g/mL by Fig. 1 d analyses S/L (g/mL).
The potassium hydroxide solution of 1.5moL/L carries out compatibility to dissolve cellulose with carbamide, with the increase of carbamide addition,
The ability of composite solution dissolving cellulose is gradually stepped up, composite solution dissolving when as shown in Figure 2 carbamide addition is 12g/100mL
The ability of cellulose tends to stable.Therefore the proportioning of composite solution is the potassium hydroxide solution that every 100mL concentration is 1.5moL/L
In 12g containing carbamide, further using falling ball method determine in every milliliter of double solventss add 0.06g celluloses can form cellulose
Gel.This double solvents is used for alkaline hydrolysis chicken feather PDI close 100%, better than KOH solution, the composition of the final double solventss for determining
And experiment condition is listed in table 1.
The preparation condition of the optimum experimental of table 1. gained Cell-CF
S/L:Solid-to-liquid ratio
2.1.2 the synthesis of gel fertilizer (Cell-CF)
As shown in Figure 3 chicken feather cross-linked cellulose prepares multi-functional zinc fertilizer one and is divided into four steps.First step feather is through hydrogen-oxygen
Change potassium/water/carbamide (KOH/H2O/CO (NH2)2) double solventss alkaline hydrolysis, the destruction of its process maintains the hydrogen of keratin space structure
Key, disconnects disulfide bond and hydrolysising peptide key so that feather keratin becomes that molecular weight is little, the protein peptide and amino of good water solubility
Acid.Second step adds cellulose in chicken feather alkali solution liquid, and this process cellulose is swelling because absorbing chicken feather hydrolyzed solution (to be accompanied by egg
The inside of white peptide, aminoacid infiltration and carbamide to cellulose), the crystal region of cellulose is destroyed with the hydrogen bond of noncrystalline domain, knot
Brilliant degree declines, and reacts accessibility raising, and this process cellulose chain and protein peptide chain carry out the interspersed folding of height.3rd step is used
The pH regulator of pluralgel is faintly acid 6.5 by dilute sulfuric acid, and because sulphuric acid has neutralized the alkalescence of gel fertilizer, alkali is to the molten of cellulose
Swollen effect disappears, and a large amount of hydrogen bonds is formed between protein peptide chain and cellulose chain, so as to both being bound together tightly, cellulose chain
Being modified becomes the compound chain of the higher cellulose polypeptide of hydrophilic and complexing of metal ion ability, and chain is lightly crosslinked with interchain
Fold and constitute tridimensional network.4th step adds metal trace element in gel, using the functional group in gel and metal
Ion carries out complexation, and this is tested and Zinc vitriol is added in gel, continues to stir 1h, pours gel fertilizer into mould
(there is the lattice of 1cm × 1cm × 1cm) drying forming in 60 DEG C of drying baker.The nutrient composition of final synthetic fertilizer is listed in
Table 2.
The element utilization rate of material is put in the multi-functional zinc fertilizer preparation process of chicken feather cross-linked cellulose almost
100%.Potassium hydroxide in double solventss, carbamide can be respectively plant and provide potassium and nitrogen nutrition, and the hydrolyzate of chicken feather is more
Peptide and aminoacid can directly be absorbed by crop, and with the effect of stimulation plant growth. hydroxyl, the carboxylic contained in gel
The functional groups such as base, amino, sulfino can occur complex reaction with trace element, make metal ion sticking in gel rubber system
In, trace element is protected, it is difficult to be converted into invalid state nutrient in soil environment.Cellulose Jing chicken feather alkaline hydrolysis products
Modified to constitute a kind of hydrophilic tridimensional network, water absorption and swelling dehydration shrinkage water capacity is improved and can change
Play a positive role in kind Soil structure.In addition gel interts life beneficial to root system of plant after water absorption and swelling in soil inside it
It is long, and plant root growth directly can draw nourishment from and absorb moisture with to water to fertilizer from inside it.
The chemical composition of the Cell-CF of table 2
2.2 FTIR and XRD analysis
Fig. 4 a for CF and U-CF infrared spectrum, from infrared spectrum it can be seen that.3297cm-1It is nearby hydroxyl characteristic absorption
The stretching vibration at peak and secondary amide N-H, the stretching vibration of primary amide N-H is the peak of two moderate strengths, respectively in 3500cm-1With
3400cm-1Nearby (corresponding to the antisymmetric stretching vibration of N-H), because the impact of hydrogen bond is moved respectively to low frequency range.
3080cm-1It is nearby the characteristic absorption peak of polypeptide (- CO-NH -), 1630-1690cm-1Wave-length coverage is that C=O is flexible shakes
The absorption of dynamic (referred to as amide I band), 1512cm-1It is nearby the absorption of secondary amide N-H bending vibrations (amide II bands), amide C-N
Absorption band is referred to as amide III bands, and the C-N absorption bands of secondary amide are in 1305-1200cm-1In wave-length coverage, the C-N of primary amide inhales
Take-up is in 1420-1400cm-1In wave-length coverage, 2929cm-1The absorption at place is shaken because the C-H of methyl and methylene is flexible
It is dynamic.CF shows peptide characteristic, rich in amido link (secondary amine), belongs to keratin.The secondary amine character absworption peak of U-CF weaken and primary
The absworption peak of amine strengthens, and the hydrolysis for being on the one hand because peptide bond generates primary amide；On the other hand it is probably similar to LiOH/
H2O/CO(NH2)2The mechanism of action of system and cellulose, potassium hydroxide/water/carbamide (KOH/H2O/CO(NH2)2System hydrolyzes plumage
The polypeptide that hair is produced can form hydrogen bond with carbamide, and carbamide is coated on the periphery of polypeptide particles, is reflected in U-CF in infrared spectrum
The C-H stretching vibration absworption peaks of methyl and methylene are weaker, while showing very strong primary amide characteristic absorption peak.
Fig. 4 b for Cell and U-Cell infrared spectrum, from infrared spectrum it can be seen that.3345cm-1The absworption peak at place is fibre
The common hydroxyl characteristic absorption peak of dimension element, 2929cm-1The absorption at place is the C-H stretching vibrations due to methyl and methylene,
1640cm-1Neighbouring absworption peak is the absworption peak that cellulose absorbs moisture, 1355cm-1Place absorbs peak-to-peak in the face of O-H
Bending vibration and CH2Rocking vibration, CH2Scissoring vibration absworption peak in wavelength 1431cm-1Locate to be composed for the crystallization of cellulose I
Band, 1050cm-1Place is one of characteristic peak that cellulose C-O stretching vibration peaks are cellulose, 1164cm-1The absworption peak at place is C-
The asymmetrical stretching vibration of O-C, 896cm-1For the vibration of ring-type C-O-C asymmetric facess external extension or CH2(CH2OH) on-plane surface is waved
The characteristic peak that vibration is produced is relevant with the noncrystalline domain of cellulose.The peak position and peak at the infrared signature peak of U-Cell compared with Cell
Intensity there occurs significant change, and the absworption peak in cellulose crystallite area disappears, and the characteristic absorption peak of cellulose weakens and the suction of carbamide
Receiving peak strengthens (characteristic absorption peak of primary amide occupies leading position).In potassium hydroxide/carbamide dicyandiamide solution, alkali destruction cellulose
Intermolecular hydrogen bonding and swollen cellulose, hydrogen bond and are coated on cellosilk outside and play a part of stabilizer in carbamide saboteur.
The infrared spectrum of Cell-CF is shown in Fig. 4 c.Its infrared spectrum is compared with U-Cell with U-CF and there occurs large change,
Wavelength 3500cm-1And 3400cm-1Nearby the peak of two moderate strengths of the antisymmetric stretching vibration of primary amide N-H disappears,
2929cm-1There are the C-H stretching vibrations of stronger methyl and methylene at place, and the characteristic peak of finger print region cellulose and protein peptide is in
Reveal and.Illustrate Cell-CF surfaces no longer based on carbamide, it may be possible to swelling mistake of the coalition of carbamide and polypeptide in cellulose
Journey is transferred to filametntary inside.1620cm-1It is the absworption peak of C=O stretching vibrations (referred to as amide I band) near wavelength；
1355cm-1Absworption peak at wavelength is the in-plane bending vibration and CH of O-H2Rocking vibration, 1050cm-1For C-O stretching vibrations
Peak is the characteristic peak of cellulose, 896cm-1For the vibration of ring-type C-O-C asymmetric facess external extension or CH2(CH2OH) on-plane surface is waved
The characteristic peak .Cell-CF surfaces that vibration is produced are based on the characteristic absorption peak of cellulose, while with amide characteristic peak, show,
Polypeptide be is combined with cellulose in the form of interspersed it is most of enter inside cellulose simultaneously partial denudation in filametntary outside.
The crystallinity of CF and U-CF is analyzed (see Fig. 5 a) using XRD.CF is have faint spreading out near 10 ° in 2 θ
It is keratin α-helixstructure diffraction to penetrate peak, and it is keratin beta sheet structure diffraction near 20 ° to be in 2 θ, and 2 θ are nearby for 30 °
Keratin beta sheet structure is overlap with β-corner structure.U-CF, keratin α-helixstructure, keratin beta sheet and β-corner
The diffraction maximum of structure disappears, and the crystalline texture for showing the hydrolysis CF through composite solution is totally disrupted.U-CF 2 θ be 20 °-
Many narrow diffraction maximums are occurred in that in the range of 27.5 °, while compared for the XRD spectrums of U-Cell (Fig. 5 b) and Cell-CF (Fig. 5 c)
Figure, find the appearance position consistency of their diffraction maximums, illustrate diffraction maximums of 2 θ in the range of 20 ° -27.5 ° be double solventss and in
With the diffraction maximum of its inner inorganic salt after pH.
The XRD spectra of Cell and U-Cell is shown in Fig. 5 b.It is cellulose Ⅰ without the leaf wood paper cellulose (Cell) of dissolving
Type crystalline texture, it is 15 ° and 22.8 ° that its 101 and 002 crystal face distinguishes corresponding diffraction maximum, the crystal region Jing after double solventss process
Diffraction maximum disappear, show that double solventss are more complete to the destruction of the crystalline texture of Cell.
The XRD spectra of Cell-CF is shown in Fig. 5 c.In addition to the diffraction maximum of inorganic salt, other diffraction maximums are had no, show chicken feather
The combination product of alkaline hydrolysis gained polypeptide and aminoacid and cellulose is a kind of disordered structure, and this is because the hydrolyzate of chicken feather is big
It is little to differ and the interspersed folding between molecule is random.
2.3 XPS analysis
XPS analysis have been carried out to Cell-CF as shown in fig. 6, XPS elements full scan collection of illustrative plates (6a) shows the table of Cell-CF
Face also has many other elements, this is because chicken feather and paper cellulose are except substantial amounts of C is contained outside N, O, S, Zn element
Natural organic matter material, it is elementary composition various, but the surface Determination of Potassium of the weaker explanation Cell-CF of photoelectron intensity of K2p compared with
It is few, it may be possible to which that the potassium hydroxide of aquation has been transferred to the inside of gel fertilizer in the swelling process for participating in cellulose.To C1s
(281-291eV), N1s (395-405eV), Znp3/2 (1019-1025eV) has carried out high-resolution light using Gauss analysis
Electron spectrum is parsed, and explores the combining form of chemical bond that may be present, the differentiation of the electron binding energy between different chemical bonds,
Primary Reference XPS analysis handbooks.C1s shown in Fig. 6 b mainly has 4 peaks of different nature, respectively positioned at 284.61eV,
286.2eV, 287.9eV, 288.7eV, represent respectively C-C, the carbon of cellulose, the carboxyl carbon of aminoacid (polypeptide c-terminuses) and
Carbamide state carbon, the characteristic peak of four kinds of different carbon keys, the predominantly organic composition in surface for disclosing Cell-CF is cellulose, aminoacid
With part carbamide.N1s shown in Fig. 6 c mainly has 2 peaks of different nature, respectively positioned at 399.5eV and 400.6eV, represents respectively
Urea nitrogen and amino-acid nitrogen.Zn2p3/2 shown in Fig. 6 d mainly has 3 peaks of different nature, respectively positioned at 1021.8eV,
1022eV, 1023.1eV, represent respectively Zn-O, Zn-S and ZnSO4State zinc, represents the zinc ion part and Cell-CF for adding
In functional group combined, also with the presence of part with dissociate state.
Bonding state and swelling behavior of the 2.4 gel fertilizer (Cell-CF) in water
It is chicken feather Jing after composite solution hydrolysis it can be seen that U-CF aqueous solutions contain many fine granularity materials from Fig. 7 A
Residue because the plumage handle and pinna rachis of chicken feather be harder and more difficult decomposition, but the grain graininess of residue is below 20 μm, right
Chicken feather hydrolyzed solution to the material migration inside cellulose and combination affect less；Fig. 7 B show the aqueous solution of U-CF present it is relatively strong and
Uniform fluorescence, illustrates the polypeptide and small molecule aminoacid that good water solubility mostly is in chicken feather hydrolyzed solution.U-Cell as seen in figure 7 c
Mutually interspersed tridimensional network is presented in water；As illustrated in fig. 7d, whole visual field is black to U-Cell fluoroscopic images, because of fibre
Dimension element is non-fluorescent material.As seen in figure 7e Cell-CF is with tridimensional network presence in water, and gelation process cellulose is molten
Swollen to absorb whole chicken feather hydrolyzed solutions, water-soluble substanceses penetrate into filametntary inside, and larger chicken feather keratin granule
Part is interspersed to be entered cellosilk inside or is attached to filament surface.Cell-CF fluoroscopic images as shown in Figure 7 F, with cellosilk
Profile present stronger fluorescence for framework, and have passed through and win over by any means up to the immersion Cell-CF cellosilks of 8h in aqueous
The trend that do not weaken of fluorescence, illustrate that polypeptide and aminoacid are big with the bond strength of cellulose, can form fine coalition.
As shown in Figure 8 Cell-CF enters to show extremely strong water absorption and swelling after water, and 10min inner volumes are expanded to rapidly original
4-5 times for coming.And U-Cell to enter do not show after water obvious swellability.Polypeptide and aminoacid contain substantial amounts of hydrophilic official
Can roll into a ball, the combination of polypeptide and aminoacid and cellulose can significantly improve the water absorbing properties of cellulose, and present between cellosilk mutual
Mutually interspersed network structure has can make Cell-CF hold large quantity of moisture.
The measure of the hydrostatic nutrient dissolved percentage of 2.5 Cell-CF
As shown in Figure 9 hydrostatic release profiles of the Zn and K in Cell-CF in 24h meet logarithmic, front four hours
Rate of release it is high, subsequently release is slow and about reaches after 12h stable.The 24h dissolution rates of Zn are the 24h dissolutions of 50.2%, k
Rate is 55.5%.The water absorption and swelling performance of Cell-CF is projected, and gel inside nutrient dissolves and formed osmotic pressure after water suction, in addition
Hole between swelling rear cellosilk increases rapidly, causes the unconjugated zinc in Cell-CF inside, potassium, the quick release of carbamide nutrient.
Decline with the reduction diffusion rate of solution nutrient concentration gradient with gel inside.In addition the functional group in gel fertilizer has stronger
Complexing power and charge attraction power, what metal cation nutrient can be bound in gel fertilizer is internally formed slow nutrient.Rear
Continuous root system of plant interts growth and the degraded of adjoint gel fertilizer can make the effective of this part nutrient change.The rate of release of K and
Dissolution rate is higher than Zn, because Zn can carry out complexation with the functional group inside gel has higher adhesion.
It is 93.8 ± 4.2% that Jing determines the 24h dissolution rates of nitrogen, it is believed that Cell-CF whole carbamide of dissolution in 24h
State nitrogen, the nitrogen of remaining non-dissolution is the polypeptide and aminoacid combined with cellulose.Nitrogen is mainly carbamide in Cell-CF, and
Carbamide water solublity preferably and for neutral molecule, so diffusion rate of the carbamide in swelling gel fertilizer is fast and dissolution rate is high.
The fertilizer efficiency evaluation of 2.6 Cell-CF
Traditional fertilizer be manured into soil after because the impact of fertilizer self property and soil environment is easily converted into invalid state nutrient, fertilizer
Material utilization rate is low.The dynamic change of the available nutrientses of different disposal ZINC IN SOIL and potassium using soil incubation experimentation,
And determine total soil nitrogen amount change.The basic fertility of experiment soil used is listed in table 3.
Table 3 tests the physicochemical property of soil
OM:Organic matter；N:Total soil nitrogen；P:Total Phosphorus In Soil；K:Available potassium in soils；Zn:Soil Available Zinc
As shown in Figure 10 a, the same change for processing total nitrogen content of soil is little in 55 days of soil incubation.Generally
CK1, CK2, Cell-CF and -20% total nitrogen content are significantly higher than CK0, and between CK1, CK2, Cell-CF and -20%
Difference it is not notable.Same process shown in Figure 10 b, available potassium in soils content is presented what is be gradually reduced with the prolongation of incubation time
Trend.Effective potassium content of CK1 between different disposal, CK2, Cell-CF and -20% is significantly higher than CK0.Other generally CK1,
The effective potassium contents of CK2 and Cell-CF are higher than CK0.And the effective potassium content difference between CK1, CK2 and Cell-CF is not notable.It is comprehensive
It is upper described, the soil incubation experiment of short-term show Cell-CF as nitrogenous fertilizer and potash fertilizer in application properties with CO (NH2)2With
K2SO4Comparing advantage of do not embody.CK1 in the 55d of soil incubation as shown in figure l oc, CK2's, Cell-CF and -20% has
Effect Zn content is all remarkably higher than CK0；Front 35 days CK2, effective Zn content of Cell-CF and -20% is all remarkably higher than CK1, says
What is just become in short time of the bright Inorganic Zn fertilizer after being manured into soil is invalid；Effective Zn content of CK2 is higher than at other in first 15 days
Manage but not notable with the difference of Cell-CF；Effective Zn content of CK2 is higher in front 15 days contents that soil incubation is tested, subsequently
Rapid to decline, effective Zn content of soil incubation CK2 after 35 days is even no longer above CK1, illustrates that EDTA fertilizer of chelated zinc simply exists
It is a kind of quick-acting zinc fertilizers that the initial stage being manured into soil can keep higher fertilizer efficiency；The full period that Cell-CF is tested in soil incubation is all
Higher effective zinc extracted amount is kept, and the effective Zn content of prolongation with incubation time does not show downward trend,
Illustrate that the zinc in Cell-CF is a kind of long-acting zinc fertilizer；Cell-CF subtract apply 20% in the case of Available Zn content in soil it is significantly high
In having applied ZnSO4Soil (CK1), and Available Zn content in soil is significantly higher than has applied EDTA always after 15 days of culture experiment
The soil (CK2) of fertilizer of chelated zinc.
What Figure 10 d reflected is the Zn content in the potted plant milpa body of different disposal.Root system and aerial partss CK1, CK2,
The Zn content of Cell-CF and -20% is all remarkably higher than CK0, in addition CK2, and Cell-CF and -20% is all remarkably higher than CK1；
Zn content CK2 in root system, Cell-CF and -20% are all remarkably higher than CK1；And CK2, Cell-CF and -20% three it
Between difference it is not notable；The Zn content of aerial partss CK2 is significantly higher than other process.These results suggest that, for this season crop
The biological effectiveness of zinc is all higher in EDTA Chelating states zinc and Cell-CF, but EDTA Chelating state zinc is being planted compared with Cell-CF
In thing in migration advantageously.Consider the long-lasting of the economy of Cell-CF preparation process, environment friendly and zinc fertilizer
Can illustrate that Cell-CF is a kind of zinc fertilizer of function admirable.
The above, preferably specific embodiment only of the invention, protection scope of the present invention not limited to this are any ripe
Those skilled in the art are known in the technical scope of present disclosure, the letter of the technical scheme that can be become apparent to
Altered or equivalence replacement are each fallen within protection scope of the present invention.
Claims (3)
1. the preparation method of the multi-functional zinc fertilizer of a kind of chicken feather cross-linked cellulose, it is characterised in that comprise the following steps：
Step 1, feather are through potassium hydroxide/water/carbamide KOH/H2O/CO(NH2)2The alkaline hydrolysis of double solventss, its process destruction dimension
It is the hydrogen bond of keratin space structure, disconnects disulfide bond and hydrolysising peptide key so that it is little that feather keratin becomes molecular weight, water solublity
Protein peptide well and aminoacid, obtain chicken feather hydrolyzed solution；
Step 2, in chicken feather hydrolyzed solution cellulose is added, this process cellulose is swelling because absorbing chicken feather hydrolyzed solution, is accompanied by
, to the inside of cellulose, the crystal region of cellulose and the hydrogen bond of noncrystalline domain are destroyed, tie for protein peptide, aminoacid infiltration and carbamide
Brilliant degree declines, and reacts accessibility raising, and this process cellulose chain and protein peptide chain carry out the interspersed folding of height, form compound
Gel；
Step 3, by the pH regulator of pluralgel it is faintly acid 6.5 with dilute sulfuric acid, sulphuric acid has neutralized the alkalescence of pluralgel fertilizer,
Alkali disappears to the swelling effect of cellulose, a large amount of hydrogen bonds is formed between protein peptide chain and cellulose chain, so as to both constraints tightly
Together, cellulose chain is modified becomes the compound chain of the higher cellulose polypeptide of hydrophilic and complexing of metal ion ability, and
Fold lightly crosslinked with interchain of chain constitutes tridimensional network；
Step 4, in pluralgel metal trace element is added, using the functional group in gel and metal ion complexation is carried out,
This is tested and Zinc vitriol is added in gel, continues to stir 1h, gel fertilizer is poured into mould, in 60 DEG C of drying baker
Middle drying forming.
2. the preparation method of the multi-functional zinc fertilizer of chicken feather cross-linked cellulose according to claim 1, it is characterised in that step 1
Middle KOH concentration is 1.5mol/L, CO (NH2)2Content is 0.12g/mL, and every milliliter of double solventss react under the conditions of 75 DEG C
120min, hydrolyzes 0.1g chicken feathers.
3. the preparation method of the multi-functional zinc fertilizer of chicken feather cross-linked cellulose according to claim 1, it is characterised in that step 2
Described in chicken feather hydrolyzed solution be cooled to -12 DEG C in advance, every milliliter of chicken feather hydrolyzed solution adds 0.06g celluloses.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721666A (en) * | 2017-11-28 | 2018-02-23 | 芜湖四高农业科技有限公司 | A kind of safe and healthy vegetables Special slow release fertilizer |
| CN108906348A (en) * | 2018-03-05 | 2018-11-30 | 中国标准化研究院 | Separate the separator and separation method of micro- plastics and cellulose crystallite in soil |
| CN111410586A (en) * | 2020-03-31 | 2020-07-14 | 农业农村部规划设计研究院 | Straw organic matter crosslinked polypeptide chelated medium-trace element slow-release fertilizer and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4999425A (en) * | 1989-06-12 | 1991-03-12 | Teepak, Inc. | Cellulose aminomethanate by ion-exchange extraction |
| US20110098384A1 (en) * | 2009-10-23 | 2011-04-28 | Blount David H | Production of amino lignin and amino lignin cellulose resins and adhesives |
| CN102093483A (en) * | 2009-12-11 | 2011-06-15 | 徐明双 | Preparation of cellulose carbamate from bamboo fibers |
| CN102815996A (en) * | 2012-07-31 | 2012-12-12 | 马鞍山科邦生态肥有限公司 | Special fertilizer for single cropping rice and preparation method of special fertilizer |
| CN102816020A (en) * | 2012-07-31 | 2012-12-12 | 马鞍山科邦生态肥有限公司 | Special fertilizer for watermelon base fertilizer as well as preparation method of special fertilizer |
| CN102826899A (en) * | 2012-07-31 | 2012-12-19 | 马鞍山科邦生态肥有限公司 | Special late rice fertilizer and preparation method of special late rice fertilizer |
| CN102826922A (en) * | 2012-07-31 | 2012-12-19 | 马鞍山科邦生态肥有限公司 | Fertilizer special for spring corn base fertilizer |
| CN103124789A (en) * | 2010-07-30 | 2013-05-29 | 加州大学评议会 | Polypeptides for use in the deconstruction of cellulose |
| CN103467760A (en) * | 2013-09-09 | 2013-12-25 | 浙江大学 | Method for preparing high-strength chitosan/cellulose composite hydrogel film |
| CN104947242A (en) * | 2015-06-26 | 2015-09-30 | 安徽皖翎羽绒制品有限公司 | Down feather composite fiber having good flame-retardant effect |
-
2016
- 2016-12-04 CN CN201611103202.4A patent/CN106588459B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4999425A (en) * | 1989-06-12 | 1991-03-12 | Teepak, Inc. | Cellulose aminomethanate by ion-exchange extraction |
| US20110098384A1 (en) * | 2009-10-23 | 2011-04-28 | Blount David H | Production of amino lignin and amino lignin cellulose resins and adhesives |
| CN102093483A (en) * | 2009-12-11 | 2011-06-15 | 徐明双 | Preparation of cellulose carbamate from bamboo fibers |
| CN103124789A (en) * | 2010-07-30 | 2013-05-29 | 加州大学评议会 | Polypeptides for use in the deconstruction of cellulose |
| CN102815996A (en) * | 2012-07-31 | 2012-12-12 | 马鞍山科邦生态肥有限公司 | Special fertilizer for single cropping rice and preparation method of special fertilizer |
| CN102816020A (en) * | 2012-07-31 | 2012-12-12 | 马鞍山科邦生态肥有限公司 | Special fertilizer for watermelon base fertilizer as well as preparation method of special fertilizer |
| CN102826899A (en) * | 2012-07-31 | 2012-12-19 | 马鞍山科邦生态肥有限公司 | Special late rice fertilizer and preparation method of special late rice fertilizer |
| CN102826922A (en) * | 2012-07-31 | 2012-12-19 | 马鞍山科邦生态肥有限公司 | Fertilizer special for spring corn base fertilizer |
| CN103467760A (en) * | 2013-09-09 | 2013-12-25 | 浙江大学 | Method for preparing high-strength chitosan/cellulose composite hydrogel film |
| CN104947242A (en) * | 2015-06-26 | 2015-09-30 | 安徽皖翎羽绒制品有限公司 | Down feather composite fiber having good flame-retardant effect |
Non-Patent Citations (4)
| Title |
|---|
| 全国科协学会工作部编: "《饲料科技发展新途径》", 31 December 1988, 饲料科技发展新途径 * |
| 关莹 等: "农林生物质材料基水凝胶的研究进展", 《林业化学与工业》 * |
| 吕昂 等: "纤维素溶剂研究进展", 《高分子学报》 * |
| 李忠正 等: "《植物纤维资源化学》", 30 June 2012, 中国轻工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721666A (en) * | 2017-11-28 | 2018-02-23 | 芜湖四高农业科技有限公司 | A kind of safe and healthy vegetables Special slow release fertilizer |
| CN108906348A (en) * | 2018-03-05 | 2018-11-30 | 中国标准化研究院 | Separate the separator and separation method of micro- plastics and cellulose crystallite in soil |
| CN108906348B (en) * | 2018-03-05 | 2023-10-10 | 中国标准化研究院 | Separation device and separation method for separating microplastic and cellulose crystals in soil |
| CN111410586A (en) * | 2020-03-31 | 2020-07-14 | 农业农村部规划设计研究院 | Straw organic matter crosslinked polypeptide chelated medium-trace element slow-release fertilizer and preparation method thereof |
| CN111410586B (en) * | 2020-03-31 | 2022-02-25 | 农业农村部规划设计研究院 | Straw organic matter crosslinked polypeptide chelated medium-trace element slow-release fertilizer and preparation method thereof |
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