CN109836278A - A kind of biologic compound fertilizer and its processing technology made of graphene oxide - Google Patents
A kind of biologic compound fertilizer and its processing technology made of graphene oxide Download PDFInfo
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Abstract
The invention discloses a kind of biologic compound fertilizer and its processing technologys made of graphene oxide, belong to agrochemical preparation technical field.The present invention is by graphene oxide, sodium azide, the reaction of dehydrated alcohol heating stirring, it is subsequently added into tetra lithium aluminium hydride, heating stirring reaction, it is subsequently added into pretreatment sisal fiber, sodium hydroxide solution is then added and adjusts pH, heating stirring reaction, filtering, it is dry, up to modified graphene oxide, by microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, modified graphene oxide, sodium alginate solution, polyethyleneimine, aniline, carbomer, calcium nitrate ion ball milling mixing, it is subsequently added into ammonium hydroxide and adjusts pH, Frozen-thawed cycled, freezing, it crushes, sieving, it is dry, up to new bio compound fertilizer.New bio compound fertilizer provided by the invention has excellent sustained release and agglomeration preventing performance, therefore has good fertilizer efficiency.
Description
Technical field
The invention discloses a kind of biologic compound fertilizer and its processing technologys made of graphene oxide, belong to chemurgy
Fertile preparation technical field.
Background technique
Chemical fertilizer is added as a kind of mode for improving crop yield, has been had been to be concerned by more and more people.Change
It learns fertilizer and granulated fertilizer is made more, granulated fertilizer can reduce the hygroscopicity of fertilizer, reduce the pollution to environment, be also convenient for applying.
However, fertilizer all has caking phenomenon to some extent, its property and service performance will affect, agglomeration is not only broken up
The free-flowing of product, and using when generally require to carry out break process, so often the agglomeration of fertilizer whether
An important indicator as product quality.With the continuous improvement of market competition to increasingly sharpen with level of farming mechanization,
The anti-caking problem of fertilizer is more and more taken seriously.The agglomeration problems for solving fertilizer, in addition to controlling suitable manufacturing condition
Outside, using anticaking agent and solution to this problem.The influence factor of fertilizer agglomeration can be divided into internal factor and outside
Factor.Internal factor refers to fertilizer itself on the influential condition of agglomeration and property, if the chemical reaction of weighing area, critical phase are to wet
Degree etc..External factor refer to water content, granularity and the uniformity of fertilizer, package temperature and in transport, storage, use process it is right
Agglomerate influential factor, such as temperature, pressure, ambient humidity.
In addition to this, in use, the utilization rate of nutrient is low in fertilizer for chemical fertilizer, is easy to be lost, this not only brings huge
Big waste, and nutrient loss will cause water resource pollution into river, lake, and the substance retained in soil can also change
Become soil constituent, deteriorates soil property, therefore, the utilization rate for improving chemical fertilizer has become a top priority.In order to reduce the leaching of fertilizer
Loss and the pollution to soil property, the rate of release for reducing quick-acting fertilizer nutrient is a kind of effective measures, so that crops can
It preferably absorbs and utilizes, the slow release for improving fertilizer is very urgent.
Therefore, how to improve conventional particles fertilizer easily to agglomerate and the disadvantage of slow release difference, to obtain more high combination property
Granulated fertilizer is that it is promoted and is applied to broader field, meets industrial production demand urgent problem to be solved.
Summary of the invention
Biologic compound fertilizer and its processing technology made of graphene oxide are used the purpose of the present invention is to provide a kind of, with
Solve the problems of the prior art.
To achieve the above object, the invention provides the following technical scheme:
A kind of biologic compound fertilizer made of graphene oxide, the raw material including following parts by weight: 3~5 parts of microorganism function
Energy microbial inoculum, 20~30 parts of chemical fertilizer, 20~30 parts of bio-feritlizers, 40~60 parts of medical stones, 10~20 parts of graphene oxides,
100~120 parts of sodium alginate solutions.
The new bio compound fertilizer further includes the raw material of following parts by weight: 3~5 parts of polyethyleneimines, and 10~20
Part aniline, 3~5 parts of carbomers, 3~5 parts of calcium nitrate solutions.
The microbial function microbial inoculum includes the raw material of following parts by weight: 1~2 part of Bacillus pasteurii, 1~2 part big
Enterobacteria, 4~6 parts of cornstarch, 0.1~0.2 part of glycerol, 0.1~0.2 part of polyethylene glycol, 20~30 parts of deionized waters；It is described
Chemical fertilizer includes the raw material composition of following parts by weight: 10~20 parts of urea, 8~10 parts of calcium monohydrogen phosphates and 3~5 parts of chlorinations
Potassium；The bio-feritlizer includes the raw material of following parts by weight: 8~10 parts of chicken manures, 8~10 parts of cow dungs, 3~5 parts of straw ashs；Institute
Stating carbomer is Carbopol 941, any one in carbomer 934 or Acritamer 940.
The medical stone can also be modified medical stone；The modified medical stone is the raw material group by following parts by weight
At 10~20 parts of medical stones, 60~80 parts of hydrofluoric acid, 60~80 parts of dopamine solutions, 3~5 parts of glycoprotein, 30~50 parts go from
Sub- water.
The graphene oxide can also be modified graphene oxide；The modified graphene oxide includes following parts by weight
Several raw material: 20~30 parts of graphene oxides, 20~30 parts of sisal fibers, 0.1~0.2 part of cellulase, 2~3 parts of Azides
Sodium, 0.2~0.3 tetra lithium aluminium hydride, 30~50 parts of deionized waters, 40~60 parts of dehydrated alcohols.
The new bio compound fertilizer includes the raw material of following parts by weight: 5 portions of microbial function microbial inoculums, 30 parts of chemistry
Fertilizer, 30 parts of bio-feritlizers, 60 parts of modified medical stones, 20 parts of modified graphene oxides, 120 parts of sodium alginate solutions, 5 parts of polyethylene
Imines, 20 parts of aniline, 5 parts of carbomers, 5 parts of calcium nitrate solutions.
A kind of processing technology of the biologic compound fertilizer made of graphene oxide, specific processing method are as follows:
(1) medical stone single treatment；
(2) medical stone secondary treatment；
(3) medical stone modification；
(4) sisal fiber pre-processes；
(5) graphene oxide modification；
(6) mixing crushes；
(7) it detects.
The specific procedure of processing of the new bio compound fertilizer are as follows:
(1) medical stone is mixed into immersion with hydrofluoric acid, filters, a processing medical stone is obtained, by acidleach, so that inside medical stone
Hole is further widened, and being conducive to subsequent raw material can be fully penetrated to inside medical stone；
(2) a processing medical stone is mixed into immersion with dopamine solution, filters, obtains secondary treatment medical stone, it is attached using dopamine
In the surface and duct of a processing medical stone, due to the attachment of dopamine, so that in a processing medical stone surface and duct
Hydroxyl and amino isoreactivity functional group are connected, so that a medical stone surface adsorption property is further promoted；
(3) glycoprotein is mixed with water, is subsequently added into secondary treatment medical stone, filtered, obtain modified medical stone, due to modified wheat meal
Stone is grafted with active function groups, can adsorb glycoprotein, and part glycoprotein is dispersed in inside medical stone；
(4) by sisal fiber, cellulase, deionized water mixed processing, heat up enzyme deactivation, filters, dry, must pre-process sisal hemp fibre
Dimension decomposes the organic matter in fiber using cellulase, so that the permeance property of sisal fiber gets a promotion, meanwhile, so that sword
The active group on flaxen fiber surface sufficiently exposes；
(5) by graphene oxide, sodium azide, dehydrated alcohol heating stirring reaction is subsequently added into tetra lithium aluminium hydride, heating stirring
Reaction, is subsequently added into pretreatment sisal fiber, and sodium hydroxide solution is then added and adjusts pH, heating stirring reaction is filtered, done
It is dry to get modified graphene oxide, in the process, firstly, using sodium azide and graphite oxide alkene reaction, so that oxidation stone
Black alkene surface forms azido, and azido can be reduced into amino by tetra lithium aluminium hydride, to improve the parent of graphene oxide
Aqueous energy；Secondly, the hydroxyl of surface of graphene oxide can be with the aldehyde on pretreatment sisal fiber surface under alkaline heating condition
Aldol reaction occurs for base, enables the pretreatment sisal fiber in system to be grafted to surface of graphene oxide, increases oxygen
The structure complexity on graphite alkene surface pre-processes the grafting of sisal fiber as the Bacillus pasteurii in later period microbial bacterial agent
Breeding place is provided with Escherichia coli, meanwhile, sodium hydroxide solution can be with the carboxyl in graphene oxide layer structural edge
Reaction, so that the carboxylic ions in graphene oxide layer structural edge, so that modified graphene oxide can be good
Be dispersed in system, since a large amount of active group is contained on modified medical stone surface, enable to modified graphene oxide energy
It is enough attached to modified medical stone surface, the nutritional ingredients such as chemical fertilizer and bio-feritlizer in raw material are able to be fixed on modified wheat meal
Shi Zhong improves the sustained release performance of product, avoids a large amount of fertilizer from being directly entered in soil and causes soil hardening, thus into one
Step improves the fertilizer efficiency of product；
(6) by microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, sodium alginate solution, polyethyleneimine, benzene
Amine, carbomer, calcium nitrate ion ball milling mixing are subsequently added into modified graphene oxide, continue ball milling mixing, are subsequently added into ammonium hydroxide
PH is adjusted, Frozen-thawed cycled freezes, and crushes, sieving, and it is dry to get new bio compound fertilizer, firstly, passing through addition microorganism
Function microbial inoculum, the Bacillus pasteurii in microbial bacterial agent generate urase in metabolic processes, and urase can will be in system
Urea, which decomposes, generates carbanion and ammonium ion, since Bacillus pasteurii cell wall is negatively charged, in system
Calcium ion, to can generate calcium carbonate around bacterium using cell as nucleus, can be formed by Bacillus pasteurii Adsorption on cell walls
Calcium carbonate microspheres, nanometer calcium carbonate are formed such that the pore structure inside modified medical stone is enriched, further delay
It include the release of various fertilizer inside modified medical stone, to further improve the sustained release performance of product；Secondly, passing through addition
Carbomer, carbomer can form good physical entanglement with the glycoprotein inside modified medical stone, it is preferably solidifying to form stickiness
Glue network, moisture and nutritional ingredient can be lockked by being modified the gel network inside medical stone, improve the sustained release performance of product, from
And further improve the fertilizer efficiency of product.
(7) performance detection is carried out to product.
The specific process of the new bio compound fertilizer are as follows:
(1) hydrofluoric acid that medical stone and mass fraction are 20~30% is placed in reaction kettle, in revolving speed be 300~500r/min
Under the conditions of, after being stirred 20~30in of immersion, filtering obtains No. 1 filter residue, and the ammonium hydroxide for being then 20~30% with mass fraction is by 1
Number residue washing to cleaning solution is neutrality, obtains a processing medical stone；
(2) dopamine solution that a processing medical stone and mass concentration are 2.6mg/mL is placed in single-necked flask, is in revolving speed
Under the conditions of 400~600r/min, after being stirred 2~3h of immersion, filtering obtains No. 2 filter residues, No. 2 filter residues is placed in baking oven, in
Under the conditions of temperature is 105~110 DEG C, secondary treatment medical stone is obtained；
(3) glycoprotein and water are placed in No. 1 beaker, under the conditions of revolving speed is 1000~1200r/min, it is stirred 40~
After 60min, secondary treatment medical stone is then added into No. 1 beaker, under the conditions of revolving speed is 800~1000r/min, stirring is mixed
After closing 40~60min, filtering obtains modified medical stone；
(4) by sisal fiber, cellulase, deionized water is placed in No. 2 beakers, then No. 2 beakers are placed in digital display and are tested the speed constant temperature
It is 30~35 DEG C in temperature, under the conditions of revolving speed is 500~600r/min, 40~60min of mixed processing is connect in magnetic stirring apparatus
Be warming up to 80~85 DEG C of 10~20min of enzyme deactivation after, filtering, obtain No. 3 filter residues, then No. 3 filter residues be placed in baking oven, Yu Wendu
It is dry to constant weight under the conditions of 105~110 DEG C, obtain pretreatment sisal fiber；
(5) by graphene oxide, sodium azide, it is 140~160 DEG C in temperature, revolving speed is that dehydrated alcohol, which is placed in reactor,
Under the conditions of 600~800r/min, heating stirring reacts 40~60min, and tetra lithium aluminium hydride, Yu Wendu are then added into reactor
It is 140~160 DEG C, under the conditions of revolving speed is 600~800r/min, heating stirring reacts 40~60min, then adds into reactor
Enter to pre-process sisal fiber, under the conditions of revolving speed is 400~600r/min, 40~60min is stirred, then in reactor
Sodium hydroxide solution is added and adjusts pH to 8.1~8.3, is 120~130 DEG C in temperature, revolving speed is 500~600r/min condition
Under, heating stirring react 40~60min after, filtering, obtain filter cake, then filter cake be placed in baking oven, in temperature be 105~110
Under the conditions of DEG C, drying is to constant weight to get modified graphene oxide；
(6) by microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, modified graphene oxide, sodium alginate
Liquid, polyethyleneimine, aniline, carbomer, nitric acid calcium ion are placed in 40~60min of ball milling mixing in ball mill, then to ball milling
The ammonium hydroxide that mass fraction is 20~30r/min is added in machine and adjusts pH to 7.8~8.0, mixed slurry is obtained, then by mixed slurry
It is placed in refrigerator, under the conditions of temperature is -1~-10 DEG C, freezes 5~8h, material must be freezed, then freezing material is placed in room temperature condition
Melt down toward complete, obtain thawing mixed liquor, such Frozen-thawed cycled 5~8 times must handle homogenate, and processing homogenate is then placed in liquid
It is freezed in nitrogen, obtains frozen block, then frozen block is crossed the sieve of 360 mesh, ball milling material is obtained, then by ball as crushing in ball mill
Abrasive material is placed in baking oven, and under the conditions of temperature is 105~110 DEG C, drying is to constant weight to get new bio compound fertilizer；
(7) performance detection is carried out to gained new bio compound fertilizer.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention is in modified medical stone preparation process, firstly, medical stone passes through acidleach, so that the hole inside medical stone
It is further widened, being conducive to subsequent raw material can be fully penetrated to inside medical stone；Secondly, utilizing cellulase point
The organic matter in fiber is solved, so that the permeance property of sisal fiber gets a promotion, meanwhile, so that the active group on sisal fiber surface
Group's sufficiently exposure, since modified medical stone is grafted with active function groups, and can adsorb glycoprotein, enable part glycoprotein
It is dispersed in inside medical stone；
(2) present invention is in graphene oxide preparation process, firstly, the organic matter in fiber is decomposed using cellulase, so that
The permeance property of sisal fiber gets a promotion, meanwhile, so that the active group on sisal fiber surface sufficiently exposes；Secondly, utilizing
Sodium azide and graphite oxide alkene reaction, so that surface of graphene oxide forms azido, azido can be by tetra lithium aluminium hydride
It is reduced into amino, to improve the hydrophilicity of graphene oxide；Again, under alkaline heating condition, graphene oxide table
With the aldehyde radical on pretreatment sisal fiber surface aldol reaction can occur for the hydroxyl in face, so that the pretreatment sisal hemp in system
Fiber can be grafted to surface of graphene oxide, increase the structure complexity of surface of graphene oxide, pre-process sisal fiber
Grafting in later period microbial bacterial agent Bacillus pasteurii and Escherichia coli provide breed place, meanwhile, sodium hydroxide solution
Can be reacted with the carboxyl in graphene oxide layer structural edge so that the carboxyl in graphene oxide layer structural edge from
Sonization, so that modified graphene oxide good can be dispersed in system；Finally, due to which modified medical stone surface is contained
A large amount of active group enables to modified graphene oxide that can be attached to modified medical stone surface, the chemistry fertilizer in raw material
The nutritional ingredients such as material and bio-feritlizer are able to be fixed in modified medical stone, improve the sustained release performance of product, avoid a large amount of
Fertilizer is directly entered in soil and causes soil hardening, to further improve the fertilizer efficiency of product；
(3) present invention is by adding microbial function microbial inoculum, and the Bacillus pasteurii in microbial bacterial agent is in metabolic processes
Middle generation urase, the urea in system can be decomposed and generate carbanion and ammonium ion by urase, due to Bacillus pasteurii
Cell wall is negatively charged, the calcium ion in system can by Bacillus pasteurii Adsorption on cell walls, thus using cell as nucleus,
Calcium carbonate can be generated around bacterium, forms calcium carbonate microspheres, and nanometer calcium carbonate is formed such that the hole inside modified medical stone
Gap structure is enriched, and has further delayed the release inside modified medical stone comprising various fertilizer, to further improve
The sustained release performance of product；Secondly, carbomer can be formed well with the glycoprotein inside modified medical stone by addition carbomer
Physical entanglement, form the preferable gel network of stickiness, the gel network inside modified medical stone can lock moisture and nutrition
Ingredient improves the sustained release performance of product, to further improve the fertilizer efficiency of product.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
In order to which clearer explanation method provided by the invention is described in detail by following embodiment, in following implementation
The test method of each index of the new bio compound fertilizer made in example is as follows:
(1) agglomeration preventing performance: taking several culture dishes, accurately weighs its quality, open after being put into the test specimen for accurately weighing quality
It is placed under room temperature, after 10d, claims its quality, it is dry in being put into vacuum oven；Sample after removal is dry is placed on
On oscillator, 10min is vibrated under fixed speed, picks the fertilizer of agglomeration, accurately weighs its quality, records data；Agglomeration
Rate is calculated by formula (1):
Caking rate (%)=[agglomeration fertilizer quality (g)/sample fertilizer quality (g)] × 100% (1)；
(2) sustained release performance: being detected according to HG/T3931, dissolution under the conditions of 25 DEG C, to test specimen 1d and 28d Nitrogen
Rate.
Example 1
A kind of biologic compound fertilizer made of graphene oxide, the raw material including following parts by weight: 5 parts of microbial function bacterium
Agent, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts of modified medical stones, 20 parts of modified graphene oxides, 120 parts of sodium alginates
Liquid, 5 parts of polyethyleneimines, 20 parts of aniline, 5 parts of carbomers, 5 parts of calcium nitrate solutions.
The microbial function microbial inoculum includes the raw material of following parts by weight: 2 parts of Bacillus pasteuriis, 2 parts of Escherichia coli,
6 parts of cornstarch, 0.2 part of glycerol, 0.2 part of polyethylene glycol, 30 parts of deionized waters.
The chemical fertilizer includes the raw material composition of following parts by weight: 20 parts of urea, 10 parts of calcium monohydrogen phosphates and 5 parts of chlorinations
Potassium.
The bio-feritlizer includes: 10 parts of chicken manures, 10 parts of cow dungs, 5 parts of straw ashs.
The carbomer is Carbopol 941.
A kind of processing technology of the biologic compound fertilizer made of graphene oxide, specific process are as follows:
(1) 20 parts of medical stones according to parts by weight, 80 parts of hydrofluoric acid, 80 parts of dopamine solutions, 5 parts of glycoprotein, 50 parts of deionizations
The hydrofluoric acid that medical stone and mass fraction are 30% is placed in reaction kettle by water, and under the conditions of revolving speed is 500r/min, stirring is mixed
It closes after impregnating 30in, filtering obtains No. 1 filter residue, No. 1 residue washing to cleaning solution is by the ammonium hydroxide for being then 30% with mass fraction
Neutrality obtains a processing medical stone；
(2) dopamine solution that a processing medical stone and mass concentration are 2.6mg/mL is placed in single-necked flask, is in revolving speed
It under the conditions of 600r/min, is stirred after impregnating 3h, filtering obtains No. 2 filter residues, No. 2 filter residues are placed in baking oven, are in temperature
Under the conditions of 110 DEG C, secondary treatment medical stone is obtained；
(3) glycoprotein and water are placed in No. 1 beaker, under the conditions of revolving speed is 1200r/min, after being stirred 60min, then
Secondary treatment medical stone is added into No. 1 beaker, under the conditions of revolving speed is 1000r/min, after being stirred 60min, filtering is obtained
Modified medical stone；
(4) according to parts by weight, 30 parts of graphene oxides, 30 parts of sisal fibers, 0.2 part of cellulase, 3 parts of Azides are successively taken
Sodium, 0.3 tetra lithium aluminium hydride, 50 parts of deionized waters, 60 parts of dehydrated alcohols, by sisal fiber, cellulase, deionized water is placed in 2
In number beakers, then No. 2 beakers are placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 35 DEG C, revolving speed 600r/min
Under the conditions of, mixed processing 60min, after being then warming up to 85 DEG C of enzyme deactivation 20min, filtering obtains No. 3 filter residues, then sets No. 3 filter residues
It is dry to constant weight under the conditions of temperature is 110 DEG C in baking oven, obtain pretreatment sisal fiber；
(5) by graphene oxide, sodium azide, dehydrated alcohol is placed in reactor, in temperature be 160 DEG C, revolving speed 800r/
Under the conditions of min, heating stirring reacts 60min, and tetra lithium aluminium hydride is then added into reactor, is 160 DEG C in temperature, revolving speed is
Under the conditions of 800r/min, heating stirring reacts 60min, and pretreatment sisal fiber is then added into reactor, is in revolving speed
Under the conditions of 600r/min, it is stirred 60min, adjusts pH to 8.3, Yu Wendu then to sodium hydroxide solution is added in reactor
It is 130 DEG C, under the conditions of revolving speed is 600r/min, after heating stirring reacts 60min, filtering obtains filter cake, filter cake is then placed in baking
In case, under the conditions of temperature is 110 DEG C, drying is to constant weight to get modified graphene oxide；
(6) according to parts by weight, 5 portions of microbial function microbial inoculums are successively taken, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts change
Property medical stone, 20 parts of modified graphene oxides, 120 parts of sodium alginate solutions, 5 parts of polyethyleneimines, 20 parts of aniline, 5 parts of carbomers,
5 parts of calcium nitrate solutions, by microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, modified graphene oxide, sea
Mosanom liquid, polyethyleneimine, aniline, carbomer, nitric acid calcium ion are placed in ball milling mixing 60min in ball mill, then to ball
The ammonium hydroxide that mass fraction is 30r/min is added in grinding machine and adjusts pH to 8.0, obtains mixed slurry, mixed slurry is then placed in ice
In case, under the conditions of temperature is -10 DEG C, 8h is freezed, material must be freezed, then freezing material is placed in room temperature condition and melts down toward complete,
Mixed liquor must be melted, such Frozen-thawed cycled 8 times must handle homogenate, and then processing homogenate is placed in liquid nitrogen and is freezed, must be freezed
Frozen block is then crossed the sieve of 360 mesh, obtains ball milling material, then ball milling material is placed in baking oven by block as crushing in ball mill,
Under the conditions of temperature is 110 DEG C, drying is to constant weight to get new bio compound fertilizer；
(7) performance detection is carried out to gained new bio compound fertilizer.
Example 2
A kind of biologic compound fertilizer made of graphene oxide, the raw material including following parts by weight: 5 parts of microbial function bacterium
Agent, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts of modified medical stones, 20 parts of modified graphene oxides, 120 parts of sodium alginates
Liquid, 5 parts of polyethyleneimines, 20 parts of aniline, 5 parts of carbomers, 5 parts of calcium nitrate solutions.
The microbial function microbial inoculum includes the raw material of following parts by weight: 2 parts of Escherichia coli, 6 parts of cornstarch, and 0.2
Part glycerol, 0.2 part of polyethylene glycol, 30 parts of deionized waters.
The chemical fertilizer includes the raw material composition of following parts by weight: 20 parts of urea, 10 parts of calcium monohydrogen phosphates and 5 parts of chlorinations
Potassium.
The bio-feritlizer includes: 10 parts of chicken manures, 10 parts of cow dungs, 5 parts of straw ashs.
The carbomer is Carbopol 941.
A kind of processing technology of the biologic compound fertilizer made of graphene oxide, specific process are as follows:
(1) 20 parts of medical stones according to parts by weight, 80 parts of hydrofluoric acid, 80 parts of dopamine solutions, 5 parts of glycoprotein, 50 parts of deionizations
The hydrofluoric acid that medical stone and mass fraction are 30% is placed in reaction kettle by water, and under the conditions of revolving speed is 500r/min, stirring is mixed
It closes after impregnating 30in, filtering obtains No. 1 filter residue, No. 1 residue washing to cleaning solution is by the ammonium hydroxide for being then 30% with mass fraction
Neutrality obtains a processing medical stone；
(2) dopamine solution that a processing medical stone and mass concentration are 2.6mg/mL is placed in single-necked flask, is in revolving speed
It under the conditions of 600r/min, is stirred after impregnating 3h, filtering obtains No. 2 filter residues, No. 2 filter residues are placed in baking oven, are in temperature
Under the conditions of 110 DEG C, secondary treatment medical stone is obtained；
(3) glycoprotein and water are placed in No. 1 beaker, under the conditions of revolving speed is 1200r/min, after being stirred 60min, then
Secondary treatment medical stone is added into No. 1 beaker, under the conditions of revolving speed is 1000r/min, after being stirred 60min, filtering is obtained
Modified medical stone；
(4) according to parts by weight, 30 parts of graphene oxides, 30 parts of sisal fibers, 0.2 part of cellulase, 3 parts of Azides are successively taken
Sodium, 0.3 tetra lithium aluminium hydride, 50 parts of deionized waters, 60 parts of dehydrated alcohols, by sisal fiber, cellulase, deionized water is placed in 2
In number beakers, then No. 2 beakers are placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 35 DEG C, revolving speed 600r/min
Under the conditions of, mixed processing 60min, after being then warming up to 85 DEG C of enzyme deactivation 20min, filtering obtains No. 3 filter residues, then sets No. 3 filter residues
It is dry to constant weight under the conditions of temperature is 110 DEG C in baking oven, obtain pretreatment sisal fiber；
(5) by graphene oxide, sodium azide, dehydrated alcohol is placed in reactor, in temperature be 160 DEG C, revolving speed 800r/
Under the conditions of min, heating stirring reacts 60min, and tetra lithium aluminium hydride is then added into reactor, is 160 DEG C in temperature, revolving speed is
Under the conditions of 800r/min, heating stirring reacts 60min, and pretreatment sisal fiber is then added into reactor, is in revolving speed
Under the conditions of 600r/min, it is stirred 60min, adjusts pH to 8.3, Yu Wendu then to sodium hydroxide solution is added in reactor
It is 130 DEG C, under the conditions of revolving speed is 600r/min, after heating stirring reacts 60min, filtering obtains filter cake, filter cake is then placed in baking
In case, under the conditions of temperature is 110 DEG C, drying is to constant weight to get modified graphene oxide；
(6) according to parts by weight, 5 portions of microbial function microbial inoculums are successively taken, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts change
Property medical stone, 20 parts of modified graphene oxides, 120 parts of sodium alginate solutions, 5 parts of polyethyleneimines, 20 parts of aniline, 5 parts of carbomers,
5 parts of calcium nitrate solutions, by microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, modified graphene oxide, sea
Mosanom liquid, polyethyleneimine, aniline, carbomer, nitric acid calcium ion are placed in ball milling mixing 60min in ball mill, then to ball
The ammonium hydroxide that mass fraction is 30r/min is added in grinding machine and adjusts pH to 8.0, obtains mixed slurry, mixed slurry is then placed in ice
In case, under the conditions of temperature is -10 DEG C, 8h is freezed, material must be freezed, then freezing material is placed in room temperature condition and melts down toward complete,
Mixed liquor must be melted, such Frozen-thawed cycled 8 times must handle homogenate, and then processing homogenate is placed in liquid nitrogen and is freezed, must be freezed
Frozen block is then crossed the sieve of 360 mesh, obtains ball milling material, then ball milling material is placed in baking oven by block as crushing in ball mill,
Under the conditions of temperature is 110 DEG C, drying is to constant weight to get new bio compound fertilizer；
(7) performance detection is carried out to gained new bio compound fertilizer.
Example 3
A kind of biologic compound fertilizer made of graphene oxide, the raw material including following parts by weight: 5 parts of microbial function bacterium
Agent, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts of medical stones, 20 parts of modified graphene oxides, 120 parts of sodium alginate solutions, 5
Part polyethyleneimine, 20 parts of aniline, 5 parts of carbomers, 5 parts of calcium nitrate solutions.
The microbial function microbial inoculum includes the raw material of following parts by weight: 2 parts of Bacillus pasteuriis, 2 parts of Escherichia coli,
6 parts of cornstarch, 0.2 part of glycerol, 0.2 part of polyethylene glycol, 30 parts of deionized waters.
The chemical fertilizer includes the raw material composition of following parts by weight: 20 parts of urea, 10 parts of calcium monohydrogen phosphates and 5 parts of chlorinations
Potassium.
The bio-feritlizer includes: 10 parts of chicken manures, 10 parts of cow dungs, 5 parts of straw ashs.
The carbomer is Carbopol 941.
A kind of processing technology of the biologic compound fertilizer made of graphene oxide, specific process are as follows:
(1) according to parts by weight, 30 parts of graphene oxides, 30 parts of sisal fibers, 0.2 part of cellulase, 3 parts of Azides are successively taken
Sodium, 0.3 tetra lithium aluminium hydride, 50 parts of deionized waters, 60 parts of dehydrated alcohols, by sisal fiber, cellulase, deionized water is placed in 2
In number beakers, then No. 2 beakers are placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 35 DEG C, revolving speed 600r/min
Under the conditions of, mixed processing 60min, after being then warming up to 85 DEG C of enzyme deactivation 20min, filtering obtains No. 3 filter residues, then sets No. 3 filter residues
It is dry to constant weight under the conditions of temperature is 110 DEG C in baking oven, obtain pretreatment sisal fiber；
(2) by graphene oxide, sodium azide, dehydrated alcohol is placed in reactor, in temperature be 160 DEG C, revolving speed 800r/
Under the conditions of min, heating stirring reacts 60min, and tetra lithium aluminium hydride is then added into reactor, is 160 DEG C in temperature, revolving speed is
Under the conditions of 800r/min, heating stirring reacts 60min, and pretreatment sisal fiber is then added into reactor, is in revolving speed
Under the conditions of 600r/min, it is stirred 60min, adjusts pH to 8.3, Yu Wendu then to sodium hydroxide solution is added in reactor
It is 130 DEG C, under the conditions of revolving speed is 600r/min, after heating stirring reacts 60min, filtering obtains filter cake, filter cake is then placed in baking
In case, under the conditions of temperature is 110 DEG C, drying is to constant weight to get modified graphene oxide；
(3) according to parts by weight, 5 portions of microbial function microbial inoculums, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 portions of wheats are successively taken
Meal stone, 20 parts of modified graphene oxides, 120 parts of sodium alginate solutions, 5 parts of polyethyleneimines, 20 parts of aniline, 5 parts of carbomers, 5 parts
Calcium nitrate solution, by microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, medical stone, modified graphene oxide, sodium alginate
Liquid, polyethyleneimine, aniline, carbomer, nitric acid calcium ion is placed in ball milling mixing 60min in ball mill, then into ball mill
The ammonium hydroxide that mass fraction is 30r/min is added and adjusts pH to 8.0, obtains mixed slurry, then mixed slurry is placed in refrigerator, in
Under the conditions of temperature is -10 DEG C, 8h is freezed, material must be freezed, then freezing material is placed in room temperature condition and melts down toward complete, must melt mixed
Liquid is closed, such Frozen-thawed cycled 8 times must handle homogenate, and then processing homogenate is placed in liquid nitrogen and is freezed, frozen block is obtained, and then will
Frozen block crosses the sieve of 360 mesh, obtains ball milling material, then ball milling material is placed in baking oven, be in temperature as crushing in ball mill
Under the conditions of 110 DEG C, drying is to constant weight to get new bio compound fertilizer；
(4) performance detection is carried out to gained new bio compound fertilizer.
Example 4
A kind of biologic compound fertilizer made of graphene oxide, the raw material including following parts by weight: 5 parts of microbial function bacterium
Agent, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts of modified medical stones, 20 parts of graphene oxides, 120 parts of sodium alginate solutions, 5
Part polyethyleneimine, 20 parts of aniline, 5 parts of carbomers, 5 parts of calcium nitrate solutions.
The microbial function microbial inoculum includes the raw material of following parts by weight: 2 parts of Bacillus pasteuriis, 2 parts of Escherichia coli,
6 parts of cornstarch, 0.2 part of glycerol, 0.2 part of polyethylene glycol, 30 parts of deionized waters.
The chemical fertilizer includes the raw material composition of following parts by weight: 20 parts of urea, 10 parts of calcium monohydrogen phosphates and 5 parts of chlorinations
Potassium.
The bio-feritlizer includes: 10 parts of chicken manures, 10 parts of cow dungs, 5 parts of straw ashs.
The carbomer is Carbopol 941.
A kind of processing technology of the biologic compound fertilizer made of graphene oxide, specific process are as follows:
(1) 20 parts of medical stones according to parts by weight, 80 parts of hydrofluoric acid, 80 parts of dopamine solutions, 5 parts of glycoprotein, 50 parts of deionizations
The hydrofluoric acid that medical stone and mass fraction are 30% is placed in reaction kettle by water, and under the conditions of revolving speed is 500r/min, stirring is mixed
It closes after impregnating 30in, filtering obtains No. 1 filter residue, No. 1 residue washing to cleaning solution is by the ammonium hydroxide for being then 30% with mass fraction
Neutrality obtains a processing medical stone；
(2) dopamine solution that a processing medical stone and mass concentration are 2.6mg/mL is placed in single-necked flask, is in revolving speed
It under the conditions of 600r/min, is stirred after impregnating 3h, filtering obtains No. 2 filter residues, No. 2 filter residues are placed in baking oven, are in temperature
Under the conditions of 110 DEG C, secondary treatment medical stone is obtained；
(3) glycoprotein and water are placed in No. 1 beaker, under the conditions of revolving speed is 1200r/min, after being stirred 60min, then
Secondary treatment medical stone is added into No. 1 beaker, under the conditions of revolving speed is 1000r/min, after being stirred 60min, filtering is obtained
Modified medical stone；
(4) according to parts by weight, 5 portions of microbial function microbial inoculums are successively taken, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts change
Property medical stone, 20 parts of graphene oxides, 120 parts of sodium alginate solutions, 5 parts of polyethyleneimines, 20 parts of aniline, 5 parts of carbomers, 5 parts
Calcium nitrate solution, by microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, graphene oxide, sodium alginate
Liquid, polyethyleneimine, aniline, carbomer, nitric acid calcium ion is placed in ball milling mixing 60min in ball mill, then into ball mill
The ammonium hydroxide that mass fraction is 30r/min is added and adjusts pH to 8.0, obtains mixed slurry, then mixed slurry is placed in refrigerator, in
Under the conditions of temperature is -10 DEG C, 8h is freezed, material must be freezed, then freezing material is placed in room temperature condition and melts down toward complete, must melt mixed
Liquid is closed, such Frozen-thawed cycled 8 times must handle homogenate, and then processing homogenate is placed in liquid nitrogen and is freezed, frozen block is obtained, and then will
Frozen block crosses the sieve of 360 mesh, obtains ball milling material, then ball milling material is placed in baking oven, be in temperature as crushing in ball mill
Under the conditions of 110 DEG C, drying is to constant weight to get new bio compound fertilizer；
(5) performance detection is carried out to gained new bio compound fertilizer.
Example 5
A kind of biologic compound fertilizer made of graphene oxide, the raw material including following parts by weight: 5 parts of microbial function bacterium
Agent, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts of modified medical stones, 20 parts of modified graphene oxides, 120 parts of sodium alginates
Liquid, 5 parts of polyethyleneimines, 20 parts of aniline, 5 parts of calcium nitrate solutions.
The microbial function microbial inoculum includes the raw material of following parts by weight: 2 parts of Bacillus pasteuriis, 2 parts of Escherichia coli,
6 parts of cornstarch, 0.2 part of glycerol, 0.2 part of polyethylene glycol, 30 parts of deionized waters.
The chemical fertilizer includes the raw material composition of following parts by weight: 20 parts of urea, 10 parts of calcium monohydrogen phosphates and 5 parts of chlorinations
Potassium.
The bio-feritlizer includes: 10 parts of chicken manures, 10 parts of cow dungs, 5 parts of straw ashs.
A kind of processing technology of the biologic compound fertilizer made of graphene oxide, specific process are as follows:
(1) 20 parts of medical stones according to parts by weight, 80 parts of hydrofluoric acid, 80 parts of dopamine solutions, 5 parts of glycoprotein, 50 parts of deionizations
The hydrofluoric acid that medical stone and mass fraction are 30% is placed in reaction kettle by water, and under the conditions of revolving speed is 500r/min, stirring is mixed
It closes after impregnating 30in, filtering obtains No. 1 filter residue, No. 1 residue washing to cleaning solution is by the ammonium hydroxide for being then 30% with mass fraction
Neutrality obtains a processing medical stone；
(2) dopamine solution that a processing medical stone and mass concentration are 2.6mg/mL is placed in single-necked flask, is in revolving speed
It under the conditions of 600r/min, is stirred after impregnating 3h, filtering obtains No. 2 filter residues, No. 2 filter residues are placed in baking oven, are in temperature
Under the conditions of 110 DEG C, secondary treatment medical stone is obtained；
(3) glycoprotein and water are placed in No. 1 beaker, under the conditions of revolving speed is 1200r/min, after being stirred 60min, then
Secondary treatment medical stone is added into No. 1 beaker, under the conditions of revolving speed is 1000r/min, after being stirred 60min, filtering is obtained
Modified medical stone；
(4) according to parts by weight, 30 parts of graphene oxides, 30 parts of sisal fibers, 0.2 part of cellulase, 3 parts of Azides are successively taken
Sodium, 0.3 tetra lithium aluminium hydride, 50 parts of deionized waters, 60 parts of dehydrated alcohols, by sisal fiber, cellulase, deionized water is placed in 2
In number beakers, then No. 2 beakers are placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 35 DEG C, revolving speed 600r/min
Under the conditions of, mixed processing 60min, after being then warming up to 85 DEG C of enzyme deactivation 20min, filtering obtains No. 3 filter residues, then sets No. 3 filter residues
It is dry to constant weight under the conditions of temperature is 110 DEG C in baking oven, obtain pretreatment sisal fiber；
(5) by graphene oxide, sodium azide, dehydrated alcohol is placed in reactor, in temperature be 160 DEG C, revolving speed 800r/
Under the conditions of min, heating stirring reacts 60min, and tetra lithium aluminium hydride is then added into reactor, is 160 DEG C in temperature, revolving speed is
Under the conditions of 800r/min, heating stirring reacts 60min, and pretreatment sisal fiber is then added into reactor, is in revolving speed
Under the conditions of 600r/min, it is stirred 60min, adjusts pH to 8.3, Yu Wendu then to sodium hydroxide solution is added in reactor
It is 130 DEG C, under the conditions of revolving speed is 600r/min, after heating stirring reacts 60min, filtering obtains filter cake, filter cake is then placed in baking
In case, under the conditions of temperature is 110 DEG C, drying is to constant weight to get modified graphene oxide；
(6) according to parts by weight, 5 portions of microbial function microbial inoculums are successively taken, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts change
Property medical stone, 20 parts of modified graphene oxides, 120 parts of sodium alginate solutions, 5 parts of polyethyleneimines, 20 parts of aniline, 5 parts of calcium nitrate
Solution, by microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, modified graphene oxide, sodium alginate solution,
Polyethyleneimine, aniline, nitric acid calcium ion are placed in ball milling mixing 60min in ball mill, and quality point is then added into ball mill
Number be 30r/min ammonium hydroxide adjust pH to 8.0, obtain mixed slurry, then mixed slurry be placed in refrigerator, in temperature be -10
Under the conditions of DEG C, 8h is freezed, material must be freezed, then freezing material is placed in room temperature condition and melts down toward complete, obtains thawing mixed liquor, so
Frozen-thawed cycled 8 times, homogenate must be handled, then processing homogenate is placed in liquid nitrogen and is freezed, obtains frozen block, then by frozen block as
It is crushed in ball mill, crosses the sieve of 360 mesh, obtain ball milling material, then ball milling material is placed in baking oven, under the conditions of temperature is 110 DEG C,
Drying is to constant weight to get new bio compound fertilizer；
(7) performance detection is carried out to gained new bio compound fertilizer.
Example 6
A kind of biologic compound fertilizer made of graphene oxide, the raw material including following parts by weight: 5 parts of microbial function bacterium
Agent, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts of modified medical stones, 20 parts of modified graphene oxides, 120 parts of sodium alginates
Liquid, 20 parts of aniline, 5 parts of carbomers, 5 parts of calcium nitrate solutions.
The microbial function microbial inoculum includes the raw material of following parts by weight: 2 parts of Bacillus pasteuriis, 2 parts of Escherichia coli,
6 parts of cornstarch, 0.2 part of glycerol, 0.2 part of polyethylene glycol, 30 parts of deionized waters.
The chemical fertilizer includes the raw material composition of following parts by weight: 20 parts of urea, 10 parts of calcium monohydrogen phosphates and 5 parts of chlorinations
Potassium.
The bio-feritlizer includes: 10 parts of chicken manures, 10 parts of cow dungs, 5 parts of straw ashs.
The carbomer is Carbopol 941.
A kind of processing technology of the biologic compound fertilizer made of graphene oxide, specific process are as follows:
(1) 20 parts of medical stones according to parts by weight, 80 parts of hydrofluoric acid, 80 parts of dopamine solutions, 5 parts of glycoprotein, 50 parts of deionizations
The hydrofluoric acid that medical stone and mass fraction are 30% is placed in reaction kettle by water, and under the conditions of revolving speed is 500r/min, stirring is mixed
It closes after impregnating 30in, filtering obtains No. 1 filter residue, No. 1 residue washing to cleaning solution is by the ammonium hydroxide for being then 30% with mass fraction
Neutrality obtains a processing medical stone；
(2) dopamine solution that a processing medical stone and mass concentration are 2.6mg/mL is placed in single-necked flask, is in revolving speed
It under the conditions of 600r/min, is stirred after impregnating 3h, filtering obtains No. 2 filter residues, No. 2 filter residues are placed in baking oven, are in temperature
Under the conditions of 110 DEG C, secondary treatment medical stone is obtained；
(3) glycoprotein and water are placed in No. 1 beaker, under the conditions of revolving speed is 1200r/min, after being stirred 60min, then
Secondary treatment medical stone is added into No. 1 beaker, under the conditions of revolving speed is 1000r/min, after being stirred 60min, filtering is obtained
Modified medical stone；
(4) according to parts by weight, 30 parts of graphene oxides, 30 parts of sisal fibers, 0.2 part of cellulase, 3 parts of Azides are successively taken
Sodium, 0.3 tetra lithium aluminium hydride, 50 parts of deionized waters, 60 parts of dehydrated alcohols, by sisal fiber, cellulase, deionized water is placed in 2
In number beakers, then No. 2 beakers are placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 35 DEG C, revolving speed 600r/min
Under the conditions of, mixed processing 60min, after being then warming up to 85 DEG C of enzyme deactivation 20min, filtering obtains No. 3 filter residues, then sets No. 3 filter residues
It is dry to constant weight under the conditions of temperature is 110 DEG C in baking oven, obtain pretreatment sisal fiber；
(5) by graphene oxide, sodium azide, dehydrated alcohol is placed in reactor, in temperature be 160 DEG C, revolving speed 800r/
Under the conditions of min, heating stirring reacts 60min, and tetra lithium aluminium hydride is then added into reactor, is 160 DEG C in temperature, revolving speed is
Under the conditions of 800r/min, heating stirring reacts 60min, and pretreatment sisal fiber is then added into reactor, is in revolving speed
Under the conditions of 600r/min, it is stirred 60min, adjusts pH to 8.3, Yu Wendu then to sodium hydroxide solution is added in reactor
It is 130 DEG C, under the conditions of revolving speed is 600r/min, after heating stirring reacts 60min, filtering obtains filter cake, filter cake is then placed in baking
In case, under the conditions of temperature is 110 DEG C, drying is to constant weight to get modified graphene oxide；
(6) according to parts by weight, 5 portions of microbial function microbial inoculums are successively taken, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts change
Property medical stone, 20 parts of modified graphene oxides, 120 parts of sodium alginate solutions, 20 parts of aniline, 5 parts of carbomers, 5 parts of calcium nitrate solutions,
By microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, modified graphene oxide, sodium alginate solution, aniline,
Carbomer, nitric acid calcium ion are placed in ball milling mixing 60min in ball mill, and it is 30r/ that mass fraction is then added into ball mill
The ammonium hydroxide of min adjusts pH to 8.0, obtains mixed slurry, then mixed slurry is placed in refrigerator, under the conditions of temperature is -10 DEG C,
8h is freezed, material must be freezed, then freezing material is placed in room temperature condition and melts down toward complete, obtains thawing mixed liquor, such Frozen-thawed cycled 8
It is secondary, homogenate must be handled, then processing homogenate is placed in liquid nitrogen and is freezed, frozen block is obtained, then by frozen block as in ball mill
It crushes, crosses the sieve of 360 mesh, obtain ball milling material, then ball milling material is placed in baking oven, it is dry to perseverance under the conditions of temperature is 110 DEG C
Weight is to get new bio compound fertilizer；
(7) performance detection is carried out to gained new bio compound fertilizer.
Example 7
A kind of biologic compound fertilizer made of graphene oxide, the raw material including following parts by weight: 5 parts of microbial function bacterium
Agent, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts of modified medical stones, 20 parts of modified graphene oxides, 120 parts of sodium alginates
Liquid, 5 parts of polyethyleneimines, 5 parts of carbomers, 5 parts of calcium nitrate solutions.
The microbial function microbial inoculum includes the raw material of following parts by weight: 2 parts of Bacillus pasteuriis, 2 parts of Escherichia coli,
6 parts of cornstarch, 0.2 part of glycerol, 0.2 part of polyethylene glycol, 30 parts of deionized waters.
The chemical fertilizer includes the raw material composition of following parts by weight: 20 parts of urea, 10 parts of calcium monohydrogen phosphates and 5 parts of chlorinations
Potassium.
The bio-feritlizer includes: 10 parts of chicken manures, 10 parts of cow dungs, 5 parts of straw ashs.
The carbomer is Carbopol 941.
A kind of processing technology of the biologic compound fertilizer made of graphene oxide, specific process are as follows:
(1) 20 parts of medical stones according to parts by weight, 80 parts of hydrofluoric acid, 80 parts of dopamine solutions, 5 parts of glycoprotein, 50 parts of deionizations
The hydrofluoric acid that medical stone and mass fraction are 30% is placed in reaction kettle by water, and under the conditions of revolving speed is 500r/min, stirring is mixed
It closes after impregnating 30in, filtering obtains No. 1 filter residue, No. 1 residue washing to cleaning solution is by the ammonium hydroxide for being then 30% with mass fraction
Neutrality obtains a processing medical stone；
(2) dopamine solution that a processing medical stone and mass concentration are 2.6mg/mL is placed in single-necked flask, is in revolving speed
It under the conditions of 600r/min, is stirred after impregnating 3h, filtering obtains No. 2 filter residues, No. 2 filter residues are placed in baking oven, are in temperature
Under the conditions of 110 DEG C, secondary treatment medical stone is obtained；
(3) glycoprotein and water are placed in No. 1 beaker, under the conditions of revolving speed is 1200r/min, after being stirred 60min, then
Secondary treatment medical stone is added into No. 1 beaker, under the conditions of revolving speed is 1000r/min, after being stirred 60min, filtering is obtained
Modified medical stone；
(4) according to parts by weight, 30 parts of graphene oxides, 30 parts of sisal fibers, 0.2 part of cellulase, 3 parts of Azides are successively taken
Sodium, 0.3 tetra lithium aluminium hydride, 50 parts of deionized waters, 60 parts of dehydrated alcohols, by sisal fiber, cellulase, deionized water is placed in 2
In number beakers, then No. 2 beakers are placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 35 DEG C, revolving speed 600r/min
Under the conditions of, mixed processing 60min, after being then warming up to 85 DEG C of enzyme deactivation 20min, filtering obtains No. 3 filter residues, then sets No. 3 filter residues
It is dry to constant weight under the conditions of temperature is 110 DEG C in baking oven, obtain pretreatment sisal fiber；
(5) by graphene oxide, sodium azide, dehydrated alcohol is placed in reactor, in temperature be 160 DEG C, revolving speed 800r/
Under the conditions of min, heating stirring reacts 60min, and tetra lithium aluminium hydride is then added into reactor, is 160 DEG C in temperature, revolving speed is
Under the conditions of 800r/min, heating stirring reacts 60min, and pretreatment sisal fiber is then added into reactor, is in revolving speed
Under the conditions of 600r/min, it is stirred 60min, adjusts pH to 8.3, Yu Wendu then to sodium hydroxide solution is added in reactor
It is 130 DEG C, under the conditions of revolving speed is 600r/min, after heating stirring reacts 60min, filtering obtains filter cake, filter cake is then placed in baking
In case, under the conditions of temperature is 110 DEG C, drying is to constant weight to get modified graphene oxide；
(6) according to parts by weight, 5 portions of microbial function microbial inoculums are successively taken, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts change
Property medical stone, 20 parts of modified graphene oxides, 120 parts of sodium alginate solutions, 5 parts of polyethyleneimines, 5 parts of carbomers, 5 parts of calcium nitrate
Solution, by microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, modified graphene oxide, sodium alginate solution,
Polyethyleneimine, carbomer, nitric acid calcium ion are placed in ball milling mixing 60min in ball mill, quality are then added into ball mill
Score be 30r/min ammonium hydroxide adjust pH to 8.0, obtain mixed slurry, then mixed slurry be placed in refrigerator, in temperature be-
Under the conditions of 10 DEG C, 8h is freezed, material must be freezed, then freezing material is placed in room temperature condition and melts down toward complete, obtains thawing mixed liquor, such as
This Frozen-thawed cycled 8 times, must handle homogenate, and then processing homogenate is placed in liquid nitrogen and is freezed, obtains frozen block, then extremely by frozen block
Crushed in ball mill, cross 360 mesh sieve, obtain ball milling material, then ball milling material be placed in baking oven, in temperature be 110 DEG C of conditions
Under, drying is to constant weight to get new bio compound fertilizer；
(7) performance detection is carried out to gained new bio compound fertilizer.
Comparative example
A kind of biologic compound fertilizer made of graphene oxide, the raw material including following parts by weight: 5 parts of microbial function bacterium
Agent, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 parts of medical stones, 20 parts of graphene oxides, 120 parts of sodium alginate solutions, 5 parts of nitre
Sour calcium solution.
The microbial function microbial inoculum includes the raw material of following parts by weight: 2 parts of Escherichia coli, 6 parts of cornstarch, and 0.2
Part glycerol, 0.2 part of polyethylene glycol, 30 parts of deionized waters.
The chemical fertilizer includes the raw material composition of following parts by weight: 20 parts of urea, 10 parts of calcium monohydrogen phosphates and 5 parts of chlorinations
Potassium.
The bio-feritlizer includes: 10 parts of chicken manures, 10 parts of cow dungs, 5 parts of straw ashs.
A kind of processing technology of the biologic compound fertilizer made of graphene oxide, specific process are as follows:
(1) according to parts by weight, 5 portions of microbial function microbial inoculums, 30 parts of chemical fertilizer, 30 parts of bio-feritlizers, 60 portions of wheats are successively taken
Meal stone, 20 parts of graphene oxides, 120 parts of sodium alginate solutions, 5 parts of calcium nitrate solutions, by microbial function microbial inoculum, chemical fertilizer is raw
Object fertilizer, medical stone, graphene oxide, sodium alginate solution, polyethyleneimine, aniline, carbomer, nitric acid calcium ion are placed in ball milling
The ammonium hydroxide that mass fraction is 30r/min is then added into ball mill and adjusts pH to 8.0, must mix by ball milling mixing 60min in machine
Mixed slurry is then placed in refrigerator by slurry, under the conditions of temperature is -10 DEG C, is freezed 8h, must be freezed material, then freezing material
It is placed in room temperature condition to melt down toward complete, obtains thawing mixed liquor, such Frozen-thawed cycled 8 times must handle homogenate, will then handle even
Slurry, which is placed in liquid nitrogen, to be freezed, and frozen block is obtained, and is then crossed the sieve of 360 mesh, is obtained ball milling material frozen block as crushing in ball mill,
Then ball milling material is placed in baking oven, under the conditions of temperature is 110 DEG C, drying is to constant weight to get new bio compound fertilizer；
(2) performance detection is carried out to gained new bio compound fertilizer.
Performance detection table:
Table 1:
As can be seen from Table 1: by example 1, example 2 and comparative example, it can be seen that utilize Pasteur's bud in microbial bacterial agent
Urase is generated in spore bacillus metabolic process and carries out a series of effects, forms calcium carbonate microspheres, nanometer calcium carbonate, which is formed such that, to be changed
Property medical stone inside pore structure enriched, further delayed include inside modified medical stone various fertilizer release,
To further improve the sustained release performance of product；Pass through example 1, example 3, example 5 and comparative example, it can be seen that by right
Medical stone passes through a series of processing, makes its internal dispersion glycoprotein, and carbomer can be with the glycoprotein shape inside modified medical stone
At good physical entanglement, the preferable gel network of stickiness is formed, the gel network inside modified medical stone can lock moisture
And nutritional ingredient, the sustained release performance of product is improved, to further improve the fertilizer efficiency of product；By example 1, example 3 is real
Example 4 and comparative example, it can be seen that by a series of processing carried out to graphene oxide, so that the pretreatment sisal hemp in system
Fiber can be grafted to surface of graphene oxide, increase the structure complexity of surface of graphene oxide, pre-process sisal fiber
Grafting in later period microbial bacterial agent Bacillus pasteurii and Escherichia coli provide breed place, meanwhile, sodium hydroxide solution
Can be reacted with the carboxyl in graphene oxide layer structural edge so that the carboxyl in graphene oxide layer structural edge from
Sonization, so that modified graphene oxide good can be dispersed in system, since modified medical stone surface is contained largely
Active group, enable to modified graphene oxide that can be attached to modified medical stone surface, the chemical fertilizer in raw material and
The nutritional ingredients such as bio-feritlizer are able to be fixed in modified medical stone, improve the sustained release performance of product, avoid a large amount of fertilizer
It is directly entered in soil and causes soil hardening, to further improve the fertilizer efficiency of product.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
Claims (9)
1. a kind of biologic compound fertilizer made of graphene oxide, it is characterised in that: the raw material including following parts by weight: 3
~5 portions of microbial function microbial inoculums, 20~30 parts of chemical fertilizer, 20~30 parts of bio-feritlizers, 40~60 parts of medical stones, 10~20 parts
Graphene oxide, 100~120 parts of sodium alginate solutions.
2. a kind of biologic compound fertilizer made of graphene oxide according to claim 1, it is characterised in that: described new
Type biologic compound fertilizer further includes the raw material of following parts by weight: 3~5 parts of polyethyleneimines, 10~20 parts of aniline, 3~5 parts of cards
Wave nurse, 3~5 parts of calcium nitrate solutions.
3. a kind of biologic compound fertilizer made of graphene oxide according to claim 2, it is characterised in that: described micro-
Biological function microbial inoculum is made after deionized water mixing by Bacillus pasteurii, Escherichia coli, cornstarch, glycerol, polyethylene glycol
?；The chemical fertilizer is made after calcium monohydrogen phosphate and potassium chloride mixing by urea；The bio-feritlizer be by chicken manure, cow dung,
Straw ash is mixed to get；The carbomer is Carbopol 941, any one in carbomer 934 or Acritamer 940.
4. a kind of biologic compound fertilizer made of graphene oxide according to claim 3, it is characterised in that: the wheat
Meal stone can also be modified medical stone；The modified medical stone be by medical stone, hydrofluoric acid, dopamine solution, glycoprotein, go from
Sub- water is modified to be made.
5. a kind of biologic compound fertilizer made of graphene oxide according to claim 4, it is characterised in that: the oxygen
Graphite alkene can also be modified graphene oxide；The modified graphene oxide is by graphene oxide, sisal fiber, fiber
Plain enzyme, sodium azide, tetra lithium aluminium hydride, deionized water, dehydrated alcohol is modified to be made.
6. a kind of biologic compound fertilizer made of graphene oxide according to claim 5, it is characterised in that: described new
Type biologic compound fertilizer includes the raw material of following parts by weight: 5 portions of microbial function microbial inoculums, 30 parts of chemical fertilizer, 30 parts of biologies
Fertilizer, 60 parts of modified medical stones, 20 parts of modified graphene oxides, 120 parts of sodium alginate solutions, 5 parts of polyethyleneimines, 20 parts of benzene
Amine, 5 parts of carbomers, 5 parts of calcium nitrate solutions.
7. a kind of processing technology of the biologic compound fertilizer made of graphene oxide, it is characterised in that specific processing method are as follows:
Medical stone single treatment；
Medical stone secondary treatment；
Medical stone modification；
Sisal fiber pretreatment；
Graphene oxide modification；
Mixing crushes；
Detection.
8. a kind of processing technology of the biologic compound fertilizer made of graphene oxide, feature exist according to claim 1
In: the specific procedure of processing of the new bio compound fertilizer are as follows:
Medical stone is mixed into immersion with hydrofluoric acid, is filtered, washing obtains a processing medical stone；
One processing medical stone is mixed into immersion with dopamine solution, filters, obtains secondary treatment medical stone；
Glycoprotein is mixed with water, secondary treatment medical stone is subsequently added into, is stirred, filters, obtains modified medical stone；
By sisal fiber, cellulase, deionized water mixed processing, heat up enzyme deactivation, filters, dry, obtains pretreatment sisal fiber；
By graphene oxide, sodium azide, the reaction of dehydrated alcohol heating stirring is subsequently added into tetra lithium aluminium hydride, heating stirring is anti-
It answers, is subsequently added into pretreatment sisal fiber, sodium hydroxide solution is then added and adjusts pH, heating stirring reaction is filtered, and it is dry,
Up to modified graphene oxide；
By microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, modified graphene oxide, sodium alginate solution,
Polyethyleneimine, aniline, carbomer, calcium nitrate ion ball milling mixing are subsequently added into ammonium hydroxide and adjust pH, Frozen-thawed cycled, freezing, powder
Broken, sieving is dry to get new bio compound fertilizer；
Performance detection is carried out to product.
9. a kind of processing technology of the biologic compound fertilizer made of graphene oxide, feature exist according to claim 1
In: the specific process of the new bio compound fertilizer are as follows:
(1) hydrofluoric acid that medical stone and mass fraction are 20~30% is placed in reaction kettle, in revolving speed be 300~500r/min
Under the conditions of, after being stirred 20~30in of immersion, filtering obtains No. 1 filter residue, and the ammonium hydroxide for being then 20~30% with mass fraction is by 1
Number residue washing to cleaning solution is neutrality, obtains a processing medical stone；
(2) dopamine solution that a processing medical stone and mass concentration are 2.6mg/mL is placed in single-necked flask, is in revolving speed
Under the conditions of 400~600r/min, after being stirred 2~3h of immersion, filtering obtains No. 2 filter residues, No. 2 filter residues is placed in baking oven, in
Under the conditions of temperature is 105~110 DEG C, secondary treatment medical stone is obtained；
(3) glycoprotein and water are placed in No. 1 beaker, under the conditions of revolving speed is 1000~1200r/min, it is stirred 40~
After 60min, secondary treatment medical stone is then added into No. 1 beaker, under the conditions of revolving speed is 800~1000r/min, stirring is mixed
After closing 40~60min, filtering obtains modified medical stone；
(4) by sisal fiber, cellulase, deionized water is placed in No. 2 beakers, then No. 2 beakers are placed in digital display and are tested the speed constant temperature
It is 30~35 DEG C in temperature, under the conditions of revolving speed is 500~600r/min, 40~60min of mixed processing is connect in magnetic stirring apparatus
Be warming up to 80~85 DEG C of 10~20min of enzyme deactivation after, filtering, obtain No. 3 filter residues, then No. 3 filter residues be placed in baking oven, Yu Wendu
It is dry to constant weight under the conditions of 105~110 DEG C, obtain pretreatment sisal fiber；
(5) by graphene oxide, sodium azide, it is 140~160 DEG C in temperature, revolving speed is that dehydrated alcohol, which is placed in reactor,
Under the conditions of 600~800r/min, heating stirring reacts 40~60min, and tetra lithium aluminium hydride, Yu Wendu are then added into reactor
It is 140~160 DEG C, under the conditions of revolving speed is 600~800r/min, heating stirring reacts 40~60min, then adds into reactor
Enter to pre-process sisal fiber, under the conditions of revolving speed is 400~600r/min, 40~60min is stirred, then in reactor
Sodium hydroxide solution is added and adjusts pH to 8.1~8.3, is 120~130 DEG C in temperature, revolving speed is 500~600r/min condition
Under, heating stirring react 40~60min after, filtering, obtain filter cake, then filter cake be placed in baking oven, in temperature be 105~110
Under the conditions of DEG C, drying is to constant weight to get modified graphene oxide；
(6) by microbial function microbial inoculum, chemical fertilizer, bio-feritlizer, modified medical stone, modified graphene oxide, sodium alginate
Liquid, polyethyleneimine, aniline, carbomer, nitric acid calcium ion are placed in 40~60min of ball milling mixing in ball mill, then to ball milling
The ammonium hydroxide that mass fraction is 20~30r/min is added in machine and adjusts pH to 7.8~8.0, mixed slurry is obtained, then by mixed slurry
It is placed in refrigerator, under the conditions of temperature is -1~-10 DEG C, freezes 5~8h, material must be freezed, then freezing material is placed in room temperature condition
Melt down toward complete, obtain thawing mixed liquor, such Frozen-thawed cycled 5~8 times must handle homogenate, and processing homogenate is then placed in liquid
It is freezed in nitrogen, obtains frozen block, then frozen block is crossed the sieve of 360 mesh, ball milling material is obtained, then by ball as crushing in ball mill
Abrasive material is placed in baking oven, and under the conditions of temperature is 105~110 DEG C, drying is to constant weight to get new bio compound fertilizer；
(7) performance detection is carried out to gained new bio compound fertilizer.
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