CN106083342A - A kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon and production technology thereof - Google Patents
A kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon and production technology thereof Download PDFInfo
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- CN106083342A CN106083342A CN201610426116.0A CN201610426116A CN106083342A CN 106083342 A CN106083342 A CN 106083342A CN 201610426116 A CN201610426116 A CN 201610426116A CN 106083342 A CN106083342 A CN 106083342A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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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
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The present invention relates to technical field of fertilizers, be specifically related to a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon and production technology thereof, this production technology comprises the steps: that biomass carbon is mixed with phosphoric acid by (1), obtains mixed liquor；(2) in mixed liquor, it is passed through ammonia to react, obtains reactant liquor；(3) in reactant liquor, it is passed through carbon dioxide to react, is dried, prepare high-efficiency environment friendly inorganic fertilizer.A kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon, described high-efficiency environment friendly inorganic fertilizer prepares according to production technology described above.The high-efficiency environment friendly inorganic fertilizer slow release of the present invention, long-acting, Ammonia valatilization speed is slow, and the leaching loss of nitrate is few, can be absorbed by plant efficient, and nitrogen use efficiency is high.
Description
Technical field
The present invention relates to technical field of fertilizers, be specifically related to a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon and life thereof
Production. art.
Background technology
Fertilising has become as one of indispensable technical measures of agricultural production, to the contribution rate of crop production more than one
Half.China's utilization rate of fertilizer ratio always is relatively low, such as the utilization rate averagely only about 30% of nitrogenous fertilizer this season crop, compares developed country
Low nearly 20 percentage points, on the one hand this be because unscientific fertilizing method, is on the other hand then due to the spy of fertilizer itself
Property.Improving utilization rate of fertilizer very urgent, Multifunction fertilizer is used in research and development, is to improve the approach that fertilizer utilization efficiency is important
One of.Biomass carbon be biomass high-temperature cracking solid product, there is the most special character, as porous, high stability,
There is substantial amounts of multiple functional group on highly aromatization, surface, simultaneous with positive and negative 2 kinds of electric charges, it is possible to binding molecule and zwitterion,
Polarity and apolar substance.Raw material, cracking temperature, pyrolysis time etc. are affect biomass carbon Wuli-Shili-Renli system approach main
Factor, it is, in general, that within the specific limits, along with rising, the prolongation in response time of cracking temperature, the specific surface of biomass carbon
Long-pending increase, aromatization structure strengthen, and content of ashes and pH raise, and available nutrient and content of calcium and magnesium also increase.
The nitrogen use efficiency of most of the nitrogen fertilizer product in the market is on the low side.The highest utilization rate of nitrogen fertilizer can be effective
Raising yield of vegetables.The poor efficiency of nitrogenous fertilizer is the loss due to nitrogen, and generally with the leaching loss of nitrate nitrogen, and gas form is released
Releasing (volatilization of ammonia, Denitrification generates nitrogen dioxide and nitrogen), earth's surface water can be produced and pollute by nitrate, concentration
Higher health of damaging, the greenhouse gases that nitrogen dioxide is the strongest simultaneously, its long lasting effect index to global warming
Higher 300 times than carbon dioxide.Therefore countries in the world are all at the nitrogenous fertilizer making great efforts development environment-friendly high-efficiency.
Summary of the invention
In order to overcome shortcoming and defect present in prior art, it is an object of the invention to provide a kind of based on biomass
The high-efficiency environment friendly inorganic fertilizer of charcoal, this high-efficiency environment friendly inorganic fertilizer slow release, long-acting, Ammonia valatilization speed is slow, and the leaching loss of nitrate is few,
Can be absorbed by plant efficient, nitrogen use efficiency is high.
Another object of the present invention is to provide the production technology of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon, should
Production craft step is simple, convenient operation and control, steady quality, and yield is high, and production efficiency is high, and production cost is low, can be extensive
Industrialized production.
The purpose of the present invention is achieved through the following technical solutions: the life of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon
Production. art, comprises the steps:
(1) biomass carbon is mixed with phosphoric acid, obtain mixed liquor；
(2) being passed through ammonia in mixed liquor to react, the surface of charcoal will soon initially form one layer of white salt deposit,
Obtain reactant liquor；
(3) in reactant liquor, it is passed through carbon dioxide to react, is dried, prepare high-efficiency environment friendly inorganic fertilizer.
The production technology of the present invention by after biomass carbon is mixed with phosphoric acid again with ammonia and carbon dioxide reaction, prepare
High-efficiency environment friendly inorganic fertilizer, step is simple, convenient operation and control, steady quality, and production efficiency is high, and production cost is low, can be extensive
Industrialized production.
Preferably, in described step (1), the mass ratio that biomass carbon mixes with phosphoric acid is 7-10:1-2, the quality of phosphoric acid
Mark >=85%.The present invention is by controlling at 7-10:1-2 by the mass ratio that biomass carbon mixes with phosphoric acid so that biomass carbon can
With fully activation, improve the slow release effect of inorganic fertilizer, reduce release and the leaching loss of nitrate of ammonia further.It is more highly preferred to
, the mass ratio that described biomass carbon mixes with phosphoric acid is 8.5:1.5.
Preferably, in described step (1), biomass carbon is made up through Pintsch process at a temperature of 550-650 DEG C of bamboo
Bamboo quality of biomass charcoal.The bamboo quality of biomass that the present invention makes through Pintsch process at a temperature of 550-650 DEG C by using bamboo
Charcoal is as biomass carbon, and it has huge specific surface area and strong absorbability so that inorganic fertilizer has slow release, long-acting, low
Release ammonia, the advantage of protonitrate leaching loss.Be more highly preferred to, described biomass carbon be by bamboo at a temperature of 600 DEG C through height
The bamboo quality of biomass charcoal that anneal crack solution is made.
The preparation method of described bamboo quality of biomass charcoal includes: bamboo is crushed to particle diameter 1-2mm, and the bamboo after pulverizing is done
Dry to moisture content less than 5%, obtain biomass material；Catalyst for cracking and biomass material are put by weight 0.5-1.5:100
Carry out Pintsch process in entering the cracking of high temperature pyrolysis stove, obtain bamboo quality of biomass charcoal and imflammable gas；Wherein, the temperature of Pintsch process
Degree is for 550-650 DEG C, and the time of Pintsch process is 60-120min.
Biomass can produce biomass carbon, tar and imflammable gas through Pintsch process, and the addition of catalyst for cracking is permissible
Catalytic tar cracks, and catalyst for cracking can obtain higher tar clearance at a lower reaction temperature, and can also improve
Gas heating value and yield.
Described catalyst for cracking is made up of the material of following percentage by weight: CeO2 10-20%、CuO 1-5%、NiO 2-
4%、RuO21-2%, surplus is catalyst carrier；Wherein, described catalyst carrier is made up of the material of following percentage by weight:
HZSM-5 molecular sieve 70-85%, alumina adhesive 15-30%；BET method specific surface area >=the 310m of described HZSM-5 molecular sieve2/
G, silica alumina ratio are 15-50, aperture is 0.53-0.58nm, relative crystallinity >=95%, residual sodium content≤0.1wt%；Described aluminium oxide
Binding agent is 240-280m through nitric acid peptization, BET method specific surface area2/ g, pore volume are the aperture oxidation of 0.35-0.45ml/g
Aluminum.
The preparation method of described catalyst for cracking comprises the steps:
(1) HZSM-5 molecular sieve is added in alumina adhesive, and adds pore creating material CMC and extrusion aid sesbania powder, through kneading,
Roll agglomerating after, then extruded moulding, be dried, roasting obtain catalyst carrier；Described pore creating material CMC and the addition of extrusion aid sesbania powder
Amount be HZSM-5 molecular sieve and alumina adhesive quality and 0.5-2%；
(2) with saturated infusion process carried metal element respectively, drying, roasting obtain catalyst.
In described step (1), the condition being dried is: 60-85 DEG C of dry 2-3h, then at 100-120 DEG C of dry 12-24h.
In described step (2), the condition being dried is to be dried 1-3h at 0.06-0.08Mpa, 60-85 DEG C, then at 0.06-
1-3h it is dried at 0.08Mpa, 60-85 DEG C.
In described step (1) and step (2), roasting condition be 400-650 DEG C at roasting 3-15h.
In described step (2), comprise the following steps with saturated infusion process carried metal element respectively:
A () uses the catalyst carrier that saturated infusion process cerous nitrate solution impregnation steps (1) obtains, dip time is 12-
20h, after 60-85 DEG C of vacuum drying 1-3h, in 400-600 DEG C of roasting temperature 5-8h；
B () uses the catalysis that saturated infusion process nickel nitrate, copper nitrate and ruthenium trichloride mixed solution impregnation steps (a) obtain
Agent carrier, dip time is 18-24h.
The catalyst for cracking of the present invention uses the HZSM-5 molecular sieve of high surface and acid appropriateness to be acid carrier, protects
The activity of card cracking；Boulton process is used so that active component radial distribution is more uniform during active metal load,
Ensure that active component has higher dispersibility, and then ensure that catalyst has high coke tar cracking activity and stability.
The catalyst for cracking of the present invention uses CeO2For promoter, add metal oxide containing precious metals RuO simultaneously2, improve and urge
The coking resistivity of agent, the Ni-Cu alloy catalyst formed in catalyst, play the synergism of metallic catalyst, with
Time noble metal Hydrogen spillover ensure that the reproducibility of metal.
The preparation method of described bamboo quality of biomass charcoal also includes: mix, bamboo quality of biomass charcoal at indifferent gas with activator
Atmosphere is warming up to activation temperature and carries out activation processing, be then cooled to room temperature, product is carried out pickling, more dry after being washed to neutrality
Dry；Described activator is potassium carbonate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium acetate, diammonium phosphate, ammonium dihydrogen phosphate and vinegar
At least one in acid ammonium；Described biomass carbon is 100:1-5 with the weight ratio of described activator；Inert atmosphere used is nitrogen
Gas, flow is 100-500mL/min；Heating rate is 4-8 DEG C/min；Activation temperature is 300-500 DEG C；During activation processing insulation
Between be 1-3h；Acid used by pickling is dilute hydrochloric acid.
Obtain activated carbon after being activated by biomass carbon, activated carbon be have high-specific surface area, high characterization of adsorption loose many
Permeability material, its pore structure is more flourishing than biomass carbon so that the penetrating gas of soil is more preferable, and beneficially microorganism aerobic respiration is made
With, promote beneficial microorganism growth, so that soil becomes more fertile, the beneficially growth of plant.Activated carbon is imposed on soil
In earth, physical arrangement and the chemical composition of soil can be improved, scalable fertilizer pesticide execute effect, thus promote the growth of plant.
Activated carbon can increase biological fixation nitrogen in soil, and makes organic nitrogen comparatively fast be changed into ammonia and nitrate, thus plays the work of fertilizer
With.
Preferably, in described step (1), the specific surface area of biomass carbon is 360-400m2/g.The application is compared by employing
Surface area is 360-400m2The biomass carbon of/g, it has huge specific surface area and strong absorbability so that inorganic fertilizer has
There is slow release, long-acting, low release ammonia, the advantage of protonitrate leaching loss.Being more highly preferred to, the specific surface area of described biomass carbon is
380m2/g。
Preferably, in described step (2), ammonia is obtained by heating evaporation ammonia, and the consumption of ammonia is biomass carbonaceous
The 25-35% of amount.The present invention by controlling the 25-35% in biomass carbon quality by the consumption of ammonia so that biomass carbon is permissible
Fully reacting with ammonia and carbon dioxide, the inorganic fertilizer prepared has slow release, long-acting, low release ammonia, protonitrate leaching loss
Advantage.Being more highly preferred to, described ammonia is obtained by heating evaporation ammonia, and the consumption of ammonia is the 30% of biomass carbonaceous amount.
Preferably, in described step (3), the consumption of carbon dioxide is the 3-7% of biomass carbonaceous amount.The present invention passes through will
The consumption of carbon dioxide is the 3-7% of biomass carbonaceous amount so that biomass carbon fully can react with ammonia and carbon dioxide,
The inorganic fertilizer prepared has slow release, long-acting, low release ammonia, the advantage of protonitrate leaching loss.It is more highly preferred to, described titanium dioxide
The consumption of carbon is the 4% of biomass carbonaceous amount.
Preferably, in described step (3), the nitrogen content of the high-efficiency environment friendly inorganic fertilizer prepared is 10%-12%.The present invention prepares
The nitrogen content of high-efficiency environment friendly inorganic fertilizer be 10%-12%, slow release, long-acting, Ammonia valatilization speed is slow, and the leaching loss of nitrate is few,
Can be absorbed by plant efficient, nitrogen use efficiency is high.
Preferably, also include that step (4) is by prepared high-efficiency environment friendly inorganic fertilizer bag last layer starch after described step (3)
Film, prepares high-efficiency environment friendly slow release inorganic fertilizer.The present invention is by by prepared high-efficiency environment friendly inorganic fertilizer bag last layer starch film, permissible
Improve the slow release effect of high-efficiency environment friendly inorganic fertilizer, reduce the rate of release of nitrogen.
In described step (4), starch film is prepared by starch gel, and starch gel is made up of the raw material of following weight portion: form sediment
Powder 50-70 part, amylase 0.01-0.05 part, acetylating agent 0.2-0.6 part, plasticizer 2-4 part, hydrophobic modifier 1-3 part and water
40-60 part.
Described starch is with weight ratio 1:1.4-2.2:2.4-3.2 group by corn starch, tapioca and potato starch
The mixture become；Described amylase is α-amylase；Described acetylating agent is with weight ratio by acetic anhydride, acetic acid and vinylacetate
The mixture of 0.5-1.5:1:1.4-2.2 composition；Described plasticizer is with weight ratio by Polyethylene Glycol, propylene glycol and sorbitol
The mixture of 0.5-1.5:1.5-2.5:1 composition；Described hydrophobic modifier is even by stearic acid, OPE and titanate esters
The mixture that connection agent forms with weight ratio 0.8-1.2:1:1.4-2.2.
The preparation method of described starch gel comprises the steps:
(1) by starch, water and amylase mix homogeneously, it is warming up to 80-120 DEG C, stirs 6-10min gelatinizing；
(2) in the product of step (1), acetylating agent is added, stirring reaction 10-30min under the mixing speed of 100-900rpm；
(3) in the product of step (2), add plasticizer, continue stirring 10-30min；
(4) in the product of step (3), add hydrophobic modifier, continue stirring 10-30min, obtain starch gel.
Another object of the present invention is achieved through the following technical solutions: a kind of high-efficiency environment friendly based on biomass carbon is inorganic
Fertilizer, described high-efficiency environment friendly inorganic fertilizer prepares according to production technology described above.
The beneficial effects of the present invention is: the production craft step of the present invention is simple, convenient operation and control, steady quality,
Yield is high, and production efficiency is high, and production cost is low, can large-scale industrial production.
The high-efficiency environment friendly inorganic fertilizer slow release that the present invention prepares, long-acting, Ammonia valatilization speed is slow, and the leaching loss of nitrate is few,
Can be absorbed by plant efficient, nitrogen use efficiency is high.
Detailed description of the invention
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, real
The content that the mode of executing is mentioned not limitation of the invention.
Embodiment 1
The production technology of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon, comprises the steps:
(1) biomass carbon is mixed with phosphoric acid, obtain mixed liquor；
(2) in mixed liquor, it is passed through ammonia to react, obtains reactant liquor；
(3) in reactant liquor, it is passed through carbon dioxide to react, is dried, prepare high-efficiency environment friendly inorganic fertilizer.
In described step (1), the mass ratio that biomass carbon mixes with phosphoric acid is 7:1, and the mass fraction of phosphoric acid is 85%.
In described step (1), the bamboo quality of biomass that biomass carbon is made up through Pintsch process at a temperature of 550 DEG C of bamboo
Charcoal.
In described step (1), the specific surface area of biomass carbon is 360m2/g。
In described step (2), ammonia is obtained by heating evaporation ammonia, and the consumption of ammonia is the 25% of biomass carbonaceous amount.
In described step (3), the consumption of carbon dioxide is the 3% of biomass carbonaceous amount.
In described step (3), the nitrogen content of the high-efficiency environment friendly inorganic fertilizer prepared is 10%.
Also include after described step (3) that step (4), by prepared high-efficiency environment friendly inorganic fertilizer bag last layer starch film, prepares
High-efficiency environment friendly slow release inorganic fertilizer.
A kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon, described high-efficiency environment friendly inorganic fertilizer is according to production described above
Technique prepares.
The high-efficiency environment friendly inorganic fertilizer prepared by the present embodiment is applied in corn field respectively with conventional nitrogenous fertilizer and tests, at fertilizer
Under the conditions of material consumption is equal, high-efficiency environment friendly inorganic fertilizer increases production Semen Maydis 152 kilograms than every mu of conventional nitrogenous fertilizer, increases production 19%.
Embodiment 2
The present embodiment is with the difference of above-described embodiment 1:
In described step (1), the mass ratio that biomass carbon mixes with phosphoric acid is 8:1.2, and the mass fraction of phosphoric acid is 88%.
In described step (1), the bamboo quality of biomass that biomass carbon is made up through Pintsch process at a temperature of 580 DEG C of bamboo
Charcoal.
In described step (1), the specific surface area of biomass carbon is 370m2/g。
In described step (2), ammonia is obtained by heating evaporation ammonia, and the consumption of ammonia is the 28% of biomass carbonaceous amount.
In described step (3), the consumption of carbon dioxide is the 4% of biomass carbonaceous amount.
In described step (3), the nitrogen content of the high-efficiency environment friendly inorganic fertilizer prepared is 10%-12%.
The high-efficiency environment friendly inorganic fertilizer prepared by the present embodiment is applied in Soybean Field respectively with conventional nitrogenous fertilizer and tests, at fertilizer
Under the conditions of material consumption is equal, high-efficiency environment friendly inorganic fertilizer increases production Semen sojae atricolor 52.5 kilograms than every mu of conventional nitrogenous fertilizer, increases production 21%.
Embodiment 3
The present embodiment is with the difference of above-described embodiment 1:
In described step (1), the mass ratio that biomass carbon mixes with phosphoric acid is 8.5:1.5, and the mass fraction of phosphoric acid is 90%.
In described step (1), the bamboo quality of biomass that biomass carbon is made up through Pintsch process at a temperature of 600 DEG C of bamboo
Charcoal.
In described step (1), the specific surface area of biomass carbon is 380m2/g。
In described step (2), ammonia is obtained by heating evaporation ammonia, and the consumption of ammonia is the 30% of biomass carbonaceous amount.
In described step (3), the consumption of carbon dioxide is the 5% of biomass carbonaceous amount.
In described step (3), the nitrogen content of the high-efficiency environment friendly inorganic fertilizer prepared is 11%.
The high-efficiency environment friendly inorganic fertilizer prepared by the present embodiment is applied in rice terrace respectively with conventional nitrogenous fertilizer and tests, at fertilizer
Under the conditions of material consumption is equal, high-efficiency environment friendly inorganic fertilizer increases production 132 kilograms of Oryza sativa L. than every mu of conventional nitrogenous fertilizer, increases production 22%.
Embodiment 4
The present embodiment is with the difference of above-described embodiment 1:
In described step (1), the mass ratio that biomass carbon mixes with phosphoric acid is 9:1.8, and the mass fraction of phosphoric acid is 92%.
In described step (1), the bamboo quality of biomass that biomass carbon is made up through Pintsch process at a temperature of 620 DEG C of bamboo
Charcoal.
In described step (1), the specific surface area of biomass carbon is 390m2/g。
In described step (2), ammonia is obtained by heating evaporation ammonia, and the consumption of ammonia is the 32% of biomass carbonaceous amount.
In described step (3), the consumption of carbon dioxide is the 6% of biomass carbonaceous amount.
In described step (3), the nitrogen content of the high-efficiency environment friendly inorganic fertilizer prepared is 11.5%.
The high-efficiency environment friendly inorganic fertilizer prepared by the present embodiment is applied in Rapeseed Field respectively with conventional nitrogenous fertilizer and tests, at fertilizer
Under the conditions of material consumption is equal, high-efficiency environment friendly inorganic fertilizer increases production Brassica campestris L 30 kilograms than every mu of conventional nitrogenous fertilizer, increases production 20%.
Embodiment 5
The present embodiment is with the difference of above-described embodiment 1:
In described step (1), the mass ratio that biomass carbon mixes with phosphoric acid is 10:2, and the mass fraction of phosphoric acid is 95%.
In described step (1), the bamboo quality of biomass that biomass carbon is made up through Pintsch process at a temperature of 650 DEG C of bamboo
Charcoal.
In described step (1), the specific surface area of biomass carbon is 400m2/g。
In described step (2), ammonia is obtained by heating evaporation ammonia, and the consumption of ammonia is the 35% of biomass carbonaceous amount.
In described step (3), the consumption of carbon dioxide is the 7% of biomass carbonaceous amount.
In described step (3), the nitrogen content of the high-efficiency environment friendly inorganic fertilizer prepared is 12%.
The high-efficiency environment friendly inorganic fertilizer prepared by the present embodiment is applied in apple orchard respectively with conventional nitrogenous fertilizer and tests, at fertilizer
Under the conditions of material consumption is equal, high-efficiency environment friendly inorganic fertilizer increases production Fructus Mali pumilae 360 kilograms than every mu of conventional nitrogenous fertilizer, increases production 18%.
Embodiment 6
The present embodiment is with the difference of above-described embodiment 1:
The preparation method of described bamboo quality of biomass charcoal includes: bamboo is crushed to particle diameter 1mm, and the bamboo after pulverizing is dried to containing
Water rate is less than 5%, obtains biomass material；Catalyst for cracking and biomass material are put into high temperature pyrolysis by weight 0.5:100
Carry out Pintsch process in stove cracking, obtain bamboo quality of biomass charcoal and imflammable gas；Wherein, the temperature of Pintsch process is 500 DEG C,
The time of Pintsch process is 60min.
Described catalyst for cracking is made up of the material of following percentage by weight: CeO2 10%、CuO 1%、NiO 2%、RuO2
1%, surplus is catalyst carrier；Wherein, described catalyst carrier is made up of the material of following percentage by weight: HZSM-5 molecule
Sieve 70%, alumina adhesive 15%；BET method specific surface area >=the 310m of described HZSM-5 molecular sieve2/ g, silica alumina ratio are 15, hole
Footpath is 0.53nm, relative crystallinity >=95%, residual sodium content≤0.1wt%；Described alumina adhesive through nitric acid peptization,
BET method specific surface area is 240m2/ g, pore volume are the little porous aluminum oxide of 0.35ml/g.
The preparation method of described bamboo quality of biomass charcoal also includes: mix, bamboo quality of biomass charcoal at indifferent gas with activator
Atmosphere is warming up to activation temperature and carries out activation processing, be then cooled to room temperature, product is carried out pickling, more dry after being washed to neutrality
Dry；Described activator is potassium carbonate；Described biomass carbon is 100:1 with the weight ratio of described activator；Inert atmosphere used is
Nitrogen, flow is 100mL/min；Heating rate is 4 DEG C/min；Activation temperature is 300 DEG C；Activation processing temperature retention time is 3h；
Acid used by pickling is dilute hydrochloric acid.
In described step (4), starch film is prepared by starch gel, and starch gel is made up of the raw material of following weight portion: form sediment
50 parts of powder, amylase 0.01 part, acetylating agent 0.2 part, plasticizer 2 parts, hydrophobic modifier 1 part and 40 parts of water.
The mixing that described starch is made up of with weight ratio 1:1.4:2.4 corn starch, tapioca and potato starch
Thing；Described amylase is α-amylase；Described acetylating agent is with weight ratio 0.5:1 by acetic anhydride, acetic acid and vinylacetate:
The mixture of 1.4 compositions；Described plasticizer is made up of with weight ratio 0.5:1.5:1 Polyethylene Glycol, propylene glycol and sorbitol
Mixture；Described hydrophobic modifier is with weight ratio 0.8:1:1.4 group by stearic acid, OPE and titanate coupling agent
The mixture become.
The preparation method of described starch gel comprises the steps:
(1) by starch, water and amylase mix homogeneously, it is warming up to 80 DEG C, stirs 10min gelatinizing；
(2) in the product of step (1), acetylating agent is added, stirring reaction 30min under the mixing speed of 100rpm；
(3) in the product of step (2), add plasticizer, continue stirring 10min；
(4) in the product of step (3), add hydrophobic modifier, continue stirring 10min, obtain starch gel.
Embodiment 7
The present embodiment is with the difference of above-described embodiment 2:
The preparation method of described bamboo quality of biomass charcoal includes: bamboo is crushed to particle diameter 1.2mm, will pulverize after bamboo be dried to
Moisture content is less than 5%, obtains biomass material；Catalyst for cracking and biomass material are put into high-temperature hot by weight 0.7:100
Carry out Pintsch process in solving stove cracking, obtain bamboo quality of biomass charcoal and imflammable gas；Wherein, the temperature of Pintsch process is 550
DEG C, the time of Pintsch process is 75min.
Described catalyst for cracking is made up of the material of following percentage by weight: CeO2 12%、CuO 2%、NiO 2.5%、RuO2
1.2%, surplus is catalyst carrier；Wherein, described catalyst carrier is made up of the material of following percentage by weight: HZSM-5 divides
Son sieve 73%, alumina adhesive 19%；BET method specific surface area >=the 310m of described HZSM-5 molecular sieve2/ g, silica alumina ratio be 25,
Aperture is 0.54nm, relative crystallinity >=95%, residual sodium content≤0.1wt%；Described alumina adhesive through nitric acid peptization,
BET method specific surface area is 250m2/ g, pore volume are the little porous aluminum oxide of 0.37ml/g.
The preparation method of described bamboo quality of biomass charcoal also includes: mix, bamboo quality of biomass charcoal at indifferent gas with activator
Atmosphere is warming up to activation temperature and carries out activation processing, be then cooled to room temperature, product is carried out pickling, more dry after being washed to neutrality
Dry；Described activator is dipotassium hydrogen phosphate；Described biomass carbon is 100:2 with the weight ratio of described activator；Indifferent gas used
Atmosphere is nitrogen, and flow is 200mL/min；Heating rate is 5 DEG C/min；Activation temperature is 350 DEG C；Activation processing temperature retention time is
2.5h；Acid used by pickling is dilute hydrochloric acid.
In described step (4), starch film is prepared by starch gel, and starch gel is made up of the raw material of following weight portion: form sediment
55 parts of powder, amylase 0.02 part, acetylating agent 0.3 part, plasticizer 2.5 parts, hydrophobic modifier 1.5 parts and 45 parts of water.
The mixing that described starch is made up of with weight ratio 1:1.6:2.6 corn starch, tapioca and potato starch
Thing；Described amylase is α-amylase；Described acetylating agent is with weight ratio 0.8:1 by acetic anhydride, acetic acid and vinylacetate:
The mixture of 1.6 compositions；Described plasticizer is made up of with weight ratio 0.8:1.8:1 Polyethylene Glycol, propylene glycol and sorbitol
Mixture；Described hydrophobic modifier is with weight ratio 0.9:1:1.6 group by stearic acid, OPE and titanate coupling agent
The mixture become.
The preparation method of described starch gel comprises the steps:
(1) by starch, water and amylase mix homogeneously, it is warming up to 90 DEG C, stirs 9min gelatinizing；
(2) in the product of step (1), acetylating agent is added, stirring reaction 25min under the mixing speed of 300rpm；
(3) in the product of step (2), add plasticizer, continue stirring 15min；
(4) in the product of step (3), add hydrophobic modifier, continue stirring 15min, obtain starch gel.
Embodiment 8
The present embodiment is with the difference of above-described embodiment 3:
The preparation method of described bamboo quality of biomass charcoal includes: bamboo is crushed to particle diameter 1.5mm, will pulverize after bamboo be dried to
Moisture content is less than 5%, obtains biomass material；Catalyst for cracking and biomass material are put into high temperature pyrolysis by weight 1:100
Carry out Pintsch process in stove cracking, obtain bamboo quality of biomass charcoal and imflammable gas；Wherein, the temperature of Pintsch process is 600 DEG C,
The time of Pintsch process is 90min.
Described catalyst for cracking is made up of the material of following percentage by weight: CeO2 15%、CuO 3%、NiO 3%、RuO2
1.5%, surplus is catalyst carrier；Wherein, described catalyst carrier is made up of the material of following percentage by weight: HZSM-5 divides
Son sieve 77%, alumina adhesive 22%；BET method specific surface area >=the 310m of described HZSM-5 molecular sieve2/ g, silica alumina ratio be 35,
Aperture is 0.55nm, relative crystallinity >=95%, residual sodium content≤0.1wt%；Described alumina adhesive through nitric acid peptization,
BET method specific surface area is 260m2/ g, pore volume are the little porous aluminum oxide of 0.4ml/g.
The preparation method of described bamboo quality of biomass charcoal also includes: mix, bamboo quality of biomass charcoal at indifferent gas with activator
Atmosphere is warming up to activation temperature and carries out activation processing, be then cooled to room temperature, product is carried out pickling, more dry after being washed to neutrality
Dry；Described activator is potassium dihydrogen phosphate；Described biomass carbon is 100:3 with the weight ratio of described activator；Indifferent gas used
Atmosphere is nitrogen, and flow is 300mL/min；Heating rate is 6 DEG C/min；Activation temperature is 400 DEG C；Activation processing temperature retention time is
2h；Acid used by pickling is dilute hydrochloric acid.
In described step (4), starch film is prepared by starch gel, and starch gel is made up of the raw material of following weight portion: form sediment
60 parts of powder, amylase 0.03 part, acetylating agent 0.4 part, plasticizer 3 parts, hydrophobic modifier 2 parts and 50 parts of water.
The mixing that described starch is made up of with weight ratio 1:1.8:2.8 corn starch, tapioca and potato starch
Thing；Described amylase is α-amylase；Described acetylating agent is with weight ratio 1:1:1.8 by acetic anhydride, acetic acid and vinylacetate
The mixture of composition；The mixture that described plasticizer is made up of with weight ratio 1:2:1 Polyethylene Glycol, propylene glycol and sorbitol；
The mixing that described hydrophobic modifier is made up of with weight ratio 1:1:1.8 stearic acid, OPE and titanate coupling agent
Thing.
The preparation method of described starch gel comprises the steps:
(1) by starch, water and amylase mix homogeneously, it is warming up to 100 DEG C, stirs 8min gelatinizing；
(2) in the product of step (1), acetylating agent is added, stirring reaction 20min under the mixing speed of 500rpm；
(3) in the product of step (2), add plasticizer, continue stirring 20min；
(4) in the product of step (3), add hydrophobic modifier, continue stirring 20min, obtain starch gel.
Embodiment 9
The present embodiment is with the difference of above-described embodiment 4:
The preparation method of described bamboo quality of biomass charcoal includes: bamboo is crushed to particle diameter 1.8mm, will pulverize after bamboo be dried to
Moisture content is less than 5%, obtains biomass material；Catalyst for cracking and biomass material are put into high-temperature hot by weight 1.3:100
Carry out Pintsch process in solving stove cracking, obtain bamboo quality of biomass charcoal and imflammable gas；Wherein, the temperature of Pintsch process is 650
DEG C, the time of Pintsch process is 105min.
Described catalyst for cracking is made up of the material of following percentage by weight: CeO2 18%、CuO 4%、NiO 3.5%、RuO2
1.8%, surplus is catalyst carrier；Wherein, described catalyst carrier is made up of the material of following percentage by weight: HZSM-5 divides
Son sieve 82%, alumina adhesive 26%；BET method specific surface area >=the 310m of described HZSM-5 molecular sieve2/ g, silica alumina ratio be 45,
Aperture is 0.56nm, relative crystallinity >=95%, residual sodium content≤0.1wt%；Described alumina adhesive through nitric acid peptization,
BET method specific surface area is 270m2/ g, pore volume are the little porous aluminum oxide of 0.43ml/g.
The preparation method of described bamboo quality of biomass charcoal also includes: mix, bamboo quality of biomass charcoal at indifferent gas with activator
Atmosphere is warming up to activation temperature and carries out activation processing, be then cooled to room temperature, product is carried out pickling, more dry after being washed to neutrality
Dry；Described activator is potassium acetate；Described biomass carbon is 100:4 with the weight ratio of described activator；Inert atmosphere used is
Nitrogen, flow is 400mL/min；Heating rate is 7 DEG C/min；Activation temperature is 450 DEG C；Activation processing temperature retention time is
1.5h；Acid used by pickling is dilute hydrochloric acid.
In described step (4), starch film is prepared by starch gel, and starch gel is made up of the raw material of following weight portion: form sediment
65 parts of powder, amylase 0.04 part, acetylating agent 0.5 part, plasticizer 3.5 parts, hydrophobic modifier 2.5 parts and 55 parts of water.
The mixture that described starch is made up of with weight ratio 1:2:3 corn starch, tapioca and potato starch；Institute
Stating amylase is α-amylase；Described acetylating agent is made up of with weight ratio 1.2:1:2 acetic anhydride, acetic acid and vinylacetate
Mixture；The mixture that described plasticizer is made up of with weight ratio 1.2:2.2:1 Polyethylene Glycol, propylene glycol and sorbitol；Institute
State the mixture that hydrophobic modifier is made up of with weight ratio 1.1:1:2 stearic acid, OPE and titanate coupling agent.
The preparation method of described starch gel comprises the steps:
(1) by starch, water and amylase mix homogeneously, it is warming up to 110 DEG C, stirs 7min gelatinizing；
(2) in the product of step (1), acetylating agent is added, stirring reaction 15min under the mixing speed of 700rpm；
(3) in the product of step (2), add plasticizer, continue stirring 25min；
(4) in the product of step (3), add hydrophobic modifier, continue stirring 25min, obtain starch gel.
Embodiment 10
The present embodiment is with the difference of above-described embodiment 5:
The preparation method of described bamboo quality of biomass charcoal includes: bamboo is crushed to particle diameter 2mm, and the bamboo after pulverizing is dried to containing
Water rate is less than 5%, obtains biomass material；Catalyst for cracking and biomass material are put into high temperature pyrolysis by weight 1.5:100
Carry out Pintsch process in stove cracking, obtain bamboo quality of biomass charcoal and imflammable gas；Wherein, the temperature of Pintsch process is 700 DEG C,
The time of Pintsch process is 120min.
Described catalyst for cracking is made up of the material of following percentage by weight: CeO2 20%、CuO 5%、NiO 4%、RuO2
2%, surplus is catalyst carrier；Wherein, described catalyst carrier is made up of the material of following percentage by weight: HZSM-5 molecule
Sieve 85%, alumina adhesive 30%；BET method specific surface area >=the 310m of described HZSM-5 molecular sieve2/ g, silica alumina ratio are 50, hole
Footpath is 0.58nm, relative crystallinity >=95%, residual sodium content≤0.1wt%；Described alumina adhesive through nitric acid peptization,
BET method specific surface area is 280m2/ g, pore volume are the little porous aluminum oxide of 0.45ml/g.
The preparation method of described bamboo quality of biomass charcoal also includes: mix, bamboo quality of biomass charcoal at indifferent gas with activator
Atmosphere is warming up to activation temperature and carries out activation processing, be then cooled to room temperature, product is carried out pickling, more dry after being washed to neutrality
Dry；Described activator is diammonium phosphate；Described biomass carbon is 100:5 with the weight ratio of described activator；Indifferent gas used
Atmosphere is nitrogen, and flow is 500mL/min；Heating rate is 8 DEG C/min；Activation temperature is 500 DEG C；Activation processing temperature retention time is
1h；Acid used by pickling is dilute hydrochloric acid.
In described step (4), starch film is prepared by starch gel, and starch gel is made up of the raw material of following weight portion: form sediment
70 parts of powder, amylase 0.05 part, acetylating agent 0.6 part, plasticizer 4 parts, hydrophobic modifier 3 parts and 60 parts of water.
The mixing that described starch is made up of with weight ratio 1:2.2:3.2 corn starch, tapioca and potato starch
Thing；Described amylase is α-amylase；Described acetylating agent is with weight ratio 1.5:1 by acetic anhydride, acetic acid and vinylacetate:
The mixture of 2.2 compositions；Described plasticizer is made up of with weight ratio 1.5:2.5:1 Polyethylene Glycol, propylene glycol and sorbitol
Mixture；Described hydrophobic modifier is with weight ratio 1.2:1:2.2 group by stearic acid, OPE and titanate coupling agent
The mixture become.
The preparation method of described starch gel comprises the steps:
(1) by starch, water and amylase mix homogeneously, it is warming up to 120 DEG C, stirs 6min gelatinizing；
(2) in the product of step (1), acetylating agent is added, stirring reaction 10min under the mixing speed of 900rpm；
(3) in the product of step (2), add plasticizer, continue stirring 30min；
(4) in the product of step (3), add hydrophobic modifier, continue stirring 30min, obtain starch gel.
The production craft step of the present invention is simple, convenient operation and control, steady quality, and yield is high, and production efficiency is high, produces
Low cost, can large-scale industrial production.
The high-efficiency environment friendly inorganic fertilizer slow release that the present invention prepares, long-acting, Ammonia valatilization speed is slow, and the leaching loss of nitrate is few,
Can be absorbed by plant efficient, nitrogen use efficiency is high.
Above-described embodiment is the present invention preferably implementation, and in addition, the present invention can realize with alternate manner,
Without departing from obvious replacement any on the premise of present inventive concept all within protection scope of the present invention.
Claims (10)
1. the production technology of a high-efficiency environment friendly inorganic fertilizer based on biomass carbon, it is characterised in that: comprise the steps:
(1) biomass carbon is mixed with phosphoric acid, obtain mixed liquor；
(2) in mixed liquor, it is passed through ammonia to react, obtains reactant liquor；
(3) in reactant liquor, it is passed through carbon dioxide to react, is dried, prepare high-efficiency environment friendly inorganic fertilizer.
The production technology of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon the most according to claim 1, its feature exists
In: in described step (1), the mass ratio that biomass carbon mixes with phosphoric acid is 7-10:1-2.
The production technology of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon the most according to claim 1, its feature exists
In: in described step (1), the mass ratio that biomass carbon mixes with phosphoric acid is 8.5:1.5.
The production technology of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon the most according to claim 1, its feature exists
In: in described step (1), the bamboo quality of biomass that biomass carbon is made up through Pintsch process at a temperature of 550-650 DEG C of bamboo
Charcoal.
The production technology of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon the most according to claim 1, its feature exists
In: in described step (1), the specific surface area of biomass carbon is 360-400m2/g。
The production technology of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon the most according to claim 1, its feature exists
In: in described step (2), ammonia is obtained by heating evaporation ammonia, and the consumption of ammonia is the 25-35% of biomass carbonaceous amount.
The production technology of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon the most according to claim 1, its feature exists
In: in described step (3), the consumption of carbon dioxide is the 3-7% of biomass carbonaceous amount.
The production technology of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon the most according to claim 1, its feature exists
In: in described step (3), the nitrogen content of the high-efficiency environment friendly inorganic fertilizer prepared is 10%-12%.
The production technology of a kind of high-efficiency environment friendly inorganic fertilizer based on biomass carbon the most according to claim 1, its feature exists
In: also include after described step (3) that step (4), by prepared high-efficiency environment friendly inorganic fertilizer bag last layer starch film, prepares efficiently
Environmental protection slow release inorganic fertilizer.
10. a high-efficiency environment friendly inorganic fertilizer based on biomass carbon, it is characterised in that: described high-efficiency environment friendly inorganic fertilizer is according to right
Require that the production technology described in any one of 1-9 prepares.
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Cited By (3)
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| CN107337543A (en) * | 2017-08-21 | 2017-11-10 | 济南大学 | A kind of salt-soda soil slow-release fertilizer and preparation method thereof |
| CN107382510A (en) * | 2017-08-21 | 2017-11-24 | 济南大学 | A kind of controllability slow-release fertilizer and preparation method thereof |
| CN108976085A (en) * | 2018-08-22 | 2018-12-11 | 北京三聚绿能科技有限公司 | A kind of preparation method of tea tree vernalization special fertilizer |
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| CN103288541A (en) * | 2013-06-03 | 2013-09-11 | 西北农林科技大学 | Carbon-based slow release nitrogen fertilizer and preparation method thereof |
| CN104258809A (en) * | 2014-09-15 | 2015-01-07 | 河南农业大学 | Modified biomass charcoal and remediation method of heavy metal contaminated soil |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288541A (en) * | 2013-06-03 | 2013-09-11 | 西北农林科技大学 | Carbon-based slow release nitrogen fertilizer and preparation method thereof |
| CN104258809A (en) * | 2014-09-15 | 2015-01-07 | 河南农业大学 | Modified biomass charcoal and remediation method of heavy metal contaminated soil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337543A (en) * | 2017-08-21 | 2017-11-10 | 济南大学 | A kind of salt-soda soil slow-release fertilizer and preparation method thereof |
| CN107382510A (en) * | 2017-08-21 | 2017-11-24 | 济南大学 | A kind of controllability slow-release fertilizer and preparation method thereof |
| CN108976085A (en) * | 2018-08-22 | 2018-12-11 | 北京三聚绿能科技有限公司 | A kind of preparation method of tea tree vernalization special fertilizer |
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Application publication date: 20161109 |