CN106423070B - A kind of melamine silkworm excrement carbon composite and the preparation method and application thereof - Google Patents

A kind of melamine silkworm excrement carbon composite and the preparation method and application thereof Download PDF

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CN106423070B
CN106423070B CN201610812056.6A CN201610812056A CN106423070B CN 106423070 B CN106423070 B CN 106423070B CN 201610812056 A CN201610812056 A CN 201610812056A CN 106423070 B CN106423070 B CN 106423070B
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silkworm excrement
melamine
carbon composite
preparation
drying
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CN106423070A (en
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赵钟兴
王欣辉
陶萌良
赵祯霞
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Guangxi University
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

The invention discloses a kind of melamine silkworm excrement carbon composites and the preparation method and application thereof.It is freeze-dried after silkworm excrement first to be mixed to swelling with water, then silkworm excrement after freeze-drying is prepared into carbonization silkworm excrement under protective gas；It is dried after adding water to mix standing melamine powder and carbonization silkworm excrement again, is passed through N2Prepare plasma modification melamine silkworm excrement carbon composite；Again by composite material crude product and ZnCl2Mixing carries out activation reaming reaction under protective gas, melamine silkworm excrement carbon composite is obtained after then cleaning, be centrifuged and drying again.The material can be applied to pesticide and delay controlled release aspect.The present invention be grafted to melamine and silkworm excrement compound using plasma modification, significantly promote the grafting recombination reaction speed of two kinds of materials, obtained carbon composite specific surface area with higher and polar group containing N, can there is higher adsorption capacity and preferable slow-releasing and controlled-releasing action to pesticide.

Description

A kind of melamine silkworm excrement carbon composite and the preparation method and application thereof
Technical field
The invention belongs to carbon composite technical fields, and in particular to melamine silkworm excrement composite material and preparation method With application.
Background technique
Pesticide can efficiently control the harm of disease, worm, grass and other harmful organisms to crops, it is as chemical prevention Important means, play irreplaceable role in agricultural production.However, pesticide only a small amount of in specific time can arrive Up to crop target site, and most of pesticide is directly released into natural environment and causes pesticide utilization efficiency low.This part is not The pesticide for playing drug effect can cause Practice for Pesticide Residue in Agricultural Products exceeded, injury and environmental pollution to non-target organism etc. many negative Face problem.The utilization efficiency and Targeting delivery function for how effectively improving pesticide are urgently to be resolved main of current pesticide field One of problem.
Slow controlled-release technology is that one kind can be such that pesticide activity component slowly releases within given time by physically or chemically means It is put in target site, and drug concentration is made to maintain the novel medicine feeding technology of effective concentration or more in a long time, and it is biological Porous charcoal is one of the main representative that can be applied to slow controlled-release technology.Silkworm excrement is the main waste of silkworm industry, is passed through in rural area Chang Suiyi discarding lead to environmental pollution, from Electron microscope from known to its with natural three-dimensional drape structure and phosphorus content height, High-ratio surface multiporous biological charcoal can be obtained through high temperature cabonization and activation, by the way that its slow controlled release ability can be promoted to its modification. Melamine is the nitrogen content with higher as triazines nitrogen heterocyclic ring organic compound, is a kind of cheap nitrogen source Material.
Summary of the invention
The invention proposes a kind of melamine silkworm excrement carbon composites and the preparation method and application thereof, first carry out to silkworm excrement It is carbonized again after swelling expanding treatment, then using plasma modification is so that melamine and silkworm excrement are quickly grafted in dozens of minutes Reaction, then high-ratio surface is formed by high-temperature activation counter-boring techniques, while achieving the purpose that regulate and control N (O) group content.This is not only The combined coefficient of material is improved, and the yield of composite material can be increased substantially, realizes the purpose of slow controlled release.
The purpose of the present invention is achieved through the following technical solutions:
A kind of melamine silkworm excrement carbon composite, the three-dimensional pore space knot which is constituted with melamine and charing silkworm excrement Structure, Langmuir specific surface area is in 950-1350m2/ g, total pore volume is about in 0.3-0.6cm3/ g or more, wherein micropore specific surface Long-pending and Kong Rong accounts for the 50~70% of total specific surface area and Kong Rong.
The preparation method of melamine silkworm excrement composite material of the invention, includes the following steps:
(1) Faeces bombycis is freeze-dried after mixing swelling with water, then by silkworm excrement after freeze-drying in N2, the protective gas such as Ar atmosphere In pass through high temperature cabonization reaction preparation carbonization silkworm excrement；
(2) it is centrifuged and dries after adding water to mix standing a period of time melamine powder and carbonization silkworm excrement, then be passed through N2System Standby plasma modification melamine silkworm excrement carbon composite, 20~30V of input voltage of plasma device, modification time 10~ 20min；It is modified to use deionized water cleaning, drying；
(3) by composite material crude product acquired in step (2) and ZnCl2It is anti-to carry out reaming in protective gas for mixing It answers, melamine silkworm excrement carbon composite is obtained after then cleaning, be centrifuged and drying again.Cleaning uses dilute hydrochloric acid and deionization Water rinses 1~3 time.
As the further preferred of scheme, step (1) Faeces bombycis is 1:100~200, mixing temperature with water mixing plastid ratio It is 30~50 DEG C, incorporation time is 0.5~3h.Freezing dry process is first 2~4h of precooling at -25 ° DEG C~-20C, then It is cooled to -60 DEG C~-40 DEG C 24~72h of freeze-drying.
As the further preferred of scheme, the carburizing temperature of silkworm excrement is at 500-1000 DEG C, reaction after being lyophilized in step (1) Between 2~4h.
As the further preferred of scheme, melamine powder and the mass ratio that mixes of carbonization silkworm excrement in the step (2) For 1:1~10.
As the further preferred of scheme, the mass ratio of melamine powder and deionized water is 1 in the step (2): 50~200, water pH are 7~9, mixing time of repose 6~for 24 hours, and 60~100 DEG C of drying temperature are centrifuged after standing.
As the further preferred of scheme, composite material crude product and ZnCl in the step (3)2Mixed mass ratio is 1:1~6.
As the further preferred of scheme, the reaming reaction temperature is 500~700 DEG C, and the reaction time is 0.5~5h. Optimum reaction condition is that reaming reaction temperature is 550~650 DEG C, and the reaction time is 2~3h.
In terms of melamine silkworm excrement carbon composite of the invention can be applicable to medicine sustained and controlled release, especially pesticide delays controlled release Aspect.
Product of the present invention, which is applied, delays controlled release field in pesticide, adsorbs anabasine pesticide Diacloden using the composite material, Absorption carriage amount can reach 500mg/g or more, and can prepare and delay controlled release farm chemical carrier within the scope of 15~60 days effective time of sustained release (using 90% Diacloden of total volume as endpoint calculation).
The principle of the invention: limited swelling work can occur in aqueous solution for the special macromolecular structure as possessed by silkworm excrement With volume will increase 1~20 times after swelling, silkworm excrement after swelling is freeze-dried by substep, freezing pretreatment can make silkworm excrement Fluffy macromolecular structure when keeping being swollen, then freeze-drying ensure that the abundant drying of silkworm excrement, and further consolidate its structure, can prolong Long silkworm excrement carbon skeleton improves the specific surface area and porosity of silkworm excrement base Carbon Materials after carbonization-activation.Silkworm excrement and melamine are gathered It closes, N (O) group content of the adjustable silkworm excrement base charcoal material surface of ratio by changing silkworm excrement and melamine.In routine In pesticide molecule mostly containing polar group (carboxyl, carbonyl, sulfur-bearing and containing cl radical etc.), and this segment polarity group is also Dominant reactive part in pesticide, these polar groups can be in conjunction with N in silkworm excrement (O) groups, by controlling silkworm excrement surface N (O) quantity of group can adjust the adsorption capacity between pesticide and Carbon Materials, reach the slow-releasing and controlled-releasing action to pesticide.
Plasma just refers to ionized gas, it is the molecular collection of the grains such as electronics, ion, atom, molecule or free radical Zoarium, these are all as lively as a cricket reactive species.Particle combines bond energy between capable of destroying original material molecule in plasma, and Molecule and plasma intermediate ion is set in material to be combined into new chemical bond, and since its energy is penetrated far below high-energy radioactive Line, thus plasma pertains only to the surface of material, does not influence the bulk properties of material, and plasma modification has efficient, ring The advantages that protecting, be easily controllable, easy to operate.
Compared with prior art, the present invention is advantageous in that:
1. the raw materials used in the present invention silkworm excrement has native three dimensional pleated structure and contains a large amount of carboxyls, hydroxyl and amino base , micro scale channel can be formed after carbonization treatment.The modified gas N that will be passed through by plasma modification2It is plasmarized, Graft reaction speed of the melamine on carbonization silkworm excrement is significantly promoted by the effect of plasma N atom, while again may be used It is lost to avoid brought product is filtered；And be modified under the voltage conditions of 20~30V, effectively increase graft reaction The syncretizing effect of melamine powder and the silkworm excrement that is carbonized is improved while speed.
2. by silkworm excrement swelling action can in the case where not changing silkworm excrement polymer configuration by silkworm excrement volume increase 1~ 20 times, its internal structure is fixed by silkworm excrement after swelling by way of freeze-drying, silkworm excrement base after carbonization-activation can be improved The porosity and specific surface area of Carbon Materials.
3. compared to the hydro-thermal of existing composite material or solvent-thermal method etc., plasma modification legal system of the present invention Standby melamine silkworm excrement activated carbon composite can greatly reduce the usage amount to solvent, can effectively reduce waste liquid discharging amount, make the present invention Synthesis process is more environmentally protective, and the harm to environment has been reduced or avoided.
4. the present invention passes through plasma modification and ZnCl2The melamine silkworm excrement carbon composite prepared after activation can shape At high-ratio surface porous structure, there can be higher adsorption capacity to pesticide.Simultaneously composite material surface group containing N can to pesticide and Adsorption capacity between composite material has an important influence on, since melamine is high compound containing N, by adjusting silkworm excrement and trimerization The graft reaction ratio of cyanamide can control the quantity of composite material surface group containing N, so regulate and control pesticide and composite material it Between adsorption capacity, achieve the purpose that slow controlled release.
5. composite material prepared by the present invention is for adsorbing anabasine pesticide Diacloden, adsorbance can reach 500mg/g or more can prepare sustained release agriculture of the slow-release time within the scope of 15~60 days by regulating and controlling melamine graft ratio Drug carrier (using 90% Diacloden of total volume as endpoint calculation).
Detailed description of the invention
Fig. 1 is that Faeces bombycis is sliced electron-microscope scanning figure.
Fig. 2 is silkworm excrement slice electron-microscope scanning figure after swelling freeze-drying.
Fig. 3 is silkworm excrement inner surface electron-microscope scanning figure after swelling freeze-drying.
Fig. 4 is 1 melamine silkworm excrement carbon composite electron-microscope scanning figure of embodiment.
Fig. 5 difference slow-release material load capacity curve
Fig. 6 difference slow-release material is sustained release profiles
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not It is confined to the range of embodiment statement.
Embodiment 1
A kind of preparation method of melamine silkworm excrement composite material, includes the following steps,
It (1) is that 1:100 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 3.0h at 30 DEG C Silkworm excrement is pulled out and is freeze-dried, first pre-processes 4h in -20 DEG C of freezings, then reduces temperature to -60 DEG C of freeze-dryings and is lyophilized for 24 hours Silkworm excrement afterwards.
In N2Silkworm excrement is raised to 500 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in atmosphere, and protects at 500 DEG C Room temperature, preparation carbonization silkworm excrement are cooled to after holding 5.0h or more.
(2) it is centrifuged and dries after adding deionized water 50mL to mix standing 6h 1.0g melamine powder and 2.0g carbonization silkworm excrement It is dry, it is passed through N2As modified gas, 1.0g mixing material is put into plasma reactor, reactor input voltage 20V changes Property time 20min, it is modified cleared up 3 times with deionized water after 60 DEG C of dry carbon composites.
(3) by composite material crude product acquired in step (2) and ZnCl2With mass ratio 1:1 mixing, in N2With 5 in atmosphere DEG C/heating rate of min is raised to 500 DEG C, and keeps 5.0h to carry out reaming reaction at 500 DEG C, to be cooled to room temperature naturally, Obtained solid is dissolved in cleaning dissolution unreacted ZnCl in the HCl of 1mol/L2, reuse after deionized water is cleaned to pH ≈ 7 from The heart is placed in baking oven and is dried overnight, and melamine silkworm excrement carbon composite is obtained after drying.
Embodiment 2
It (1) is that 1:120 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 2.5h at 35 DEG C Silkworm excrement is pulled out and is freeze-dried, first pre-processes 3h in -20 DEG C of freezings, then reduces temperature extremely -55 DEG C of freeze-drying 36h and is lyophilized Silkworm excrement afterwards.In N2Silkworm excrement is raised to 600 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in atmosphere, and protects at 600 DEG C Room temperature, preparation carbonization silkworm excrement are cooled to after holding 4.0h or more.
(2) it is centrifuged and dries after adding deionized water 75mL to mix standing 10h 1.0g melamine powder and 4.0g carbonization silkworm excrement It is dry, it is passed through N2As modified gas, 1.0g mixing material is put into plasma reactor, reactor input voltage 22V changes Property time 18min, it is modified cleared up 3 times with deionized water after 60 DEG C of dry carbon composites.
(3) by composite material crude product acquired in step (2) and ZnCl2With mass ratio 1:2 mixing, in N2With 5 in atmosphere DEG C/heating rate of min is raised to 550 DEG C, and keeps 4.0h at 550 DEG C, it is to be cooled to room temperature naturally, obtained solid is molten The cleaning dissolution unreacted ZnCl in the HCl of 1mol/L2, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven It is dried overnight, melamine silkworm excrement carbon composite is obtained after drying.
Embodiment 3
It (1) is that 1:140 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 2.0h at 40 DEG C Silkworm excrement is pulled out and is freeze-dried, first pre-processes 2h in -25 DEG C of freezings, then reduces temperature extremely -50 DEG C of freeze-drying 48h and is lyophilized Silkworm excrement afterwards.In N2Silkworm excrement is raised to 700 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in atmosphere, and protects at 700 DEG C Room temperature, preparation carbonization silkworm excrement are cooled to after holding 3.0h or more.
(2) it is centrifuged and dries after adding deionized water 100mL to mix standing 14h 1.0g melamine powder and 5.0g carbonization silkworm excrement It is dry, it is passed through N2As modified gas, 1.0g mixing material is put into plasma reactor, reactor input voltage 24V changes Property time 16min, it is modified cleared up 3 times with deionized water after 70 DEG C of dry carbon composites.
(3) by composite material crude product acquired in step (2) and ZnCl2With mass ratio 1:3 mixing, in N2With 5 in atmosphere DEG C/heating rate of min is raised to 600 DEG C, and keeps 3.0h at 600 DEG C, it is to be cooled to room temperature naturally, obtained solid is molten The cleaning dissolution unreacted ZnCl in the HCl of 1mol/L2, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven It is dried overnight, melamine silkworm excrement carbon composite is obtained after drying.
Embodiment 4
It (1) is that 1:160 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 1.5h at 40 DEG C Silkworm excrement is pulled out and is freeze-dried, first pre-processes 2.5h in -25 DEG C of freezings, then reduces temperature extremely -40 DEG C of freeze-drying 72h and is frozen Silkworm excrement after dry.In N2Silkworm excrement is raised to 700 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in atmosphere, and at 700 DEG C Room temperature, preparation carbonization silkworm excrement are cooled to after keeping 3.0h or more.
(2) it is centrifuged and dries after adding deionized water 150mL to mix standing 18h 1.0g melamine powder and 6.0g carbonization silkworm excrement It is dry, it is passed through N2As modified gas, 1.0g mixing material is put into plasma reactor, reactor input voltage 26V changes Property time 14min, it is modified cleared up 3 times with deionized water after 70 DEG C of dry carbon composites.
(3) by composite material crude product acquired in step (2) and ZnCl2With mass ratio 1:2.7 mixing, in N2With 5 in atmosphere DEG C/heating rate of min is raised to 600 DEG C, and keeps 2.0h at 600 DEG C, it is to be cooled to room temperature naturally, obtained solid is molten The cleaning dissolution unreacted ZnCl in the HCl of 1mol/L2, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven It is dried overnight, melamine silkworm excrement carbon composite is obtained after drying.
Embodiment 5
It (1) is that 1:180 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 1.0h at 45 DEG C Silkworm excrement is pulled out and is freeze-dried, first pre-processes 4h in -20 DEG C of freezings, then reduces temperature extremely -45 DEG C of freeze-drying 60h and is lyophilized Silkworm excrement afterwards.In N2Silkworm excrement is raised to 900 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in atmosphere, and protects at 900 DEG C Room temperature, preparation carbonization silkworm excrement are cooled to after holding 2.0h or more.
(2) add deionized water 200mL to mix 1.0g melamine powder and 8.0g carbonization silkworm excrement and stand for 24 hours centrifugation baking afterwards It is dry, it is passed through N2As modified gas, 1.0g mixing material is put into plasma reactor, reactor input voltage 28V changes Property time 12min, it is modified cleared up 3 times with deionized water after 80 DEG C of dry carbon composites.
(3) by composite material crude product acquired in step (2) and ZnCl2With mass ratio 1:5 mixing, in N2With 5 in atmosphere DEG C/heating rate of min is raised to 650 DEG C, and keeps 1.0h at 650 DEG C, it is to be cooled to room temperature naturally, obtained solid is molten The cleaning dissolution unreacted ZnCl in the HCl of 1mol/L2, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven It is dried overnight, melamine silkworm excrement carbon composite is obtained after drying.
Embodiment 6
It (1) is that 1:200 carries out mixing swelling according to plastid ratio with deionized water by Faeces bombycis, after being swollen 0.5h at 50 DEG C Silkworm excrement is pulled out and is freeze-dried, first pre-processes 4h in -20 DEG C of freezings, then reduces temperature extremely -40 DEG C of freeze-drying 72h and is lyophilized Silkworm excrement afterwards.In N2Silkworm excrement is raised to 1000 DEG C with the heating rate of 5 DEG C/min after 10.0g is lyophilized in atmosphere, and at 1000 DEG C Room temperature, preparation carbonization silkworm excrement are cooled to after keeping 2.0h or more.
(2) it is centrifuged after adding deionized water 100mL to mix standing 12h 1.0g melamine powder and 10.0g carbonization silkworm excrement Drying, is passed through N2As modified gas, 1.0g mixing material is put into plasma reactor, reactor input voltage 30V, Modification time 10min, it is modified cleared up 3 times with deionized water after 80 DEG C of dry carbon composites.
(3) by composite material crude product acquired in step (2) and ZnCl2With mass ratio 1:6 mixing, in N2With 5 in atmosphere DEG C/heating rate of min is raised to 700 DEG C, and keeps 0.5h at 700 DEG C, it is to be cooled to room temperature naturally, obtained solid is molten The cleaning dissolution unreacted ZnCl in the HCl of 1mol/L2, reuse after deionized water is cleaned to pH ≈ 7 and be centrifuged, be placed in baking oven It is dried overnight, melamine silkworm excrement carbon composite is obtained after drying.
Material properties test:
(1) electron microscope of melamine silkworm excrement carbon composite
Using Japanese Hitachi S-3400N type low power scanning electron microscope to silkworm after Faeces bombycis slice, swelling freeze-drying Melamine silkworm excrement carbon composite obtained by silkworm excrement inner surface and the embodiment of the present invention 1 carries out after sand slice, swelling freeze-drying The characterization of material surface pattern, as shown in Figure 1, Figure 2, Figure 3, Figure 4.
By Fig. 1 and Fig. 2 comparison it is found that silkworm excrement volume becomes larger after swelling and internal layer generates a large amount of pore structures.Fig. 3 It is silkworm excrement inner surface electron-microscope scanning figure after being swollen, embodies silkworm excrement tridimensional network.Fig. 4 is the compound raw material of wood-charcoal of melamine silkworm excrement Expect electron-microscope scanning figure, it can be seen that pass through plasma modification and ZnCl2After activation, a large amount of three are formed in silkworm excrement base porous charcoal Poly cyanamid bead forms melamine silkworm excrement carbon composite.
(2) pore structure study of melamine silkworm excrement carbon composite
Use Micro company of the U.S. produce 3-Flex specific surface pore-size distribution instrument to prepared by the present invention not to be swollen Silkworm excrement is that raw material prepares silkworm excrement porous carbon material (according to 1 activation condition of embodiment), melamine after processing silkworm excrement and swelling treatment The pore structure of amine silkworm excrement carbon composite is measured, and the results are shown in Table 1.
The specific surface area and pore-size distribution of the resulting melamine silkworm excrement carbon composite of 1. 6 kinds of embodiments of table.
Smicro, VtAnd VmicroRespectively indicate specific surface area provided by micropore, Kong Rong provided by total pore volume and micropore.
According to 1 column data of table it is found that melamine silkworm excrement carbon composite prepared by six kinds of embodiments Langmuir specific surface area is in 950-1350m2/ g, total pore volume is about in 0.3-0.6cm3/ g or more, wherein micropore specific area and hole Appearance accounts for the 50~70% of total specific surface area and Kong Rong.Silkworm excrement is prepared with silkworm excrement after non-swelling treatment silkworm excrement and swelling treatment respectively Porous carbon material, specific surface area and porosity have significant difference, are not swollen the specific surface area and porosity of silkworm excrement base Carbon Materials 60% or so of silkworm excrement base Carbon Materials after being only swollen.This explanation, in the embodiment of the present invention coverage area, obtained by preparation Melamine silkworm excrement carbon composite be a kind of with relatively long-pending porous carbon material.
(3) different melamine silkworm excrement base carbon composites and the analysis of Faeces bombycis constituent content rate
It is real to Faeces bombycis, the present invention using Japanese Hitachi S-3400N type low power scanning electron microscope energy spectrum analysis It is more as shown in table 2 to apply the progress of melamine silkworm excrement base carbon composite obtained by example 1~6 C, N, O elemental composition.
The different melamine silkworm excrement base carbon composites of table 2 and Faeces bombycis elemental analysis
From 2 data of table it is found that as the compositely proportional of the carbonization silkworm excrement of case 1~6 and melamine is continuously increased, element point The content of nitrogen is constantly reduced in analysis, i.e., the compositely proportional by adjusting silkworm excrement and melamine can change in composite material N element content, due to carbonization silkworm excrement and melamine it is compound only occur in carbonization silkworm excrement surface, so by control silkworm excrement with The compositely proportional of melamine can regulate and control the quantity of composite material surface group containing N.
(4) melamine silkworm excrement carbon composite sustained release performance is analyzed
To case study on implementation 2,4,6 prepare melamine silkworm excrement carbon composite carry out pesticide Diacloden absorption carriage amount and Elution profiles analysis, wherein the adsorption conditions of carbon composite are that be put into 50mL0.8g/L Diacloden molten for 50mg composite slow release material Absorption is vibrated in liquid, 30 DEG C of bath temperature, vibrates 200 revs/min of revolving speed；The sustained release condition of carbon composite is after 50mg is adsorbed Composite slow release material is put into 120mL deionized water, is changed water 100mL daily, 30 DEG C of bath temperature, is vibrated 200 revs/min of revolving speed Clock, experimental result difference are as shown in Figure 5, Figure 6.From figure 5 it can be seen that 3 kinds of slow-release materials are after absorption Diacloden 48 hours Load capacity all reaches 500mg/g or more, and without apparent difference between three kinds of materials, illustrates that such material has difference Similar adsorption effect is able to maintain while slow release effect.From fig. 6, it can be seen that complete at 15 days, 30 days and 60 days or so respectively At release process (using 90% Diacloden of total volume as endpoint calculation), it is able to satisfy the requirement of different times pesticide slow-release.
The above embodiment of the present invention is only intended to clearly illustrate examples made by the present invention, and is not to of the invention The restriction of embodiment.For those of ordinary skill in the art, other can also be made on the basis of the above description Various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all in spirit of the invention With any modifications, equivalent replacements, and improvements made within principle etc., the protection scope of the claims in the present invention should be included in Within.

Claims (9)

1. a kind of preparation method of melamine silkworm excrement carbon composite, it is characterised in that: include the following steps,
(1) Faeces bombycis is freeze-dried after mixing swelling with water, then silkworm excrement after freeze-drying is anti-by high temperature cabonization in protective gas Carbonization silkworm excrement should be prepared；
(2) it is centrifuged and dries after adding water to mix standing a period of time melamine powder and carbonization silkworm excrement, then be passed through N2Preparation etc. Gas ions modified cyanurotriamide silkworm excrement carbon composite, 20 ~ 30 V of input voltage of plasma device, modification time 10 ~ 20 min；It is modified to wash with water drying；
(3) by composite material crude product acquired in step (2) and ZnCl2Mixing carries out reaming reaction, then in protective gas Melamine silkworm excrement carbon composite is obtained after cleaning, be centrifuged and drying again；The material is with melamine and charing silkworm excrement structure At three dimensional pore structures, Langmuir specific surface area is in 950-1350 m2/ g, total pore volume is in 0.3-0.6 cm3/ g, wherein micro- Pore specific surface area and Kong Rong account for the 50 ~ 70% of total specific surface area and Kong Rong.
2. the preparation method of melamine silkworm excrement carbon composite according to claim 1, it is characterised in that: the step (1) silkworm excrement is 1:100 ~ 200 with water mixing plastid ratio in, and mixing temperature is 30 ~ 50 o C, and incorporation time is 0.5 ~ 3 h.
3. the preparation method of melamine silkworm excrement carbon composite according to claim 1, it is characterised in that: the step (1) freezing dry process is first 2 ~ 4h of precooling at -25 o o of C ~ -20 C in, is then cooled to -60 o C ~ -40 24 ~ 72h is lyophilized in o C.
4. the preparation method of melamine silkworm excrement carbon composite according to claim 1, it is characterised in that: the step (2) mass ratio that melamine powder is mixed with carbonization silkworm excrement in is 1:1 ~ 10.
5. the preparation method of melamine silkworm excrement carbon composite according to claim 1, it is characterised in that: the step (2) mass ratio of melamine powder and water is 1:50 ~ 200 in, and water pH is 7 ~ 9, mixing 6 ~ 24 h of time of repose, after standing It is centrifuged 60 ~ 100 oC of drying temperature.
6. the preparation method of melamine silkworm excrement carbon composite according to claim 1, it is characterised in that: the step (3) composite material crude product and ZnCl in2Mixed mass ratio is 1:1 ~ 6, and the reaming reaction temperature is 500 ~ 700 oC, Reaction time is 0.5 ~ 5 h.
7. the preparation method of melamine silkworm excrement carbon composite according to claim 1 or 6, it is characterised in that: described Reaming reaction temperature is 550 ~ 650 oC, and the reaction time is 2 ~ 3 h.
8. the preparation method of melamine silkworm excrement carbon composite according to claim 1, it is characterised in that: step (1) The carburizing temperature of silkworm excrement is in 500-1000oC, 2 ~ 4 h of reaction time after middle freeze-drying.
9. the application for the melamine silkworm excrement carbon composite that preparation method as described in claim 1 obtains, it is characterised in that: Its application in terms of pesticide delays controlled release.
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