CN109201001A - A kind of preparation method of selective absorbent - Google Patents
A kind of preparation method of selective absorbent Download PDFInfo
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- CN109201001A CN109201001A CN201811304196.8A CN201811304196A CN109201001A CN 109201001 A CN109201001 A CN 109201001A CN 201811304196 A CN201811304196 A CN 201811304196A CN 109201001 A CN109201001 A CN 109201001A
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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
- B01J20/02—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
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
Abstract
The present invention provides a kind of method for preparing selective absorbent, comprising: the solid biomass material of crushing is integrated to 10~15min of infiltration in compound calcium salt soln, and controls Ca in the compound calcium salt soln2+Weight ratio with biological material is 0.05~1.00；The compound calcium salt soln is by CaCl2Solution and other calcium salt solns compound, wherein the CaCl2It is 5~7:3~5 with other calcium salt molar ratios；By the biological material isolation air charing by infiltration, biomass carbon is obtained；Obtained biomass carbon is further impregnated activation 2 hours or more with HCl solution, is then separated by solid-liquid separation and obtains solid and solution；It is dried after obtained solid is washed to neutrality to get the selective absorbent is arrived.Preparation method of the invention greatly reduces the production cost of adsorbent material while significantly improving selective absorbing effect of the material to the anion of nuisance, so that being adapted to China needs the national conditions of a wide range of environmental improvement.
Description
Technical field
The present invention relates to the preparation method of the adsorbent material for the depollution of environment more particularly to the systems of selective absorbent
Preparation Method.
Background technique
The stalk annual output that China's agricultural production is had in one's care reaches more than 800,000,000 tons, wherein mainly agricultural crop straw, removes small part
As returning to the field, papermaking and feeding livestock etc. outside, the direct of big Tanaka burns the waste for not only having caused the energy and resource, but also causes
Environmental pollution.
Agricultural crop straw can prepare biological straw charcoal after thermal cracking, and agricultural crop straw charcoal is as active carbon, charcoal
Change body and form cellular porous structure, the surface area of every gram of straw charcoal is up to 200~400m2, higher porosity knot
Structure, surface area, surface negative charge and charge density show damping dehumidifying, the good suction to mineral ion and organic matter
The characteristic of attached effect can be sterilized effectively, deodorization and guarantor store soil nutrient, therefore have good answer in terms of the depollution of environment
Use prospect.
It is very cheap that straw charcoal as adsorbent material its advantage first consists in price.Secondly, crop material stock number is abundant,
In addition forestry thinnings, waste wood, hill residue, processing of farm products solid slag, livestock and poultry cultivation solid waste etc. is abundant
It utilizes, is conducive to the sustainable development of ecological environment.After agricultural crop straw charcoal and soil or water mixing, there is very strong stabilization
Property, and have adsorptivity to many material compositions.It is applied in soil and water body, energy each pollutant of Adsorption, and energy
Fertilizer conservation is adsorbed, fertilising utilization efficiency is improved；And it can be used as soil conditioner in the soil, can improve soil physical chemistry spy
Property, improve soil quality and adsorb soil in pollutant, thus have wide matrixing Utilization prospects.
The active carbon prepared in the past is limited for the suction-operated of anion, especially reduces nitre state for farm environment
The adsorbent material of the leaching loss of nitrogen, nitrite nitrogen, adsorption function can not achieve the desired results.It is dirty applied to environment and water body
Dye repairs the purification of fluorine ion, arsenic ion, cryanide ion, also needs the material with selective absorption anionic functional.About
The related patents of the preparation method of selective absorbent have JP2005-296923A, JP2006-015216A, JP2006-
061769A, JP2005-296924A, they are by biological material CaCl2Solution is handled, and carries out charcoal after dry again
Change.
Currently, be usually the nitrogenous fertilizer such as crops application urea, ammonium state and nitre state in agricultural production, in the soil urea and
Ammoniacal nitrogen fertilizer nitrifies to form nitrate anions after, be very easy to be leached and lost, cause underground water and river and lake etc.
Water body nitrate-N pollution also reduces crop to the utilization rate of nitrogenous fertilizer nutrition.Therefore, the utilization efficiency of nitrogenous fertilizer how is improved, it is right
In the loss for inhibiting Nitrate Nutrition in agricultural land soil, crop is promoted to efficiently use and blocked to water body environment to fertilizer nutrient
Eutrophic pollution source for, have great significance.Simultaneously as the anion selectivity suction-operated prepared at present
Limitation in terms of material its quantity, type and effect, for the large-scale depollution of environment, especially for large area soil and
Harmful anion purified treatment in water body environment is not all satisfied urgent environmental improvement demand.
Therefore, it needs to develop a kind of adsorbent material that can significantly improve anion selectivity adsorption effect, while can drop again
The production cost of low adsorption material, to be adapted to the national conditions of Chinese a wide range of environmental improvement.
Summary of the invention
It is an object of the invention to: a kind of charcoal adsorption material with excellent anion selectivity adsorption effect is provided
Material and its preparation method and application.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
A kind of method preparing selective absorbent is provided, comprising the following steps:
1) solid biomass material of crushing is integrated to 10~15min of infiltration in compound calcium salt soln, and described in control
Ca in compound calcium salt soln2+Weight ratio with biological material is 0.05~1.00；The compound calcium salt soln is by CaCl2It is molten
Liquid and other calcium salt solns compound, wherein the CaCl2It is 5~7:3~5 with other calcium salt molar ratios；
2) by the biological material isolation air charing by step 1) infiltration, biomass carbon is obtained；
3) biomass carbon for obtaining step 2) is further impregnated activation 2 hours or more with HCl solution, is then separated by solid-liquid separation
Obtain solid and solution；It is dried after obtained solid is washed to neutrality to get the selective absorbent is arrived.
In the solution of the present invention, solid biomass material described in step 1) be can be from agricultural, forestry or animal husbandry
The various common biological materials of production, including crop material, forestry thinnings and waste wood, hill residue, feces of livestock and poultry are solid
One of body object, processing of farm products solid slag or a variety of mixtures.Preferred solid biomass material is in the present invention
Crop material or waste wood.One of the further preferred wheat of the crop material, corn, rice, soybean or cotton
Or the stalk of multiple kinds of crops.
In the solution of the present invention, compound calcium salt soln described in step 1) can be CaCl2It is multiple with other soluble calcium salts
The solution being made into, is also possible to CaCl2The dirty solution being re-dubbed with insoluble calcium phosphate；Calcium ion conduct in compound calcium salt soln
Activator is in conjunction with the C in biological material, to play activation to biological material.In preferred embodiments of the present invention,
The CaCl2It is 6:4 with other calcium salt molar ratios.
In preferred embodiments of the present invention, other described soluble calcium salts are in calcium nitrate, calcium acetate or calcium citrate
Any one or two or more mixtures；The mixing of any one or two kinds in further preferred calcium nitrate or calcium acetate
Object, the participation process of calcium nitrate or calcium acetate mixed solution are more advantageous to C-N, C-Ca combination, so as to improve gained biomass carbon
The adsorption capacity of material.
In preferred embodiments of the present invention, the insoluble calcium phosphate is any in calcium sulfate, calcium phosphate or calcium oxalate
One or more kinds of mixtures；The participation of the insoluble calcium phosphates such as calcium sulfate, calcium phosphate or oxalic acid makes have S, P in activation process
Or the presence of oxalic acid calcium salt structure, the combination of C-S, C-P and C-Ca equivalence bond structure is produced, to be more advantageous to improvement
The selective adsorption capacity of gained biomass carbon.
In preferred embodiments of the present invention, Ca described in step 1)2+It controls with the weight ratio of stalk 0.1~0.5；More preferably
Control is 0.2~0.3.
In preferred embodiments of the present invention, before charing described in step 2), in the biological material of the infiltration further
Add carbonized structure reinforcing agent and/or foaming agent；The carbonized structure reinforcing agent be selected from urea formaldehyde polymer, novolac polymer,
Water soluble alkyd resin, polyvinyl acetate, aqueous polyurethane, polyvinyl alcohol, pitch, silicate contain SiO2Substance (such as glass
Powder) one of or it is a variety of, the 5%~10% of mixed material total weight is accounted for after addition；The foaming agent is with high temperature point
Solve the inorganic salts of foaming effect, further preferred carbonate (such as ammonium carbonate, magnesium carbonate or sodium carbonate), sulfate (such as aluminum sulfate
Deng) or one of chlorate (such as ammonium chloride) or a variety of, the 1%~15% of mixed material total weight is accounted for after addition.It is described
Carbonized structure reinforcing agent be used for strengthen selective absorbent carbonized structure stablize；The foaming agent can make charing
The charing micropore of selective absorbent increases, to improve the adsorption efficiency of adsorbent material, while the carbon in the foaming agent
Hydrochlorate or sulfate can also participate in when biological material carbonizes or promote chemical activating process.
In the preferred scheme of the present invention, the carbonized structure reinforcing agent and/or foaming agent are added to described by step 2)
In the biological material of infiltration after mixing, it places 2~36 hours, the solid hard molding of formation is sufficiently adhered and strengthened to material
Afterwards, then the charing for completely cutting off air is carried out, further promotes the formation for stablizing porous structure with this, to increase adsorption material after charing
The adsorption capacity of material.
In preferred embodiments of the present invention, the charing of isolation air described in step 2), is at 300~900 DEG C, more preferably
At 600~650 DEG C, 100min is carbonized.
In preferred embodiments of the present invention, activation described in step 3) is that the biomass carbon for obtaining step 2) is with concentration
The HCl of 1mol/L infiltrates 3 hours.
In the further preferred scheme of the present invention, step 3) is separated by solid-liquid separation to the obtained solution return step 1), system
The standby compound calcium salt soln.Step 3), which is separated by solid-liquid separation in the obtained solution, contains a large amount of CaCl2It, can with a small amount of KCl
Activated solution to recycle as step 1) recycles.
In preferred embodiments of the present invention, drying described in step 3) is dried to constant weight for 75 DEG C in merging baking oven.
The present invention is to contain CaCl2Solution impregnation aqueous medium formed H2O and CO2Physically activated basis, in oxygen barrier height
H under the conditions of temperature2O、CO2And CaCl2Three forms second segment chemical process, the CaCO of generation3、CaO、HCl、H2And constituting of CO
Learn activation basis, the HCl or Cl of generation—It is free, the consumption of C atom can be promoted to shift, and then advance the migration of C atom
Displacement and recombination cohesive process, optimization form the multi-pore structure material of charing, advanced optimize to prepare adsorption function
Improved selective absorbent.Specific activation process includes following several stages:
Steam activation, it is completed by reaction as follows:
C+H2O→H2+CO；CO+H2O→CO2+H2
Carbon dioxide activation, it is completed by reaction as follows:
C+CO2→CO；CO+O2→CO2；H2+O2→H2O；
CaCl2+CO2+H2O→CaCO3+HCl；
Chemical activation, it is completed by reaction as follows:
CaCO3+C→Ca+CO
CaO+C→Ca+CO
CO+O2→CO2
On this basis, in the compound calcium salt soln that the present invention uses, the participation of the calcium salt solns such as calcium nitrate or calcium acetate
It is more advantageous to C-N, C-Ca combination, to further improve the adsorption capacity of gained biomass carbon material；And compound calcium salt is molten
The participation of the insoluble calcium phosphates such as calcium sulfate, calcium phosphate or oxalic acid in liquid makes to have in activation process S, P or oxalic acid calcium salt structure
In the presence of the combination of producible C-S, C-P and C-Ca equivalence bond structure also can further improve the choosing of gained biomass carbon
Selecting property adsorption capacity.In short, the present invention is activated by using compound calcium salt soln, the absorption obtained after carbonizing biological material
Material improves 10~20% to the adsorption capacity of anion.
In addition, further biological material and the carbonized structure are enhanced before charing in the preferred solution of the invention
Agent and/or foaming agent mixing, can make biological material form more stable carbonized structure in carbonization process, and formed more
More charing micropore, to further significantly improve the adsorption efficiency of selective absorbent of the present invention, while the hair
Carbonate or sulfate in infusion can also participate in when biological material carbonizes or promote the chemical activating process.
Active carbon adsorption material according to the method for the present invention preparation has excellent Anion-adsorption effect, especially applies
Farm environment is lost and is applied to environment and aqueous pollution remediation fluorine ion, arsenic to reduce the leaching of nitrate nitrogen, nitrite nitrogen
The purification aspect of ion, cryanide ion, there is significant effect.Preparation method of the invention is significantly improving material to the yin of nuisance
While the selective absorbing effect of ion, the production cost of adsorbent material is greatly reduced, so that being adapted to China needs big model
Enclose the national conditions of environmental improvement.
Specific embodiment
It is more at large solved below by way of preparation method of the more specific embodiment to above-mentioned selective absorbent
It releases.In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can also use
Implement different from other way described herein, those skilled in the art can do without violating the connotation of the present invention
It is similar to promote, therefore the present invention is not limited by the specific embodiments disclosed below.
Embodiment 1
The rice of 300g weight or the stalk segment (1-2cm) or stalk powder of soybean or cotton are weighed, 1000ml is soaked in
In compound calcium salt soln, compound calcium salt soln is by CaCl2Solution is compounded with calcium acetate solution with the molar ratio of 5:4, wherein
Ca2+Weight ratio with stalk is 0.5；The stalk of immersion is sufficiently integrated to infiltration 15 minutes；Wet stalk is put into retort
The charing for carrying out isolation air takes out cooling after charing 100min under the conditions of carbonization temperature is 600 DEG C, 1000ml concentration is added
It is infiltrated 3 hours for the HCl of 1mol/L, then the straw charcoal filtering by infiltration in HCl liquid is washed till neutrality, is placed into 75 in baking oven
It DEG C dries to constant weight, obtains selective absorption straw charcoal material I.
Embodiment 2
The heavy forestry thinnings of 300g and/or waste wood biological material segment (1-2cm) or biological material powder are weighed,
It is soaked in the compound calcium salt soln of 1000ml, compound calcium salt soln is by CaCl2Solution and calcium acetate solution are multiple with the molar ratio of 6:4
With forming, wherein Ca2+Weight ratio with biological material is 1.00, and the biological material of immersion is sufficiently integrated to 15 points of infiltration
Clock；The charing that wet stalk investment retort is carried out to isolation air, carbonizes 100min under the conditions of carbonization temperature is 800 DEG C
Cooling is taken out afterwards, HCl infiltration 3 hours that 1000ml concentration is 1mol/L is added, then the biomass carbon by infiltration in HCl liquid
Filtering is washed till neutrality, is placed into baking oven and dries to constant weight for 75 DEG C, obtains selective absorption biomass carbon material II.
Embodiment 3
Weigh the waste wood and/or processing of farm products solid slag (such as coffee grounds) biological material segment (1- of 300g weight
2cm) or biological material powder, it is soaked in the compound calcium salt soln of 1000ml, compound calcium salt soln is by CaCl2Solution and sulphur
Sour calcium is compounded with the molar ratio of 5:3, wherein Ca2+Weight ratio with biological material is 1.00, by the biological material of immersion
Material sufficiently kneading infiltration 15 minutes；Stalk investment retort after immersion carries out the charing of isolation air, and carbonization temperature is 800 DEG C
Under the conditions of carbonize 100min after take out cooling, be added 1000ml concentration be 1mol/L HCl infiltrate 3 hours, then will infiltration exist
Biomass carbon filtering in HCl liquid, obtains filtrate and (wherein contains CaCl2Weight is about 830.0g) and solid biomass charcoal, it will
Solid biomass charcoal is washed till neutrality, is placed into baking oven and dries to constant weight for 75 DEG C, obtains selective absorption biomass carbon material III.
It is described to contain a large amount of CaCl2Filtrate return to initial impregnation stage, be used to prepare the compound calcium salt soln of 1000ml.
Embodiment 4
Weigh the heavy wheat of 300g or corn stover or forestry thinnings or waste wood biological material segment (1-2cm) or broken
End is soaked in the compound calcium salt soln of 1000ml, and compound calcium salt soln is by CaCl2Solution, calcium nitrate are compounded with calcium acetate,
Wherein CaCl2It is 6:4 with the molar ratio of calcium nitrate and acetic acid calcium compound, and controls Ca2+With the weight of stalk or biological material
For amount than being 0.3, the stalk or biological material of immersion sufficiently integrate infiltration 15 minutes；Then add in wet biological material
Add carbonized structure reinforcing agent (mixture of Lauxite and phenolic resin) and foaming agent (mixture of sodium carbonate and ammonium chloride),
It is uniformly mixed, the 8% of material total weight after making carbonized structure reinforcing agent account for addition, foaming agent accounts for material total weight after addition
10%；The charing that uniformly mixed material investment retort is carried out to isolation air, carbonizes under the conditions of carbonization temperature is 650 DEG C
Cooling is taken out after 100min, HCl infiltration 3 hours that 1000ml concentration is 1mol/L is added, then the straw by infiltration in HCl liquid
Stalk charcoal or biomass carbon filtering, obtain filtrate and (wherein contain CaCl2Weight is about 249.0g) and solid biomass charcoal, by solid
Biomass carbon is washed till neutrality, is placed into baking oven and dries to constant weight for 75 DEG C, obtains selective absorbent IV.
Embodiment 5
It weighs the rice of 300g weight or the stalk or hill residue or processing of farm products solid slag of soybean or livestock and poultry is supported
Solid waste biological material segment (1-2cm) or powder are grown, 1000ml is soaked in and meets calcium salt soln, the compound calcium salt is molten
Liquid filters gained filtrate by embodiment 4 and calcium oxalate compounds, wherein CaCl2Molar ratio with calcium oxalate is 6:4, and is controlled
Ca2+It is 0.30 with the weight ratio of stalk or biological material, sufficiently kneading infiltration 15 minutes；By wet stalk or biological material
Material investment retort carries out the charing of isolation air, takes out cooling after charing 100min under the conditions of carbonization temperature is 600 DEG C, adds
Enter the HCl that 1000ml concentration is 1mol/L to infiltrate 3 hours, then the straw charcoal by infiltration in HCl liquid or biomass carbon filter
It is washed till neutrality, is placed into baking oven and dries to constant weight for 75 DEG C, obtain selective absorbent V.
Embodiment 6
Weigh the soybean of 300g weight or the stalk or dry branches and fallen leaves or hill residue biological material segment (1- of cotton
2cm) or powder, it is soaked in the compound calcium salt soln of 1000ml, compound calcium salt soln is by CaCl2With nitric acid acid calcium rubbing with 6:4
You compound ratio, wherein Ca2+It is 0.25 with the weight ratio of stalk or biological material, by the stalk or biological material of immersion
Sufficiently kneading infiltration 15 minutes；Carbonized structure reinforcing agent (polyvinyl alcohol and phenol are added in wet stalk or biological material
The mixture of urea formaldehyde) and foaming agent (mixture of ammonium carbonate and ammonium chloride), it is uniformly mixed, accounts for carbonized structure reinforcing agent and add
Add the 10% of rear material total weight, foaming agent accounts for 15% of material total weight after addition；Material puts into retort after mixing
The charing for carrying out isolation air takes out cooling after charing 100min under the conditions of carbonization temperature is 630 DEG C, 1000ml concentration is added
It is infiltrated 3 hours for the HCl of 1mol/L, then the straw charcoal by infiltration in HCl liquid or biomass carbon filtering are washed till neutrality, juxtaposition
Enter in baking oven and dry to constant weight for 75 DEG C, obtains selective absorbent VI.
Comparative example 1
Weigh the heavy wheat of 300g or corn stover or forestry thinnings or waste wood biological material segment (1-2cm) or broken
End is soaked in 1000ml CaCl2In solution, wherein Ca2+It is 0.3 (or by Ca with the weight ratio of stalk or biological material2+Folding
It is counted as CaCl2Weight is 249.7g), the stalk or biological material of immersion sufficiently integrate infiltration 15 minutes；Wet nothing is dissociated
CaCl2Stalk or biological material the investment retort of solution carry out the charing of isolation air, are 650 DEG C of conditions in carbonization temperature
Cooling is taken out after lower charing 100min, and the HCl that 1000ml concentration is 1mol/L is added and infiltrates 3 hours, will then infiltrate in HCl liquid
In straw charcoal or biomass carbon filtering be washed till neutrality, be placed into baking oven and dry to constant weight for 75 DEG C, obtain selective absorption control
Material I.
The present invention has made the experiment of adsorpting anion nitrate nitrogen effect for above-described embodiment one by one, and obtains experimental result
Data, as listed in table 1.
Experimental program:
Material I~the VI and control material I that take 0.1g embodiment 1-6 to prepare respectively are added to the 40mg/L concentration of 30mL
KNO3In solution, 3h, filtering, using nitrogen concentration in Pbenoldisulfonic Acid colorimetric method for determining filtrate, wavelength 420nm are shaken.Every kind of material
Material, which is repeated 3 times, averages.Adsorbance is calculated by lower formula (I):
(I)
Wherein, the adsorbance (mg/g) when qe is adsorption equilibrium；C0 is initial soln concentration (mg/L)；Ce is adsorption equilibrium
When solution concentration (mg/L)；V is liquor capacity (L)；M is charcoal dosage (g).
Measurement result see the table below 1:
Table 1
| Embodiment sequence number | Adsorb nitrate nitrogen (NO3 -- N) amount (mg/g) | Removal rate (%) |
| Embodiment 1 | 37.5 | 90.0 |
| Embodiment 2 | 36.2 | 91.1 |
| Embodiment 3 | 39.3 | 98.5 |
| Embodiment 4 | 38.9 | 99.6 |
| Embodiment 5 | 36.5 | 97.9 |
| Embodiment 6 | 39.6 | 99.5 |
| Comparative example 1 | 32.1 | 75.8 |
Adsorptivity of the selective absorbent of method of the invention preparation for nitrate nitrogen it can be seen from upper table data
Existing material can be significantly better than.
Claims (10)
1. a kind of method for preparing selective absorbent, comprising the following steps:
1) solid biomass material of crushing is integrated to 10~15min of infiltration in compound calcium salt soln, and is controlled described compound
Ca in calcium salt soln2+Weight ratio with biological material is 0.05~1.00；The compound calcium salt soln is by CaCl2Solution and
Other calcium salt solns compound, wherein the CaCl2It is 5~7:3~5 with other calcium salt molar ratios；
2) by the biological material isolation air charing by step 1) infiltration, biomass carbon is obtained；
3) biomass carbon for obtaining step 2) is further impregnated activation 2 hours or more with HCl solution, is then separated by solid-liquid separation and is obtained
Solid and solution；It is dried after obtained solid is washed to neutrality to get the selective absorbent is arrived.
2. method described in claim 1, which is characterized in that solid biomass material described in step 1) is crop material, gives up
Abandon timber, processing of farm products solid slag or livestock and poultry cultivation solid waste；Further preferred wheat, corn, rice, soybean or
The stalk of one of cotton or multiple kinds of crops.
3. method described in claim 1, which is characterized in that in compound calcium salt soln described in step 1), the CaCl2With
Other calcium salt molar ratios are 6:4.
4. method described in claim 1, which is characterized in that in compound calcium salt soln described in step 1), other described calcium
Salt is soluble calcium salt, any one in calcium nitrate, calcium acetate or calcium citrate or two or more mixtures；It is preferred that
The mixture of any one or two kinds in calcium nitrate or calcium acetate.
5. method described in claim 1, which is characterized in that in compound calcium salt soln described in step 1), other described calcium
Salt is insoluble calcium phosphate, any one in calcium sulfate, calcium phosphate or calcium oxalate or two or more mixtures.
6. method described in claim 1, which is characterized in that Ca described in step 1)2+With the control of the weight ratio of stalk 0.1~
0.5；It is preferably controlled in 0.2~0.3.
7. method described in claim 1, before charing described in step 2), further add in the biological material of the infiltration
Add carbonized structure reinforcing agent and/or foaming agent；The carbonized structure reinforcing agent is selected from urea formaldehyde polymer, novolac polymer, water
Dissolubility alkyd resin, polyvinyl acetate, aqueous polyurethane, polyvinyl alcohol, pitch, silicate contain SiO2Substance (such as glass powder)
One of or it is a variety of, the 5%~10% of mixed material total weight is accounted for after addition；The foaming agent is with pyrolytic hair
The inorganic salts of bubble effect, preferably carbonate (such as ammonium carbonate, magnesium carbonate or sodium carbonate), sulfate (such as aluminum sulfate) or chlorate
It is one of (such as ammonium chloride) or a variety of, the 1%~15% of mixed material total weight is accounted for after addition.
8. method of claim 7, the carbonized structure reinforcing agent and/or foaming agent are added to the infiltration by step 2)
Biological material in after mixing, place 2~36 hours, after material sufficiently adheres and strengthens formation consolidate hard molding after,
The charing of isolation air is carried out again.
9. method described in claim 1, the charing of isolation air described in step 2), is at 300~900 DEG C more preferable 600
At~650 DEG C, 100min is carbonized.
10. method described in claim 1, step 3) is separated by solid-liquid separation to the obtained solution return step 1), described in preparation
Compound calcium salt soln.
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| CN110305674A (en) * | 2019-07-10 | 2019-10-08 | 青岛农业大学 | A kind of modification biological charcoal, soil-repairing agent and its preparation method and application |
| CN112410037A (en) * | 2020-10-15 | 2021-02-26 | 南京工业大学 | Composite functional material for soil pollution treatment and preparation method thereof |
| CN112938973A (en) * | 2021-03-22 | 2021-06-11 | 淮北市大华环保科技有限公司 | Production method of special active carbon for pressure swing adsorption with high separation coefficient |
| CN114570177A (en) * | 2022-03-30 | 2022-06-03 | 江苏敏禾科技有限公司 | Biomass calcium-based solid denitration agent and preparation method thereof |
| CN116495733A (en) * | 2023-06-21 | 2023-07-28 | 成都达奇科技股份有限公司 | Preparation method of bamboo activated carbon with high specific surface area and bamboo activated carbon |
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| CN110305674A (en) * | 2019-07-10 | 2019-10-08 | 青岛农业大学 | A kind of modification biological charcoal, soil-repairing agent and its preparation method and application |
| CN110305674B (en) * | 2019-07-10 | 2021-03-02 | 青岛农业大学 | Modified biochar, soil remediation agent and preparation method and application thereof |
| CN112410037A (en) * | 2020-10-15 | 2021-02-26 | 南京工业大学 | Composite functional material for soil pollution treatment and preparation method thereof |
| CN112938973A (en) * | 2021-03-22 | 2021-06-11 | 淮北市大华环保科技有限公司 | Production method of special active carbon for pressure swing adsorption with high separation coefficient |
| CN114570177A (en) * | 2022-03-30 | 2022-06-03 | 江苏敏禾科技有限公司 | Biomass calcium-based solid denitration agent and preparation method thereof |
| CN116495733A (en) * | 2023-06-21 | 2023-07-28 | 成都达奇科技股份有限公司 | Preparation method of bamboo activated carbon with high specific surface area and bamboo activated carbon |
| CN116495733B (en) * | 2023-06-21 | 2023-10-13 | 成都达奇科技股份有限公司 | Preparation method of bamboo activated carbon with high specific surface area and bamboo activated carbon |
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Effective date of registration: 20211210 Address after: 810021 office building 128 Chuangye Road, Nanchuan Industrial Park, Xining City, Qinghai Province Patentee after: Zhongling environmental protection Co.,Ltd. Address before: 100081 No. 12 South Main Street, Haidian District, Beijing, Zhongguancun Patentee before: INSTITUTE OF ENVIRONMENT AND SUSTAINABLE DEVELOPMENT IN AGRICULTURE, CHINESE ACADEMY OF AGRICULTURAL SCIENCES |