CN109821515A - Preparation method based on biological material and magnesium ore compound adsorbent - Google Patents
Preparation method based on biological material and magnesium ore compound adsorbent Download PDFInfo
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- CN109821515A CN109821515A CN201910240161.0A CN201910240161A CN109821515A CN 109821515 A CN109821515 A CN 109821515A CN 201910240161 A CN201910240161 A CN 201910240161A CN 109821515 A CN109821515 A CN 109821515A
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- magnesium ore
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- compound adsorbent
- magnesium
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 239000011777 magnesium Substances 0.000 title claims abstract description 187
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 187
- 150000001875 compounds Chemical class 0.000 title claims abstract description 125
- 239000003463 adsorbent Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 91
- 239000012620 biological material Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 231
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 141
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 93
- 239000004411 aluminium Substances 0.000 claims abstract description 89
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 83
- 239000000203 mixture Substances 0.000 claims abstract description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 64
- 239000002028 Biomass Substances 0.000 claims abstract description 46
- 150000001412 amines Chemical class 0.000 claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 22
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 80
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 61
- 239000012266 salt solution Substances 0.000 claims description 61
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 40
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 33
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 33
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 33
- 239000011425 bamboo Substances 0.000 claims description 33
- 235000009496 Juglans regia Nutrition 0.000 claims description 32
- 235000020234 walnut Nutrition 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 26
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 25
- 244000105624 Arachis hypogaea Species 0.000 claims description 25
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 25
- 235000018262 Arachis monticola Nutrition 0.000 claims description 25
- 235000020232 peanut Nutrition 0.000 claims description 25
- 238000001179 sorption measurement Methods 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 229960001484 edetic acid Drugs 0.000 claims description 14
- 239000001095 magnesium carbonate Substances 0.000 claims description 14
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 14
- 239000012265 solid product Substances 0.000 claims description 14
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000003352 sequestering agent Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 25
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 241001330002 Bambuseae Species 0.000 description 32
- 241000758789 Juglans Species 0.000 description 31
- 230000000694 effects Effects 0.000 description 21
- 239000010902 straw Substances 0.000 description 20
- 239000011257 shell material Substances 0.000 description 16
- -1 antibiotic Substances 0.000 description 15
- 235000014380 magnesium carbonate Nutrition 0.000 description 13
- 239000007789 gas Substances 0.000 description 8
- 238000010129 solution processing Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000011162 core material Substances 0.000 description 6
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical compound O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 229910052599 brucite Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002916 wood waste Substances 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The preparation method based on biological material and magnesium ore compound adsorbent that the present invention relates to a kind of.Preparation including biomass carbon material: biological material is crushed; then biological material, acid and water are mixed into obtain mixture in proportion; then mixture is subjected to first time heating treatment; treatment temperature is 100-120 DEG C; handling the time is 1-2 hour, and first time heating treatment treated product carries out under nitrogen protection high-temperature process, treatment temperature is 200-400 DEG C; handling the time is 0.5-2 hours, obtains biomass carbon material；Biomass carbon aluminium handles the preparation of material, biomass carbon aluminum material and magnesium ore it is compound, amine processing: the untreated compound adsorbent of previous step is mixed and dried with aq. polyethyleneimine, obtains biological material and magnesium ore compound adsorbent.Using cheap biological material and magnesium ore come synthesizing new compound adsorbent, cost of material is cheap, from a wealth of sources.
Description
Technical field
The present invention relates to a kind of adsorbent more particularly to a kind of systems based on biological material and magnesium ore compound adsorbent
Preparation Method.
Background technique
Biological material is a kind of important biomass resource.Biological material is many kinds of in nature, and distribution is wide
It is general, enormous amount.According to its source can be divided into production of forestry trees fell industrial wood waste, stalk and farming in agricultural production
The excrement and have that the biological activities such as house refuse, the people and animals generated during object industrial wood waste, urban life generate in the process
Machine waste water etc..These annual biological materials are all as industrial production, agricultural production, daily life etc. largely generate.If no
Carrying out processing and utilization to these biological materials not only will cause the waste of resource, also will increase garbage disposal burden, or even dirty
Contaminate environment.Therefore, development and utilization biological material is the demand of previous cycle economic development.
Magnesium mine is a kind of important ore resource.By taking Liaoning Province as an example, there are a large amount of magnesite, brucite mineral etc..It uses
Magnesite can produce light-burned, dead burned magnesia, the production for refractory material；Halogen-free flameproof can be produced using brucite mineral
Agent etc..The development and utilization of these magnesium mines are that the construction of national economy is made that important contribution.But opening with all kinds of magnesium mines
It adopts, various high-grade magnesium mines are constantly consumed.And low-grade magnesium mine cannot be used directly since its magnesia equal size is not up to standard
In the production of related magnesium products.Currently, the ratio that the low-grade magnesium mine in Liaoning Province accounts for magnesium mine gross reserves rises year by year.How to develop
Become an important topic in terms of comprehensive utilization of resources using these low-grade magnesium mines.
Adsorbent is that one kind can be effectively from the solids of the certain ingredients adsorbed in these media in gas or liquid
Matter.In general, adsorbent has big specific surface area, suitable pore structure and surface texture.There is strong suction to adsorbed material
Attached ability, at the same it is general do not chemically reacted with adsorbed material etc., and there is fabulous adsorptivity and mechanicalness characteristic.Cause
This, adsorbent has important application in the process field of the pollutants such as waste water, exhaust gas.However, with the rapid development of industry and work
Industry degree is increasingly sharpened, and the oxious component in waste water, exhaust gas is increasingly sophisticated.As usually contained heavy metal in current waste water
Ion, small organic molecule, the various ingredients of dyestuff, antibiotic, agrochemical, and currently have obvious adsorption effect to one-component
Adsorbent in the presence of multiple pollutant, overall adsorption effect can be declined.
Therefore, compound-type adsorbent is produced using the magnesium ore resource of biological material and various grades, is improved compound
Type adsorbent can promote biological material and magnesium ore (especially low-grade magnesium ore) to the adsorption effect of multiple pollutant
Comprehensive utilization, extends the application field of adsorbent, promotes the development of environmental protection cause.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides one kind to be based on biological material and magnesium ore compound adsorbent
Preparation method, it is therefore an objective to improve biological material and magnesium ore (especially low-grade magnesium ore) using horizontal, prepare
It is that good adsorption effect all had to multiple pollutant and be expected to the compound-type adsorbent to come into operation.
In order to achieve the above object, a kind of preparation method based on biological material and magnesium ore compound adsorbent of the present invention, packet
It includes the preparation of biomass carbon material: biological material is crushed, biological material, acid and water are then mixed into obtain mixing in proportion
Object, the wherein mass parts ratio of biological material, acid and water are as follows: then mixture is carried out first time liter by 1:0.7-2:2-6
Temperature processing, treatment temperature are 100-120 DEG C, and the processing time is 1-2 hours, and first time heating treatment treated product is in nitrogen
High-temperature process is carried out under gas shielded, treatment temperature is 200-400 DEG C, and the processing time is 0.5-2 hours, obtains biomass carbon materials
Material；
The preparation of biomass carbon aluminium processing material: the biomass carbon material of above-mentioned preparation is directly mixed to obtain and is mixed with aluminum salt solution
Liquid, wherein the mass parts ratio that mixed ratio is biomass carbon material and aluminum salt solution is 1:1-3, mixed liquor is protected in nitrogen
Under the conditions of shield in 300-500 DEG C processing 1-3 hours, be cooled to room temperature obtain biomass carbon aluminium processing material；
The preparation of magnesium ore material: being milled to 1250-5000 mesh for magnesium ore, in 400-700 DEG C calcining 1-10 hours, drop
It warms to room temperature to obtain magnesium ore material；
Biomass carbon aluminum material and magnesium ore it is compound: biomass carbon aluminium is handled into material, magnesium ore material and water and is mixed, wherein
Biomass carbon aluminium handles material, the mass parts ratio of magnesium ore material and water is 1:0.05-1:3-10, and with alkali by solution PH
Value is adjusted to 7-11, and mixture is placed in hydrothermal reaction kettle, in 100-130 DEG C reaction 10-17 hours, will mix after reaction
Object filtering is closed, solid product is washed with water to neutrality, obtains untreated compound adsorbent；
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine according to the weight of mass ratio 1:0.1-1
Amount ratio is mixed, and is dried after mixing 0.5-1 hours in 90-100 degrees Celsius, is obtained biological material and magnesium ore composite adsorption
Agent.
The biological material includes stalk, peanut shell, corncob, walnut shell, bamboo or sawdust.
The acid is phosphoric acid, and the concentration of phosphoric acid is 85%.
The aluminum salt solution is the mixed solution of aluminum nitrate, organic sequestering agent and water, wherein aluminum nitrate, organic sequestering agent
Mass parts ratio with water is 1:0.5-2:10-100.
The organic sequestering agent is ethylenediamine tetra-acetic acid, iminodisuccinic acid and citric acid.
The magnesium ore is the mixture of giobertite, shepardite ore, or both, magnesium carbonate in giobertite
Content is 60%-90%, and the content of magnesium hydroxide is 60%-90% in shepardite ore.
The alkali is sodium hydroxide or potassium hydroxide.
The mass concentration of the aq. polyethyleneimine is 0.5-5%.
The polyethyleneimine molecular weight is 15000-50000.
Advantages of the present invention effect: using cheap biological material and magnesium ore come synthesizing new compound adsorbent, original
Expect cheap, from a wealth of sources.When preparing biomass carbon material, due to using aluminium treatment process, without to biomass
Carbon material is cleaned, and the problem of environmental pollution of residual acid in biomass carbon material is eliminated, and the phosphor-aluminum material of generation can improve
The absorption property of composite adsorbing material.In addition, the biomass carbon material and magnesium material compound tense of aluminum salt solution processing, due to the two
Between there are hydrotalcite structures so that bonding between the two is even closer, to guarantee that the adsorbent can guarantee performance
In the case where recycle for a long time.Meanwhile amine treatment process can also effectively improve the knot between biomass carbon and other components
With joint efforts, it ensure that the stability of absorption property when long-time is recycled of the adsorbent.The magnesium ore used can be effective
The magnesium ore using middle-low grade, the development and utilization for middle-low grade magnesium ore provide approach.The composite adsorption material of preparation
Material ensure that good adsorption effect, to heavy metal ion, small organic molecule, dyestuff while reducing material preparation cost
Molecule, pesticide molecule etc. have good adsorption effect, can be used for the purified treatment of water body, gas etc., are such NEW TYPE OF COMPOSITE
The practical application of adsorbent lays the foundation.
Specific embodiment
Below with reference to the present embodiment, the invention will be further described.
Embodiment 1
The present invention is based on the preparation methods of biological material and magnesium ore compound adsorbent, include the following steps:
1, by aluminum salt solution handle and by amine processing compound adsorbent prepare it is as follows:
The preparation of biomass carbon material: corncob is crushed, and then mixes corncob, phosphoric acid (concentration 85%) and water in proportion
It closes, wherein the mass parts ratio of corn core material, phosphoric acid (concentration 85%) and water is 1:2:6.Then mixture is carried out first
Secondary heating treatment, treatment temperature are 120 DEG C, and the processing time is 2 hours.First time heating treatment treated product is protected in nitrogen
Shield is lower to carry out high-temperature process, and treatment temperature is 400 DEG C, and the processing time is 2 hours, obtains corncob carbon material.
The preparation of corncob carbon aluminium processing material: the corncob carbon material of above-mentioned preparation is directly mixed with aluminum salt solution,
Wherein the mass parts ratio of aluminum nitrate, ethylenediamine tetra-acetic acid and water is 1:0.5:10, wherein corncob carbon material and aluminum salt solution
Mass parts ratio be 1:3.Mixture is handled 3 hours under the conditions of nitrogen protection in 400 DEG C.It is cooled to room temperature and obtains corncob
Carbon aluminium handles material.
The preparation of magnesium ore material: being milled to 5000 mesh for giobertite (content of magnesium carbonate is 90% in giobertite),
It is calcined 10 hours in 700 DEG C, is cooled to room temperature and obtains magnesium ore material.
Corncob carbon aluminum material and magnesium ore material it is compound: corncob carbon aluminium is handled into material, magnesium ore material and water
Mixing, wherein the mass parts ratio of corncob carbon aluminium processing material, magnesium ore material and water is 1:1:10, and will with sodium hydroxide
Solution pH value is adjusted to 11.Mixture is placed in hydrothermal reaction kettle, is reacted 17 hours in 130 DEG C.After reaction by mixture mistake
Filter, solid product are washed with water to neutrality, obtain untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 5%, poly- second
Alkene imines molecular weight is 50000) to be mixed according to the ratio of mass ratio 1:1, is dried after mixing 1 hour in 100 DEG C.Obtain jade
Rice core carbon aluminium processing material and magnesium ore compound adsorbent.
2, without aluminum salt solution handle and without amine handle compound adsorbent prepare it is as follows:
The preparation of biomass carbon material: corncob is crushed, and then mixes corncob, phosphoric acid (concentration 85%) and water in proportion
It closes, wherein the mass parts ratio of corn core material, phosphoric acid (concentration 85%) and water is 1:2:6.Then mixture is carried out first
Secondary heating treatment, treatment temperature are 120 DEG C, and the processing time is 2 hours.First time heating treatment treated product is protected in nitrogen
Shield is lower to carry out high-temperature process, and treatment temperature is 400 DEG C, and the processing time is 2 hours, obtains corncob carbon material.By this kind of material
Wash with distilled water, remaining acidic materials are removed.
The preparation of magnesium ore material: being milled to 5000 mesh for giobertite (content of magnesium carbonate is 90% in giobertite),
It is calcined 10 hours in 700 DEG C, is cooled to room temperature and obtains magnesium ore material.
Corncob carbon material and magnesium ore material it is compound: corncob carbon material, magnesium ore material and water are mixed, wherein
The mass parts ratio of corncob carbon material, magnesium ore material and water is 1:1:10, and solution pH value is adjusted to 11 with sodium hydroxide.
Mixture is placed in hydrothermal reaction kettle, is reacted 17 hours in 130 DEG C.Mixture is filtered after reaction, solid product water
It is washed till neutrality, is not carried out the biological material of aluminum salt solution processing and amine processing and the compound adsorbent of magnesium ore.
The comparison of 1 two kinds of composite material adsorbent adsorption effects of table
。
Annotate a by aluminum salt solution handle and by amine processing compound adsorbent b without aluminum salt solution handle and
The compound adsorbent handled without amine
Embodiment 2
1, by aluminum salt solution handle and by amine processing compound adsorbent prepare it is as follows:
The preparation of biomass carbon material: stalk is crushed, and then mixes stalk, phosphoric acid (concentration 85%) and water in proportion,
The mass parts ratio of middle stalk material, phosphoric acid (concentration 85%) and water is 1:1.5:5.Then mixture is subjected to first time liter
Temperature processing, treatment temperature are 110 DEG C, and the processing time is 1.5 hours.First time heating treatment treated product is in nitrogen protection
Lower carry out high-temperature process, treatment temperature are 300 DEG C, and the processing time is 1 hour, obtain stalk carbon material.
Straw carbon aluminium processing material preparation: by the stalk carbon material of above-mentioned preparation directly and aluminum salt solution (aluminum nitrate, second
The mass parts ratio of ethylenediamine tetraacetic acid (EDTA) and water is 1:1:15) mixing, wherein the mass parts ratio of stalk carbon material and aluminum salt solution
For 1:2.Mixture is handled 3 hours under the conditions of nitrogen protection in 500 DEG C.It is cooled to room temperature and obtains straw carbon aluminium processing material.
The preparation of magnesium ore material: water magnesium ore (content of magnesium hydroxide is 90% in water magnesium ore) is milled to 4500
Mesh is calcined 9 hours in 600 DEG C, is cooled to room temperature and obtains magnesium ore material.
Straw carbon aluminum material and magnesium ore material it is compound: straw carbon aluminium is handled into material, magnesium ore material and water and is mixed,
Wherein straw carbon aluminium processing material, magnesium ore material and water mass parts ratio be 1:0.05:5, and with potassium hydroxide by solution
PH value is adjusted to 11.Mixture is placed in hydrothermal reaction kettle, is reacted 15 hours in 130 DEG C.Mixture is filtered after reaction, Gu
Body product is washed with water to neutrality, obtains untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 4%, poly- second
Alkene imines molecular weight is 45000) to be mixed according to the ratio of mass ratio 1:0.9, is dried after mixing 0.8 hour in 95 DEG C.?
Material and magnesium ore compound adsorbent are handled to straw carbon aluminium.
2, without aluminum salt solution handle and by amine processing compound adsorbent prepare it is as follows:
The preparation of biomass carbon material: stalk is crushed, and then mixes stalk, phosphoric acid (concentration 85%) and water in proportion,
The mass parts ratio of middle stalk material, phosphoric acid (concentration 85%) and water is 1:1.5:5.Then mixture is subjected to first time liter
Temperature processing, treatment temperature are 110 DEG C, and the processing time is 1.5 hours.First time heating treatment treated product is in nitrogen protection
Lower carry out high-temperature process, treatment temperature are 300 DEG C, and the processing time is 1 hour, obtain stalk carbon material.This kind of material is steamed
Distilled water cleaning, removes remaining acidic materials.
The preparation of magnesium ore material: water magnesium ore (content of magnesium hydroxide is 90% in water magnesium ore) is milled to 4500
Mesh is calcined 9 hours in 600 DEG C, is cooled to room temperature and obtains magnesium ore material.
Stalk carbon material and magnesium ore material it is compound: straw carbon is handled into material, magnesium ore material and water and is mixed, wherein
Straw carbon handles material, the mass parts ratio of magnesium ore material and water is 1:0.05:5, and with potassium hydroxide by solution pH value tune
To 11.Mixture is placed in hydrothermal reaction kettle, is reacted 15 hours in 130 DEG C.Mixture is filtered after reaction, solid product
It is washed with water to neutrality, obtains untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 4%, poly- second
Alkene imines molecular weight is 45000) to be mixed according to the ratio of mass ratio 1:0.9, is dried after mixing 0.8 hour in 95 DEG C.Instead
Mixture is filtered after answering, solid product is washed with water to neutrality, is not carried out aluminum salt solution processing and handled by amine
Biological material and magnesium ore compound adsorbent.
The comparison of 2 two kinds of composite material adsorbent adsorption effects of table
。
Annotate a by aluminum salt solution handle and by amine processing compound adsorbent b without aluminum salt solution handle and
The compound adsorbent handled by amine
Embodiment 3
1, by aluminum salt solution handle and by amine processing compound adsorbent prepare it is as follows:
The preparation of biomass carbon material: peanut shell is crushed, and then mixes peanut shell, phosphoric acid (concentration 85%) and water in proportion
It closes, wherein the mass parts ratio of peanut shell material, phosphoric acid (concentration 85%) and water is 1:1:4.Then mixture is carried out first
Secondary heating treatment, treatment temperature are 100 DEG C, and the processing time is 1 hour.First time heating treatment treated product is protected in nitrogen
Shield is lower to carry out high-temperature process, and treatment temperature is 200 DEG C, and the processing time is 0.5 hour, obtains peanut shell carbon material.
Peanut shell carbon aluminium processing material preparation: by the peanut shell carbon material of above-mentioned preparation directly and aluminum salt solution (nitric acid
The mass parts ratio of aluminium, ethylenediamine tetra-acetic acid and water is 1:1.5:25) mixing, wherein the matter of peanut shell carbon material and aluminum salt solution
Amount portion rate is 1:1.Mixture is handled 1 hour under the conditions of nitrogen protection in 400 DEG C.It is cooled to room temperature and obtains peanut shell carbon aluminium
Handle material.
The preparation of magnesium ore material: being milled to 4000 mesh for giobertite (content of magnesium carbonate is 80% in giobertite),
It is calcined 8 hours in 500 DEG C, is cooled to room temperature and obtains magnesium ore material.
Peanut shell carbon aluminum material and magnesium ore material it is compound: peanut shell carbon aluminium is handled into material, magnesium ore material and water
Mixing, wherein the mass parts ratio of peanut shell carbon aluminium processing material, magnesium ore material and water is 1:0.1:5, and uses sodium hydroxide
Solution pH value is adjusted to 10.Mixture is placed in hydrothermal reaction kettle, is reacted 15 hours in 120 DEG C.After reaction by mixture
Filtering, solid product are washed with water to neutrality, obtain untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 3%, poly- second
Alkene imines molecular weight is 45000) to be mixed according to the ratio of mass ratio 1:0.8, is dried after mixing 0.6 hour in 90 DEG C.?
Material and magnesium ore compound adsorbent are handled to peanut shell carbon aluminium.
2, by aluminum salt solution handle and without amine handle compound adsorbent prepare it is as follows:
The preparation of biomass carbon material: peanut shell is crushed, and then mixes peanut shell, phosphoric acid (concentration 85%) and water in proportion
It closes, wherein the mass parts ratio of peanut shell material, phosphoric acid (concentration 85%) and water is 1:1:4.Then mixture is carried out first
Secondary heating treatment, treatment temperature are 100 DEG C, and the processing time is 1 hour.First time heating treatment treated product is protected in nitrogen
Shield is lower to carry out high-temperature process, and treatment temperature is 200 DEG C, and the processing time is 0.5 hour, obtains peanut shell carbon material.
Peanut shell carbon aluminium processing material preparation: by the peanut shell carbon material of above-mentioned preparation directly and aluminum salt solution (nitric acid
The mass parts ratio of aluminium, ethylenediamine tetra-acetic acid and water is 1:1.5:25) mixing, wherein the matter of peanut shell carbon material and aluminum salt solution
Amount portion rate is 1:1.Mixture is handled 1 hour under the conditions of nitrogen protection in 400 DEG C.It is cooled to room temperature and obtains peanut shell carbon aluminium
Handle material.
The preparation of magnesium ore material: being milled to 4000 mesh for giobertite (content of magnesium carbonate is 80% in giobertite),
It is calcined 8 hours in 500 DEG C, is cooled to room temperature and obtains magnesium ore material.
Peanut shell carbon aluminum material and magnesium ore material it is compound: peanut shell carbon aluminium is handled into material, magnesium ore material and water
Mixing, wherein the mass parts ratio of peanut shell carbon aluminium processing material, magnesium ore material and water is 1:0.1:5, and uses sodium hydroxide
Solution pH value is adjusted to 10.Mixture is placed in hydrothermal reaction kettle, is reacted 15 hours in 120 DEG C.After reaction by mixture
Filtering, solid product are washed with water to neutrality, obtain the biological material and magnesium for carrying out aluminum salt solution processing and handling without amine
The compound adsorbent of ore.
The comparison of 3 two kinds of composite material adsorbent adsorption effects of table
。
Annotate a by aluminum salt solution handle and by amine processing compound adsorbent b by aluminum salt solution processing and
The compound adsorbent handled without amine
Embodiment 4
1, by aluminum salt solution handle and by amine processing compound adsorbent prepare it is as follows:
The preparation of biomass carbon material: walnut shell is crushed, and then mixes walnut shell, phosphoric acid (concentration 85%) and water in proportion
It closes, wherein the mass parts ratio of walnut shell material, phosphoric acid (concentration 85%) and water is 1:0.8:2.Then mixture is carried out the
Heating treatment, treatment temperature are 120 DEG C, and the processing time is 1.6 hours.First time heating treatment treated product is in nitrogen
High-temperature process is carried out under gas shielded, treatment temperature is 400 DEG C, and the processing time is 2 hours, obtains walnut shell carbon material.
Walnut shell carbon aluminium processing material preparation: by the walnut shell carbon material of above-mentioned preparation directly and aluminum salt solution (nitric acid
The mass parts ratio of aluminium, ethylenediamine tetra-acetic acid and water is 1:2:50) mixing, wherein the quality of walnut shell carbon material and aluminum salt solution
Portion rate is 1:1.Mixture is handled 3 hours under the conditions of nitrogen protection in 400 DEG C.Room temperature is cooled to obtain at walnut shell carbon aluminium
Manage material.
The preparation of magnesium ore material: water magnesium ore (content of magnesium hydroxide is 80% in water magnesium ore) is milled to 3500
Mesh is calcined 5 hours in 400 DEG C, is cooled to room temperature and obtains magnesium ore material.
Walnut shell carbon aluminum material and magnesium ore material it is compound: walnut shell carbon aluminium is handled into material, magnesium ore material and water
Mixing, wherein the mass parts ratio of walnut shell carbon aluminium processing material, magnesium ore material and water is 1:0.05:5, and uses potassium hydroxide
Solution pH value is adjusted to 10.Mixture is placed in hydrothermal reaction kettle, is reacted 13 hours in 110 DEG C.After reaction by mixture
Filtering, solid product are washed with water to neutrality, obtain untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 2%, poly- second
Alkene imines molecular weight is 30000) to be mixed according to the ratio of mass ratio 1:0.7, is dried after mixing 0.5 hour in 90 DEG C.?
Material and magnesium ore compound adsorbent are handled to walnut shell carbon aluminium.
2, without aluminum salt solution handle and without amine handle compound adsorbent prepare it is as follows:
The preparation of biomass carbon material: walnut shell is crushed, and then mixes walnut shell, phosphoric acid (concentration 85%) and water in proportion
Close, wherein walnut shell material, phosphoric acid (concentration 85%) and water mass parts ratio are as follows: 1:0.8:2.Then mixture is carried out
First time heating treatment, treatment temperature are 120 DEG C, and the processing time is 1.6 hours.Treated that product exists for first time heating treatment
High-temperature process is carried out under nitrogen protection, treatment temperature is 400 DEG C, and the processing time is 2 hours, obtains walnut shell carbon material.It should
Kind material wash with distilled water, removes remaining acidic materials.
The preparation of magnesium ore material: water magnesium ore (content of magnesium hydroxide is 80% in water magnesium ore) is milled to 3500
Mesh is calcined 5 hours in 400 DEG C, is cooled to room temperature and obtains magnesium ore material.
Walnut shell carbon material and magnesium ore material it is compound: walnut shell carbon aluminium is handled into material, magnesium ore material and water and is mixed
It closes, wherein the mass parts ratio of walnut shell carbon aluminium processing material, magnesium ore material and water is 1:0.05:5, and will with potassium hydroxide
Solution pH value is adjusted to 10.Mixture is placed in hydrothermal reaction kettle, is reacted 13 hours in 110 DEG C.After reaction by mixture mistake
The biological material and magnesium ore for not carried out aluminum salt solution processing and amine processing to neutrality is washed with water in filter, solid product
Compound adsorbent.
The comparison of 4 two kinds of composite material adsorbent adsorption effects of table
。
Annotate a by aluminum salt solution handle and by amine processing compound adsorbent b without aluminum salt solution at
Reason and the compound adsorbent handled without amine
Embodiment 5
1, by aluminum salt solution handle and by amine processing compound adsorbent prepare it is as follows:
The preparation of biomass carbon material: bamboo is crushed, and then mixes bamboo, phosphoric acid (concentration 85%) and water in proportion,
The mass parts ratio of middle bamboo material, phosphoric acid (concentration 85%) and water are as follows: 1:1:4.Then mixture is subjected to first time heating
Processing, treatment temperature are 120 DEG C, and the processing time is 1 hour.First time heating treatment treated product under nitrogen protection into
Row high-temperature process, treatment temperature are 300 DEG C, and the processing time is 2 hours, obtain bamboo carbon material.
Bamboo carbon aluminium processing material preparation: by the bamboo carbon material of above-mentioned preparation directly and aluminum salt solution (aluminum nitrate, second
The mass parts ratio of ethylenediamine tetraacetic acid (EDTA) and water is 1:0.6:14) mixing, wherein the mass fraction of bamboo carbon material and aluminum salt solution
Than for 1:3.Mixture is handled 2 hours under the conditions of nitrogen protection in 400 DEG C.It is cooled to room temperature and obtains bamboo carbon aluminium processing material
Material.
The preparation of magnesium ore material: being milled to 3000 mesh for giobertite (content of magnesium carbonate is 70% in giobertite),
It is calcined 10 hours in 400 DEG C, is cooled to room temperature and obtains magnesium ore material.
Bamboo carbon aluminum material and magnesium ore material it is compound: bamboo carbon aluminium is handled into material, magnesium ore material and water and is mixed,
Wherein bamboo carbon aluminium processing material, magnesium ore material and water mass parts ratio be 1:1:5, and with sodium hydroxide by solution pH value
It is adjusted to 9.Mixture is placed in hydrothermal reaction kettle, is reacted 12 hours in 100 DEG C.Mixture is filtered after reaction, solid produces
Object is washed with water to neutrality, obtains untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 1%, poly- second
Alkene imines molecular weight is 25000) to be mixed according to the ratio of mass ratio 1:0.6, is dried after mixing 1 hour in 95 DEG C.It obtains
Bamboo carbon aluminium handles material and magnesium ore compound adsorbent.
2, without aluminum salt solution handle and by amine processing compound adsorbent prepare it is as follows:
The preparation of biomass carbon material: bamboo is crushed, and then mixes bamboo, phosphoric acid (concentration 85%) and water in proportion,
The mass parts ratio of middle bamboo material, phosphoric acid (concentration 85%) and water are as follows: 1:1:4.Then mixture is subjected to first time heating
Processing, treatment temperature are 120 DEG C, and the processing time is 1 hour.First time heating treatment treated product under nitrogen protection into
Row high-temperature process, treatment temperature are 300 DEG C, and the processing time is 2 hours, obtain bamboo carbon material.By this kind of material distilled water
Cleaning removes remaining acidic materials.
The preparation of magnesium ore material: being milled to 3000 mesh for giobertite (content of magnesium carbonate is 70% in giobertite),
It is calcined 10 hours in 400 DEG C, is cooled to room temperature and obtains magnesium ore material.
Bamboo carbon aluminum material and magnesium ore material it is compound: bamboo carbon aluminium is handled into material, magnesium ore material and water and is mixed,
Wherein bamboo carbon aluminium processing material, magnesium ore material and water mass parts ratio be 1:1:5, and with sodium hydroxide by solution pH value
It is adjusted to 9.Mixture is placed in hydrothermal reaction kettle, is reacted 12 hours in 100 DEG C.Mixture is filtered after reaction, solid produces
Object is washed with water to neutrality, obtains untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 1%, poly- second
Alkene imines molecular weight is 25000) to be mixed according to the ratio of mass ratio 1:0.6, is dried after mixing 1 hour in 95 DEG C.It obtains
The compound adsorbent of aluminum salt solution processing and biological material and magnesium ore by amine processing is not carried out.
The comparison of 5 two kinds of composite material adsorbent adsorption effects of table
。
Annotate a by aluminum salt solution handle and by amine processing compound adsorbent b without aluminum salt solution at
Reason and the compound adsorbent handled by amine
Embodiment 6
The preparation of biomass carbon material: sawdust is crushed, and then mixes sawdust, phosphoric acid (concentration 85%) and water in proportion,
The mass parts ratio of middle sawdust materials, phosphoric acid (concentration 85%) and water are as follows: 1:0.7:2.Then mixture is subjected to first time liter
Temperature processing, treatment temperature are 110 DEG C, and the processing time is 1.5 hours.First time heating treatment treated product is in nitrogen protection
Lower carry out high-temperature process, treatment temperature are 400 DEG C, and the processing time is 1 hour, obtain sawdust carbon material.
Sawdust carbon aluminium processing material preparation: by the sawdust carbon material of above-mentioned preparation directly and aluminum salt solution (aluminum nitrate, second
The mass parts ratio of ethylenediamine tetraacetic acid (EDTA) and water is 1:1.2:22) mixing, wherein the mass fraction of sawdust carbon material and aluminum salt solution
Than for 1:3.Mixture is handled 3 hours under the conditions of nitrogen protection in 400 DEG C.It is cooled to room temperature and obtains sawdust carbon aluminium processing material
Material.
The preparation of magnesium ore material: by water magnesium ore and giobertite mixing, (content of magnesium hydroxide is in water magnesium ore
70%, giobertite carbonic acid content of magnesium is 60%) to be milled to 2500 mesh, calcines 10 hours in 700 DEG C, is cooled to room temperature and obtains magnesium mine
Stone material.
Sawdust carbon aluminum material and magnesium ore material it is compound: sawdust carbon aluminium is handled into material, magnesium ore material and water and is mixed,
Wherein sawdust carbon aluminium processing material, magnesium ore material and water mass parts ratio be 1:1:5, and with potassium hydroxide by solution pH value
It is adjusted to 9.Mixture is placed in hydrothermal reaction kettle, is reacted 15 hours in 120 DEG C.Mixture is filtered after reaction, solid produces
Object is washed with water to neutrality, obtains untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine, (mass concentration 0.5% is gathered
Aziridine molecular weight is 15000) to be mixed according to the ratio of mass ratio 1:0.5, is dried after mixing 0.9 hour in 100 DEG C.
Obtain sawdust carbon aluminium processing material and magnesium ore compound adsorbent.
Adsorption effect of the table 6 based on biological material and magnesium ore compound adsorbent
。
Embodiment 7
The preparation of biomass carbon material: corncob is crushed, and then mixes corncob, phosphoric acid (concentration 85%) and water in proportion
It closes, wherein corn core material, the mass parts ratio of phosphoric acid (concentration 85%) and water are as follows: 1:2:6.Then mixture is carried out the
Heating treatment, treatment temperature are 100 DEG C, and the processing time is 1 hour.First time heating treatment treated product is in nitrogen
Protection is lower to carry out high-temperature process, and treatment temperature is 300 DEG C, and the processing time is 2 hours, obtains corncob carbon material.
Corncob carbon aluminium processing material preparation: by the corncob carbon material of above-mentioned preparation directly and aluminum salt solution (nitric acid
The mass parts ratio of aluminium, iminodisuccinic acid and water is 1:1:20) mixing, wherein the matter of corncob carbon material and aluminum salt solution
Amount portion rate is 1:3.Mixture is handled 3 hours under the conditions of nitrogen protection in 300 DEG C.It is cooled to room temperature and obtains corncob carbon aluminium
Handle material.
The preparation of magnesium ore material: being milled to 2000 mesh for giobertite (content of magnesium carbonate is 60% in giobertite),
It is calcined 8 hours in 600 DEG C, is cooled to room temperature and obtains magnesium ore material.
Corncob carbon aluminum material and magnesium ore material it is compound: corncob carbon aluminium is handled into material, magnesium ore material and water
Mixing, wherein the mass parts ratio of corncob carbon aluminium processing material, magnesium ore material and water is 1:0.8:6, and uses sodium hydroxide
Solution pH value is adjusted to 8.Mixture is placed in hydrothermal reaction kettle, is reacted 13 hours in 125 DEG C.After reaction by mixture mistake
Filter, solid product are washed with water to neutrality, obtain untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 4%, poly- second
Alkene imines molecular weight is 25000) to be mixed according to the ratio of mass ratio 1:0.4, is dried after mixing 1 hour in 93 DEG C.It obtains
Corncob carbon aluminium handles material and magnesium ore compound adsorbent.
Adsorption effect of the table 7 based on biological material and magnesium ore compound adsorbent
。
Embodiment 8
The preparation of biomass carbon material: stalk is crushed, and then mixes stalk, phosphoric acid (concentration 85%) and water in proportion,
The mass parts ratio of middle stalk material, phosphoric acid (concentration 85%) and water are as follows: 1:2:5.Then mixture is subjected to first time heating
Processing, treatment temperature are 120 DEG C, and the processing time is 2 hours.First time heating treatment treated product under nitrogen protection into
Row high-temperature process, treatment temperature are 400 DEG C, and the processing time is 1 hour, obtain stalk carbon material.
Straw carbon aluminium processing material preparation: by the stalk carbon material of above-mentioned preparation directly and aluminum salt solution (aluminum nitrate, lemon
The mass parts ratio of lemon acid and water is 1:1.5:25) mixing, wherein the mass parts ratio of stalk carbon material and aluminum salt solution is 1:
2.5.Mixture is handled 2 hours under the conditions of nitrogen protection in 500 DEG C.It is cooled to room temperature and obtains straw carbon aluminium processing material.
The preparation of magnesium ore material: water magnesium ore (content of magnesium hydroxide is 60% in water magnesium ore) is milled to 1500
Mesh is calcined 1 hour in 700 DEG C, is cooled to room temperature and obtains magnesium ore material.
Straw carbon aluminum material and magnesium ore material it is compound: straw carbon aluminium is handled into material, magnesium ore material and water and is mixed,
Wherein straw carbon aluminium processing material, magnesium ore material and water mass parts ratio be 1:1:3, and with potassium hydroxide by solution pH value
It is adjusted to 10.Mixture is placed in hydrothermal reaction kettle, is reacted 15 hours in 110 DEG C.Mixture is filtered after reaction, solid produces
Object is washed with water to neutrality, obtains untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 5%, poly- second
Alkene imines molecular weight is 45000) to be mixed according to the ratio of mass ratio 1:0.3, is dried after mixing 0.5 hour in 100 DEG C.?
Material and magnesium ore compound adsorbent are handled to straw carbon aluminium.
Adsorption effect of the table 8 based on biological material and magnesium ore compound adsorbent
。
Embodiment 9
The preparation of biomass carbon material: walnut shell is crushed, and then mixes walnut shell, phosphoric acid (concentration 85%) and water in proportion
It closes, wherein corn core material, the mass parts ratio of phosphoric acid (concentration 85%) and water are as follows: 1:2:4.Then mixture is carried out the
Heating treatment, treatment temperature are 110 DEG C, and the processing time is 1.5 hours.First time heating treatment treated product is in nitrogen
High-temperature process is carried out under gas shielded, treatment temperature is 300 DEG C, and the processing time is 0.5 hour, obtains walnut shell carbon material.
Walnut shell carbon aluminium processing material preparation: by the walnut shell carbon material of above-mentioned preparation directly and aluminum salt solution (nitric acid
The mass parts ratio of aluminium, ethylenediamine tetra-acetic acid and water is 1:1.8:42) mixing, wherein the matter of walnut shell carbon material and aluminum salt solution
Amount portion rate is 1:1.5.Mixture is handled 1 hour under the conditions of nitrogen protection in 400 DEG C.It is cooled to room temperature and obtains walnut shell carbon
Aluminium handles material.
The preparation of magnesium ore material: being milled to 1250 mesh for giobertite (content of magnesium carbonate is 85% in giobertite),
It is calcined 2 hours in 600 DEG C, is cooled to room temperature and obtains magnesium ore material.
Walnut shell carbon aluminum material and magnesium ore material it is compound: walnut shell carbon aluminium is handled into material, magnesium ore material and water
Mixing, wherein the mass parts ratio of walnut shell carbon aluminium processing material, magnesium ore material and water is 1:0.4:9, and uses sodium hydroxide
Solution pH value is adjusted to 8.Mixture is placed in hydrothermal reaction kettle, is reacted 16 hours in 130 DEG C.After reaction by mixture mistake
Filter, solid product are washed with water to neutrality, obtain untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 3%, poly- second
Alkene imines molecular weight is 35000) to be mixed according to the ratio of mass ratio 1:0.2, is dried after mixing 1 hour in 96 DEG C.It obtains
Walnut shell carbon aluminium handles material and magnesium ore compound adsorbent.
Adsorption effect of the table 9 based on biological material and magnesium ore compound adsorbent
。
Embodiment 10
The preparation of biomass carbon material: bamboo is crushed, and then mixes bamboo, phosphoric acid (concentration 85%) and water in proportion,
The mass parts ratio of middle bamboo material, phosphoric acid (concentration 85%) and water are as follows: 1:1:4.Then mixture is subjected to first time heating
Processing, treatment temperature are 110 DEG C, and the processing time is 2 hours.First time heating treatment treated product under nitrogen protection into
Row high-temperature process, treatment temperature are 400 DEG C, and the processing time is 1 hour, obtain bamboo carbon material.
Bamboo carbon aluminium processing material preparation: by the bamboo carbon material of above-mentioned preparation directly and aluminum salt solution (aluminum nitrate, second
The mass parts ratio of ethylenediamine tetraacetic acid (EDTA) and water is 1:1.7:46) mixing, wherein the mass fraction of bamboo carbon material and aluminum salt solution
Than for 1:1.Mixture is handled 1 hour under the conditions of nitrogen protection in 300 DEG C.It is cooled to room temperature and obtains bamboo carbon aluminium processing material
Material.
The preparation of magnesium ore material: water magnesium ore (content of magnesium hydroxide is 75% in water magnesium ore) is milled to 2000
Mesh is calcined 10 hours in 400 DEG C, is cooled to room temperature and obtains magnesium ore material.
Bamboo carbon aluminum material and magnesium ore material it is compound: bamboo carbon aluminium is handled into material, magnesium ore material and water and is mixed,
Wherein bamboo carbon aluminium processing material, magnesium ore material and water mass parts ratio be 1:0.08:7, and with potassium hydroxide by solution
PH value is adjusted to 11.Mixture is placed in hydrothermal reaction kettle, is reacted 17 hours in 100 DEG C.Mixture is filtered after reaction, Gu
Body product is washed with water to neutrality, obtains untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 3%, poly- second
Alkene imines molecular weight is 40000) to be mixed according to the ratio of mass ratio 1:0.1, is dried after mixing 0.6 hour in 98 DEG C.?
Material and magnesium ore compound adsorbent are handled to bamboo carbon aluminium.
Adsorption effect of the table 10 based on biological material and magnesium ore compound adsorbent
。
Embodiment 11
The preparation of biomass carbon material: sawdust is crushed, and then mixes sawdust, phosphoric acid (concentration 85%) and water in proportion,
The mass parts ratio of middle sawdust materials, phosphoric acid (concentration 85%) and water are as follows: 1:0.7:2.Then mixture is subjected to first time liter
Temperature processing, treatment temperature are 110 DEG C, and the processing time is 2 hours.First time heating treatment treated product is under nitrogen protection
High-temperature process is carried out, treatment temperature is 300 DEG C, and the processing time is 2 hours, obtains sawdust carbon material.
Sawdust carbon aluminium processing material preparation: by the sawdust carbon material of above-mentioned preparation directly and aluminum salt solution (aluminum nitrate, second
The mass parts ratio of ethylenediamine tetraacetic acid (EDTA) and water is 1:1:10) mixing, wherein the mass parts ratio of sawdust carbon material and aluminum salt solution
For 1:3.Mixture is handled 1 hour under the conditions of nitrogen protection in 500 DEG C.It is cooled to room temperature and obtains sawdust carbon aluminium processing material.
The preparation of magnesium ore material: being milled to 5000 mesh for giobertite (content of magnesium carbonate is 65% in giobertite),
It is calcined 2 hours in 700 DEG C, is cooled to room temperature and obtains magnesium ore material.
Sawdust carbon aluminum material and magnesium ore material it is compound: sawdust carbon aluminium is handled into material, magnesium ore material and water and is mixed,
Wherein sawdust carbon aluminium processing material, magnesium ore material and water mass parts ratio be 1:0.1:6, and with sodium hydroxide by solution PH
Value is adjusted to 7.Mixture is placed in hydrothermal reaction kettle, is reacted 15 hours in 100 DEG C.Mixture is filtered after reaction, solid
Product is washed with water to neutrality, obtains untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 4%, poly- second
Alkene imines molecular weight is 50000) to be mixed according to the ratio of mass ratio 1:0.8, is dried after mixing 0.5 hour in 100 DEG C.?
Material and magnesium ore compound adsorbent are handled to sawdust carbon aluminium.
Adsorption effect of the table 11 based on biological material and magnesium ore compound adsorbent
。
Embodiment 12
The preparation of biomass carbon material: stalk is crushed, and then mixes stalk, phosphoric acid (concentration 85%) and water in proportion,
The mass parts ratio of middle stalk material, phosphoric acid (concentration 85%) and water are as follows: 1:0.8:6.Then mixture is subjected to first time liter
Temperature processing, treatment temperature are 120 DEG C, and the processing time is 1.5 hours.First time heating treatment treated product is in nitrogen protection
Lower carry out high-temperature process, treatment temperature are 300 DEG C, and the processing time is 1.7 hours, obtain stalk carbon material.
Straw carbon aluminium processing material preparation: by the stalk carbon material of above-mentioned preparation directly and aluminum salt solution (aluminum nitrate, second
The mass parts ratio of ethylenediamine tetraacetic acid (EDTA) and water is 1:0.9:19) mixing, wherein the mass fraction of stalk carbon material and aluminum salt solution
Than for 1:2.5.Mixture is handled 3 hours under the conditions of nitrogen protection in 400 DEG C.It is cooled to room temperature and obtains straw carbon aluminium processing material
Material.
The preparation of magnesium ore material: water magnesium ore (content of magnesium hydroxide is 85% in water magnesium ore) is milled to 5000
Mesh is calcined 3 hours in 500 DEG C, is cooled to room temperature and obtains magnesium ore material.
Straw carbon aluminum material and magnesium ore material it is compound: straw carbon aluminium is handled into material, magnesium ore material and water and is mixed,
Wherein straw carbon aluminium processing material, magnesium ore material and water mass parts ratio be 1:0.59:10, and with potassium hydroxide by solution
PH value is adjusted to 10.Mixture is placed in hydrothermal reaction kettle, is reacted 14 hours in 115 DEG C.Mixture is filtered after reaction, Gu
Body product is washed with water to neutrality, obtains untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 5%, poly- second
Alkene imines molecular weight is 45000) to be mixed according to the ratio of mass ratio 1:0.5, is dried after mixing 1 hour in 100 DEG C.It obtains
Straw carbon aluminium handles material and magnesium ore compound adsorbent.
Adsorption effect of the table 12 based on biological material and magnesium ore compound adsorbent
。
Embodiment 13
The preparation of biomass carbon material: corncob is crushed, and then mixes corncob, phosphoric acid (concentration 85%) and water in proportion
It closes, wherein corn core material, the mass parts ratio of phosphoric acid (concentration 85%) and water are as follows: 1:2:6.Then mixture is carried out the
Heating treatment, treatment temperature are 115 DEG C, and the processing time is 1.5 hours.First time heating treatment treated product is in nitrogen
High-temperature process is carried out under gas shielded, treatment temperature is 400 DEG C, and the processing time is 2 hours, obtains corncob carbon material.
Corncob carbon aluminium processing material preparation: by the corncob carbon material of above-mentioned preparation directly and aluminum salt solution (nitric acid
The mass parts ratio of aluminium, ethylenediamine tetra-acetic acid and water is 1:2:50) mixing, wherein the quality of corncob carbon material and aluminum salt solution
Portion rate is 1:3.Mixture is handled 3 hours under the conditions of nitrogen protection in 500 DEG C.Room temperature is cooled to obtain at corncob carbon aluminium
Manage material.
The preparation of magnesium ore material: being milled to 2000 mesh for giobertite (content of magnesium carbonate is 75% in giobertite),
It is calcined 5 hours in 400 DEG C, is cooled to room temperature and obtains magnesium ore material.
Corncob carbon aluminum material and magnesium ore material it is compound: corncob carbon aluminium is handled into material, magnesium ore material and water
Mixing, wherein the mass parts ratio of corncob carbon aluminium processing material, magnesium ore material and water is 1:0.3:8, and uses sodium hydroxide
Solution pH value is adjusted to 11.Mixture is placed in hydrothermal reaction kettle, is reacted 17 hours in 120 DEG C.After reaction by mixture
Filtering, solid product are washed with water to neutrality, obtain untreated compound adsorbent.
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine (mass concentration 3%, poly- second
Alkene imines molecular weight is 50000) to be mixed according to the ratio of mass ratio 1:0.8, is dried after mixing 1 hour in 100 DEG C.It obtains
Corncob carbon aluminium handles material and magnesium ore compound adsorbent.
Adsorption effect of the table 13 based on biological material and magnesium ore compound adsorbent
。
By above-described embodiment it is known that during preparing compound adsorbent, by aluminum salt solution processing and amine
Processing can effectively improve the adsorption effect of composite adsorption, improve adsorbent to the absorption property of metal ion and dye molecule.Together
When, moreover it is possible to effectively extend recycling number of compound adsorbent under the conditions of keeping good adsorption properties.
Claims (9)
1. the preparation method based on biological material and magnesium ore compound adsorbent, it is characterised in that the system of biomass carbon material
It is standby: biological material is crushed, biological material, acid and water are then mixed into obtain mixture in proportion, wherein biological material,
The mass parts ratio of acid and water are as follows: then mixture is carried out first time heating treatment by 1:0.7-2:2-6, treatment temperature is
100-120 DEG C, the processing time is 1-2 hours, and treated that product carries out high temperature under nitrogen protection for first time heating treatment
Processing, treatment temperature are 200-400 DEG C, and the processing time is 0.5-2 hours, obtain biomass carbon material；
The preparation of biomass carbon aluminium processing material: the biomass carbon material of above-mentioned preparation is directly mixed to obtain and is mixed with aluminum salt solution
Liquid, wherein the mass parts ratio that mixed ratio is biomass carbon material and aluminum salt solution is 1:1-3, mixed liquor is protected in nitrogen
Under the conditions of shield in 300-500 DEG C processing 1-3 hours, be cooled to room temperature obtain biomass carbon aluminium processing material；
The preparation of magnesium ore material: being milled to 1250-5000 mesh for magnesium ore, in 400-700 DEG C calcining 1-10 hours, drop
It warms to room temperature to obtain magnesium ore material；
Biomass carbon aluminum material and magnesium ore it is compound: biomass carbon aluminium is handled into material, magnesium ore material and water and is mixed, wherein
Biomass carbon aluminium handles material, the mass parts ratio of magnesium ore material and water is 1:0.05-1:3-10, and with alkali by solution PH
Value is adjusted to 7-11, and mixture is placed in hydrothermal reaction kettle, in 100-130 DEG C reaction 10-17 hours, will mix after reaction
Object filtering is closed, solid product is washed with water to neutrality, obtains untreated compound adsorbent；
Amine processing: by the untreated compound adsorbent of previous step and aq. polyethyleneimine according to the weight of mass ratio 1:0.1-1
Amount ratio is mixed, and is dried after mixing 0.5-1 hours in 90-100 degrees Celsius, is obtained biological material and magnesium ore composite adsorption
Agent.
2. the preparation method according to claim 1 based on biological material and magnesium ore compound adsorbent, feature exist
In the biological material include stalk, peanut shell, corncob, walnut shell, bamboo or sawdust.
3. the preparation method according to claim 1 based on biological material and magnesium ore compound adsorbent, feature exist
It is phosphoric acid in the acid, the concentration of phosphoric acid is 85%.
4. the preparation method according to claim 1 based on biological material and magnesium ore compound adsorbent, feature exist
In the mixed solution that the aluminum salt solution is aluminum nitrate, organic sequestering agent and water, wherein aluminum nitrate, organic sequestering agent and water
Mass parts ratio is 1:0.5-2:10-50.
5. the preparation method according to claim 4 based on biological material and magnesium ore compound adsorbent, feature exist
In the organic sequestering agent be ethylenediamine tetra-acetic acid, iminodisuccinic acid and citric acid.
6. the preparation method according to claim 1 based on biological material and magnesium ore compound adsorbent, feature exist
The content of magnesium carbonate is in the mixture that the magnesium ore is giobertite, shepardite ore, or both, giobertite
60%-90%, the content of magnesium hydroxide is 60%-90% in shepardite ore.
7. the preparation method according to claim 1 based on biological material and magnesium ore compound adsorbent, feature exist
In the alkali be sodium hydroxide or potassium hydroxide.
8. the preparation method according to claim 1 based on biological material and magnesium ore compound adsorbent, feature exist
In the aq. polyethyleneimine mass concentration be 0.5-5%.
9. the preparation method according to claim 8 based on biological material and magnesium ore compound adsorbent, feature exist
In the polyethyleneimine molecular weight be 15000-50000.
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