CN112316901A - Production process for preparing calcium-lanthanum modified phosphorus removal biomass charcoal - Google Patents
Production process for preparing calcium-lanthanum modified phosphorus removal biomass charcoal Download PDFInfo
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- CN112316901A CN112316901A CN202011122109.4A CN202011122109A CN112316901A CN 112316901 A CN112316901 A CN 112316901A CN 202011122109 A CN202011122109 A CN 202011122109A CN 112316901 A CN112316901 A CN 112316901A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 42
- 239000003610 charcoal Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- -1 calcium-lanthanum modified phosphorus Chemical class 0.000 title claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 8
- 239000001110 calcium chloride Substances 0.000 claims abstract description 8
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000005498 polishing Methods 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- ARWMTMANOCYRLU-UHFFFAOYSA-N [Ca].[La] Chemical compound [Ca].[La] ARWMTMANOCYRLU-UHFFFAOYSA-N 0.000 claims 3
- 238000004227 thermal cracking Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 240000008042 Zea mays Species 0.000 description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 235000005822 corn Nutrition 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a production process for preparing calcium-lanthanum modified phosphorus removal biomass charcoal, which comprises the following steps: step S1, dissolving calcium chloride and lanthanum chloride in water to obtain a mixture; step S2, drying the corncobs, crushing the dried corncobs into corncob particles, and polishing the corncob particles; s3, putting the polished corncob particles into the mixture obtained in the S1 for soaking, and then obtaining a carbonized raw material; step S4, drying the carbonized raw material to obtain a dried carbonized raw material; step S5, carbonizing the dried carbonized raw material to obtain biomass charcoal; the method has the characteristics of easy control, low cost and high yield, and the produced modified biomass charcoal has the advantages of high phosphorus removal adsorption performance, high selectivity, availability and the like, and has great application potential in the field of wastewater treatment.
Description
Technical Field
The invention relates to the technical field of biomass charcoal materials, in particular to a production process for preparing calcium-lanthanum modified phosphorus removal biomass charcoal.
Background
Phosphorus is an important index for measuring the water quality condition of surface water and is one of the main factors causing water eutrophication, and the restriction of the discharge of phosphorus is crucial to the treatment of water eutrophication and the promotion of the stability of an ecological system. Common phosphorus removal methods include a chemical method, a biological method, an electrolytic method, an adsorption method and the like, wherein the adsorption method is simple to put into use and can efficiently recycle phosphorus resources. The main adsorption materials for removing phosphorus comprise ion exchange resin, ferrihydrite, modified ceramsite, modified biomass carbon and the like, the modified biomass carbon is a new technology which is concerned about, and compared with the traditional adsorption materials, the modified biomass carbon has the advantages of high adsorption effect, low cost, good environmental compatibility, high application adaptability and the like.
The biomass charcoal is a carbon-rich and small-particle porous material produced by pyrolysis of biomass under the condition of oxygen deficiency and high temperature, has a large amount of negative charges on the surface, can adsorb heavy metals and organic pollutants in a water environment, and has great application potential in the field of wastewater treatment by utilizing the biomass charcoal. Although the general biomass charcoal has a porous structure with more micropores and a large specific surface area, the regulation range of surface groups is narrow, and the adsorption selectivity is poor. The biomass carbon is generally modified, and the surface functional groups of the biomass carbon are changed by utilizing metal modification, so that the adsorption capacity and selectivity of the biomass carbon are improved.
According to the invention, calcium chloride and lanthanum chloride are used as modifiers, corncob particles are used as biomass charcoal carbonization raw materials, and the biomass charcoal is carbonized by internal circulation closed oxygen-limited biomass charcoal pyrolysis rotary kiln equipment, so that the large-scale production process of the biomass charcoal with efficient phosphorus removal characteristic is realized.
Disclosure of Invention
In view of the above defects in the prior art, the technical problem to be solved by the present invention is to provide a production process for preparing calcium-lanthanum modified phosphorus removal biomass charcoal, comprising the following steps:
step S1, dissolving calcium chloride and lanthanum chloride in water to obtain a mixture;
step S2, drying the corncobs, crushing the dried corncobs into corncob particles with the particle size of 5-8mm, and polishing the corncob particles;
s3, putting the polished corncob particles into the mixture obtained in the S1 for soaking, mixing the corncob particles and the mixture according to a proportion, and then obtaining a carbonized raw material;
step S4, drying the carbonized raw material to obtain a dried carbonized raw material;
and step S5, carbonizing the dried carbonized raw material to obtain the biomass charcoal.
Preferably, the obtained biomass charcoal is sprayed for cooling and then is dried; the operation of spraying and cooling is specifically to spray by using neutral tap water.
Preferably, in the step S2, the corncob is dried to a moisture content of less than 10%.
Preferably, in the step S3, the amount of residue after the soaking is less than 2%.
Preferably, in the step S4, when the drying process is performed, the moisture content after drying is less than 8%;
preferably, in the step S5, the carbonization treatment is specifically performed by putting the dried product into an internal circulation closed oxygen-limited biomass charcoal pyrolysis rotary kiln for carbonization; when the carbonization treatment is carried out, the carbonization temperature is 600-800 ℃.
The invention has the beneficial effects that:
1. the invention adopts the corncob particles as the carbonization raw material, and the corncob particles have better water absorption and certain strength, and the raw material is easy to obtain and has rich yield.
2. The invention adopts calcium chloride and lanthanum chloride with good water solubility, is economic and safe, can effectively crystallize flaky metal on the surface or in the biomass charcoal, can generate electrostatic interaction with anion adsorbate (phosphate) with negative charges, and forms a mononuclear or polynuclear compound.
3. The invention realizes the application conversion in academic research, and successfully completes the process determination of the large-scale production of the modified biomass charcoal according to the characteristics of the large-scale production.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order that the invention may be better understood, the invention will now be further illustrated by the following examples, which are intended to be illustrative only and are not to be construed as limiting the invention in any way: the invention is not described in detail, but is well known to those skilled in the art.
Example 1
Referring to fig. 1, the embodiment provides a production process for preparing calcium-lanthanum modified phosphorus removal biomass charcoal, which specifically comprises the following steps:
and step S1, preparing a mixture, selecting a 120-square cement pool, placing calcium chloride, lanthanum chloride and water in the cement pool, dissolving the calcium chloride, the lanthanum chloride and the water in proportion, stirring in the dissolving process, and obtaining the mixture after the calcium chloride and the lanthanum chloride are completely dissolved.
Step S2, drying the corn cob until the water content of the corn cob is lower than 10%, then crushing the corn cob into corn cob particles with a particle size of 5mm, in this embodiment, drying the corn cob until the water content is 9%, crushing, and polishing the carbonized raw material; for the production process, the carbonized raw material is polished until the polishing degree is higher than or equal to 60%, and the process is not limited, in this embodiment, the corncob particles are polished until the polishing degree is 80%; .
S3, putting the polished corncob particles into the mixture obtained in the S1 for soaking, wherein the mass ratio of the corncob particles to the mixture is 4: 1; then obtaining a carbonized raw material;
for the present process, the stirring is continued until the residue amount at the bottom of the tank is less than 2%, in this embodiment, the residue amount at the bottom of the tank is 1.9%.
And S4, drying the carbonized raw material, wherein in the step, the carbonized raw material obtained in the step S3 is placed in a rotary carbon furnace drying device for drying through machines and tools such as a forklift, and the moisture content of the dried product is less than 8% through instrument detection.
Step S5, carbonizing the dried carbonized raw material, namely putting the carbonized raw material into an internal circulation closed oxygen-limited biomass charcoal pyrolysis rotary kiln for carbonization to obtain biomass charcoal, wherein the feeding mode is spiral feeding, the carbonization temperature is 800 ℃, spraying and cooling are carried out on the obtained biomass charcoal after discharging, and then drying treatment is carried out; the operation of spraying and cooling is to spray neutral tap water.
The corncob raw materials selected by the process are sourced from an agricultural science and technology company in Shandong province, the purchase amount is 40t, the implementation site of the process is located in a carbonization company in Jiangsu province, carbonization equipment is an internal circulation closed oxygen-limited biomass charcoal pyrolysis rotary kiln, the throughput of the equipment is 80t/d, and drying equipment is rotary carbon furnace drying equipment.
The weight of the raw materials for the production is 40t, the weight is increased to 72t after the raw materials are soaked, and the yield of the modified biomass charcoal is 54.2 t.
Aiming at the phosphorus removal effect detection of the modified biomass carbon, the production process is divided into batches, phosphorus standard solution with potassium dihydrogen phosphate ratio is adopted, an antimony molybdate spectrophotometer method is adopted for detection, and the average adsorption saturation amount of the detection is 120 mg/g.
Example 2
The embodiment also provides a production process for preparing calcium-lanthanum modified phosphorus removal biomass charcoal, which is different from the production process in embodiment 2 in that:
in step S2, the corncob is dried to a moisture content of 7%, the corncob is crushed into particles having a particle size of 8mm, and the corncob particles are polished until the polishing degree is 65%;
in step S3, mixing and soaking the corn cob particles and the mixture in a mass ratio of 6: 1; the residue amount after soaking was 1.5%; then obtaining a carbonized raw material;
in step S4, drying the carbonized raw material, wherein the drying moisture content is less than 6%;
in step S5, the dried carbonized material is carbonized at 700 ℃.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (6)
1. A production process for preparing calcium-lanthanum modified phosphorus removal biomass charcoal is characterized by comprising the following steps:
step S1, dissolving calcium chloride and lanthanum chloride in water to obtain a mixture;
step S2, drying the corncobs, crushing the dried corncobs into corncob particles with the particle size of 5-8mm, and polishing the corncob particles;
s3, putting the polished corncob particles into the mixture obtained in the S1 for soaking, mixing the corncob particles and the mixture according to a proportion, and then obtaining a carbonized raw material;
step S4, drying the carbonized raw material to obtain a dried carbonized raw material;
and step S5, carbonizing the dried carbonized raw material to obtain the biomass charcoal.
2. The production process for preparing the calcium-lanthanum modified dephosphorization biomass charcoal according to claim 1, characterized in that the obtained biomass charcoal is subjected to spray cooling and then is subjected to drying treatment; the operation of spraying and cooling is specifically to spray by using neutral tap water.
3. The production process for preparing the calcium-lanthanum modified phosphorus removal biomass charcoal as claimed in claim 2, wherein in the step S2, the corncob is dried to a moisture content of less than 10%.
4. The production process for preparing the calcium-lanthanum modified dephosphorization biochar as claimed in claim 3, wherein in the step S3, the residue amount after soaking is less than 2%.
5. The production process for preparing the calcium-lanthanum modified dephosphorization biochar as claimed in claim 4, wherein in the step S4, the moisture content after drying is less than 8% when drying treatment is performed.
6. The production process for preparing the calcium-lanthanum modified phosphorus removal biomass charcoal as claimed in claim 5, wherein in the step S5, the carbonization treatment is specifically performed by putting the dried product into an internal circulation closed oxygen-limited biomass charcoal thermal cracking rotary kiln for carbonization; when the carbonization treatment is carried out, the carbonization temperature is 600-800 ℃.
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| CN202011122109.4A CN112316901A (en) | 2020-10-20 | 2020-10-20 | Production process for preparing calcium-lanthanum modified phosphorus removal biomass charcoal |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721677A (en) * | 2014-01-13 | 2014-04-16 | 农业部沼气科学研究所 | Preparation method of biomass carbon composite material for removing phosphorus in wastewater |
| CN105536704A (en) * | 2016-01-11 | 2016-05-04 | 湖南大学 | Calcium modified biochar and preparation method and application thereof |
| CN109012593A (en) * | 2018-08-29 | 2018-12-18 | 农业部环境保护科研监测所 | A kind of biomass carbon material and its preparation method and application |
| CN109248649A (en) * | 2018-11-13 | 2019-01-22 | 李思原 | The composite modified vermiculite absorbent of magnesium aluminium lanthanum and its preparation process for Adsorption phosphorus |
| AU2019101523A4 (en) * | 2019-06-06 | 2020-01-23 | Central South University | Two-dimensional clay based composite phosphorus removing agent and preparation method and application thereof |
| CN110756166A (en) * | 2019-12-03 | 2020-02-07 | 四川农业大学 | Corncob-loaded magnesium-modified adsorption material and preparation method and application thereof |
-
2020
- 2020-10-20 CN CN202011122109.4A patent/CN112316901A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721677A (en) * | 2014-01-13 | 2014-04-16 | 农业部沼气科学研究所 | Preparation method of biomass carbon composite material for removing phosphorus in wastewater |
| CN105536704A (en) * | 2016-01-11 | 2016-05-04 | 湖南大学 | Calcium modified biochar and preparation method and application thereof |
| CN109012593A (en) * | 2018-08-29 | 2018-12-18 | 农业部环境保护科研监测所 | A kind of biomass carbon material and its preparation method and application |
| CN109248649A (en) * | 2018-11-13 | 2019-01-22 | 李思原 | The composite modified vermiculite absorbent of magnesium aluminium lanthanum and its preparation process for Adsorption phosphorus |
| AU2019101523A4 (en) * | 2019-06-06 | 2020-01-23 | Central South University | Two-dimensional clay based composite phosphorus removing agent and preparation method and application thereof |
| CN110756166A (en) * | 2019-12-03 | 2020-02-07 | 四川农业大学 | Corncob-loaded magnesium-modified adsorption material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| LINGCHAO KONG ET AL.: ""Needle-like Mg-La bimetal oxide nanocomposites derived from periclase and lanthanum for cost-effective phosphate and fluoride removal: Characterization, performance and mechanism"", 《CHEMICAL ENGINEERING JOURNAL》 * |
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