CN109797022A - A kind of preparation of clay-calcium based sulphur-fixation reagent and application in fixed cow dung/sulphur coal composite briquette - Google Patents
A kind of preparation of clay-calcium based sulphur-fixation reagent and application in fixed cow dung/sulphur coal composite briquette Download PDFInfo
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- CN109797022A CN109797022A CN201910165195.8A CN201910165195A CN109797022A CN 109797022 A CN109797022 A CN 109797022A CN 201910165195 A CN201910165195 A CN 201910165195A CN 109797022 A CN109797022 A CN 109797022A
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- sulphur
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
It is by calcium oxide through tartaric acid acidification, after drying, grinding, calcining obtains acidification calcium oxide in Muffle furnace the present invention provides a kind of preparation of clay-calcium based sulphur-fixation reagent；It will be acidified calcium oxide and natural clay mechanical mixture again, grind uniformly to get clay-calcium based sulphur-fixation reagent.The sulphur-fixing agent structure is fluffy, even particle distribution, specific surface area increase, and has many advantages, such as that sulfur-fixing rate height, sulfur retention products thermal stability are good, for the solid sulphur of cow dung/high-sulfur composite briquette, moulded coal sulfur content (St,ad) less than 0.50%, sulfur-fixing rate effectively reduces the discharge of sulfide when cow dung/sulphur coal composite briquette burns up to 70.0% or so.In addition, sulphur-fixing agent prepared by the present invention it is raw materials used it is economical and easily available, using safe, preparation process is simple, have preferable economy and application.
Description
Technical field
The present invention relates to a kind of preparations of clay-calcium based sulphur-fixation reagent, compound for cow dung/sulphur coal mainly as sulphur-fixing agent
The preparation of moulded coal, belongs to technical field of desulfurization.
Background technique
Under China's current social background, problem of environmental pollution caused by the traditional combustion of sulphur coal and biomass is
Clean energy, which efficiently utilizes in process, one of mainly to be solved the problems, such as.Cow dung is as one of waste material the most abundant on the earth, big
The ground such as most developing countries especially pastoral area are chiefly used in domestic fuel, however there are cow dung moldings for this traditional Land use systems
The difficult, drawbacks such as soot emissions object is serious, capacity usage ratio is low.Cow dung is mixed with sulphur coal, is assisted in sulphur-fixing agent, binder etc.
Under the action of prepare the cow dung moulded coal that pollutant discharge amount is low, mechanical performance is up to standard, combustion characteristics is excellent, not only solve cow dung
The problems such as hardly possible forms, calorific value is low, smoke is big, moreover it is possible to sulphur emissions exceeded problem when high sulfur coal combustion is effectively relieved.
The calcium based sulphur-fixation reagents such as lime stone, white lime are easy to operate equal the reason is that studying more one kind at present because of small investment
Sulphur-fixing agent, but add single Cabase compound there are calcium utilizations the problems such as low, sulfur retention products thermal stability is poor.Based on upper
Background is stated, the present invention draws up for a kind of economic security, nonhazardous, large specific surface area, sulfur retention products calcium based sulphur-fixation reagent resistant to high temperature,
To improve to cow dung/sulphur coal composite briquette sulfur-fixing rate, the atmosphere pollution of high-sulfur combustor bring is reduced.
Summary of the invention
The object of the present invention is to provide a kind of clay-acidification calcium based sulphur-fixation reagent preparation methods；
It is a further object of the present invention to provide above-mentioned acidification calcium based sulphur-fixation reagent answering in preparation cow dung/sulphur coal composite briquette
With.
One, clay-calcium based sulphur-fixation reagent preparation
The preparation method of clay-calcium based sulphur-fixation reagent of the present invention is by calcium oxide through tartaric acid acidification, after drying, grinding,
Calcining obtains acidification calcium oxide in Muffle furnace；It will be acidified calcium oxide and natural clay mechanical mixture again, grinding is uniformly to get glutinous
Soil-calcium based sulphur-fixation reagent.
The preparation process of acidic oxidation calcium are as follows: (oxidation is added in 5.0 ~ 6.0% tartaric acid solution of mass concentration in calcium oxide
The solid-to-liquid ratio of calcium and tartaric acid solution is 0.05 ~ 0.07 g/mL), 75 ~ 85 DEG C are heated to after stirring and evenly mixing, processing 2.5 ~ 4.5
h。
The drying temperature for being acidified calcium oxide is 95 ~ 105 DEG C；Calcining heating rate be 4 ~ 6 DEG C/min, calcination temperature be 850 ~
950 DEG C, calcination time is 2 ~ 3h.
Natural clay is attapulgite or red clay, and natural clay and the mass ratio for being acidified calcium oxide are 1:3 ~ 1:4.
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of untreated calcium oxide and acidification calcium oxide prepared by the present invention.It can be with by Fig. 1
Find out, the calcium oxide structure after acidification is substantially change, and even particle distribution, structure are fluffy, partial size becomes smaller.
Table 1 is specific surface area, Kong Rong and the aperture number of untreated calcium oxide and acidification calcium oxide prepared by the present invention.By
Table 1 can be seen that acidification calcium oxide specific surface area increases, and hole Rong Zeng great, this structure change is necessary to sulfur-fixing rate is improved
, therefore cooperateed with natural clay and can be used for the solid sulphur of cow dung/sulphur coal composite briquette.
Two, clay-acidity calcium based sulphur-fixation reagent sulfur fixation performance
Sulfur content test: clay-acidity calcium based sulphur-fixation reagent is added in cow dung/sulphur coal composite briquette, in full-automatic sulphur meter
In be measured.Each sample takes 50.0 ± 1 mg, surveys 5 groups of data and is averaged.Needing before test sample will with sulphur coal
Electrolyte is washed open.
Test result: the clay of above-mentioned preparation-acidity calcium based sulphur-fixation reagent difference compounding when additive amount to cow dung/sulphur coal
Test results are shown in figure 2 for composite briquette sulfur fixation performance: when acidification calcium oxide is compounded with clay than being 3:1 ~ 4:1(mass
Than), when additive amount is 6.0 ~ 7.0 %, cow dung/sulphur coal composite briquette sulfur content (St,ad) less than 0.50 %, sulfur-fixing rate reaches
70.00 % or so.
2, sulfur retention products measure
X-ray diffraction (XRD) characterization is carried out to the moulded coal coal ash before and after addition clay-acidity calcium based sulphur-fixation reagent, the results showed that, it sticks
Moulded coal coal ash after soil-acidic oxidation calcium sulphur-fixing agent effect generates the calcium sulfide complex of high temperature resistant, better heat stability
3CaO·3Al2O3·CaSO4And 4CaO2SiO2·CaSO4(attached drawing 3).
In conclusion the present invention is fluffy by structure after the acidified processing of calcium oxide, even particle distribution, specific surface area increases
Greatly, it is cooperateed with natural clay, for the solid sulphur of cow dung/sulphur coal composite briquette, and there is sulfur-fixing rate height, sulfur retention products thermostabilization
Property it is good the advantages that, the discharge of sulfide when effectively reducing the burning of cow dung/sulphur coal composite briquette.In addition, clay-of the present invention
Acidic oxidation calcium sulphur-fixing agent preparation process is simple, raw material economics is easy to get, using safe, has preferable applied economics and application
Property.
Detailed description of the invention
Fig. 1 is the SEM figure of untreated calcium oxide and acidification calcium oxide prepared by the present invention.
Fig. 2 is calcium based sulphur-fixation reagent prepared by the present invention to the captured sulfur result figure being applied in cow dung/sulphur coal composite briquette.
Fig. 3 is clay prepared by the present invention-acidic oxidation calcium sulphur-fixing agent addition front and back moulded coal coal ash XRD diagram.
Specific embodiment
To the preparation of clay-calcium based sulphur-fixation reagent of the present invention and cow dung capturing sulfur briquette performance to be used for below by specific embodiment
It is described further.
Embodiment one
1, clay-calcium based sulphur-fixation reagent preparation
At room temperature, the tartaric acid of 10.5 g is dissolved in the water of 200 mL in beaker, the calcium oxide of 10.0 g is then added, mixed
Close uniformly after in 75 DEG C of waters bath with thermostatic control 4 h(of heating stirring to guarantee that quick lime is acidified completely), obtain acidizing product；Acidification is produced
Object is dried in 105 DEG C of baking ovens, and grinding is then placed in the Muffle furnace of air atmosphere, is heated up with the heating rate of 5 DEG C/min
To 900 DEG C, 2 h are calcined, obtain acidification calcium oxide；
Calcium oxide and red clay will be acidified by the quality of 3.5:1 than mechanical mixture, ground uniformly to get clay-calcium based sulphur-fixation reagent.
2, the preparation of moulded coal
The dry cow dung for taking 6.0 g is uniformly mixed with the high-sulfur foam coal (crossing 18 meshes) of 18.0 g, then adds 2.6 g's or so
Clay-calcium based sulphur-fixation reagent of binder and 1.4 g, and suitable water is added and stirs evenly, in the cylindricality of the cm of 10.0 cm × 7.5
Then extrusion forming in mold is dried in 65 DEG C of baking oven to get cow dung/sulphur coal composite briquette.In full-automatic sulphur meter
Middle measurement, the S of the composite briquettet,adFor 0.31 %, sulfur-fixing rate is up to 69.23 %.
Embodiment two
1, clay-calcium based sulphur-fixation reagent preparation
It takes the tartaric acid of 12.8 g to be dissolved in the water of 200 mL, the calcium oxide of 14.0 g is then added, after mixing at 85 DEG C
4 h(of heating stirring is in water bath with thermostatic control to guarantee that quick lime is acidified completely), obtain acidizing product；By acidizing product in 100 DEG C of baking ovens
Middle drying, grinding, is then placed in the Muffle furnace of air atmosphere, is warming up to 950 DEG C with the heating rate of 6 DEG C/min, calcining
2.5h obtains acidification calcium oxide；
Calcium oxide and red clay will be acidified by the quality of 4:1 than mechanical mixture, ground uniformly to get clay-calcium based sulphur-fixation reagent.
2, the preparation of moulded coal
The dry cow dung for taking 6.0 g is uniformly mixed with the high-sulfur foam coal (crossing 18 meshes) of 18.0 g, then adds 2.6 g's or so
Binder and 1.6 g clay-calcium based sulphur-fixation reagent, and suitable water is added and stirs evenly, in the cylindrical die of the cm of 10.0 cm × 7.5
Then extrusion forming in tool is dried in 65 DEG C of baking oven to get cow dung/sulphur coal composite briquette.In full-automatic sulphur meter
Measurement, the S of the composite briquettet,adFor 0.30 %, sulfur-fixing rate is up to 70.02%.
Embodiment three
1, clay-calcium based sulphur-fixation reagent preparation
It takes the tartaric acid of 11 g to be dissolved in the water of 200 mL, the calcium oxide of 12.0 g is then added, after mixing in 80 DEG C of perseverances
4 h(of heating stirring is in tepidarium to guarantee that quick lime is acidified completely), obtain acidizing product；By acidizing product in 95 DEG C of baking ovens
Drying, grinding, is then placed in the Muffle furnace of air atmosphere, is warming up to 950 DEG C with the heating rate of 4.5 DEG C/min, calcines 2h,
Obtain acidification calcium oxide；
Calcium oxide and red clay will be acidified by the quality of 4.5:1 than mechanical mixture, ground uniformly to get clay-calcium based sulphur-fixation reagent.
2, the preparation of moulded coal
The dry cow dung for taking 6.0 g is uniformly mixed with the high-sulfur foam coal (crossing 18 meshes) of 18.0 g, then adds 2.6 g's or so
Binder and 1.7 g clay-calcium based sulphur-fixation reagent, and suitable water is added and stirs evenly, in the cylindrical die of the cm of 10.0 cm × 7.5
Then extrusion forming in tool is dried in 65 DEG C of baking oven to get cow dung/sulphur coal composite briquette.In full-automatic sulphur meter
Measurement, the S of the composite briquettet,adIt is 0.28%, sulfur-fixing rate is up to 70.80%.
Example IV
1, clay-calcium based sulphur-fixation reagent preparation
It takes the tartaric acid of 10.5 g to be dissolved in the water of 200 mL, the calcium oxide of 13.0 g is then added, after mixing at 80 DEG C
4 h(of heating stirring is in water bath with thermostatic control to guarantee that quick lime is acidified completely), obtain acidizing product；By acidizing product in 105 DEG C of baking ovens
Middle drying, grinding, is then placed in the Muffle furnace of air atmosphere, is warming up to 880 DEG C with the heating rate of 4 DEG C/min, calcines 3h,
Obtain acidification calcium oxide；
Calcium oxide and red clay will be acidified by the quality of 4.5:1 than mechanical mixture, ground uniformly to get clay-calcium based sulphur-fixation reagent.
2, the preparation of moulded coal
The dry cow dung for taking 6.0 g is uniformly mixed with the high-sulfur foam coal (crossing 18 meshes) of 18.0 g, then adds 2.6 g's or so
Binder and 1.6 g clay-calcium based sulphur-fixation reagent, and suitable water is added and stirs evenly, in the cylindrical die of the cm of 10.0 cm × 7.5
Then extrusion forming in tool is dried in 65 DEG C of baking oven to get cow dung/sulphur coal composite briquette.In full-automatic sulphur meter
Measurement, the S of the composite briquettet,adIt is 0.39%, sulfur-fixing rate is up to 61.93%.
Claims (8)
1. a kind of preparation method of clay-calcium based sulphur-fixation reagent is by calcium oxide through tartaric acid acidification, after drying, grinding,
Calcining obtains acidification calcium oxide in Muffle furnace；It will be acidified calcium oxide and natural clay mechanical mixture again, grinding is uniformly to get glutinous
Soil-calcium based sulphur-fixation reagent.
2. the preparation method of clay-calcium based sulphur-fixation reagent as described in claim 1, it is characterised in that: the preparation work of acidic oxidation calcium
Skill are as follows: calcium oxide is added in 5.0 ~ 6.0% tartaric acid solution of mass concentration, 75 ~ 85 DEG C are heated to after stirring and evenly mixing, processing
2.5~4.5 h。
3. the preparation method of clay-calcium based sulphur-fixation reagent as claimed in claim 2, it is characterised in that: calcium oxide and tartaric acid solution
Solid-to-liquid ratio be 0.05 ~ 0.07 g/mL.
4. the preparation method of clay-calcium based sulphur-fixation reagent as described in claim 1, it is characterised in that: be acidified the dry temperature of calcium oxide
Degree is 95 ~ 105 DEG C.
5. the preparation method of clay-calcium based sulphur-fixation reagent as described in claim 1, it is characterised in that: calcining heating rate is 4 ~ 6
DEG C/min, calcination temperature is 850 ~ 950 DEG C, and calcination time is 2 ~ 3h.
6. the preparation method of clay-calcium based sulphur-fixation reagent as described in claim 1, it is characterised in that: natural clay is attapulgite
Or red clay, natural clay and the mass ratio for being acidified calcium oxide are 1:3 ~ 1:4.
7. method as described in claim 1 prepares clay-calcium based sulphur-fixation reagent in the application of fixed cow dung/sulphur coal composite briquette.
8. method as claimed in claim 7 prepares clay-calcium based sulphur-fixation reagent in the application of fixed cow dung/sulphur coal composite briquette,
It is characterized by: clay-calcium based sulphur-fixation reagent additive amount is 6.0 ~ 7.0 % of moulded coal gross mass.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910165195.8A CN109797022A (en) | 2019-03-05 | 2019-03-05 | A kind of preparation of clay-calcium based sulphur-fixation reagent and application in fixed cow dung/sulphur coal composite briquette |
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| CN201910165195.8A CN109797022A (en) | 2019-03-05 | 2019-03-05 | A kind of preparation of clay-calcium based sulphur-fixation reagent and application in fixed cow dung/sulphur coal composite briquette |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057604A (en) * | 2019-12-06 | 2020-04-24 | 清华大学 | Method for improving sulfur fixation efficiency in sulfur removal and thermal conversion of coal |
| CN112760149A (en) * | 2019-10-21 | 2021-05-07 | 中国农业大学 | Composite briquette prepared by mixing cow dung and coal and preparation method thereof |
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| CN1227257A (en) * | 1998-12-30 | 1999-09-01 | 宝山钢铁(集团)公司 | Method of producing sulfur fixing agent for briquette |
| CN1263933A (en) * | 2000-02-03 | 2000-08-23 | 王茂春 | Equipment and process for producing clean coal series |
| CN106431779A (en) * | 2016-12-28 | 2017-02-22 | 贵州大学 | Phenanthrene-contaminated soil restoring fertilizer |
| CN106833804A (en) * | 2017-03-14 | 2017-06-13 | 兰州兰煤节净能源有限公司 | A kind of depth compound sulphur-fixing agent suitable for low-sulfur point barbecue coal |
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2019
- 2019-03-05 CN CN201910165195.8A patent/CN109797022A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227257A (en) * | 1998-12-30 | 1999-09-01 | 宝山钢铁(集团)公司 | Method of producing sulfur fixing agent for briquette |
| CN1263933A (en) * | 2000-02-03 | 2000-08-23 | 王茂春 | Equipment and process for producing clean coal series |
| CN106431779A (en) * | 2016-12-28 | 2017-02-22 | 贵州大学 | Phenanthrene-contaminated soil restoring fertilizer |
| CN106833804A (en) * | 2017-03-14 | 2017-06-13 | 兰州兰煤节净能源有限公司 | A kind of depth compound sulphur-fixing agent suitable for low-sulfur point barbecue coal |
Non-Patent Citations (1)
| Title |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112760149A (en) * | 2019-10-21 | 2021-05-07 | 中国农业大学 | Composite briquette prepared by mixing cow dung and coal and preparation method thereof |
| CN111057604A (en) * | 2019-12-06 | 2020-04-24 | 清华大学 | Method for improving sulfur fixation efficiency in sulfur removal and thermal conversion of coal |
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