CN108057310A - A kind of solid deodorizer and its preparation method and application - Google Patents
A kind of solid deodorizer and its preparation method and application Download PDFInfo
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- CN108057310A CN108057310A CN201711467453.5A CN201711467453A CN108057310A CN 108057310 A CN108057310 A CN 108057310A CN 201711467453 A CN201711467453 A CN 201711467453A CN 108057310 A CN108057310 A CN 108057310A
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- deodorant
- refining slag
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0266—Other waste gases from animal farms
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
The invention belongs to deodorization technology fields, and in particular to a kind of solid deodorizer and its preparation method and application, deodorant described in per 100g include the component of following weight：22~36wt% of porous hydroxyapatite powder, 6~12wt% of 32~65wt% of anode furnace refining slag and mesoporous silicon oxide.Solid deodorizer of the present invention can be substantially reduced the concentration of the odorous gas substance such as ammonia in animal farm, hydrogen sulfide and methane, and at low cost, repeat and utilize, achieve significant progress.
Description
Technical field
The invention belongs to deodorization technology fields, and in particular to a kind of solid deodorizer and its preparation method and application.
Background technology
Animal farm odorous gas substance is mainly derived from the excreta of animal and the feed the like waste corruption of waste is decomposed
Product.Mainly include sulfide, nitrogen compound, aliphatic compound, carbon dioxide and first in the odorous gas substance of generation
Alkane etc..On the one hand the generation of above-mentioned stink substance can influence the growth and development of livestock and poultry, on the other hand, can seriously endanger people from periphery
The health of group, therefore, it is necessary to provide a kind of deodorant suitable for animal farm.
Mainly include chemical classes deodorant and biological agent class deodorization in the prior art for the deodorant of animal farm.Chemistry
Class deodorant, mainly by being chemically reacted with the malodor molecules in farm air, thoroughly decompose foul smell molecule for water,
The inaction innocuous substance such as ammonia.But such deodorant cannot reuse.Biological agent class deodorant generally includes substantial amounts of
The biological enzyme such as the beneficial bacteriums such as hay bacillus, Aspergillus and protease, lipase, fiber can effectively digest degradation excrement,
Fermented waste, so as to effective deodorization.But such deodorant manufacturing cost is high, and is difficult to stay active for long periods, is not suitable for big rule
Mould application.Therefore, it is necessary to provide a kind of utilization at low cost, repeatable, the deodorant of wide adaptation range.
Anode furnace refining slag is the byproduct generated during fire refined copper, due to China be copper production and consumption it is big
State, the annual yield of refined copper are more than 400t, tens thousand of tons of refining slag will be generated every year therewith, due to also containing in refining slag
CaO、SiO2、Al2O3With the ingredients such as FeO, therefore the technical issues of recycling refining slag is urgent need to resolve how is efficiently used, at present
Effect of the refining slag in terms of deodorization is not disclosed.
Hydroxyapatite is the main inorganic composition in skeleton and dental tissue, because it has to most protein nucleic acids
Molecule displays go out the advantages that adsorptivity, high associativity, outstanding biocompatibility, have been widely used in biomedicine field,
Such as organism implantation material, bone injury reparation, pharmaceutical carrier, anti-biotic material, immunosensor and gene therapy.It is but undisclosed
Its effect in terms of deodorization.
At present, and have no using anode furnace refining slag and hydroxyapatite mixing as one kind to being directed to animal farm odorous gas
The deodorant of substance.
The content of the invention
The present invention is intended to provide a kind of solid deodorizer, deodorization of the deodorant particularly suitable for animal farm, are mainly used for
Except odoring substances such as ammonia, hydrogen sulfide, methane and methylamines, there is at low cost, repeatable utilize.
In order to achieve the above object, the present invention uses following technical scheme：A kind of solid deodorizer, per 100g deodorant bags
Component containing following weight：22~36wt% of porous hydroxyapatite powder, 32~65wt% of anode furnace refining slag and mesoporous two
6~12wt% of silica.
Further, deodorant described in every 100g includes the component of following weight：Porous hydroxyapatite powder 22~
8~12wt% of 30wt%, 45~65wt% of anode furnace refining slag and mesoporous silicon oxide.
Further, deodorant described in every 100g includes the component of following weight：Porous hydroxyapatite powder 28wt%,
Anode furnace refining slag 60wt% and mesoporous silicon oxide 12wt%.
Further, deodorant described in every 100g includes the component of following weight：Porous hydroxyapatite powder 30wt%,
Anode furnace refining slag 58wt% and mesoporous silicon oxide 12wt%
Further, deodorant described in every 100g includes the component of following weight：Porous hydroxyapatite powder 23wt%,
Anode furnace refining slag 65wt% and mesoporous silicon oxide 12wt%.
Further, the porous hydroxyapatite particle is in porous spherical, and average diameter is 20~45 μm, and crystallinity is
30~50%.
Further, the anode furnace refining slag mainly includes the component of following weight：6.2~8.3wt% of CaO, SiO2
25.6~29.2wt%, Al2O36.3~9.4wt% and FeO25.4~35.8wt%.
Correspondingly, the present invention also provides a kind of method for preparing above-mentioned deodorant, comprise the following steps：
A) the preparation of anode furnace refining slag：
S1, sintering：Copper-contained sludge is taken, is sintered, agglomerate is moved into smelting furnace, adds in 10~12kg/t of lime stone
Cu, carbon 3~4kg/t Cu, while the air for being continually fed into the oxygen containing 20~30% (v/v) is calcined, and is obtained thick
Copper, wherein the temperature calcined is 1100~1200 DEG C；
S2, refining：Above-mentioned blister copper is moved into refining furnace, is continually fed into while adding in 3~4kg/t Cu heavy oil containing 90
The air mixing of the oxygen of~95% (v/v) dissolves blister copper, adds in carbon dust 2kg/t Cu and 4kg/t Cu quartzs, obtains sun
Pole copper coin and anode furnace refining slag, wherein the temperature calcined is 1200~1250 DEG C；
C) prepared by porous hydroxyapatite powder：
Iii Tween-80) is taken to add in the toluene that 100ml concentration is 0.3~0.5%, concussion adds in 30~50ml after shaking up
1mol/L sodium carbonate liquors, 10~15min of ultrasonic emulsification, the calcium chloride for pouring the emulsion into 0.1~0.3mol/L of 300ml are molten
In liquid, 1~2h is stirred to react, ageing 12~for 24 hours, the solution after ageing is filtered, obtains white precipitate, is washed, it is dry, it obtains porous
Spherical calcium carbonate powder；
Iv above-mentioned porous spherical carbonic acid calcium powder) is taken to add in the suspension that purified water is allowed to be formed 0.05g/ml, is being stirred
Under the conditions of, the disodium phosphate soln of 0.01~0.03mol/L is added in, pH10~11 is kept, is stirred to react 12~30h, is aged
12~for 24 hours；Solution after ageing is filtered, obtains white precipitate, is washed, it is dry, by above-mentioned white precipitate at 500~600 DEG C
Calcining is to get porous spherical hydroxyapatite powder；
C) by the above-mentioned porous spherical hydroxyapatite powder being prepared, anode furnace refining slag and mesoporous silicon oxide by
Corresponding weight mixing to get.
Further, above-mentioned deodorant is for reducing odorous gas content of material in animal farm.
Further, the odorous gas substance includes ammonia, hydrogen sulfide, methane and methylamine.
Except, the present invention also provides a kind of deodorizing methods, and above-mentioned deodorant is hung in odorous gas substance place.
Deodorant provided by the invention is pressed centainly by porous hydroxyapatite, anode furnace refining slag and mesoporous silicon oxide
Proportioning composition, has reached excellent deodorizing effect.Experiment proves that three, which is used in combination, can make ammonia in animal farm, hydrogen sulfide
Reach more than 50% with the reduced rate of methane, achieve synergistic effect.
It is emphasized that the physical property of porous hydroxyapatite also has a certain impact to deodorizing effect, as diameter,
Crystallinity etc..Inventor is long-term to grope, and draws finally, and average diameter is 20~45 μm, crystallinity be 30~50% it is porous
Hydroxyapatite is more advantageous to the promotion of deodoriging properties.
The present invention has the following advantages：
Deodorant provided by the invention can be substantially reduced the odorous gas substance such as ammonia in animal farm, hydrogen sulfide and methane
Concentration, it is and at low cost, repeat and utilize, achieve significant progress.
Specific embodiment
The specific embodiment of form by the following examples is described in further detail the above of invention.
But the scope that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following embodiment.
The preparation of embodiment 1, porous hydroxyapatite
I) Tween-80 is taken to add in the toluene that 100ml concentration is 0.5%, concussion adds in 50ml1mol/L carbonic acid after shaking up
Sodium solution, ultrasonic emulsification 15min are poured the emulsion into the calcium chloride solution of 300ml 0.2mol/L, are stirred to react 2h, ageing
For 24 hours, the solution after ageing is filtered, obtains white precipitate, with distilled water and absolute ethyl alcohol respectively washing 3 times, 80 DEG C of dry 12h are obtained
Porous spherical carbonic acid calcium powder；
Ii above-mentioned porous spherical carbonic acid calcium powder) is taken to add in the suspension that purified water is allowed to be formed 0.05g/ml, is being stirred
Under the conditions of, the disodium phosphate soln of 0.03mol/L is added in, it is 11 to keep pH, is stirred to react 12h, ageing is for 24 hours；After being aged
Solution filter, white precipitate is obtained, with respectively washing 3 times of distilled water and absolute ethyl alcohol, 80 DEG C of dry 12h, by above-mentioned white precipitate
Calcining is to get porous spherical hydroxyapatite powder at 600 DEG C.
The preparation of embodiment 2, anode furnace refining slag
S1, sintering：Copper-contained sludge is taken, is sintered, agglomerate is moved into smelting furnace, adds in lime stone 10kg/t Cu, charcoal
Smart 3kg/t Cu, while the air for being continually fed into the oxygen containing 25% (v/v) is calcined, and obtains blister copper, wherein calcine
Temperature is 1100 DEG C；
S2, refining：Above-mentioned blister copper is moved into refining furnace, is continually fed into while adding in 3kg/t Cu heavy oil containing 95%
(v/v) the air mixing of oxygen dissolves blister copper, adds in carbon dust 2kg/t Cu and 4kg/t Cu quartzs, obtains anode copper coin
With anode furnace refining slag, wherein the temperature calcined be 1200 DEG C.
1~4 deodorant composition and ratio of 1 embodiment of the present invention 3~5 of table and comparative example
Preparation process：
By corresponding weight, take above-mentioned raw materials, mix to get.
Test example one, deodorizing effect experiment
Select weight 6.0kg weanling pigs 700, be assigned randomly to 7 pig houses, be respectively labeled as embodiment 3~5 and
1~4 group of comparative example, correspondence place deodorant in pig house, and 100 every, every group feeds identical corn-soybean meal base daily
Plinth daily ration, free choice feeding and drinking-water.It is to be carried out disinfection by preceding with 1% thimerosal to pig house, every pig house area is 500m2,
16 swinery vent windows of even setting.Test period is 28d, during experiment, with Drager X-am7000 Walkie pneumatic detectors
The concentration of pig house ammonia, hydrogen sulfide and methane is measured daily three times, i.e. morning (6:00~7:00) (12 in,:00~13：00) it is, late
(19:00~20：00) each survey once, selects three points, apart from 50~80cm of ground, by Drager on the central axes of pig house respectively
X-am7000 Walkie pneumatic detectors are hung in air, etc. record after data stabilizations and be averaged, calculate ammonia, vulcanization
The depletion factor of hydrogen and methane.Result of the test is as shown in table 2.
Highest during depletion factor (%)=(minimum concentration value during maximum concentration value-experiment during experiment)/experiment
Concentration value × 100%
The different deodorant deodorization comparing results of table 2
As seen from the above table, the embodiment of the present invention 3~5 achieves optimal reduction ammonia, hydrogen sulfide compared with remaining each group
With the effect of methane concentration, reduced rate reaches more than 50%, is this hair wherein with deodorant best results described in embodiment 3
Bright most preferred embodiment.
1~3 deodorant of comparative example is respectively mesoporous silicon oxide, anode furnace refining slag, porous hydroxyapatite, deodorization
Effect has compared with Example 3 significantly to be declined, and three is applied in combination the deodorizing effect reached and is used alone more than three
The addition of effect, this explanation, three, which is applied in combination, achieves synergistic effect.
And the deodorant deodorization that comparative example 4 (compared with Example 3, replacing anode furnace refining slag with activated carbon) is prepared
Effect also has compared with Example 3 significantly to be declined.
The influence of test example two, the porous hydroxyapatite of different physical properties to deodorizing effect
Research 1, influence of the porous hydroxyapatite diameter to deodorizing effect
In addition to the diameter of porous hydroxyapatite is different, remaining is same as Example 3, is investigated according to one method of test example each
Influence of the group deodorant to deodorizing effect, result of the test are as shown in table 2.
Influence of the 2 porous hydroxyapatite diameter of table to deodorizing effect
As seen from the above table, the diameter of porous hydroxyapatite has a certain impact to deodorizing effect tool, but this influence is
Irregular in the least, porous hydroxyapatite has deodorizing effect positive influence in 20~45 μ ms, wherein with 35 μm of effects
Fruit is optimal.
Research 2, influence of the porous hydroxyapatite crystallinity to deodorizing effect
In addition to the crystallinity of porous hydroxyapatite is different, remaining is same as Example 3, is investigated according to one method of test example
Influence of each group deodorant to deodorizing effect, result of the test are as shown in table 3.
Influence of the 3 porous hydroxyapatite crystallinity of table to deodorizing effect
As seen from the above table, the crystallinity of porous hydroxyapatite also has a certain impact to the effect of deodorization, wherein with
Best results in the range of 30~50%.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (9)
1. a kind of solid deodorizer, which is characterized in that the component of following weight is included per 100g deodorant：Porous hydroxyapatite
6~12wt% of 22~36wt% of powder, 32~65wt% of anode furnace refining slag and mesoporous silicon oxide.
2. deodorant as described in claim 1, which is characterized in that the component of following weight is included per 100g deodorant：It is porous
8~12wt% of 22~30wt% of hydroxyapatite powder, 45~65wt% of anode furnace refining slag and mesoporous silicon oxide.
3. deodorant as claimed in claim 2, which is characterized in that the component of following weight is included per 100g deodorant：It is porous
Hydroxyapatite powder 28wt%, anode furnace refining slag 60wt% and mesoporous silicon oxide 12wt%.
4. deodorant as claimed in claim 3, which is characterized in that the porous hydroxyapatite particle is spherical in shape, average straight
Footpath is 20~45 μm, and crystallinity is 30~50%.
5. the deodorant as described in claims 1 to 3 is any, which is characterized in that the anode furnace refining slag mainly includes following
The component of weight：6.2~8.3wt% of CaO, SiO225.6~29.2wt%, Al2O36.3~9.4wt% and FeO25.4~
35.8wt%.
A kind of 6. method for preparing the deodorant as described in Claims 1 to 5 is any, which is characterized in that comprise the following steps：
A) the preparation of anode furnace refining slag：
S1, sintering：Copper-contained sludge is taken, is sintered, agglomerate is moved into smelting furnace, adds in lime stone 10~12kg/t Cu, charcoal
Essence 3~4kg/t Cu, while the air for being continually fed into the oxygen containing 20~30% (v/v) is calcined, and obtains blister copper, wherein
The temperature of calcining is 1100~1200 DEG C；
S2, refining：Above-mentioned blister copper is moved into refining furnace, be continually fed into while adding in 3~4kg/t Cu heavy oil containing 90~
The air mixing of the oxygen of 95% (v/v) dissolves blister copper, adds in carbon dust 2kg/t Cu and 4kg/t Cu quartzs, obtains anode
Copper coin and anode furnace refining slag, wherein the temperature calcined is 1200~1250 DEG C；
B) prepared by porous hydroxyapatite powder：
I) Tween-80 is taken, adds in the toluene that 100ml concentration is 0.3~0.5%, concussion adds in 30~50ml 1mol/L after shaking up
Sodium carbonate liquor, 10~15min of ultrasonic emulsification are poured the emulsion into the calcium chloride solution of 0.1~0.3mol/L of 300ml, stirred
Mix 1~2h of reaction, ageing 12~for 24 hours, the solution after ageing is filtered, obtains white precipitate, is washed, it is dry, obtain porous spherical carbonaceous
Sour calcium powder；
Ii above-mentioned porous spherical carbonic acid calcium powder) is taken to add in the suspension that purified water is allowed to be formed 0.05g/ml, in stirring condition
Under, the disodium phosphate soln of 0.01~0.03mol/L is added in, pH10~11 is kept, is stirred to react 12~30h, ageing 12~
24h；Solution after ageing is filtered, obtains white precipitate, is washed, it is dry, above-mentioned white precipitate is calcined at 500~600 DEG C,
Up to porous spherical hydroxyapatite powder；
C) by the above-mentioned porous spherical hydroxyapatite powder being prepared, anode furnace refining slag and mesoporous silicon oxide by corresponding
Weight mix to get.
7. deodorant or such as purposes for the deodorant that claim 6 is prepared as described in Claims 1 to 5 is any, special
Sign is, for reducing odorous gas content of material in animal farm.
8. purposes as claimed in claim 7, which is characterized in that the odorous gas substance include ammonia, hydrogen sulfide, methane and
Methylamine.
9. a kind of deodorizing method, which is characterized in that by the deodorant as described in Claims 1 to 5 is any or as claim 6 is made
Standby obtained deodorant is hung in odorous gas substance place.
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| CN201711467453.5A CN108057310B (en) | 2017-12-29 | 2017-12-29 | A kind of solid deodorizer and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112156645A (en) * | 2020-09-23 | 2021-01-01 | 柳州市宝净科技有限公司 | Composite biological enzyme deodorant and preparation method thereof |
| CN112871134A (en) * | 2021-01-18 | 2021-06-01 | 重庆大学 | Cu-HAP-biochar composite material for adsorbing hydrogen sulfide and preparation method thereof |
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| CN103551170A (en) * | 2013-10-23 | 2014-02-05 | 三棵树涂料股份有限公司 | Hydroxyl apatite layer-wrapped photocatalytic nano titanium dioxide powder and application thereof |
| CN105709699A (en) * | 2016-04-18 | 2016-06-29 | 华中科技大学 | Soil heavy metal adsorbent and preparation method thereof |
| CN106924103A (en) * | 2015-12-30 | 2017-07-07 | 焦秀花 | A kind of deodorizing sterilizing toothpaste |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316289A (en) * | 2001-01-16 | 2001-10-10 | 史汉祥 | Chemical absorbent for treating waste gas containing SO2 |
| CN103551170A (en) * | 2013-10-23 | 2014-02-05 | 三棵树涂料股份有限公司 | Hydroxyl apatite layer-wrapped photocatalytic nano titanium dioxide powder and application thereof |
| CN106924103A (en) * | 2015-12-30 | 2017-07-07 | 焦秀花 | A kind of deodorizing sterilizing toothpaste |
| CN105709699A (en) * | 2016-04-18 | 2016-06-29 | 华中科技大学 | Soil heavy metal adsorbent and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112156645A (en) * | 2020-09-23 | 2021-01-01 | 柳州市宝净科技有限公司 | Composite biological enzyme deodorant and preparation method thereof |
| CN112156645B (en) * | 2020-09-23 | 2021-04-27 | 柳州市宝净科技有限公司 | Composite biological enzyme deodorant and preparation method thereof |
| CN112871134A (en) * | 2021-01-18 | 2021-06-01 | 重庆大学 | Cu-HAP-biochar composite material for adsorbing hydrogen sulfide and preparation method thereof |
| CN112871134B (en) * | 2021-01-18 | 2022-04-15 | 重庆大学 | Cu-HAP-biochar composite material for adsorbing hydrogen sulfide and preparation method thereof |
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| CN108057310B (en) | 2019-07-02 |
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