CN108057310B - 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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- CN108057310B CN108057310B CN201711467453.5A CN201711467453A CN108057310B CN 108057310 B CN108057310 B CN 108057310B CN 201711467453 A CN201711467453 A CN 201711467453A CN 108057310 B CN108057310 B CN 108057310B
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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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- 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, more particularly to a kind of solid deodorizer and its preparation method and application, deodorant described in every 100g includes 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, reusable, 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 technique
Animal farm odorous gas substance is mainly derived from the decomposition of the wastes corruption such as the excreta of animal and the feed of waste
Product.It 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 substances will affect 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.
It mainly include in the prior art chemical classes deodorant and biological agent class deodorization for the deodorant of animal farm.Chemistry
Class deodorant, mainly by being chemically reacted with the malodor molecules in farm's air, thoroughly decompose foul smell molecule be water,
The inaction innocuous substance such as ammonia.But such deodorant cannot reuse.Biological agent class deodorant generally includes a large amount 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, thus 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 at low cost, reusable, 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 of thousands 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.But it is undisclosed
Its effect in terms of deodorization.
Currently, and having no anode furnace refining slag and hydroxyapatite mixing as a kind of to for animal farm odorous gas
The deodorant of substance.
Summary 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, have the characteristics that at low cost, reusable.
In order to achieve the above object, the invention adopts the following technical scheme: a kind of solid deodorizer, every 100g deodorant
Component comprising following weight: 22~36wt% of porous hydroxyapatite powder, 32~65wt% of anode furnace refining slag and mesoporous
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,
SiO225.6~29.2wt%, Al2O36.3~9.4wt% and FeO25.4~35.8wt%.
Correspondingly, the present invention also provides a kind of methods for preparing above-mentioned deodorant, comprising the following steps:
A) the preparation of anode furnace refining slag:
S1, sintering: taking copper-contained sludge, is sintered, and agglomerate is moved into smelting furnace, 10~12kg/t of lime stone is added
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 3~4kg/t Cu heavy oil is added containing 90
The air mixing of the oxygen of~95% (v/v) melts blister copper, and carbon dust 2kg/t Cu and 4kg/t Cu quartz is added, obtains
Anode copper sheet and anode furnace refining slag, wherein the temperature calcined is 1200~1250 DEG C；
C) prepared by porous hydroxyapatite powder:
Iii) take Tween-80 be added 100ml concentration be 0.3~0.5% toluene in, concussion shake up after be added 30~
50ml 1mol/L sodium carbonate liquor, 10~15min of ultrasonic emulsification pour the emulsion into the chlorine of 0.1~0.3mo of 300ml l/L
Change in calcium solution, is stirred to react 1~2h, ageing 12~for 24 hours, the solution after ageing is filtered, white precipitate is obtained, is washed, it is dry,
Obtain porous spherical calcium carbonate powder；
Iv it) takes above-mentioned porous spherical carbonic acid calcium powder that purified water is added to be allowed to form the suspension of 0.05g/ml, stir
Under the conditions of, the disodium phosphate soln of 0.01~0.03mol/L is added, keeps pH10~11, is stirred to react 12~30h, is aged
12~for 24 hours；Solution after ageing is filtered, white precipitate is obtained, 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 methodss, 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
Proportion composition, has reached excellent deodorizing effect.Test proves that three, which is used in combination, can make ammonia in animal farm, hydrogen sulfide
Reach 50% or more with the reduced rate of methane, achieves 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 obtains 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 invention has the following advantages that
Deodorant provided by the invention can be substantially reduced the odorous gas substance such as ammonia in animal farm, hydrogen sulfide and methane
Concentration, and it is at low cost, it is reusable, achieve significant progress.
Specific embodiment
The specific embodiment of form by the following examples is described in further detail the above content of invention.
But the range 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 be added in the toluene that 100ml concentration is 0.5%, 50ml1mol/L carbonic acid is added after shaking up in concussion
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, respectively washed 3 times with distilled water and dehydrated alcohol, 80 DEG C of dry 12h is obtained
Porous spherical carbonic acid calcium powder；
Ii it) takes above-mentioned porous spherical carbonic acid calcium powder that purified water is added to be allowed to form the suspension of 0.05g/ml, stir
Under the conditions of, the disodium phosphate soln of 0.03mol/L is added, keeping pH is 11, is stirred to react 12h, ageing is for 24 hours；After being aged
Solution filter, obtain white precipitate, respectively washed 3 times with distilled water and dehydrated alcohol, 80 DEG C of dry 12h, by above-mentioned white precipitate
Calcining is at 600 DEG C to get porous spherical hydroxyapatite powder.
The preparation of embodiment 2, anode furnace refining slag
S1, sintering: taking copper-contained sludge, is sintered, and agglomerate is moved into smelting furnace, lime stone 10kg/t Cu, charcoal is added
Smart 3kg/t Cu, while the air for being continually fed into the oxygen containing 25% (v/v) is calcined, and blister copper is obtained, wherein calcine
Temperature is 1100 DEG C；
S2, refining: above-mentioned blister copper is moved into refining furnace, is continually fed into while 3kg/t Cu heavy oil is added containing 95%
(v/v) the air mixing of oxygen melts blister copper, and carbon dust 2kg/t Cu and 4kg/t Cu quartz is added, obtains anode copper
Plate and anode furnace refining slag, wherein the temperature calcined is 1200 DEG C.
1 embodiment of the present invention 3~5 of table and the deodorant composition and ratio of comparative example 1~4
Preparation process:
By corresponding weight, take above-mentioned raw materials, mixing to get.
Test example one, deodorizing effect test
Select weight 6.0kg weanling pig 700, be assigned randomly to 7 pig houses, be respectively labeled as embodiment 3~5 with
And 1~4 group of comparative example, correspondence places deodorant in pig house, and 100 every, every group feeds identical corn-soybean meal daily
Basal diet is freely eaten and drinks water.It is to be carried out disinfection with 1% thimerosal to pig house by preceding, every pig house area is 500m2,
It is uniformly arranged 16 swinery vent windows.Test period is 28d, during test, is detected with Drager X-am7000 portable gas
Device measures the concentration of pig house ammonia, hydrogen sulfide and methane three times daily, i.e., early (6:00~7:00), in (12:00~13:00),
Late (19:00~20:00) is each respectively to be surveyed once, and three points are selected on the central axes of pig house, will apart from 50~80cm of ground
Drager X-am7000 Walkie pneumatic detector is hung in air, etc. record after data stabilizations and be averaged, calculate ammonia
The depletion factor of gas, hydrogen sulfide and methane.Test result is as shown in table 2.
Highest during depletion factor (%)=(minimum concentration value during maximum concentration value-test during test)/test
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 50% or more, wherein it is best with deodorant effect described in embodiment 3, it is this hair
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 greater 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 active carbon) is prepared
Effect also has compared with Example 3 significantly to be declined.
Influence of the porous hydroxyapatite to deodorizing effect of test example two, different physical properties
Study 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, investigates according to one method of test example each
Influence of the group deodorant to deodorizing effect, test result 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 positive influence to deodorizing effect in 20~45 μ ms, wherein being imitated with 35 μm
Fruit is best.
Study 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, investigates according to one method of test example
Influence of each group deodorant to deodorizing effect, test result 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
Effect is best in 30~50% ranges.
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
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (8)
1. a kind of solid deodorizer, which is characterized in that every 100g deodorant includes the component of following weight: porous hydroxyapatite
6~12wt% of 22~36wt% of powder, 32~65wt% of anode furnace refining slag and mesoporous silicon oxide；The preparation of the deodorant
Method the following steps are included:
A) the preparation of anode furnace refining slag:
S1, sintering: taking copper-contained sludge, is sintered, and agglomerate is moved into smelting furnace, lime stone 10~12kg/t Cu, charcoal is added
Essence 3~4kg/t Cu, while the air for being continually fed into the oxygen containing 20~30% (v/v) is calcined, and blister copper is obtained, wherein
The temperature of calcining is 1100~1200 DEG C；
S2, refining: above-mentioned blister copper is moved into refining furnace, is continually fed into while 3~4kg/tCu heavy oil is added containing 90~95%
(v/v) the air mixing of oxygen melts blister copper, and carbon dust 2kg/t Cu and 4kg/t Cu quartz is added, obtains anode copper
Plate 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, the toluene that 100ml concentration is 0.3~0.5% is added, 30~50ml 1mol/L is added after shaking up in concussion
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, are stirred
Mix 1~2h of reaction, ageing 12~for 24 hours, the solution after ageing is filtered, white precipitate is obtained, is washed, it is dry, obtain porous spherical carbonaceous
Sour calcium powder；
Ii it) takes above-mentioned porous spherical carbonic acid calcium powder that purified water is added to be allowed to form the suspension of 0.05g/ml, in stirring condition
Under, the disodium phosphate soln of 0.01~0.03mol/L is added, keeps pH10~11, is stirred to react 12~30h, ageing 12~
24h；Solution after ageing is filtered, white precipitate is obtained, 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 mixing to get.
2. deodorant as described in claim 1, which is characterized in that every 100g deodorant includes the component of following weight: 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 every 100g deodorant includes the component of following weight: 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
Diameter 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%.
6. the purposes of the deodorant as described in Claims 1 to 5 is any, which is characterized in that for reducing stink gas in animal farm
Body content of material.
7. purposes as claimed in claim 6, which is characterized in that the odorous gas substance include ammonia, hydrogen sulfide, methane and
Methylamine.
8. a kind of deodorizing methods, which is characterized in that the deodorant as described in Claims 1 to 5 is any is hung on odorous gas
In substance place.
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| 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 |
| 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 |
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 |
| 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 |
-
2017
- 2017-12-29 CN CN201711467453.5A patent/CN108057310B/en active Active
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 |
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