CN106732387A - A kind of modified kaolin and its preparation method and application - Google Patents
A kind of modified kaolin and its preparation method and application Download PDFInfo
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- CN106732387A CN106732387A CN201611093269.4A CN201611093269A CN106732387A CN 106732387 A CN106732387 A CN 106732387A CN 201611093269 A CN201611093269 A CN 201611093269A CN 106732387 A CN106732387 A CN 106732387A
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- parts
- tbhp
- barium acetate
- kaolin
- itaconic acid
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
Abstract
The invention discloses a kind of modified kaolin and its preparation method and application, the modified kaolin is made up of the following raw material according to weight portion：31 39 parts of kaolin, 9 17 parts of itaconic acid, 37 parts of TBHP, 15 parts of cerous nitrate, 5 13 parts of barium acetate.The present invention is processed, adsorbent obtained in ultrasonication, the NO for adsorbing high concentration to kaolin and cerous nitrate mixed grinding using itaconic acid, TBHP, barium acetateX, purifying rate is high, and harmless to people and animals and plants, cost is not high, renewable recycling.After adsorption saturation, desorption and regeneration treatment can be carried out to adsorbent, can be absorbed with water and be made HNO3, as byproduct, non-secondary pollution.Preparation process is simple of the present invention, it is easy to operate, low cost, high-efficiency environment friendly is easy to industrialized production.
Description
Technical field
The present invention relates to environment-friendly materials technical field, specifically a kind of modified kaolin and its preparation method and application.
Background technology
All there is large area haze in many areas of China, especially in city.Its main cause is all types of industries combustion furnace
Discharge contains contaminant gases, and automobile quantity increases too fast, total release and sharply increases.The NO of exhaust emissionsXIt is haze shape
Into one of key factor, it forms HNO with vapor in atmosphere2And HNO3Tiny liquid grain, belongs to aerosol；Also can be
Photochemical fog is formed under effect of sunlight, excessive ozone is produced；NOXIt is also one of the important origin cause of formation to form acid rain.Therefore administer
Containing NOXTail gas pollution is significant.The NO that industrial combustion furnace and combustion in IC engine are producedXThe origin cause of formation is by the N in air2And O2
It is bound up at a temperature of more than 700 DEG C.And when typically ignition temperature is above 700 DEG C, otherwise fuel combustion is difficult.So only
There is burning just to have NOXProduce, and uprised with temperature elevated concentrations.
NO is reduced at presentXDischarge it is main take catalytic reduction method to process tail gas in NOX.Current catalyst cost is very high,
It is less efficient, using when it is complicated to condition requirement, and need highly energy-consuming, (reducing agent is multiplex must largely to consume reducing agent
NH3、CO2Or CH4Deng), therefore be not also preferable NOXAdministering method.And be current main flow purification techniques using adsorption technology
One of, it is widely used because being less subject to the influence of other conditions for using.Absorption NOXThe active charcoal of adsorbent,
SDG adsorbents.Activated carbon high cost, regenerates difficult after absorption.SDG adsorbents are larger to NOX ratio of adsorption, but it is also once
Property is used, non-renewable.For continuous middle and high concentration NOXThe discharge fume treatment of content still has higher cost.
The content of the invention
It is an object of the invention to provide a kind of low cost, renewable recycling, the modified kaolin of high-efficiency environment friendly and
Its preparation method and application, to solve the problems, such as to be proposed in above-mentioned background technology.
To achieve the above object, the present invention provides following technical scheme：
A kind of modified kaolin, is made up of the following raw material according to weight portion：Kaolin 31-39 parts, itaconic acid 9-17 parts,
TBHP 3-7 parts, cerous nitrate 1-5 parts, barium acetate 5-13 parts.
As further scheme of the invention：The modified kaolin, is made up of the following raw material according to weight portion：Kaolinite
It is native 33-37 parts, itaconic acid 11-15 parts, TBHP 4-6 parts, cerous nitrate 2-4 parts, barium acetate 7-11 parts.
As further scheme of the invention：The modified kaolin, is made up of the following raw material according to weight portion：Kaolinite
35 parts of soil, 13 parts of itaconic acid, 5 parts of TBHP, 3 parts of cerous nitrate, 9 parts of barium acetate.
Another object of the present invention is to provide a kind of preparation method of modified kaolin, comprises the steps of：
1) ethanol of 2.8 times of TBHP and its quality is mixed, TBHP solution is obtained；By clothing
Health acid mixes with the deionized water of 9.2 times of its quality, prepared itaconic acid solution；By barium acetate and the deionization of 1.1 times of its quality
Water mixes, and barium acetate solution is obtained；
2) by kaolin and cerous nitrate mixed grinding, itaconic acid solution is added, is heated to 74 DEG C and seals at such a temperature
Stir process 95min, is subsequently adding TBHP solution, is cooled to 68 DEG C and at such a temperature stir process 44min,
Then barium acetate solution is added dropwise, then carries out microwave treatment 38min, microwave power is 1000W, then is stirred at a temperature of 98-100 DEG C
Mix to dry, 4h is then calcined in 430 DEG C of Muffle furnace and obtains final product modified kaolin.
Another object of the present invention is to provide the modified kaolin in NOxApplication in treatment.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention to kaolin and cerous nitrate mixed grinding, at itaconic acid, TBHP, barium acetate
Reason, adsorbent obtained in ultrasonication, the NO for adsorbing high concentrationX.The present invention uses natural minerals, to people and animals and plants without
Evil.With respect to other NOXProcessing method, its cost is not high, renewable recycling.Preparation process is simple of the present invention, it is easy to operate,
Low cost, high-efficiency environment friendly is easy to industrialized production.The present invention is that it can at normal temperatures by NO in gasXAbsorption, adsorbs NOXSuction
NO in the gas discharged after attached dose of absorptionXContent is controlled in 100mg/m3Within, it is more excellent in 20mg/m3, the purifying rate of adsorbent
Up to more than 99%.After adsorption saturation, desorption and regeneration treatment can be carried out to adsorbent.Regenerate the NO for comingXThe thousands of mg/m of content3,
Can be absorbed with water and be made HNO3, as byproduct, non-secondary pollution.So economically more superior much than catalysis reduction.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of modified kaolin is made up of the following raw material according to weight portion：31 parts of kaolin,
9 parts of itaconic acid, 3 parts of TBHP, 1 part of cerous nitrate, 5 parts of barium acetate.
2.8 times of ethanol of TBHP and its quality is mixed, TBHP solution is obtained；By clothing health
Acid mixes with the deionized water of 9.2 times of its quality, prepared itaconic acid solution；By barium acetate and the deionized water of 1.1 times of its quality
Mixing, is obtained barium acetate solution.By kaolin and cerous nitrate mixed grinding, itaconic acid solution is added, be heated to 74 DEG C and at this
At a temperature of seal stir process 95min, be subsequently adding TBHP solution, be cooled to 68 DEG C and stir at such a temperature
Treatment 44min, is then added dropwise barium acetate solution, then carries out microwave treatment 38min, and microwave power is 1000W, then in 98 DEG C of temperature
Then the lower stirring of degree calcines 4h in 430 DEG C of Muffle furnace and obtains final product modified kaolin to dry.
Embodiment 2
In the embodiment of the present invention, a kind of modified kaolin is made up of the following raw material according to weight portion：39 parts of kaolin,
17 parts of itaconic acid, 7 parts of TBHP, 5 parts of cerous nitrate, 13 parts of barium acetate.
2.8 times of ethanol of TBHP and its quality is mixed, TBHP solution is obtained；By clothing health
Acid mixes with the deionized water of 9.2 times of its quality, prepared itaconic acid solution；By barium acetate and the deionized water of 1.1 times of its quality
Mixing, is obtained barium acetate solution.By kaolin and cerous nitrate mixed grinding, itaconic acid solution is added, be heated to 74 DEG C and at this
At a temperature of seal stir process 95min, be subsequently adding TBHP solution, be cooled to 68 DEG C and stir at such a temperature
Treatment 44min, is then added dropwise barium acetate solution, then carries out microwave treatment 38min, and microwave power is 1000W, then at 100 DEG C
At a temperature of stir to dry, 4h is then calcined in 430 DEG C of Muffle furnace and obtains final product modified kaolin.
Embodiment 3
In the embodiment of the present invention, a kind of modified kaolin is made up of the following raw material according to weight portion：33 parts of kaolin,
11 parts of itaconic acid, 4 parts of TBHP, 2 parts of cerous nitrate, 7 parts of barium acetate.
2.8 times of ethanol of TBHP and its quality is mixed, TBHP solution is obtained；By clothing health
Acid mixes with the deionized water of 9.2 times of its quality, prepared itaconic acid solution；By barium acetate and the deionized water of 1.1 times of its quality
Mixing, is obtained barium acetate solution.By kaolin and cerous nitrate mixed grinding, itaconic acid solution is added, be heated to 74 DEG C and at this
At a temperature of seal stir process 95min, be subsequently adding TBHP solution, be cooled to 68 DEG C and stir at such a temperature
Treatment 44min, is then added dropwise barium acetate solution, then carries out microwave treatment 38min, and microwave power is 1000W, then in 99 DEG C of temperature
Then the lower stirring of degree calcines 4h in 430 DEG C of Muffle furnace and obtains final product modified kaolin to dry.
Embodiment 4
In the embodiment of the present invention, a kind of modified kaolin is made up of the following raw material according to weight portion：37 parts of kaolin,
15 parts of itaconic acid, 6 parts of TBHP, 4 parts of cerous nitrate, 11 parts of barium acetate.
2.8 times of ethanol of TBHP and its quality is mixed, TBHP solution is obtained；By clothing health
Acid mixes with the deionized water of 9.2 times of its quality, prepared itaconic acid solution；By barium acetate and the deionized water of 1.1 times of its quality
Mixing, is obtained barium acetate solution.By kaolin and cerous nitrate mixed grinding, itaconic acid solution is added, be heated to 74 DEG C and at this
At a temperature of seal stir process 95min, be subsequently adding TBHP solution, be cooled to 68 DEG C and stir at such a temperature
Treatment 44min, is then added dropwise barium acetate solution, then carries out microwave treatment 38min, and microwave power is 1000W, then in 99 DEG C of temperature
Then the lower stirring of degree calcines 4h in 430 DEG C of Muffle furnace and obtains final product modified kaolin to dry.
Embodiment 5
In the embodiment of the present invention, a kind of modified kaolin is made up of the following raw material according to weight portion：35 parts of kaolin,
13 parts of itaconic acid, 5 parts of TBHP, 3 parts of cerous nitrate, 9 parts of barium acetate.
2.8 times of ethanol of TBHP and its quality is mixed, TBHP solution is obtained；By clothing health
Acid mixes with the deionized water of 9.2 times of its quality, prepared itaconic acid solution；By barium acetate and the deionized water of 1.1 times of its quality
Mixing, is obtained barium acetate solution.By kaolin and cerous nitrate mixed grinding, itaconic acid solution is added, be heated to 74 DEG C and at this
At a temperature of seal stir process 95min, be subsequently adding TBHP solution, be cooled to 68 DEG C and stir at such a temperature
Treatment 44min, is then added dropwise barium acetate solution, then carries out microwave treatment 38min, and microwave power is 1000W, then in 99 DEG C of temperature
Then the lower stirring of degree calcines 4h in 430 DEG C of Muffle furnace and obtains final product modified kaolin to dry.
Comparative example 1
In addition to itaconic acid is not contained, its material content and preparation process are consistent with embodiment 5.
Comparative example 2
In addition to barium acetate is not contained, its material content and preparation process are consistent with embodiment 5.
Comparative example 3
In addition to itaconic acid and barium acetate is not contained, its material content and preparation process are consistent with embodiment 5.
Embodiment 6
The present embodiment is that high concentration nitrogen oxide processes example, and affiliated waste gas is silver dissolving generation containing NOxWaste gas, tolerance
In 14000~15000m3/ h fluctuates.
After testing, entrance concentration is in 14000~15000mg/m3In the range of when fluctuating, each modified height in the embodiment of the present invention
Ridge soil makes its removal efficiency up to more than 99% under the interaction of each raw material, is shown in Table 1.And with commercially available adsorbent be contrast.
Table 1 is using the present embodiment modified kaolin to NOxRemoval efficiency
| Import NOxConcentration (mg/m3) | Outlet NOxConcentration (mg/m3) | Purifying rate (%) | |
| Embodiment 1 | 14485 | 98.6 | 99.32 |
| Embodiment 2 | 14682 | 90.7 | 99.38 |
| Embodiment 3 | 14286 | 16.1 | 99.89 |
| Embodiment 4 | 14893 | 15.3 | 99.90 |
| Embodiment 5 | 14826 | 11.1 | 99.93 |
| Comparative example 1 | 14285 | 8262.5 | 42.16 |
| Comparative example 2 | 14367 | 3559.1 | 75.23 |
| Comparative example 3 | 14751 | 9565.4 | 35.15 |
| Commercially available adsorbent | 14569 | 903.1 | 93.80 |
Understand, lacking itaconic acid or barium acetate in the present invention acts on kaolinic treatment, and obtained material is to NOxWaste gas
Suction-operated is not high, the collective effect of itaconic acid and barium acetate, and combines the obtained materials such as other raw materials to NOxWaste gas
With significant adsorption effect.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be in other specific forms realized.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires to be limited rather than described above, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each implementation method is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should
Specification an as entirety, the technical scheme in each embodiment can also be formed into those skilled in the art through appropriately combined
May be appreciated other embodiment.
Claims (5)
1. a kind of modified kaolin, it is characterised in that be made up of the following raw material according to weight portion：Kaolin 31-39 parts, clothing health
It is sour 9-17 parts, TBHP 3-7 parts, cerous nitrate 1-5 parts, barium acetate 5-13 parts.
2. modified kaolin according to claim 1, it is characterised in that be made up of the following raw material according to weight portion：It is high
33-37 parts, itaconic acid 11-15 parts, TBHP 4-6 parts, cerous nitrate 2-4 parts, barium acetate 7-11 parts of ridge soil.
3. modified kaolin according to claim 1, it is characterised in that be made up of the following raw material according to weight portion：It is high
35 parts of ridge soil, 13 parts of itaconic acid, 5 parts of TBHP, 3 parts of cerous nitrate, 9 parts of barium acetate.
4. the preparation method of a kind of modified kaolin as described in claim 1-3 is any, it is characterised in that by following steps group
Into：
1) ethanol of 2.8 times of TBHP and its quality is mixed, TBHP solution is obtained；By itaconic acid
Mix with 9.2 times of deionized water of its quality, itaconic acid solution is obtained；1.1 times of deionized water of barium acetate and its quality is mixed
Close, barium acetate solution is obtained；
2) by kaolin and cerous nitrate mixed grinding, itaconic acid solution is added, is heated to 74 DEG C and at such a temperature sealing stirring
Treatment 95min, is subsequently adding TBHP solution, is cooled to 68 DEG C and at such a temperature stir process 44min, then
Barium acetate solution is added dropwise, then microwave treatment 38min is carried out, microwave power is 1000W, then stirred at a temperature of 98-100 DEG C to
It is dry, 4h is then calcined in 430 DEG C of Muffle furnace and obtains final product modified kaolin.
5. the modified kaolin as described in claim 1-3 is any is in NOxApplication in treatment.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611093269.4A CN106732387A (en) | 2016-12-02 | 2016-12-02 | A kind of modified kaolin and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201611093269.4A CN106732387A (en) | 2016-12-02 | 2016-12-02 | A kind of modified kaolin and its preparation method and application |
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| CN106732387A true CN106732387A (en) | 2017-05-31 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020103078A1 (en) * | 2001-01-26 | 2002-08-01 | Zhicheng Hu | SOx trap for enhancing NOx trap performance and methods of making and using the same |
| CN101693192A (en) * | 2009-10-23 | 2010-04-14 | 中国科学院过程工程研究所 | Process for preparing nitric oxide adsorbent with high adsorption capacity |
| CN101987294A (en) * | 2009-08-04 | 2011-03-23 | 深圳市海仕通投资有限公司 | Method for preparing honeycomb ceramic adsorbent material by utilizing attapulgite clay |
| CN102335589A (en) * | 2011-09-16 | 2012-02-01 | 昆明理工大学 | Adsorbent and preparation method and use thereof |
| CN105478134A (en) * | 2014-09-19 | 2016-04-13 | 合众（佛山）化工有限公司 | Applicable load-type catalyst for purifying air at room temperature |
| CN105771617A (en) * | 2016-03-22 | 2016-07-20 | 天津滨环化学工程技术研究院有限公司 | Flue gas desulfurization and denitrification method |
-
2016
- 2016-12-02 CN CN201611093269.4A patent/CN106732387A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020103078A1 (en) * | 2001-01-26 | 2002-08-01 | Zhicheng Hu | SOx trap for enhancing NOx trap performance and methods of making and using the same |
| CN101987294A (en) * | 2009-08-04 | 2011-03-23 | 深圳市海仕通投资有限公司 | Method for preparing honeycomb ceramic adsorbent material by utilizing attapulgite clay |
| CN101693192A (en) * | 2009-10-23 | 2010-04-14 | 中国科学院过程工程研究所 | Process for preparing nitric oxide adsorbent with high adsorption capacity |
| CN102335589A (en) * | 2011-09-16 | 2012-02-01 | 昆明理工大学 | Adsorbent and preparation method and use thereof |
| CN105478134A (en) * | 2014-09-19 | 2016-04-13 | 合众（佛山）化工有限公司 | Applicable load-type catalyst for purifying air at room temperature |
| CN105771617A (en) * | 2016-03-22 | 2016-07-20 | 天津滨环化学工程技术研究院有限公司 | Flue gas desulfurization and denitrification method |
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