CN110423027A - The recovery and treatment method of Desulphurization - Google Patents
The recovery and treatment method of Desulphurization Download PDFInfo
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- CN110423027A CN110423027A CN201910724739.XA CN201910724739A CN110423027A CN 110423027 A CN110423027 A CN 110423027A CN 201910724739 A CN201910724739 A CN 201910724739A CN 110423027 A CN110423027 A CN 110423027A
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- recovery
- desulphurization
- treatment method
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- catalyst
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
- C04B11/264—Gypsum from the desulfurisation of flue gases
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention discloses a kind of recovery and treatment method of Desulphurization, which includes: that Desulphurization, catalyst and hydrogenperoxide steam generator 1) are carried out haptoreaction to obtain oxidation product；2) oxidation product, waste acid liquor are subjected to haptoreaction, filter cake is then collected by filtration；3) filter cake is cleaned by water, is then aged, is heat-treated；Wherein, catalyst is selected from least one of nano-titanium dioxide, nano zircite, nano yttrium oxide, nanoscale molybdenum oxide.The recovery and treatment method of the Desulphurization can be effectively reduced the content of calcium sulfite and free chloro ion.
Description
Technical field
The present invention relates to the post-processings of Desulphurization, and in particular, to a kind of recovery and treatment method of Desulphurization.
Background technique
Desulphurization refers to quick lime (CaO) for desulfurizing agent, and moisture or the penetrating in desulfurizing agent are evaporated using obvious heat of smoke
The atomized water of desulfurizing tower, flue-gas temperature moment reduces and relative humidity greatly increases, and the sulfur dioxide in desulfurizing agent and flue gas is sent out
Biochemical reaction, the dry state desulfurizing byproduct then obtained through bag filter gas solid separation.
Contain a large amount of calcium sulfite and free chloro ion in Desulphurization, have hydration reaction slow, cannot condense quickly hard
Change, causes cement or production of construction materials slow setting；In addition have stability poor, meeting can slowly aoxidize under water or natural conditions, thus body
Product expansion, destroys concrete or construction material intensity；It meets under high temperature or acid condition, SO2It can discharge again, cause secondary dirt
Dye.Therefore lime semi-dry desulphurization ash cannot be dosed directly in concrete or for producing the Building woods such as cement, building block, plate
Material, it is even more impossible to utilize in other fields.
Simultaneously as Desulphurization property is unstable and is in alkalinity, stacks naturally and do not only take up a large amount of soils, cause underground water
Pollution, and since its density is smaller, light weight, dust pollution can be generated once wind, simultaneously because wherein containing a large amount of sub-
Calcium sulfate will cause sulfur dioxide secondary pollution using improper.
Summary of the invention
The object of the present invention is to provide a kind of recovery and treatment method of Desulphurization, the recovery and treatment method of the Desulphurization can
It is effectively reduced the content of calcium sulfite and free chloro ion.
To achieve the goals above, the present invention provides a kind of recovery and treatment methods of Desulphurization, comprising:
1) Desulphurization, catalyst and hydrogenperoxide steam generator are subjected to haptoreaction to obtain oxidation product；
2) oxidation product, waste acid liquor are subjected to haptoreaction, filter cake is then collected by filtration；
3) filter cake is cleaned by water, is then aged, is heat-treated；
Wherein, catalyst in nano-titanium dioxide, nano zircite, nano yttrium oxide, nanoscale molybdenum oxide at least
One.
In the above-mentioned technical solutions, the present invention passes through catalyst first and hydrogen peroxide makes the major part in Desulphurization sub-
Calcium sulfate is converted to calcium sulfate, and remaining inferior sulfate radical is further made to be converted to sulfur dioxide discharge followed by spent acid,
Then free chloro ion therein is removed by water cleaning, the processing finally by ageing, heat treatment further guarantees sulfurous
Sour calcium is substantially all to be converted into calcium sulfate.By above-mentioned multi step strategy so that the calcium sulfite and free chlorine of Desulphurization from
The content of son is effectively reduced, so that the performance of Desulphurization is stabilized so that Desulphurization is applicable to cement or builds
In material production.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of recovery and treatment methods of Desulphurization, comprising:
1) Desulphurization, catalyst and hydrogenperoxide steam generator are subjected to haptoreaction to obtain oxidation product；
2) oxidation product, waste acid liquor are subjected to haptoreaction, filter cake is then collected by filtration；
3) filter cake is cleaned by water, is then aged, is heat-treated；
Wherein, catalyst in nano-titanium dioxide, nano zircite, nano yttrium oxide, nanoscale molybdenum oxide at least
One.
In step 1) of the invention, the dosage of each material can select in a wide range, but in order to further drop
The content of calcium sulfite and free chloro ion after reduction process in Desulphurization, it is preferable that in step 1), Desulphurization, catalyst
Weight ratio with hydrogenperoxide steam generator is 100:1.5-4:300-500；And the concentration of hydrogenperoxide steam generator is 30 weight %-40
Weight %.
In step 1) of the invention, catalytic condition can select in a wide range, but in order to further
The content of calcium sulfite and free chloro ion after reduction processing in Desulphurization, it is preferable that in step 1), haptoreaction meets
The following conditions: reaction temperature is 15-35 DEG C, reaction time 8-12h.
In step 1) of the invention, the type of catalyst can select in a wide range, but in order to further drop
The content of calcium sulfite and free chloro ion after reduction process in Desulphurization, it is preferable that in step 1), catalyst is by nanometer two
Titanium oxide, nano zircite composition, and the weight ratio of nano-titanium dioxide, nano zircite is 1:0.2-0.5.
In step 1) of the invention, the dosage of each material can select in a wide range, but in order to further drop
The content of calcium sulfite and free chloro ion after reduction process in Desulphurization, it is preferable that in step 2), oxidation product, spent acid
The weight ratio of solution is 10:30-50, and the pH of waste acid liquor is 1-3.
In step 2) of the invention, catalytic condition can select in a wide range, but in order to further
The content of calcium sulfite and free chloro ion after reduction processing in Desulphurization, it is preferable that in step 2), haptoreaction meets
The following conditions: reaction temperature is 15-35 DEG C, reaction time 5-10h.
In step 3) of the invention, the number of cleaning can select in a wide range, but in order to further decrease
The content of calcium sulfite and free chloro ion after processing in Desulphurization, it is preferable that in step 3), the number of cleaning is 3-5
It is secondary.
In step 3) of the invention, the condition of ageing can select in a wide range, but in order to further decrease
Preferably, in step 3), ageing meets the following conditions to the content of calcium sulfite and free chloro ion after processing in Desulphurization:
Aging Temperature is 15-35 DEG C, digestion time 36-72h.
In step 3) of the invention, the condition of heat treatment can select in a wide range, but in order to further drop
The content of calcium sulfite and free chloro ion after reduction process in Desulphurization is preferably, it is preferable that in step 3), heat treatment is full
Sufficient the following conditions: heat treatment temperature is 400-480 DEG C, heat treatment time 60-80min.
The present invention will be described in detail by way of examples below.
Embodiment 1
1) by Desulphurization, catalyst (weight ratio is the nano-titanium dioxide of 1:0.3, nano zircite composition) and peroxidating
Hydrogen solution (35 weight %) according to the weight ratio of 100:2:400 carries out haptoreaction, and (reaction temperature is 25 DEG C, and the reaction time is
10h) to obtain oxidation product；
2) oxidation product, waste acid liquor (pH 2) are subjected to haptoreaction according to the weight ratio of 10:40 (reaction temperature is
25 DEG C, reaction time 8h), filter cake is then collected by filtration；
3) filter cake is subjected to cleaning 4 times by water, be then aged (Aging Temperature be 25 DEG C, digestion time 48h),
Heat treatment (heat treatment temperature is 450 DEG C, heat treatment time 70min).
Embodiment 2
1) by Desulphurization, catalyst (weight ratio is the nano-titanium dioxide of 1:0.2, nano zircite composition) and peroxidating
Hydrogen solution (30 weight %) according to the weight ratio of 100:1.5:300 carries out haptoreaction, and (reaction temperature is 15 DEG C, and the reaction time is
12h) to obtain oxidation product；
2) oxidation product, waste acid liquor (pH 1) are subjected to haptoreaction according to the weight ratio of 10:30 (reaction temperature is
15 DEG C, reaction time 10h), filter cake is then collected by filtration；
3) filter cake is subjected to cleaning 3 times by water, be then aged (Aging Temperature be 15 DEG C, digestion time 72h),
Heat treatment (heat treatment temperature is 400 DEG C, heat treatment time 80min).
Embodiment 3
1) by Desulphurization, catalyst (weight ratio is the nano-titanium dioxide of 1:0.5, nano zircite composition) and peroxidating
Hydrogen solution (40 weight %) according to the weight ratio of 100:4:500 carries out haptoreaction, and (reaction temperature is 35 DEG C, and the reaction time is
8h) to obtain oxidation product；
2) oxidation product, waste acid liquor (pH 3) are subjected to haptoreaction according to the weight ratio of 10:50 (reaction temperature is
35 DEG C, reaction time 5h), filter cake is then collected by filtration；
3) filter cake is subjected to cleaning 5 times by water, be then aged (Aging Temperature be 15 DEG C, digestion time 72h),
Heat treatment (heat treatment temperature is 400 DEG C, heat treatment time 60min).
Detect example 1
The Desulphurization before above-mentioned processing and each embodiment are detected treated Desulphurization according to JC T 2074-2011
In calcium sulphate dihydrate, half-H 2 O calcium sulphate, chloride ion content, concrete outcome is shown in Table 1.
Table 1
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (9)
1. a kind of recovery and treatment method of Desulphurization characterized by comprising
1) Desulphurization, catalyst and hydrogenperoxide steam generator are subjected to haptoreaction to obtain oxidation product；
2) oxidation product, waste acid liquor are subjected to haptoreaction, filter cake is then collected by filtration；
3) filter cake is cleaned by water, is then aged, is heat-treated；
Wherein, the catalyst in nano-titanium dioxide, nano zircite, nano yttrium oxide, nanoscale molybdenum oxide at least
One.
2. recovery and treatment method according to claim 1, wherein in step 1), the Desulphurization, catalyst and peroxide
The weight ratio for changing hydrogen solution is 100:1.5-4:300-500；And the concentration of the hydrogenperoxide steam generator is 30 weight %-40 weight
Measure %.
3. recovery and treatment method according to claim 1, wherein in step 1), the haptoreaction meets following item
Part: reaction temperature is 15-35 DEG C, reaction time 8-12h.
4. recovery and treatment method according to claim 1, wherein in step 1), the catalyst is by nanometer two
Titanium oxide, nano zircite composition, and the weight ratio of the nano-titanium dioxide, nano zircite is 1:0.2-0.5.
5. recovery and treatment method according to claim 1, wherein in step 2), the oxidation product, waste acid liquor
Weight ratio is 10:30-50, and the pH of the waste acid liquor is 1-3.
6. recovery and treatment method according to claim 1, wherein in step 2), the haptoreaction meets following item
Part: reaction temperature is 15-35 DEG C, reaction time 5-10h.
7. recovery and treatment method according to claim 1, wherein in step 3), the number of the cleaning is 3-5 times.
8. recovery and treatment method according to claim 1, wherein in step 3), the ageing meets the following conditions: old
Changing temperature is 15-35 DEG C, digestion time 36-72h.
9. recovery and treatment method according to claim 1, wherein in step 3), the heat treatment meets the following conditions:
Heat treatment temperature is 400-480 DEG C, heat treatment time 60-80min.
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| CN201910724739.XA CN110423027A (en) | 2019-08-07 | 2019-08-07 | The recovery and treatment method of Desulphurization |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114226421A (en) * | 2021-12-23 | 2022-03-25 | 上海电气电站环保工程有限公司 | Treatment method of semidry desulfurization ash |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734875A (en) * | 2009-12-28 | 2010-06-16 | 华北电力大学（保定） | Method for catalytic oxidation of calcium sulfite in desulphurization ash by dry method and semi-dry method |
| CN102912445A (en) * | 2012-10-22 | 2013-02-06 | 浙江天蓝环保技术股份有限公司 | Process and device for preparing gypsum whisker by semi-dry desulfurized fly ash and waste acid |
-
2019
- 2019-08-07 CN CN201910724739.XA patent/CN110423027A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734875A (en) * | 2009-12-28 | 2010-06-16 | 华北电力大学（保定） | Method for catalytic oxidation of calcium sulfite in desulphurization ash by dry method and semi-dry method |
| CN102912445A (en) * | 2012-10-22 | 2013-02-06 | 浙江天蓝环保技术股份有限公司 | Process and device for preparing gypsum whisker by semi-dry desulfurized fly ash and waste acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114226421A (en) * | 2021-12-23 | 2022-03-25 | 上海电气电站环保工程有限公司 | Treatment method of semidry desulfurization ash |
| CN114226421B (en) * | 2021-12-23 | 2024-03-15 | 上海电气电站环保工程有限公司 | Treatment method of semi-dry desulfurization ash |
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Application publication date: 20191108 |
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