CN105272110B - A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid - Google Patents
A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid Download PDFInfo
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- CN105272110B CN105272110B CN201510718700.9A CN201510718700A CN105272110B CN 105272110 B CN105272110 B CN 105272110B CN 201510718700 A CN201510718700 A CN 201510718700A CN 105272110 B CN105272110 B CN 105272110B
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The present invention relates to a kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid.Its technical scheme is：First using 60 ~ 90wt% ardealite and 10 ~ 40wt% charring rice husk as raw material, pug is made in additional 0.5 ~ 2.0wt% of raw material water reducer and 50 ~ 100wt% water, mixing.Then the foam made by the additional 0.5 ~ 1.0wt% of raw material foaming agent, stirring, then the additional 1.0 ~ 2.5wt% of raw material gel, stirring, cast molding, are spontaneously dried, the demoulding.110 DEG C of dry 5 ~ 10h, 170 DEG C of 5 ~ 10h of baking, are made porous preforming block.Porous preforming block is finally subjected to cartalytic decomposition effect under the conditions of nitrogen atmosphere and 800 ~ 1000 DEG C, porous building-brick and sulfur dioxide gas is made；Obtained sulfur dioxide is oxidized and absorption produces sulfuric acid.Cost of the present invention is low, energy consumption is small and sulphur high conversion rate, and efficiently porous building-brick can be prepared using reacting tailings while production sulfuric acid, and the porous building-brick bulk density of preparation is small and low thermal conductivity.
Description
Technical field
The invention belongs to ardealite processing technology field.Specifically related to a kind of decomposing phosphogypsum prepares porous building-brick and sulfuric acid
Method.
Background technology
Ardealite is the discarded object of power boiler discharge of phosphorus chemical industry, and its main component is dihydrate gypsum（CaSO42H2O）With half water
Gypsum（CaSO4·0.5H2O）.According to incompletely statistics, China's ardealite year total emission volumn exceedes fifty-five million ton（Butt meter）, add up
Volume of cargo in storage exceedes 2.5 hundred million tons.With the development of China's high concentration phosphate fertilizer, the discharge capacity of ardealite will be increasing.Current phosphorus stone
Cream mainly using processing mode is stacked, not only occupies substantial amounts of soil, wastes the sulphur and calcium resource of preciousness, can more cause tight
The environmental pollution of weight, constrains the development of sulphur dioxide of phosphor chemical industry to a certain degree.Although the comprehensive utilization to ardealite is carried out both at home and abroad
Extensive research, but its utilization rate is not still high, only 10%.Therefore, urgent need to resolve ardealite stacks problem, to realize phosphatization
Lasting, the stable and sound development of work industry.
It is one of most potential research method using ardealite production sulfuric acid, but still suffers from larger defect.Industrial phosphorus
The method of producing sulfate acid from gypsum mainly uses reductive coke ardealite, and its reaction principle is mainly C and CaSO4Redox
Reaction, but because the reactivity ratio of coke is relatively low, the contact surface with ardealite is small, makes the decomposition temperature of ardealite high, reaction
Energy consumption is big.In addition, being also related to reducibility gas（Such as CH4、CO、H2）And sulphur reduces the research of ardealite, but its process is multiple
High and ardealite the decomposition temperature reduction of miscellaneous, production cost is not obvious（More than 1100 DEG C）, do not obtain popularity application so far.
Also sulphur reduces the research of ardealite Sulphuric acid, such as Sichuan University is on the basis of ardealite comprehensive utilizating research is carried out, rate
The method that sulphur reduces ardealite Sulphuric acid is first proposed, but this method uses sulphur as reducing agent, had both improved and has been produced into
This does not meet China's Sulphur ressource big situation in short supply yet.In addition, the ardealite taken at present produces the technical method of sulfuric acid, to it
Tailings is mainly used for co-producing cement, but the production capacity that faces of cement industry it is serious superfluous the problem of, also greatly hinder above-mentioned
Effective popularization of technology.
" one kind utilizes biomass reduction decomposing phosphogypsum Sulphuric acid "（CN201110097225.X）Patented technology, propose
Produced using biomass material as reducing agent decomposing phosphogypsum Sulphuric acid, but this method just with biomass incomplete oxidation
Reducibility gas make reducing agent, catalyst content is few in its ash content, and catalytic effect is not obvious, still suffers from greater energy consumption.It is " a kind of
The method of ardealite is catalytically decomposed "（CN201410095622.7）Patented technology, propose to be used as reducing agent using charring rice husk
Decomposing phosphogypsum, but this method does not carry out high value added utilization for the tailings that Sulphuric acid is remained, and there is tailings utilization rate not
High the problem of.
The content of the invention
It is contemplated that overcoming prior art defect, it is therefore an objective to provide a kind of decomposing phosphogypsum and prepare porous building-brick and sulfuric acid
Method, this method production cost is low, energy consumption is small and sulphur high conversion rate, can be efficiently using reacting tailings system while production sulfuric acid
Standby porous building-brick, the porous building-brick bulk density of preparation is small and low thermal conductivity.
To achieve the above object, the technical solution adopted by the present invention is：First with 60 ~ 90wt% ardealite and 10 ~ 40wt%
Charring rice husk be raw material, the additional 0.5 ~ 2.0wt% of raw material water reducer and the water of the 50 ~ 100wt% of raw material, mixing 3 ~
5min, is made pug.Then the foam made by the additional 0.5 ~ 1.0wt% of raw material foaming agent, stirs, then additional
The gel of the 1.0 ~ 2.5wt% of raw material, stirs 3 ~ 5min, and cast molding spontaneously dries 1 ~ 3h, the demoulding.Finally at 110 DEG C
Under the conditions of dry 5 ~ 10h, 5 ~ 10h is toasted under the conditions of 160 ~ 180 DEG C, porous preforming block is made.
Obtained porous preforming block is subjected to cartalytic decomposition effect under the conditions of nitrogen atmosphere and 800 ~ 1000 DEG C, is made many
Hole building block and sulfur dioxide gas；Obtained sulfur dioxide is oxidized and absorption produces sulfuric acid.
CaSO in the ardealite4≥50wt%；Particle diameter≤0.200mm.
The Main chemical component of the charring rice husk is：C >=10wt%, SiO2≥30wt%；Particle diameter≤0.200mm.
The water reducer is one or more of sodium tripolyphosphate, calgon.
The gel is one kind in silica sol, alumina sol, aluminium Ludox.
Due to using above-mentioned technical proposal, the present invention has the following advantages that compared with prior art：
（1）Because the reducing agent that uses of the present invention is agricultural wastes rice husk through charring rice husk, its source obtained by light-burned
It is extensively and with low cost, therefore the production cost of the present invention is relatively low.
（2）Because the charring rice husk of the invention used is natural porous structure, with larger specific surface area, can effectively it increase
Plus the contact surface between charring rice husk and ardealite, so as to reduce reaction temperature, reduce energy consumption.
（3）The main chemical compositions of charring rice husk of the present invention are C and SiO2, C can be used as decomposing phosphogypsum
Reducing agent, and SiO2Can as decomposing phosphogypsum effective catalyst, can further reduce the reaction temperature of decomposing ardealite, and
The conversion ratio of sulphur in ardealite is improved, the conversion ratio of sulphur is 70 ~ 80wt%.
（4）The present invention prepares porous preforming block using charring rice husk and ardealite, by porous preforming block in nitrogen atmosphere and
Cartalytic decomposition effect is carried out under the conditions of 800 ~ 1000 DEG C, while preparing porous building-brick and sulfur dioxide, can effectively be realized in production
Reaction tailings is efficiently utilized while sulfuric acid, the bulk density of prepared porous building-brick is 0.5 ~ 1.0g/cm3, lead
Hot coefficient is 0.3 ~ 0.6 W/mK, and compressive resistance is 2.5 ~ 5.0MPa.
Therefore, production cost of the present invention is low, energy consumption is small and sulphur high conversion rate, and reaction can be efficiently utilized while production sulfuric acid
Tailings prepares porous building-brick, and the porous building-brick bulk density of preparation is small and low thermal conductivity.
Embodiment
With reference to embodiment, the invention will be further described, not to the limitation of its protection domain.
To avoid repeating, by the raw material ardealite and charring rice husk Unify legislation employed in present embodiment such as first
Under, repeated no more in embodiment：
CaSO in the ardealite4≥50wt%；Particle diameter≤0.200mm.
The Main chemical component of the charring rice husk is：C >=10wt%, SiO2≥30wt%；Particle diameter≤0.200mm.
Embodiment 1
A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid.First with 60 ~ 70wt% ardealite and 30 ~ 40wt%
Charring rice husk be raw material, the additional 0.5 ~ 1.0wt% of raw material sodium tripolyphosphate and the water of the 70 ~ 100wt% of raw material, mix
3 ~ 5min is closed, pug is made.Then the foam made by the additional 0.7 ~ 1.0wt% of raw material foaming agent, stirs, then
Additional 1.0 ~ the 1.5wt% of raw material gel, stirs 3 ~ 5min, and cast molding spontaneously dries 1 ~ 3h, the demoulding.Finally exist
5 ~ 10h is dried under the conditions of 110 DEG C, 5 ~ 10h is toasted under the conditions of 160 ~ 180 DEG C, porous preforming block is made.
Obtained porous preforming block is subjected to cartalytic decomposition effect under the conditions of nitrogen atmosphere and 800 ~ 900 DEG C, is made many
Hole building block and sulfur dioxide gas；Obtained sulfur dioxide is oxidized and absorption produces sulfuric acid.
Gel is silica sol in the present embodiment.
Embodiment 2
A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid.The present embodiment is alumina sol except gel
Outside, remaining be the same as Example 1.
Embodiment 3
A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid.The present embodiment except gel be aluminium Ludox in addition to,
Remaining be the same as Example 1.
In the present embodiment 1-3：The conversion ratio of sulphur is 76 ~ 80wt% in ardealite；The bulk density of prepared porous building-brick
For 0.5 ~ 0.8g/cm3, thermal conductivity factor is 0.3 ~ 0.4W/mK, and compressive resistance is 2.5 ~ 4.0MPa.
Embodiment 4
A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid.First with 70 ~ 80wt% ardealite and 20 ~ 30wt%
Charring rice husk be raw material, the additional 1.0 ~ 1.5wt% of raw material sodium tripolyphosphate and the water of the 60 ~ 90wt% of raw material, mix
3 ~ 5min is closed, pug is made.Then the foam made by the additional 0.6 ~ 0.9wt% of raw material foaming agent, stirs, then
Additional 1.5 ~ the 2.0wt% of raw material gel, stirs 3 ~ 5min, and cast molding spontaneously dries 1 ~ 3h, the demoulding.Finally exist
5 ~ 10h is dried under the conditions of 110 DEG C, 5 ~ 10h is toasted under the conditions of 160 ~ 180 DEG C, porous preforming block is made.
Obtained porous preforming block is subjected to cartalytic decomposition effect under the conditions of nitrogen atmosphere and 850 ~ 950 DEG C, is made many
Hole building block and sulfur dioxide gas；Obtained sulfur dioxide is oxidized and absorption produces sulfuric acid.
Gel is silica sol in the present embodiment.
Embodiment 5
A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid.Except gel is alumina sol in the present embodiment
Outside, remaining be the same as Example 4.
Embodiment 6
A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid.Except gel is aluminium Ludox in the present embodiment
Outside, remaining be the same as Example 4.
In the present embodiment 4-6：The conversion ratio of sulphur is 73 ~ 77wt% in ardealite；The bulk density of prepared porous building-brick
For 0.6 ~ 0.9g/cm3, thermal conductivity factor is 0.4 ~ 0.5W/mK, and compressive resistance is 3.0 ~ 4.5MPa.
Embodiment 7
A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid.First with 80 ~ 90wt% ardealite and 10 ~ 20wt%
Charring rice husk be raw material, it is the additional 0.5 ~ 1.0wt% of raw material sodium tripolyphosphate, the six of the 0.5 ~ 1.0wt% of raw material inclined
The water of sodium phosphate and the 50 ~ 80wt% of raw material, mixes 3 ~ 5min, pug is made.Then the additional 0.5 ~ 0.8wt% of raw material
Foam made by foaming agent, stirs, then the additional 2.0 ~ 2.5wt% of raw material gel, stir 3 ~ 5min, casting
Shaping, spontaneously dries 1 ~ 3h, the demoulding.5 ~ 10h is finally dried under the conditions of 110 DEG C, 5 ~ 10h is toasted under the conditions of 160 ~ 180 DEG C,
Porous preforming block is made.
Obtained porous preforming block is subjected to cartalytic decomposition effect under the conditions of nitrogen atmosphere and 900 ~ 1000 DEG C, is made many
Hole building block and sulfur dioxide gas；Obtained sulfur dioxide is oxidized and absorption produces sulfuric acid.
Gel is silica sol in the present embodiment.
Embodiment 8
A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid.Except gel is alumina sol in the present embodiment
Outside, remaining be the same as Example 7.
Embodiment 9
A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid.Except gel is aluminium Ludox in the present embodiment
Outside, remaining be the same as Example 7.
In the present embodiment 7-9：The conversion ratio of sulphur is 70 ~ 74wt% in ardealite；The bulk density of prepared porous building-brick
For 0.7 ~ 1.0g/cm3, thermal conductivity factor is 0.5 ~ 0.6W/mK, and compressive resistance is 3.5 ~ 5.0MPa.
Present embodiment has the following advantages that compared with prior art：
（1）The reducing agent used due to present embodiment is agricultural wastes rice husk through charring rice husk obtained by light-burned, its
Wide material sources and with low cost, therefore present embodiment technical scheme has relatively low production cost.
（2）The charring rice husk used due to present embodiment, with larger specific surface area, can have for natural porous structure
Contact surface between effect increase charring rice husk and ardealite, so as to reduce reaction temperature, reduces energy consumption.
（3）The main chemical compositions for the charring rice husk that present embodiment is used is C and SiO2, C can as decompose phosphorus stone
The reducing agent of cream, and SiO2Can as decomposing phosphogypsum effective catalyst, can further reduce the reaction temperature of decomposing ardealite
Degree, and the conversion ratio of sulphur in ardealite is improved, the conversion ratio of sulphur is 70 ~ 80wt%.
（4）Present embodiment prepares porous preforming block using charring rice husk and ardealite first, by porous preforming block in nitrogen
Cartalytic decomposition effect is carried out under the conditions of gas atmosphere and 900-1000 DEG C, while porous building-brick and sulfur dioxide are prepared, can be effectively real
Reaction tailings is efficiently utilized while production sulfuric acid now, the bulk density of prepared porous building-brick is 0.5 ~
1.0g/cm3, thermal conductivity factor is 0.3 ~ 0.6W/mK, and compressive resistance is 2.5 ~ 5.0MPa.
Therefore, present embodiment production cost is low, energy consumption is small and sulphur high conversion rate, can efficiently be utilized while production sulfuric acid
Reaction tailings prepares porous building-brick, and the porous building-brick bulk density of preparation is small and low thermal conductivity.
Claims (5)
1. a kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid, it is characterised in that first with 60 ~ 90wt% ardealite and
10 ~ 40wt% charring rice husk is raw material, the additional 0.5 ~ 2.0wt% of raw material water reducer and the 50 ~ 100wt%'s of raw material
Water, mixes 3 ~ 5min, pug is made；Then the foam made by the additional 0.5 ~ 1.0wt% of raw material foaming agent, stirs equal
It is even, then the additional 1.0 ~ 2.5wt% of raw material gel, stir 3 ~ 5min, cast molding, spontaneously dry 1 ~ 3h, the demoulding；Most
5 ~ 10h is dried under the conditions of 110 DEG C afterwards, 5 ~ 10h is toasted under the conditions of 160 ~ 180 DEG C, porous preforming block is made；
Obtained porous preforming block is subjected to cartalytic decomposition effect under the conditions of nitrogen atmosphere and 800 ~ 1000 DEG C, is made porous and builds
Block and sulfur dioxide gas；Obtained sulfur dioxide is oxidized and absorption produces sulfuric acid.
2. the method that decomposing phosphogypsum as claimed in claim 1 prepares porous building-brick and sulfuric acid, it is characterised in that the phosphorus stone
CaSO in cream4≥50wt%；Particle diameter≤0.200mm.
3. the method that decomposing phosphogypsum as claimed in claim 1 prepares porous building-brick and sulfuric acid, it is characterised in that the charing
The Main chemical component of rice husk is：C >=10wt%, SiO2≥30wt%；Particle diameter≤0.200mm.
4. the method that decomposing phosphogypsum as claimed in claim 1 prepares porous building-brick and sulfuric acid, it is characterised in that the diminishing
Agent is one or more of sodium tripolyphosphate, calgon.
5. the method that decomposing phosphogypsum as claimed in claim 1 prepares porous building-brick and sulfuric acid, it is characterised in that the gel
Agent is one kind in silica sol, alumina sol, aluminium Ludox.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510718700.9A CN105272110B (en) | 2015-10-30 | 2015-10-30 | A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid |
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| CN201510718700.9A CN105272110B (en) | 2015-10-30 | 2015-10-30 | A kind of method that decomposing phosphogypsum prepares porous building-brick and sulfuric acid |
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| CN105272110B true CN105272110B (en) | 2017-08-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SU1328331A1 (en) * | 1983-06-03 | 1987-08-07 | Белорусский Политехнический Институт | Method of preparing asphalt-concrete mixture |
| CN101891160B (en) * | 2010-06-21 | 2011-10-26 | 尹小林 | Method for directly preparing sulfur trioxide and sulfuric acid from plaster |
| CN102515681B (en) * | 2011-12-12 | 2014-07-02 | 昆明理工大学 | Method for producing aerated building block with phosphogypsum as main raw material |
| CN103864024B (en) * | 2014-03-17 | 2016-01-27 | 武汉科技大学 | A kind of method of catalytic decomposition phosphogypsum |
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