CN115124062B - Desulfurization gypsum recycling comprehensive utilization system and process - Google Patents
Desulfurization gypsum recycling comprehensive utilization system and process Download PDFInfo
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- 239000010440 gypsum Substances 0.000 title claims abstract description 56
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 56
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 40
- 230000023556 desulfurization Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 30
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 66
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 58
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 33
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 29
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 27
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 26
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 26
- 238000010521 absorption reaction Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 45
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 24
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 24
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 13
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003546 flue gas Substances 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 238000003795 desorption Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000011268 mixed slurry Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 2
- 238000000197 pyrolysis Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geology (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a desulfurization gypsum recycling comprehensive utilization system and process, comprising a double decomposition reaction tower, a solid-liquid separator and a hypergravity reactor which are sequentially connected, wherein the double decomposition reaction tower is respectively connected with a carbon dioxide source, an ammonia water source and a desulfurization gypsum slurry source; the solid-liquid separator is connected with an ammonia water source through a thermal decomposition reaction kettle, and the thermal decomposition reaction kettle is connected with an acid absorption tower. The invention converts the desulfurization gypsum into the nano calcium carbonate with high economic value, solves the problems of difficult treatment, low value and the like of the desulfurization gypsum in the past, and realizes the recycling utilization of the desulfurization gypsum.
Description
Technical Field
The invention belongs to the technical field of solid waste utilization, and particularly relates to a desulfurization gypsum recycling comprehensive utilization system and process.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The limestone-gypsum wet flue gas desulfurization technology is the desulfurization technology with the widest application range, the industrial desulfurization gypsum produced in China every year is more than 7000 ten thousand tons, the comprehensive utilization way of the desulfurization gypsum in China is single at the present stage, most of the desulfurization gypsum recycling processes are used for processing the desulfurization gypsum and selling as building materials, the limestone-gypsum wet flue gas desulfurization technology is mainly used as a cement retarder and used for producing novel wall materials such as gypsum boards, gypsum blocks and the like, and proper disposal of desulfurization byproducts-the desulfurization gypsum becomes a key influencing factor for restricting the development of industries.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a desulfurization gypsum recycling comprehensive utilization system and process. Under the condition of lower temperature, the carbon dioxide and the ammonia gas are utilized to react, the desulfurization gypsum is converted into nano calcium carbonate with higher economic value, and meanwhile, the concentrated sulfuric acid is prepared, so that the harmless treatment and the recycling of the desulfurization gypsum are realized.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a desulfurization gypsum recycling comprehensive utilization system, which comprises a double decomposition reaction tower, a solid-liquid separator and a hypergravity reactor which are sequentially connected, wherein,
the double decomposition reaction tower is respectively connected with a carbon dioxide source, an ammonia water source and a desulfurized gypsum slurry source;
the solid-liquid separator is connected with an ammonia water source through a thermal decomposition reaction kettle, and the thermal decomposition reaction kettle is connected with an acid absorption tower.
In a second aspect, the invention provides a desulfurization gypsum recycling comprehensive utilization process, which comprises the following steps:
carrying out double decomposition reaction on desulfurized gypsum slurry, carbon dioxide and ammonia water to obtain ammonium sulfate and calcium carbonate mixed slurry, and conveying the mixed slurry to a solid-liquid separator for solid-liquid separation to obtain ammonium sulfate aqueous solution and calcium carbonate solid;
adding calcium carbonate solid into a hypergravity reactor to prepare nano calcium carbonate;
the ammonium sulfate aqueous solution is thermally decomposed to prepare ammonia gas, sulfur trioxide gas and water vapor, the ammonia gas and the water vapor are mixed and absorbed to obtain ammonia water, and the ammonia water is recycled to the double decomposition step;
absorbing the sulfur trioxide gas to obtain concentrated sulfuric acid.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
(1) The invention converts the desulfurization gypsum into the nano calcium carbonate with high economic value, solves the problems of difficult treatment, low value and the like of the desulfurization gypsum in the past, and realizes the recycling utilization of the desulfurization gypsum. The gypsum double decomposition reaction process can be carried out under normal temperature without heating.
(2) Carbon dioxide required in the process treatment is sourced from flue gas discharged by a boiler, so that carbon dioxide emission reduction can be realized. Ammonia gas is prepared from urea, and cyanuric acid with high economic value is generated. Ammonia gas required by the gypsum double decomposition reaction is generated by urea pyrolysis and ammonium sulfate pyrolysis, which are both prepared on site, so that potential safety hazards caused by using liquid ammonia are avoided.
And (3) pyrolyzing the ammonium sulfate to prepare ammonia water and concentrated sulfuric acid. Ammonia water can be recycled to the gypsum double decomposition reaction tower, concentrated sulfuric acid can be recycled to the cyanuric acid pickling device, and recycling and self-supply of process materials are realized.
(3) The whole process treatment process has no pollutant and waste, and is green and environment-friendly; the reaction temperature in the whole process treatment is low, the highest reaction temperature is only 300-350 ℃, and the operation safety is high.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the invention provides a desulfurization gypsum recycling comprehensive utilization system, which comprises a double decomposition reaction tower, a solid-liquid separator and a hypergravity reactor which are sequentially connected, wherein,
the double decomposition reaction tower is respectively connected with a carbon dioxide source, an ammonia water source and a desulfurized gypsum slurry source;
the solid-liquid separator is connected with an ammonia water source through a thermal decomposition reaction kettle, and the thermal decomposition reaction kettle is connected with an acid absorption tower.
In some embodiments, the ammonia source comprises a thermal decomposition device and an ammonia absorption tower connected to each other, the thermal decomposition device being connected to a urea source; the ammonia absorption tower is connected with the thermal decomposition reaction kettle.
Preferably, the thermal decomposition device is connected with a pickling device, and the pickling device is connected with a thermal decomposition reaction kettle. The method is used for washing cyanuric acid obtained by thermal decomposition of urea, and an ammonium sulfate solution obtained by washing is introduced into a thermal decomposition reaction kettle for thermal decomposition to obtain ammonia gas and sulfur trioxide.
In some embodiments, the carbon dioxide source comprises a carbon absorber and a carbon desorber interconnected, the carbon absorber being filled with an adsorbent layer that is connected to the flue gas source, the carbon desorber being connected to the metathesis tower.
The carbon dioxide in the flue gas is adsorbed and enriched by the carbon absorption tower, and the saturated adsorbent is transferred into the carbon desorption tower for desorption, so that the concentration of the carbon dioxide can be increased, and the flue gas can be effectively utilized.
In a second aspect, the invention provides a desulfurization gypsum recycling comprehensive utilization process, which comprises the following steps:
carrying out double decomposition reaction on desulfurized gypsum slurry, carbon dioxide and ammonia water to obtain ammonium sulfate and calcium carbonate mixed slurry, and conveying the mixed slurry to a solid-liquid separator for solid-liquid separation to obtain ammonium sulfate aqueous solution and calcium carbonate solid;
and adding the calcium carbonate solid into a hypergravity reactor to prepare nano calcium carbonate, wherein the hypergravity reactor has the functions of heating, drying and hypergravity grinding, and then, in the process of drying the calcium carbonate solid obtained by solid-liquid separation, steam generated in the solid has a crushing effect on particles, and then, under the action of hypergravity grinding, the hyperfine nano calcium carbonate is obtained.
The nano calcium carbonate is mature in application in high-grade plastic products, can be used for PVC (polyvinyl chloride) acceleration sol for sealing the inside of an automobile, and can improve rheological property and formability of plastic master batches. The plastic filler has the functions of toughening and reinforcing, improves the bending strength and bending elastic modulus, the heat distortion temperature and the dimensional stability of the plastic, and also ensures that the plastic has the performances of heat retention and the like.
In addition, the nano calcium carbonate can be used in ink products, paper industry, rubber industry, feed industry and the like.
The traditional preparation method of nano calcium carbonate is to introduce carbon dioxide gas into calcium hydroxide suspension for carbonization, and adjust the nucleation rate by controlling parameters such as system temperature, carbon dioxide flow and the like, so that the preparation method is more complicated, the process parameter control is more strict, and the preparation cost is higher.
The ammonium sulfate aqueous solution is subjected to thermal decomposition to prepare ammonia gas, sulfur trioxide gas and water vapor, and the thermal decomposition of the ammonium sulfate aqueous solution adopts staged intermittent operation;
firstly, under the temperature of 200-250 ℃, ammonium sulfate is pyrolyzed to obtain ammonia gas and water vapor, the ammonia gas and the water vapor are mixed and absorbed to obtain ammonia water, and the ammonia water is recycled to the double decomposition step;
and then continuously pyrolyzing at the temperature of 300-350 ℃ to obtain sulfur trioxide gas, and absorbing the sulfur trioxide gas to obtain concentrated sulfuric acid.
In some embodiments, the solids content of the desulfurized gypsum slurry is from 20% to 30%. The desulfurization slurry with higher concentration is beneficial to improving the material reaction rate, reducing the water content of the subsequent ammonium sulfate solution and reducing the energy consumption of the thermal decomposition unit; however, too high concentration of the desulfurization slurry is not suitable, and the too high concentration of the slurry is easy to cause the supersaturation of the ammonium sulfate solution, so that the ammonium sulfate is crystallized and separated out in advance.
In some embodiments, the method of producing carbon dioxide is: firstly, absorbing and enriching carbon dioxide in the flue gas by adopting an absorbing filler, and then desorbing the saturated absorbing filler to obtain high-concentration carbon dioxide gas.
Preferably, the catalyst used in the desorption process of carbon dioxide is a transition metal oxide, a solid super acid catalyst or a carrier-supported super acid catalyst.
Preferably, the adsorption filler is selected from natural zeolite, molecular sieve, activated alumina, silica gel or carbon-based adsorbent.
In some embodiments, the ammonia water is prepared by catalytic pyrolysis of urea to generate ammonia and cyanuric acid, the generated ammonia enters an ammonia absorption tower to prepare 15-30% ammonia water, and cyanuric acid is pickled to prepare cyanuric acid product.
The invention is further described below with reference to the drawings and examples.
As shown in figure 1, the desulfurization gypsum comprehensive utilization process route comprises five units, namely a carbon dioxide enrichment unit, a urea pyrolysis unit, a gypsum double decomposition reaction unit, an ammonium sulfate pyrolysis unit and a nano calcium carbonate preparation unit.
The reaction processes of the five units are described below, respectively.
(1) Carbon dioxide enrichment unit
The carbon dioxide enrichment unit comprises a carbon adsorption tower and a carbon desorption tower. Firstly, introducing flue gas discharged by a coal-fired boiler into a carbon adsorption tower, wherein adsorption filler is filled in the tower, the adsorption filler is natural zeolite, and the adsorption filler absorbs carbon dioxide in the flue gas.
And transferring the adsorption filler with saturated adsorption into a carbon desorption tower, adding a transition metal oxide catalyst, uniformly mixing the catalyst and the adsorption filler with saturated adsorption in the carbon desorption tower by using a stirring device, and performing catalytic desorption under the action of the catalyst to obtain carbon dioxide gas with higher concentration. Through the unit operation, the concentration of carbon dioxide in the flue gas can be purified from 10% to more than 90%.
(2) Urea pyrolysis unit
The urea pyrolysis unit comprises a pyrolysis device, an ammonia absorption tower and an acid washer. Firstly, fully mixing urea and a catalyst, quantitatively adding the mixture into a pyrolysis device, and heating the mixture to 220-300 ℃ to generate ammonia and cyanuric acid. The generated ammonia enters an ammonia absorption tower to prepare ammonia water with the concentration of 15-30 percent. The produced cyanuric acid enters a pickling device and is washed by sulfuric acid with the concentration of 20 percent to prepare cyanuric acid products with the purity of more than 98.5 percent, and the cyanuric acid products are sold as high value-added products.
(3) Gypsum double decomposition reaction unit
The gypsum double decomposition reaction unit comprises a double decomposition reaction tower and a solid-liquid separator. Preparing the desulfurized gypsum into slurry with the concentration of 20-30% in a double decomposition reaction tower, and then adding ammonia water prepared by a urea pyrolysis unit and carbon dioxide gas extracted by a carbon dioxide enrichment unit.
The reaction process in the double decomposition reaction tower can be carried out at normal temperature, gypsum is converted into mixed slurry of ammonium sulfate and calcium carbonate under the action of a catalyst, wherein the catalyst is an inorganic catalyst, and the mixed slurry is conveyed to a solid-liquid separator for separation to obtain an ammonium sulfate aqueous solution and calcium carbonate solid.
(4) Ammonium sulfate pyrolysis unit
The ammonium sulfate pyrolysis unit comprises a thermal decomposition reaction kettle and an acid absorption tower. Introducing an ammonium sulfate aqueous solution prepared by a gypsum double decomposition reaction unit into a thermal decomposition reaction kettle, firstly pyrolyzing the ammonium sulfate at the temperature of 200-250 ℃ to obtain ammonia gas and water vapor, and introducing the ammonia gas into an ammonia gas absorption tower of a urea pyrolysis unit to prepare ammonia water with the concentration of 15-30%, thereby realizing cyclic utilization;
and then continuously pyrolyzing at the temperature of 300-350 ℃ to obtain sulfur trioxide gas, and enabling the sulfur trioxide gas to enter an acid absorption tower for absorption to obtain concentrated sulfuric acid. Part of the concentrated sulfuric acid is recycled to the acid washer of the urea pyrolysis unit, so that the recycling is realized, and part of the concentrated sulfuric acid can be used as a product for sale.
(5) Nanometer calcium carbonate preparation unit
The nano calcium carbonate preparation unit comprises a hypergravity reactor, a dryer and the like. The calcium carbonate solid prepared by the gypsum double decomposition reaction unit is input into a hypergravity reactor to prepare nano calcium carbonate, the mass content of the calcium carbonate is more than 80 percent, and the average particle size is less than 100nm, so that the nano calcium carbonate can be used as a product for sale.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A desulfurization gypsum recycling comprehensive utilization process is characterized in that: the method comprises the following steps:
carrying out double decomposition reaction on desulfurized gypsum slurry, carbon dioxide and ammonia water to obtain ammonium sulfate and calcium carbonate mixed slurry, and conveying the mixed slurry to a solid-liquid separator for solid-liquid separation to obtain ammonium sulfate aqueous solution and calcium carbonate solid;
adding calcium carbonate solid into a hypergravity reactor to prepare nano calcium carbonate;
firstly, under the temperature of 200-250 ℃, ammonium sulfate is pyrolyzed to obtain ammonia gas and water vapor, the ammonia gas and the water vapor are mixed and absorbed to obtain ammonia water, and the ammonia water is recycled to the double decomposition step;
then continuously pyrolyzing at 300-350 ℃ to obtain sulfur trioxide gas, and absorbing the sulfur trioxide gas to obtain concentrated sulfuric acid;
the preparation method of the carbon dioxide comprises the following steps: firstly, absorbing and enriching carbon dioxide in flue gas by adopting an absorbing filler, and then desorbing the saturated absorbing filler to obtain high-concentration carbon dioxide gas;
the preparation method of the ammonia water comprises the steps of catalytically pyrolyzing urea to generate ammonia and cyanuric acid, enabling the generated ammonia to enter an ammonia absorption tower to prepare 15-30% ammonia water by mass percent, and pickling cyanuric acid to prepare cyanuric acid products;
the adopted desulfurization gypsum recycling comprehensive utilization system comprises a double decomposition reaction tower, a solid-liquid separator and a hypergravity reactor which are connected in sequence, wherein,
the double decomposition reaction tower is respectively connected with a carbon dioxide source, an ammonia water source and a desulfurized gypsum slurry source;
the solid-liquid separator is connected with an ammonia water source through a thermal decomposition reaction kettle, and the thermal decomposition reaction kettle is connected with an acid absorption tower.
2. The desulfurization gypsum recycling comprehensive utilization process according to claim 1, characterized in that: the ammonia water source comprises a thermal decomposition device and an ammonia absorption tower which are connected with each other, and the thermal decomposition device is connected with a urea source; the ammonia absorption tower is connected with the thermal decomposition reaction kettle.
3. The desulfurization gypsum recycling comprehensive utilization process according to claim 2, characterized in that: the thermal decomposition device is connected with the acid washing device, and the acid washing device is connected with the thermal decomposition reaction kettle.
4. The desulfurization gypsum recycling comprehensive utilization process according to claim 1, characterized in that: the carbon dioxide source comprises a carbon absorption tower and a carbon desorption tower which are connected with each other, an adsorbent layer is filled in the carbon absorption tower, the adsorbent layer is connected with the flue gas source, and the carbon desorption tower is connected with the double decomposition reaction tower.
5. The desulfurization gypsum recycling comprehensive utilization process according to claim 1, characterized in that: the solid content in the desulfurized gypsum slurry is 20% -30%.
6. The desulfurization gypsum recycling comprehensive utilization process according to claim 1, characterized in that: the catalyst adopted in the carbon dioxide desorption process is transition metal oxide and solid super acidic catalyst.
7. The desulfurization gypsum recycling comprehensive utilization process according to claim 1, characterized in that: the catalyst adopted in the carbon dioxide desorption process is a carrier-supported super acidic catalyst.
8. The desulfurization gypsum recycling comprehensive utilization process according to claim 1, characterized in that: the adsorption filler is selected from natural zeolite, activated alumina, silica gel or carbon-based adsorbent.
9. The desulfurization gypsum recycling comprehensive utilization process according to claim 1, characterized in that: the adsorption filler is a molecular sieve.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210718972.9A CN115124062B (en) | 2022-06-23 | 2022-06-23 | Desulfurization gypsum recycling comprehensive utilization system and process |
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| CN202210718972.9A CN115124062B (en) | 2022-06-23 | 2022-06-23 | Desulfurization gypsum recycling comprehensive utilization system and process |
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