CN116002741A - Quality improvement method for desulfurized gypsum - Google Patents
Quality improvement method for desulfurized gypsum Download PDFInfo
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- CN116002741A CN116002741A CN202310004196.0A CN202310004196A CN116002741A CN 116002741 A CN116002741 A CN 116002741A CN 202310004196 A CN202310004196 A CN 202310004196A CN 116002741 A CN116002741 A CN 116002741A
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- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 423
- 239000010440 gypsum Substances 0.000 title claims abstract description 423
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000006872 improvement Effects 0.000 title abstract description 62
- 239000002002 slurry Substances 0.000 claims abstract description 123
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 99
- 230000023556 desulfurization Effects 0.000 claims abstract description 99
- 239000013078 crystal Substances 0.000 claims abstract description 67
- 239000002245 particle Substances 0.000 claims abstract description 35
- 238000010521 absorption reaction Methods 0.000 claims abstract description 29
- 238000002425 crystallisation Methods 0.000 claims abstract description 21
- 230000008025 crystallization Effects 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 13
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 150000007524 organic acids Chemical group 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
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- 239000007788 liquid Substances 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
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- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- 239000003945 anionic surfactant Substances 0.000 description 1
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- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- -1 tricarboxylic acid organic acid Chemical class 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
The invention provides a desulfurization gypsum upgrading method. The quality improvement method of the desulfurized gypsum comprises the following steps: in the operation process of the desulfurization system, part of gypsum slurry in an absorption tower of the desulfurization system is sent to a gypsum upgrading box which is independently arranged outside the desulfurization system, seed crystals and crystallization promoters are added into the gypsum upgrading box for upgrading treatment, and the gypsum slurry after upgrading treatment is sent to a cyclone of the desulfurization system and a vacuum belt conveyor for separation and drying, so that high-quality desulfurized gypsum is obtained. According to the quality improvement method for the desulfurization gypsum, disclosed by the invention, the gypsum slurry is subjected to quality improvement treatment through the gypsum quality improvement boxes which are independently arranged outside the desulfurization system, so that high-quality desulfurization gypsum with larger particle size can be obtained, the quality of the desulfurization gypsum is improved efficiently, the normal operation of the desulfurization system can be ensured, and the method has the remarkable advantages of low cost, good quality improvement effect, high quality improvement efficiency, no influence on desulfurization efficiency and the like.
Description
Technical Field
The invention relates to the technical field of desulfurization, in particular to a desulfurization gypsum upgrading method.
Background
At present, the total amount of the industrial byproduct gypsum in China is about 200Mt, wherein the yield of the desulfurized gypsum is 39%, the comprehensive utilization rate is about 80%, and the product has the highest utilization rate in all byproduct gypsum. Compared with natural gypsum, the qualified industrial byproduct gypsum has the advantages of high purity, stable components, compact structure and the like, and if the industrial byproduct gypsum can be comprehensively utilized, the natural gypsum exploitation, the resource saving, the ecological environment damage and pollution in the exploitation and transportation process can be reduced, and the accumulated occupied area can be reduced.
Along with the popularization of the wastewater zero-discharge technology, high-salt high-chlorine wastewater is discharged into an absorption tower of a desulfurization system, so that the produced desulfurization gypsum has the problems of small particle size, difficult dehydration, high water content and the like, the safe operation of the desulfurization system is influenced, and the comprehensive utilization and market price of the desulfurization gypsum as a building gypsum raw material are also influenced. Therefore, it is necessary to upgrade the desulfurized gypsum.
The quality improvement measures of the desulfurization gypsum of the prior desulfurization system mainly comprise: 1) Optimizing a desulfurizing tower slurry supply system: the method mainly adjusts parameters of the desulfurization slurry, and is mostly applied to the conditions of over-high supersaturation ratio of the desulfurization slurry, insufficient oxidation wind and the like; 2) Improving the water supply quality: when the quality of the water supply is poor, COD, ammonia nitrogen and Cl in the water supply - Exceeding the standard of hardness or the like can negatively affect the desulfurization system and the quality of gypsum, such as Cl in water - An out of specification will result in Cl in the absorber slurry - When the COD content exceeds the standard, the slurry of the absorption tower is foamed, so that the normal adjustment of a desulfurization system is influenced, and the quality of the desulfurized gypsum is seriously influenced; therefore, the water quality directly entering the desulfurization system needs to be controlled, and generally, the water supply is required to contain no oil substances, the total hardness is less than or equal to 450mg/L, the chloride ion is less than or equal to 300mg/L, the COD is less than or equal to 30mg/L, the ammonia nitrogen is less than or equal to 10mg/L, and the anionic surfactant is less than or equal to 0.5mg/L; 3) Replacement of desulfurization slurry: in this way, two adjacent desulfurization towers that are operated separately are provided in a power plant, and when the gypsum quality in one desulfurization tower is deteriorated, desulfurization slurry in the adjacent desulfurization tower is introduced into the other desulfurization tower through a pump and a pipe.
Although the quality improvement mode of the desulfurized gypsum can be realizedThe quality of the desulfurized gypsum is improved to some extent, however, the following drawbacks still exist: 1) The adjustment speed of the optimization mode of the slurry supply system of the desulfurizing tower is slower, the quality improvement effect is not obvious, the quality improvement efficiency is poor, the operation process is required to meet the environmental protection requirement, the desulfurizing efficiency is generally considered, and the adjustment is carried out to ensure the SO at the outlet 2 The concentration is below the emission limit, but is not aimed at improving the gypsum quality, so the quality of the desulfurized gypsum cannot be well ensured; 2) In the mode of improving the water supply quality, the water supply quality depends on factors such as chemical water treatment, and the like, so that specific requirements can not be made on water quality components entering a desulfurization system, and particularly under the background of zero emission of wastewater in a whole plant, high-salt high-chlorine water inevitably enters the desulfurization system, and the water supply quality is difficult to ensure; 3) The desulfurization slurry replacement mode cannot ensure the quality of replacement slurry when the slurry replacement is carried out, if the slurry quality of the two absorption towers is poor, the quality of the replaced slurry is still poor, the desulfurization gypsum is difficult to crystallize and the efficiency is poor, so the mode is generally only used for a starting process, but cannot be well used for a normal operation process.
In summary, the quality improving effect of the current quality improving method of the desulfurized gypsum is generally poor, the particle size of the generated desulfurized gypsum is still smaller, the D50 is mostly only about 30 mu m, and the quality of the desulfurized gypsum is still to be improved; meanwhile, the desulfurization gypsum produced by the mode has the problems of high water content, difficult dehydration and the like, and is difficult to dry by a vacuum belt conveyor, and meanwhile, the production efficiency of the desulfurization gypsum is greatly reduced; in addition, the existing method has the defects of high treatment cost, incapability of efficiently improving quality, stable operation of a desulfurization system and the like.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a desulfurization gypsum upgrading method which can efficiently improve the quality of desulfurization gypsum and ensure the normal operation of a desulfurization system.
The invention provides a desulfurization gypsum upgrading method, which comprises the following steps: in the operation process of the desulfurization system, part of gypsum slurry in an absorption tower of the desulfurization system is sent to a gypsum upgrading box which is independently arranged outside the desulfurization system, seed crystals and crystallization promoters are added into the gypsum upgrading box for upgrading treatment, and the gypsum slurry after upgrading treatment is sent to a cyclone of the desulfurization system and a vacuum belt conveyor for separation and drying, so that high-quality desulfurized gypsum is obtained.
According to the desulfurization gypsum upgrading method, the independent gypsum upgrading box is arranged outside the desulfurization system and used for efficiently improving the quality of gypsum, and part of gypsum slurry in the absorption tower of the desulfurization system is sent into the gypsum upgrading box for upgrading treatment, so that the quality of the desulfurization slurry can be independently regulated, and the normal operation of the desulfurization system is not influenced by the mode, so that the desulfurization effect of the desulfurization system is not influenced; in addition, the crystal seeds and the crystallization accelerator are added into the gypsum quality improvement box for quality improvement treatment, so that the growth of the gypsum crystal seeds is promoted, and the quality of the desulfurized gypsum is remarkably improved.
In the desulfurization gypsum upgrading method of the present invention, the desulfurization system is a conventional desulfurization system in the art, and a gypsum upgrading tank needs to be separately provided outside the desulfurization system. The desulfurization system mainly comprises an absorption tower, a cyclone and a vacuum belt conveyor, wherein the outlet end of the absorption tower is communicated with the inlet end of the cyclone through a liquid conveying pipeline, the vacuum belt conveyor is arranged at the outlet end of the cyclone, a quality improving pipeline is arranged outside the liquid conveying pipeline in parallel, a gypsum quality improving box is arranged on the quality improving pipeline, a gypsum slurry inlet, a seed crystal inlet, a hot water inlet, a crystallization accelerator inlet and a gypsum slurry outlet are formed in the gypsum quality improving box, and a stirring device is arranged in the gypsum quality improving box.
The invention does not limit the seed crystal adopted by the gypsum quality-improving box strictly; in particular, the seed crystal may be a gypsum seed crystal. Studies have shown that: by adding gypsum seed crystals into the gypsum upgrading box, the crystallization quality can be improved; specifically, the gypsum seed crystal has the effect of inducing nucleation, and the gypsum seed crystal can be added into the gypsum slurry to enable the gypsum slurry to form crystal nucleus under lower saturation degree, so that the gypsum seed crystal with thick particles is formed; the affinity of the surface of the crystal seed to sulfate ions and calcium ions separated out from the gypsum slurry is larger, the sulfate ions and the calcium ions in the gypsum slurry are preferentially attached to the gypsum crystal seed, and meanwhile, the nucleation and growth of gypsum on the wall surface can be avoided, so that scaling is reduced. The gypsum seed crystal also has the function of inducing crystallization, and promotes the growth of gypsum in the metastable area of gypsum slurry. The source of the gypsum seed is not critical and may be, for example, from a vacuum extractor belt or a pre-stored gypsum seed. The adding amount of the gypsum seed crystal is 5-10% of the mass of the gypsum slurry in the gypsum quality improving box, and the gypsum seed crystal can be added into the gypsum quality improving box from a seed crystal inlet above the gypsum quality improving box.
In addition, the invention does not impose strict limitation on the crystallization promoter; specifically, the crystallization accelerator may be an organic acid, preferably citric acid. Studies have shown that: citric acid has the effect of promoting gypsum crystal growth, probably for the following reasons: citric acid is tricarboxylic acid organic acid, and the interaction of carboxyl groups of the citric acid and sulfate molecules can change the morphology of crystals due to the crystal adjusting effect of the carboxylic acid groups in the citric acid on a crystal plane parallel to the c axis; the crystal adjusting effect of the citric acid is mainly realized by adsorption, and carboxyl and Ca 2+ The complexing action of the catalyst causes the organic acid to be adsorbed on the {111} surface of the gypsum, thereby promoting the growth of the gypsum. 3 carboxyl groups of citric acid are respectively combined with Ca 2+ Complexation takes place while Ca 2+ Has the ability to coordinate with 2 carboxyl groups simultaneously; thus, when citric acid and Ca on the gypsum surface 2+ At the time of complexing, 2 carboxyl groups are simultaneously combined with Ca 2+ Binding to form a multi-ring complex on the surface of gypsum, and binding Ca 2+ ，SO 4 2- And the diffusion and surface adsorption of (c) causes steric hindrance. The {111} plane of gypsum is mainly composed of Ca 2+ The organic acid selectively adsorbs the crystal face through complexation to inhibit the growth of the crystal face in the direction of the c axis, the different axial growth rates are different, and the growth of the long axis is inhibited, so that the crystal is changed from needle shape to short column shape. The citric acid adsorption reduces the crystal face energy of gypsum, increases the nucleation barrier, and the crystal nucleus has sufficient time and space growth, so that the crystal size can be obviously increased. That is, citric acid has the effect of promoting gypsum crystal growth.
In particular, the pH of the gypsum slurry in the gypsum upgrading tank can be controlled to between 4 and 6, preferably 5, by the addition of citric acid. Studies have shown that: pH mainlyBy influencing SO 2 Dissolution and absorption and calcium carbonate dissolution affect gypsum quality, SO at too high pH values 2 The dissolution and absorption of calcium carbonate are increased, but the dissolution process of calcium carbonate and the oxidation of calcium sulfite are inhibited, the sulfite is increased, the calcium ions are reduced to be unfavorable for the nucleation of gypsum, and the supersaturation ratio is reduced to be unfavorable for the growth of gypsum; at too low a pH, calcium carbonate is dissolved more, but SO 2 Is inhibited and pushes SO 2 The difference between the dissolution and absorption concentration of (c) disappears, calcium ions are increased but sulfate ions are reduced, which is unfavorable for the nucleation of gypsum, and the supersaturation ratio is reduced, which is unfavorable for the growth of gypsum. Therefore, the pH can be controlled in the above-mentioned proper range to further improve the quality of the desulfurized gypsum.
In addition, an increase in pH can also affect the solubility of the desulfurized gypsum. When the pH value is raised, [ OH ] in the slurry - ]Increase to form Ca (OH) )2 Or [ CaOH ] + ]The possibility of the crystallization solution of calcium sulfate is increased, and the supersaturation degree of the crystallization solution of calcium sulfate is reduced, so that the crystallization nucleation of calcium sulfate dihydrate is inhibited; pH decreases, [ HSO ] 4 - ]The possibility of existence also increases, caSO in an acidic medium 4 The solubility of (c) increases gradually and the supersaturation decreases gradually, resulting in a decrease in nucleation rate. Impurity ion [ HSO ] when pH is controlled to 4-6 4 - ][ CaOH ] + ]The influence of the calcium sulfate dihydrate is negligible, so that the induction time of gypsum crystallization is reduced instead, and the increase of the nucleation rate of the calcium sulfate dihydrate is facilitated. Thus, controlling the pH in the proper range of 4-6 facilitates gypsum crystallization. By controlling the pH of the gypsum slurry to between 4 and 6 by adding citric acid, a favorable environment for gypsum crystal growth can be ensured.
In the present invention, the density of the gypsum slurry in the gypsum upgrading tank can be controlled to be 50-150kg/m higher than that in the absorption tower of the desulfurization system 3 . Studies have shown that: the gypsum slurry in the gypsum upgrading box has too low liquid density, which can cause the desulfurized gypsum to not grow normally; meanwhile, the density of the gypsum slurry in the gypsum quality-improving box is too high, and new gypsum crystal nucleus is generated in the gypsum slurry, which is unfavorable for the growth of gypsum. Thus, the density of the gypsum slurry in the gypsum upgrading tank is controlled to within the reasonable range described aboveIn, adding gypsum seed to a gypsum upgrading tank, monitoring the density of gypsum slurry in the gypsum upgrading tank by a densitometer, controlling the density ρ of gypsum slurry in the gypsum upgrading tank 2 Density ρ of gypsum slurry in absorber of desulfurization system 1 The height is 50-150kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the That is, Δρ=ρ is ensured 2 -ρ 1 Maintained at 50-150kg/m 3 Within the range. Further, Δρ can be reduced appropriately for an absorber with a higher slurry density; for an absorption column with a smaller slurry density, Δρ can be increased appropriately. The specific gypsum particle size growth time is determined by controlling the density of the gypsum slurry in the gypsum upgrading bin. More specifically, the gypsum slurry density in the gypsum upgrading tank can be maintained at 1200-1300kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the In addition, the stirring speed in the gypsum upgrading tank can be maintained at 140-160r/min, preferably 150r/min. The gypsum slurry density in the gypsum upgrading bin is greater than 1300kg/m 3 And when the gypsum slurry in the absorption tower of the desulfurization system stops being sent to the gypsum quality-improving box, the gypsum slurry in the gypsum quality-improving box is sent to a cyclone of the desulfurization system and a vacuum belt conveyor for separation and drying.
In the invention, hot water can be added into the gypsum quality-improving box during quality-improving treatment to control the temperature of gypsum slurry to be within +/-10 ℃ of the optimum temperature for gypsum growth, preferably +/-5 ℃ of the optimum temperature for gypsum growth; wherein, the optimal temperature for gypsum growth can be determined by a gypsum crystallization test; the optimum temperature for gypsum growth is, for example, 50-70 ℃. Studies have shown that: at low temperatures, where the temperature primarily affects the chemical reaction rate and diffusion rate of gypsum crystallization, ca 2+ With SO 4 2- The probability of mutual collision is low, ca 2+ With SO 4 2- The activity product is low, and gypsum nucleation is inhibited; the supersaturation degree of gypsum in the slurry is low, and the nucleation of gypsum is inhibited. When the temperature is increased, ca 2+ With SO 4 2- The activity product is increased, and the nucleation rate of gypsum is increased; the supersaturation degree increases and the gypsum growth rate increases. When the temperature is too high, the nucleation rate of gypsum tends to be gentle, but the nucleation rate is larger than the growth rate, and the particle size of the generated gypsum crystal is smaller. The temperature is increased to enable the arrangement of particles in the crystal to be regular and the junction to be formedThe crystallinity is better than when the temperature is low, and the dehydration efficiency is higher than when the temperature is low. Therefore, controlling the temperature in a proper range can further improve the quality of the desulfurized gypsum.
The gypsum crystallization test can be performed as follows: at different temperatures (T 1 、T 2 、T 3 、T 4 、T 5 ) Gypsum crystallization was carried out under the condition, and the particle diameters (D10, D50, D90, D3, 2 of gypsum samples were measured]、D[4,3]) The method comprises the steps of carrying out a first treatment on the surface of the The temperature corresponding to the maximum particle diameter of the gypsum sample is determined as the optimum temperature for gypsum growth, and further the optimum temperature for gypsum growth is determined as the temperature of the gypsum slurry at + -10deg.C, preferably + -5deg.C. The method of controlling the temperature of the gypsum slurry by adding hot water into the gypsum quality improving box is beneficial to avoiding local high temperature of the gypsum slurry, the temperature of the gypsum slurry in the gypsum quality improving box can be monitored through the thermocouple, and when the display temperature of the thermocouple is different from the optimal temperature for gypsum growth (namely the optimal operation temperature of the gypsum quality improving box) by 5-10 ℃, the addition of the hot water into the gypsum quality improving box is stopped.
According to the desulfurization gypsum upgrading method, when the particle size of desulfurization gypsum generated by a desulfurization system is smaller than 30 mu m, part of gypsum slurry in an absorption tower of the desulfurization system is sent to a gypsum upgrading box for upgrading treatment; after the quality improvement treatment, the grain diameter of the obtained high-quality desulfurized gypsum is more than 80 mu m, for example, 125-155 mu m, and the quality of the desulfurized gypsum is greatly improved.
Further, the desulfurization gypsum upgrading method of the present invention further comprises: and recycling the obtained high-quality desulfurized gypsum into a desulfurization system. The high-quality desulfurized gypsum obtained by upgrading in the gypsum upgrading box is recycled in the desulfurization system, so that high-quality seed crystals can be provided for gypsum slurry in the absorption tower, the grain size growth of desulfurized gypsum crystals in the absorption tower is promoted, the gypsum crystal quality in the absorption tower of the desulfurization system is improved, the gypsum grain size is increased, the overall quality of desulfurized gypsum produced by the desulfurization system is improved, the grain size of desulfurized gypsum produced by the desulfurization system reaches more than 80 mu m, the water content is as low as below 10 percent before drying, the subsequent dehydration is easy, and the quality and the production efficiency of the desulfurized gypsum are greatly improved. In addition, the surplus high-quality desulfurized gypsum in the gypsum upgrading box can be sold outwards, so that the gypsum upgrading box has better economic benefit.
According to the invention, the gypsum quality-improving box is independently arranged outside the desulfurization system, part of gypsum slurry in the absorption tower of the desulfurization system is sent to the gypsum quality-improving box according to working conditions, and crystal seeds are added into the gypsum quality-improving box to serve as crystal nucleus, so that the crystallization process is easier to carry out, the gypsum growth is facilitated, and the crystal seeds can enable the grown crystals to be uniform and consistent, thereby improving the yield and quality of the crystals; meanwhile, citric acid is added into the gypsum upgrading box to adsorb and reduce the crystal face energy of gypsum, and a nucleation barrier is increased, so that the crystal nucleus has sufficient time and space growth, the crystal size is obviously increased, and the high-quality desulfurized gypsum with larger grain size is further obtained. In addition, the high-quality desulfurized gypsum generated by the gypsum quality-improving box is added into the desulfurization system at regular intervals to serve as seed crystals, so that gypsum particles in the desulfurization system grow up, the particle size distribution of the desulfurized gypsum is improved, the water content of the desulfurized gypsum is reduced, and the quality of the desulfurized gypsum of the desulfurization system are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a desulfurization gypsum upgrading system according to an embodiment of the present invention.
Reference numerals illustrate:
1: a demister; 2: a flue gas inlet; 3: an absorption tower; 4.: an absorption tower gypsum discharge pump; 5: a gypsum slurry buffer tank; 6: a vacuum belt conveyor; 7: a primary cyclone; 8: a secondary cyclone; 9: a factory vehicle; 10: gypsum warehouse; 11: gypsum upgrading box.
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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular forms also include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
In the gypsum upgrading box, the temperature of the desulfurization slurry is controlled in the range of X+/-5 ℃, and the optimal operation temperature of the gypsum upgrading box is X ℃. And (3) leading a stream of hot water from the unit into the gypsum quality improving box, monitoring the temperature in the gypsum quality improving box through the thermocouple, and stopping adding the hot water into the gypsum quality improving box when the display temperature of the thermocouple is 5-10 ℃ different from the optimal operation temperature X ℃ in the gypsum quality improving box. Optimum temperature of the upgrading box X < deg. > C the gypsum sample particle size (D10, D50, D90, D3, 2, D4, 3) was measured by gypsum crystallization experiments to determine the optimum temperature for gypsum growth, and the results are shown in Table 1.
Table 1 particle size measurement results of gypsum crystals at different temperatures
In Table 1, D10, D50 and D90 represent particle diameters of 10%, 50% and 90% of cumulative particle distribution, D3, 2 represents surface area average particle diameter, and D4, 3 represents volume average particle diameter.
According to the results in table 1: the optimum temperature for gypsum growth is X deg.c. When the temperature is raised to X+20deg.C, the gypsum particle size is smaller than that at X-20deg.C. And obtaining the supersaturation ratio at different temperatures through simulation calculation. As the temperature increases, the supersaturation ratio of gypsum increases. The temperature was raised from the first X-20 c to X +20 c and the supersaturation ratio increased by 14.3%. The supersaturation ratio is a main driving force for gypsum growth, the temperature is increased, the supersaturation ratio in the solution is increased, the growth rate of crystals is accelerated due to the enhancement of the driving force, and the growth of gypsum is facilitated; therefore, as the temperature increases, the gypsum particle size becomes larger. However, too high a temperature is detrimental to gypsum growth and when the temperature reaches x+10 ℃ and x+20 ℃, the gypsum particle size decreases.
Example 2
The gypsum slurry is sent into a gypsum quality improvement box, gypsum seed crystal and citric acid are added into the gypsum quality improvement box, the adding amount of the gypsum seed crystal is 10 percent of the mass of the gypsum slurry in the gypsum quality improvement box, the adding amount of the citric acid enables the pH value of the gypsum slurry in the gypsum quality improvement box to be 4, the stirring speed in the gypsum quality improvement box is maintained at 150r/min, hot water is added into the gypsum quality improvement box to maintain the temperature of the gypsum slurry at 50 ℃, and the density of the gypsum slurry is controlled to be 1300kg/m 3 About, after the gypsum is upgraded for 24 hours in a gypsum upgrading box, the sample is separated and dried, and the granularity is measured by using a Winner ZD 2000 laser particle sizer manufactured by Jinan micro-nano company, and the result is shown in Table 2.
Example 3
The gypsum slurry is sent into a gypsum quality improvement box, gypsum seed crystal and citric acid are added into the gypsum quality improvement box, the adding amount of the gypsum seed crystal is 10 percent of the mass of the gypsum slurry in the gypsum quality improvement box, the adding amount of the citric acid ensures that the pH value of the gypsum slurry in the gypsum quality improvement box is 6, the stirring speed in the gypsum quality improvement box is maintained at 150r/min, hot water is added into the gypsum quality improvement box to maintain the temperature of the gypsum slurry at 50 ℃, and the density of the gypsum slurry is controlled to be maintained at 1150kg/m 3 Left and right, atAfter the gypsum is upgraded for 6 hours in a gypsum upgrading box, sampling, separating and drying are carried out, and the granularity is measured by using a Winner ZD 2000 laser particle sizer manufactured by Jinan micro-nano company, and the result is shown in table 2.
Example 4
As shown in fig. 1, the desulfurization system of the present embodiment includes a demister 1, a flue gas inlet 2, an absorption tower 3, an absorption tower gypsum discharge pump 4, a gypsum slurry buffer tank 5, a vacuum belt conveyor 6, a primary cyclone 7, a secondary cyclone 8, all of which are connected in a conventional manner in the art. The outlet end of the absorption tower 3 is communicated with the inlet end of the primary cyclone 7 through a liquid conveying pipeline, an upgrading pipeline is arranged outside the liquid conveying pipeline in parallel, a gypsum upgrading box 11 is arranged on the upgrading pipeline, a gypsum slurry inlet, a hot water inlet, a seed crystal inlet, a crystallization accelerator inlet and a gypsum slurry outlet are arranged on the gypsum upgrading box 11, and sensors for detecting relevant quality parameters of the gypsum slurry, including but not limited to a pH value sensor, a density sensor, a thermocouple and the like, are also arranged on the gypsum upgrading box 11.
When the particle size of desulfurized gypsum generated by the desulfurization system is smaller than 30 mu m, part of gypsum slurry in an absorption tower 3 of the desulfurization system is sent to a gypsum quality improvement box 11, gypsum seed crystals and citric acid are added into the gypsum quality improvement box 11, the addition amount of the gypsum seed crystals is 10% of the mass of the gypsum slurry in the gypsum quality improvement box 11, the addition amount of the citric acid enables the pH value of the gypsum slurry in the gypsum quality improvement box 11 to be 4, and the density of the gypsum slurry in the gypsum quality improvement box 11 is controlled to be 150kg/m higher than that in the absorption tower 3 of the desulfurization system 3 The stirring speed in the gypsum upgrading tank 11 is maintained at 150r/min, the temperature is maintained at 50 ℃, and the gypsum slurry density in the gypsum upgrading tank 11 is higher than 1300kg/m 3 The gypsum slurry in the gypsum upgrading box 11 and the gypsum slurry of the desulfurization system are sent to a first cyclone 7 and a second cyclone 8 of the desulfurization system together for separation, the water content of the separated gypsum slurry is reduced to below 10 percent, and then the gypsum slurry is sent to a vacuum belt conveyor 6 for drying, and the desulfurized gypsum with the D50 of about 80 mu m is obtained after drying.
Comparative example 1
Feeding gypsum slurry to gypsum for upgradingIn the box, adding HCl into the gypsum quality-improving box to adjust the pH value of the gypsum slurry to be 4, maintaining the stirring speed in the gypsum quality-improving box to be 150r/min, adding hot water into the gypsum quality-improving box to maintain the temperature of the gypsum slurry to be 50 ℃, and controlling the density of the gypsum slurry to be 1300kg/m 3 About, after the gypsum is upgraded for 24 hours in a gypsum upgrading box, the sample is separated and dried, and the granularity is measured by using a Winner ZD 2000 laser particle sizer manufactured by Jinan micro-nano company, and the result is shown in Table 2.
Comparative example 2
The gypsum slurry is sent into a gypsum quality improvement box, gypsum seed crystal and HCl are added into the gypsum quality improvement box, the adding amount of the gypsum seed crystal is 10 percent of the mass of the gypsum slurry in the gypsum quality improvement box, the adding amount of the HCl enables the pH value of the gypsum slurry in the gypsum quality improvement box to be 4, the stirring speed in the gypsum quality improvement box is maintained at 150r/min, hot water is added into the gypsum quality improvement box to maintain the temperature of the gypsum slurry at 50 ℃, and the density of the gypsum slurry is controlled to be maintained at 1300kg/m 3 About, after the gypsum is upgraded for 24 hours in a gypsum upgrading box, the sample is separated and dried, and the granularity is measured by using a Winner ZD 2000 laser particle sizer manufactured by Jinan micro-nano company, and the result is shown in Table 2.
Comparative example 3
The gypsum slurry is sent into a gypsum quality improvement box, citric acid is added into the gypsum quality improvement box, the addition amount of the citric acid ensures that the pH value of the gypsum slurry in the gypsum quality improvement box is 4, the stirring speed in the gypsum quality improvement box is maintained at 150r/min, hot water is added into the gypsum quality improvement box to maintain the temperature of the gypsum slurry at 50 ℃, and the density of the gypsum slurry is controlled to be maintained at 1300kg/m 3 About, after the gypsum is upgraded for 24 hours in a gypsum upgrading box, the sample is separated and dried, and the granularity is measured by using a Winner ZD 2000 laser particle sizer manufactured by Jinan micro-nano company, and the result is shown in Table 2.
Comparative example 4
Sending the gypsum slurry into a gypsum quality-improving box, adding oxalic acid into the gypsum quality-improving box, wherein the adding amount of the oxalic acid enables the pH value of the gypsum slurry in the gypsum quality-improving box to be 4, maintaining the stirring speed in the gypsum quality-improving box to be 150r/min, adding hot water into the gypsum quality-improving box to maintain the temperature of the gypsum slurry to be 50 ℃, and controlling the density of the gypsum slurryThe degree is maintained at 1300kg/m 3 About, after the gypsum is upgraded for 24 hours in a gypsum upgrading box, the sample is separated and dried, and the granularity is measured by using a Winner ZD 2000 laser particle sizer manufactured by Jinan micro-nano company, and the result is shown in Table 2.
Comparative example 5
Sending the gypsum slurry into a gypsum quality improvement box, adding gypsum seed crystal and HCl into the gypsum quality improvement box, wherein the addition amount of the gypsum seed crystal is 10% of the mass of the gypsum slurry in the gypsum quality improvement box, the addition amount of the HCl enables the pH value of the gypsum slurry in the gypsum quality improvement box to be 4, the stirring speed in the gypsum quality improvement box is maintained at 150r/min, hot water is added into the gypsum quality improvement box to maintain the temperature of the gypsum slurry at 50 ℃, and the density of the gypsum slurry is controlled to be maintained at 1150kg/m 3 About, after the gypsum is upgraded for 6 hours in a gypsum upgrading box, the gypsum is sampled, separated and dried, and the granularity is measured by using a Winner ZD 2000 laser particle sizer manufactured by Jinan micro-nano company, and the result is shown in Table 2.
Comparative example 6
Sending the gypsum slurry into a gypsum quality improvement box, adding gypsum seed crystal and HCl into the gypsum quality improvement box, wherein the addition amount of the gypsum seed crystal is 10% of the mass of the gypsum slurry in the gypsum quality improvement box, the addition amount of the HCl enables the pH value of the gypsum slurry in the gypsum quality improvement box to be 5, the stirring speed in the gypsum quality improvement box is maintained at 150r/min, hot water is added into the gypsum quality improvement box to maintain the temperature of the gypsum slurry at 50 ℃, and the density of the gypsum slurry is controlled to be maintained at 1150kg/m 3 About, after the gypsum is upgraded for 6 hours in a gypsum upgrading box, the gypsum is sampled, separated and dried, and the granularity is measured by using a Winner ZD 2000 laser particle sizer manufactured by Jinan micro-nano company, and the result is shown in Table 2.
Comparative example 7
Sending the gypsum slurry into a gypsum quality improvement box, adding gypsum seed crystal and HCl into the gypsum quality improvement box, wherein the addition amount of the gypsum seed crystal is 10% of the mass of the gypsum slurry in the gypsum quality improvement box, the addition amount of the HCl enables the pH value of the gypsum slurry in the gypsum quality improvement box to be 6, the stirring speed in the gypsum quality improvement box is maintained at 150r/min, hot water is added into the gypsum quality improvement box to maintain the temperature of the gypsum slurry at 50 ℃, and the density of the gypsum slurry is controlled to be maintained at 1150kg/m 3 Left and right, in the gypsum quality-improving boxAfter the quality improvement treatment for 6 hours, the sample was separated and dried, and the particle size was measured by using a Winner ZD 2000 laser particle sizer manufactured by Jinan micro-nano company, and the result is shown in Table 2.
Table 2 results of particle size detection of desulfurized gypsum in each gypsum upgrading bin
| Desulfurized gypsum | D50/μm |
| Example 2 | 154.44 |
| Example 3 | 125.84 |
| Comparative example 1 | 39.74 |
| Comparative example 2 | 88.73 |
| Comparative example 3 | 71.24 |
| Comparative example 4 | 52.37 |
| Comparative example 5 | 46.01 |
| Comparative example 6 | 54.15 |
| Comparative example 7 | 45.02 |
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A method for upgrading desulfurized gypsum, comprising: in the operation process of the desulfurization system, part of gypsum slurry in an absorption tower of the desulfurization system is sent to a gypsum upgrading box which is independently arranged outside the desulfurization system, seed crystals and crystallization promoters are added into the gypsum upgrading box for upgrading treatment, and the gypsum slurry after upgrading treatment is sent to a cyclone of the desulfurization system and a vacuum belt conveyor for separation and drying, so that high-quality desulfurized gypsum is obtained.
2. The method of upgrading desulfurized gypsum according to claim 1, further comprising: and recycling the obtained high-quality desulfurized gypsum into a desulfurization system.
3. The method for upgrading desulfurized gypsum according to claim 1, wherein the seed crystal is a gypsum seed crystal; preferably, the gypsum seed is added in an amount of 5-10% by mass of the gypsum slurry in the gypsum upgrading box.
4. The method for upgrading desulfurization gypsum according to claim 1, wherein the crystallization promoter is an organic acid, preferably citric acid; preferably, the amount of citric acid added is to control the pH of the gypsum slurry in the gypsum upgrading tank to between 4 and 6.
5. The method for upgrading desulfurized gypsum according to claim 1, wherein the gypsum slurry density in the gypsum upgrading tank is controlled to be 50-150kg/m higher than the gypsum slurry density in the absorber tower of the desulfurization system 3 。
6. The method of claim 1, wherein the gypsum slurry density in the gypsum upgrading bin is controlled to be maintained at 1200-1300kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the stirring speed in the gypsum upgrading tank is maintained at 140-160r/min, more preferably 150r/min.
7. The method of claim 1, wherein hot water is added to the gypsum upgrading box during the upgrading process to control the temperature of the gypsum slurry to be at a temperature of about 10 ℃ or less, preferably about 5 ℃ or less, of the optimum gypsum growth temperature; preferably, the optimum temperature for gypsum growth is determined by a gypsum crystallization test; preferably, the optimum temperature for gypsum growth is 50-70 ℃.
8. The method for upgrading desulfurization gypsum according to claim 1, wherein when the particle size of the desulfurization gypsum produced in the desulfurization system is less than 30 μm, a part of the gypsum slurry in the absorption tower of the desulfurization system is sent to a gypsum upgrading tank for upgrading treatment.
9. The method of claim 1, wherein the gypsum slurry density in the gypsum upgrading bin is greater than 1300kg/m 3 And when the gypsum slurry in the absorption tower of the desulfurization system stops being sent to the gypsum quality-improving box, the gypsum slurry in the gypsum quality-improving box is sent to a cyclone of the desulfurization system and a vacuum belt conveyor for separation and drying.
10. The method for upgrading desulfurization gypsum according to claim 1, wherein the high-quality desulfurization gypsum has a particle size of more than 80 μm, preferably 125-155 μm.
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