CN103708750B - A kind of pretreatment technology of phosphogypsum - Google Patents
A kind of pretreatment technology of phosphogypsum Download PDFInfo
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- CN103708750B CN103708750B CN201310733822.6A CN201310733822A CN103708750B CN 103708750 B CN103708750 B CN 103708750B CN 201310733822 A CN201310733822 A CN 201310733822A CN 103708750 B CN103708750 B CN 103708750B
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Abstract
The invention discloses a kind of pretreatment technology of phosphogypsum, first this technique be scattered in water with by phosphogypsum, stratification, removes the organic impurity swimming in upper strata, then add calcium oxide, removes the P of solubility
2o
5and fluorochemical, again the mixed solution of phosphogypsum and water is added in sorting mineral post post, control mineral deposit height in sorting mineral post, by control and recharge discharge, adjustment air compressor machine arranges the air pressure into system, air flow quantity, air pressurized time and air pressure relief time, control the amplitude of the pulsed system water-level fluctuation in pulsating water water inlet pipe in sorting mineral post, the frequency that pulsed system fluctuates up and down, the discharge capacity of sorting mineral post upper outlet, phosphogypsum is effectively separated with light constituent with the heavy constituent in the mixed solution of water, thus reach deimpurity object.This process economics environmental protection, effectively can remove or reduce the impurity in phosphogypsum, improves the quality of phosphogypsum, and treatment capacity is large, is applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of pretreatment technology of phosphogypsum, belong to renewable resource and field of environmental technology.
Background technology
Phosphogypsum is the solid waste with discharging when sulfuric acid and phosphorus ore effect Wet-process phosphoric acid (WPPA), and main component is terra alba (CaSO
42H
2o), but also containing undecomposed phosphorus ore, SiO
2, aluminum oxide, ferric oxide, magnesium oxide, fluorine-containing material, acid insoluble organism etc. are multiple is detrimental to health and biologically increases, and affect the impurity of phosphogypsum product quality.Wherein, solubility P
2o
5ca is converted into when plaster of Paris aquation
3(PO
4)
2precipitation, covers semi-hydrated gypsum plane of crystal, and reduce dihydrate gypsum crystallization degree of supersaturation, make dihydrate gypsum crystal alligatoring, show as significant prolongation time of coagulation of plaster of Paris, intensity significantly reduces; Soluble fluoride makes shorten the time of coagulation of gypsum, and the increase blood coagulation enhancing effect with F-volume strengthens; Organism makes the water requirement of gypsum increase, and setting and harden slows down, and slackens the combination between dihydrate gypsum crystal, and hardening structure is loosened, and intensity reduces.The transformation of crystal formation and the minimizing of point of contact are the reasons causing phosphogypsum hardenite intensity to reduce, and soluble impurity is the most serious influence factor.Phosphogypsum is different from the plaster of paris, although its CaSO
42H
2the content of O is higher, but contains the P of 0.3% ~ 2.0%
2o
5, the F of 0.1% ~ 1.5%, wet basis phosphogypsum is in acid, and some phosphogypsums also have higher radioactivity.Therefore, any discharge of phosphogypsum, not only takies a large amount of soil, cause serious environmental pollution, and it is healthy to affect people.If phosphogypsum is directly applied, very large impact will certainly be caused on the quality of phosphogypsum product, therefore, pre-treatment be carried out to phosphogypsum, remove or reduce impurity wherein, the content improving dihydrate gypsum in phosphogypsum is the steps necessary of comprehensive utilization phosphogypsum.
Pre-treatment is carried out to phosphogypsum there are chemistry, physics, physical chemistry and heat treating method both at home and abroad at present.In method of chemical treatment, adopt limestone vegetation, impact that the method such as acid-soluble can eliminate Leaching Properties of Soluble Phosphorus, fluorine, but organism and SiO in phosphogypsum can only be applicable to
2the not high and situation that quality is more stable Deng hard impurity content.Flotation process can effective organics removal, thus eliminates organic deleterious effect, but the equipment of flotation process, medicament etc. are expensive, should not carry out pre-treatment to phosphogypsum.In physical treatment method, need not chemical agent be added, but the problem such as its technique exists that one-time investment is large, energy consumption is high, seriously polluted and complex process.In physics removal of impurities, washing is most efficient manner, soluble impurity and organism can be removed, Cerphos purifying process mainly processes footpath grain at the impurity of about 20 μm, wet screening eddy flow method removal effect is also better, can remove oarse-grained quartz and unreacted impurity, the ball milling of appropriateness fundamentally can improve that hardenite porosity is high, the defect of short texture.It is uneven that sieving technology can change Impurity Distribution in phosphogypsum, and its treatment effect depends on the distribution situation of impurity with particle.Dodging burning method is a kind of new thermal treatment process occurred at present, is to eliminate the unique effective approach of eutectic phosphorus impact, and its secondary pollution is little, and device fabrication energy consumption is low, but current treatment capacity is less.Calcination processing method is difficult to removing eutectic phosphorus when temperature is low, and it is large to process energy consumption.Microwave heating treatment phosphogypsum is also a kind of new impurity-removing method, and it does not exist secondary pollution, and faster and energy-conservation than traditional heating mode, can remove organism very soon, but research technique is ripe not enough at present.
Therefore, provide a kind of economic environmental protection, efficient remove or reduce impurity and the large phosphogypsum pretreatment process for the treatment of capacity become phosphogypsum pre-treatment industry in the urgent need to.
Summary of the invention
The invention provides a kind of pretreatment technology of phosphogypsum, this process economics environmental protection, effectively can remove or reduce the impurity in phosphogypsum, improve the quality of phosphogypsum, and treatment capacity is large, be applicable to suitability for industrialized production.
For achieving the above object, the present invention take technical scheme be:
A pretreatment technology for phosphogypsum, comprises the steps:
1) in the ratio that phosphogypsum quality is phosphogypsum and water total mass 15% ~ 30%, phosphogypsum is scattered in water, stratification after stirring, remove the organic impurity swimming in upper strata, then the calcium oxide that quality is phosphogypsum quality 0.5% ~ 2.0% is added, stir rear use 30 ~ 60 object sieve to carry out sieving every slightly, remove oarse-grained hard impurity;
2) mixed solution of sieve in the step 1) phosphogypsum after thick and water is added in taper agitation vat stir, continue sample introduction from the middle part of sorting mineral post after stirring and carry out sorting, separation, the bottom of sorting mineral post continues to supplement supplementary feed, bottom is arranged by air compressor machine and is passed into air into system simultaneously, the top of sorting mineral post is communicated with air, and controlling mineral deposit height in sorting mineral post is 80cmH
2o ~ 120cmH
2o, control and recharge discharge, adjustment air compressor machine arranges the air pressure into system, air flow quantity, air pressurized time and air pressure relief time, the amplitude making the pulsed system water-level fluctuation in pulsating water water inlet pipe in sorting mineral post is 5cm ~ 25cm, the frequency that pulsed system fluctuates up and down is 15 ~ 60 beats/min, the discharge capacity of sorting mineral post upper outlet is 0.3L/min ~ 1.0L/min, heavy constituent in the mixed solution of phosphogypsum and water is discharged from lower row's mouth of sorting mineral post, row's thing is oarse-grained hard solid impurity, light constituent in the mixed solution of phosphogypsum and water is discharged from upper outlet, row's thing is through sorting, phosphogypsum after separation, impurity removal and the mixed solution of water, again by the mixed solution suction filtration of the phosphogypsum after removal of impurities and water, gained filter cake is dried.
Technique scheme is further improved, described taper agitation vat be can laterally stir, longitudinally circulation and accurately can control the whipping appts of its stirring velocity; Continue sample introduction from the middle part of sorting mineral post after stirring and carry out sorting, separation, the bottom of sorting mineral post continues to supplement supplementary feed, makes the mass ratio of phosphogypsum and water in sorting mineral post be 0.15:1 ~ 0.43:1; After the mixed solution suction filtration of the phosphogypsum after removal of impurities and water, filtrate is recycled as supplementary feed.
As shown from the above technical solution: first this technique be scattered in water with by phosphogypsum, stratification, remove the organic impurity swimming in upper strata, then add calcium oxide, remove the P of solubility
2o
5and fluorochemical, again the mixed solution of phosphogypsum and water is added in sorting mineral post post, control mineral deposit height in sorting mineral post, by control and recharge discharge, adjustment air compressor machine arranges the air pressure into system, air flow quantity, air pressurized time and air pressure relief time, control the amplitude of the pulsed system water-level fluctuation in pulsating water water inlet pipe in sorting mineral post, the frequency that pulsed system fluctuates up and down, the discharge capacity of sorting mineral post upper outlet, phosphogypsum is effectively separated with light constituent with the heavy constituent in the mixed solution of water, thus reach deimpurity object.Sorting mineral post is a container be filled with, and has the ascending current that a stable state has pulsation simultaneously, and it utilizes the fine particle in feed to produce density gradient, produces complicated density gradient in a reservoir and stablized with distinctive filling method.Feed feeds at the middle part of sorting mineral post, ore pulp enters after in post, along density gradient separation under the effect of pulse water flow, the top that low-density particles moves to sorting mineral post flows away with overflow, and high density granular moves to sorting mineral column bottom to be become underflow and flow away.Be provided with spiralling metal catch in cylinder, liquid rises under pulse action, and solid particulate wherein and metal catch constantly collide, separating for several times, and the particle of different densities in ore pulp is separated to the full extent.Sample introduction is continued at the middle part of sorting mineral post, bottom continues to supplement the ratio that supplementary feed controls phosphogypsum and water, can continuously process pending phosphogypsum, and the filtrate of mixed solution gained after suction filtration of phosphogypsum after removal of impurities and water is as supplementary feed recycle, avoids secondary pollution and the wasting of resources.Therefore, the amount of this art breading phosphogypsum is large, can also avoid the waste of secondary pollution and water resources.And after testing, adopt the content of dihydrate gypsum in the phosphogypsum after this art breading to reach more than 90%.
Compared with prior art, its beneficial effect and advantage are in the present invention:
1) Pretreatment Technology of Phosphogypsum provided by the invention is simple to operation, and processing condition are easy to control, and the amount of process phosphogypsum is large, is applicable to industrialization scale operation.
2) do not discharge harmful solid waste, toxic gas and harmful liquid in whole technical process, very environmental protection, stopped secondary pollution, and solve phosphogypsum and stack arbitrarily the problem such as environmental pollution, land occupation brought.
3) this technique adopts sorting mineral post to carry out sorting, separation to phosphogypsum, and effectively can remove the impurity in phosphogypsum, after testing, in the phosphogypsum after process, the content of dihydrate gypsum is up to more than 90%, higher than national standard.
4) adopt processing method pretreated ardealite of the present invention, the productive rate of phosphogypsum is high, reaches more than 85% at the productive rate of sorting mineral post upper outlet place phosphogypsum.
5) water in Pretreatment Technology of Phosphogypsum process provided by the invention can recycle, has not only stopped the secondary pollution that sewage discharge causes, and has reduced cost.
Embodiment
Below in conjunction with embodiment, the present invention is specifically described.
Embodiment 1
Take 5.0kg Guangxi Luzhai phosphogypsum, being scattered in 28.3kg meets in the tap water of national domestic water hygienic standard, 10min is left standstill after stirring, remove the organic impurity swimming in upper strata, then add the analytically pure calcium oxide of 75.0g, general industrial oxidation calcium impurities is more, impurity is introduced herein for avoiding, therefore use analytically pure calcium oxide, stir rear use 40 object sieve and carry out sieving every slightly, remove oarse-grained hard impurity.
The phosphogypsum after thick that sieves is joined with the mixed solution of water can laterally stir, longitudinal direction circulates and can accurately control in the taper agitation vat of its stirring velocity, stir after 15 minutes, carry out sorting, separation from the middle part sample introduction of sorting mineral post, the bottom of sorting mineral post continues to supplement supplementary feed, the ratio of phosphogypsum and water in sorting mineral post is made to be 1:6.5, bottom is arranged by air compressor machine and is passed into air into system simultaneously, the top of sorting mineral post is communicated with air, and the mineral deposit height controlling sorting mineral post is 105cmH
2o, the discharge of control and recharge water, adjustment air compressor machine arranges the air pressure into system, air flow quantity, air pressurized time and air pressure relief time, the amplitude making the pulsed system water-level fluctuation in pulsating water water inlet pipe in sorting mineral post is 10cm, the frequency that pulsed system fluctuates up and down is 45 beats/min, the discharge capacity of sorting mineral post upper outlet is 0.9L/min, thus phosphogypsum is effectively separated with light constituent with the heavy constituent in the mixed solution of water, row's thing of lower row's mouth of sorting mineral post is oarse-grained hard solid impurity, row's thing of upper outlet is through sorting, phosphogypsum after separation, impurity removal and the mixed solution of water, again by the mixed solution suction filtration of the phosphogypsum after removal of impurities and water, filter cake is dried, obtain pretreated phosphogypsum.After the mixed solution suction filtration of the phosphogypsum after removal of impurities and water, gained filtrate recycles as supplementary feed.
Embodiment 2
Take 5.0kg phosphogypsum, be scattered in 20.0kg water, after stirring, leave standstill 15min, remove the organic impurity swimming in upper strata, then add the analytically pure calcium oxide of 100g, stir rear use 60 object sieve and carry out sieving every slightly, remove oarse-grained hard impurity.
The mixed solution of the sieve phosphogypsum after thick and water is added in taper agitation vat, stir after 15 minutes, carry out sorting, separation from the middle part sample introduction of sorting mineral post, the bottom of sorting mineral post continues supplementary supplementary feed to control the ratio of phosphogypsum and water in sorting mineral post for 1:4, bottom is arranged by air compressor machine and is passed into air into system simultaneously, the top of sorting mineral post is communicated with air, and the mineral deposit height controlling sorting mineral post is 80cmH
2o, control and recharge discharge, adjustment air compressor machine arranges the air pressure into system, air flow quantity, air pressurized time and air pressure relief time, the amplitude making the pulsed system water-level fluctuation in pulsating water water inlet pipe in sorting mineral post is 15cm, the frequency that pulsed system fluctuates up and down is 20 beats/min, the discharge capacity of sorting mineral post upper outlet is 0.45L/min, thus phosphogypsum is effectively separated with light constituent with the heavy constituent in the mixed solution of water, row's thing of lower row's mouth of sorting mineral post is oarse-grained hard solid impurity, row's thing of upper outlet is through sorting, phosphogypsum after separation, impurity removal and the mixed solution of water, again by the mixed solution suction filtration of the phosphogypsum after removal of impurities and water, filter cake is dried, obtain pretreated phosphogypsum.Phosphogypsum after removal of impurities and the mixed solution of water are after suction filtration, and filtrate can be used as supplementary feed and recycles.
Embodiment 3
Take 5.0kg phosphogypsum, being scattered in 15.0kg meets in the tap water of national domestic water hygienic standard, 10min is left standstill after stirring, remove the organic impurity swimming in upper strata, then the analytically pure calcium oxide of 50.0g is added, stir rear use 40 object sieve to carry out sieving every slightly, remove oarse-grained hard impurity.
The phosphogypsum after thick that sieves is added with the mixed solution of water can laterally stir, longitudinal direction circulates and can accurately control in the taper agitation vat of its stirring velocity, stir after 20 minutes, carry out sorting, separation from the middle part sample introduction of sorting mineral post, the bottom of sorting mineral post continues supplementary supplementary feed to control the ratio of phosphogypsum and water in sorting mineral post for 1:3, bottom is arranged by air compressor machine and is passed into air into system simultaneously, the top of sorting mineral post is communicated with air, and the mineral deposit height controlling sorting mineral post is 120cmH
2o, control and recharge discharge, adjustment air compressor machine arranges the air pressure into system, air flow quantity, air pressurized time and air pressure relief time, the amplitude making the pulsed system water-level fluctuation in pulsating water water inlet pipe in sorting mineral post is 20cm, the frequency that pulsed system fluctuates up and down is 60 beats/min, the discharge capacity of sorting mineral post upper outlet is 0.3L/min, thus phosphogypsum is effectively separated with light constituent with the heavy constituent in the mixed solution of water, row's thing of lower row's mouth of sorting mineral post is oarse-grained hard solid impurity, row's thing of upper outlet is through sorting, phosphogypsum after separation, impurity removal and the mixed solution of water, again by the mixed solution suction filtration of the phosphogypsum after removal of impurities and water, filter cake is dried, obtain pretreated phosphogypsum.Phosphogypsum after removal of impurities and the mixed solution of water are after suction filtration, and filtrate can be used as supplementary feed and recycles.
Embodiment 1, embodiment 2 and the pretreated phosphogypsum of embodiment 3 are carried out ultimate analysis test, and the result of test is as shown in the table:
As seen from the above table, in the pretreated phosphogypsum of Pretreatment Technology of Phosphogypsum provided by the invention, the content of dihydrate gypsum is high, and foreign matter content is low, wherein content>=90% of dihydrate gypsum, higher than national standard, and solubility P
2o
5content lower than 0.25%, far below national standard, the content of soluble fluoride lower than 0.2%, far below national standard.
Above-mentioned test shows, adopt the content of dihydrate gypsum in phosphogypsum after Pretreatment Technology of Phosphogypsum pre-treatment provided by the invention high, impurity is low, and wherein the content of dihydrate gypsum reaches more than 90%.
Claims (3)
1. a pretreatment technology for phosphogypsum, is characterized in that comprising the steps:
1) in the ratio that phosphogypsum quality is phosphogypsum and water total mass 15% ~ 30%, phosphogypsum is scattered in water, stratification after stirring, remove the organic impurity swimming in upper strata, then the calcium oxide that quality is phosphogypsum quality 0.5% ~ 2.0% is added, stir rear use 30 ~ 60 object sieve to carry out sieving every slightly, remove oarse-grained hard impurity;
2) by step 1) in the sieve mixed solution of the phosphogypsum after thick and water add in taper agitation vat and stir, continue sample introduction from the middle part of sorting mineral post after stirring and carry out sorting, separation, the bottom of sorting mineral post continues to supplement supplementary feed, the mass ratio of phosphogypsum and water in sorting mineral post is made to be 0.15:1 ~ 0.43:1, bottom is arranged by air compressor machine and is passed into air into system simultaneously, the top of sorting mineral post is communicated with air, and controlling mineral deposit height in sorting mineral post is 80cmH
2o ~ 120cmH
2o, control and recharge discharge, adjustment air compressor machine arranges the air pressure into system, air flow quantity, air pressurized time and air pressure relief time, the amplitude making the pulsed system water-level fluctuation in pulsating water water inlet pipe in sorting mineral post is 5cm ~ 25cm, the frequency that pulsed system fluctuates up and down is 15 ~ 60 beats/min, the discharge capacity of sorting mineral post upper outlet is 0.3L/min ~ 1.0L/min, heavy constituent in the mixed solution of phosphogypsum and water is discharged from lower row's mouth of sorting mineral post, row's thing is oarse-grained hard solid impurity, light constituent in the mixed solution of phosphogypsum and water is discharged from upper outlet, row's thing is through sorting, phosphogypsum after separation, impurity removal and the mixed solution of water, again by the mixed solution suction filtration of the phosphogypsum after removal of impurities and water, gained filter cake is dried.
2. the pretreatment technology of phosphogypsum according to claim 1, is characterized in that: described taper agitation vat be can laterally stir, longitudinally circulation and accurately can control the whipping appts of its stirring velocity.
3. the pretreatment technology of phosphogypsum according to claim 1, is characterized in that: after the mixed solution suction filtration of the phosphogypsum after removal of impurities and water, filtrate recycled as supplementary feed.
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Cited By (1)
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| CN112978780A (en) * | 2021-03-19 | 2021-06-18 | 华南理工大学 | Method for purifying phosphogypsum by using aerated concrete steam-pressing condensed water |
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| CN106006698B (en) * | 2016-05-23 | 2018-02-06 | 中国建筑第八工程局有限公司 | A kind of ardealite removal of impurities processing method |
| CN106517292B (en) * | 2016-10-28 | 2019-02-05 | 湖北宜化集团有限责任公司 | A kind of method and device of ardealite purification |
| CN110482889A (en) * | 2019-09-18 | 2019-11-22 | 云南凝创环保科技有限公司 | A kind of technique of bioanalysis pretreated ardealite |
| CN111393052B (en) * | 2020-03-06 | 2021-11-02 | 三峡大学 | Device and method for pretreating phosphogypsum by using magnesium hydroxide |
| CN112062530A (en) * | 2020-08-20 | 2020-12-11 | 李文广 | Process flow for changing physical and chemical properties of new phosphogypsum by using calcium hydroxide |
| CN112871457A (en) * | 2021-01-11 | 2021-06-01 | 西南科技大学 | Method for purifying and decontaminating phosphogypsum |
| CN114210693A (en) * | 2021-12-23 | 2022-03-22 | 贵州蓝图新材料股份有限公司 | Deep purification treatment process for chemical waste residues |
| CN114653473B (en) * | 2022-03-30 | 2023-11-17 | 云南磷化集团有限公司 | Flotation method for efficiently purifying phosphogypsum |
| CN115092951B (en) * | 2022-07-26 | 2023-11-17 | 一夫科技股份有限公司 | Method for removing phosphorus-containing impurities in phosphogypsum |
| CN116040970B (en) * | 2022-09-08 | 2023-08-18 | 河南建筑材料研究设计院有限责任公司 | Eutectic phosphorus removal system of phosphogypsum |
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