CN103073207B - Method for phosphogypsum harmless treatment and conversion into regeneration gypsum resource - Google Patents
Method for phosphogypsum harmless treatment and conversion into regeneration gypsum resource Download PDFInfo
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- CN103073207B CN103073207B CN201210171552.XA CN201210171552A CN103073207B CN 103073207 B CN103073207 B CN 103073207B CN 201210171552 A CN201210171552 A CN 201210171552A CN 103073207 B CN103073207 B CN 103073207B
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Abstract
The present invention discloses a method for a phosphogypsum harmless treatment and conversion into a regeneration gypsum resource, and belongs to phosphorus chemical industry solid waste treatments and inorganic non-metallic material industry. The method comprises the following steps: preparing a phosphogypsum modifier, wherein the phosphogypsum modifier is superfine cement clinker micro-powder with a specific surface area of more than or equal to 300 m<2>/kg; and mixing the phosphogypsum modifier and the justly-discharged phosphogypsum according to a mass ratio of 1:9-2:8, and carrying out homogenizing stirring through a special homogenizing stirrer, wherein the special homogenizing stirrer comprises a cylinder provided with a material inlet and a material outlet, a vibratable bush arranged inside the cylinder, a material mixing mechanism arranged inside the bush, and a drive mechanism connected with the material mixing mechanism.
Description
Technical field
The present invention relates to a kind of method of phosphogypsum processing, relate in particular to a kind of ardealite innocent and process and the method that changes reclaimed gypsum resource into.
Background technology
A large amount of powdery solid industrial residues of discharging when phosphogypsum is sulphur dioxide of phosphor chemical industry production phosphate fertilizer preparing phosphoric acid, often produce 1 ton of phosphoric acid and need produce 3 ~ 5 tons of phosphogypsums.To 2007, the phosphate fertilizer production of China ranked first in the world.Existing China phosphate fertilizer gross annual output amount is approximately 1,500 ten thousand tons, and year discharge phosphogypsum is up to more than 6,000 ten thousand tons.
The chemical composition of phosphogypsum is taking terra alba as main.Undecomposed phosphorus ore when its impurities is mainly phosphorus ore acid hydrolysis, fluorine cpd, acid non-soluble substance, carbonized organism and not clean phosphoric acid etc.The chemical composition of phosphogypsum is taking terra alba as main.Undecomposed phosphorus ore when its impurities is mainly phosphorus ore acid hydrolysis, fluorine cpd, acid non-soluble substance, carbonized organism and not clean phosphoric acid etc.Not only a large amount of land occupation of the discharge of phosphogypsum, but also because phosphogypsum is after rainwater long period of soaking, wherein contained solubility Vanadium Pentoxide in FLAKES, solubility inorganic fluoride etc. by water body with wind erosion for medium to environment transmission, thereby cause soil, water system, atmosphere integrated environment pollute.State Environmental Protection Administration in 2006 is carrying out environmental protection risk investigation to Yunnan Prov Sanhuan Chemical Co., Ltd's 1,200,000 phosphorus ammonium engineerings and Yunnan Fu Rui Chemical Co., Ltd. 300,000 phosphoric acid and 600,000 monoammonium phosphate devices production domesticization demonstration project, in the report of risk investigation by qualitative phosphogypsum be dangerous emissions.
The application of phosphogypsum is a global difficult problem.Whole world phosphogypsum utilization ratio is less than 10%, external unemployed phosphogypsum or directly enter ocean or be backfilling into old pit or build slag field and store up.According to Chinese phosphate fertilizer association statistics, the phosphogypsum overall utilization of China is less than 10%.In order to eliminate and to reduce the harmful effect of contained various impurity to its use properties in phosphogypsum, phosphogypsum need do pre-treatment.Current pretreated main method has: purify washing, dodge burn, in lime and the method such as modification, but owing to existing the problems that secondary pollution and pre-treatment cost are higher, thus badly influence system phosphogypsum is carried out to the process that discharge after harmless treatment is fully utilized with being converted into reclaimed gypsum resource on a large scale.And the phosphogypsum of discharging in production process to be carried out to harmless treatment completely and regeneration by existing technology and equipment, will significantly improve production cost and the one-time investment of manufacturing enterprise.Also do not have at home at present a Jia Lin ammonium manufacturing enterprise to accomplish the discharge of harmless treatment completely.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of ardealite innocent to process and the method that changes reclaimed gypsum resource into.Investment that can be few, simple technique, cheap processing cost complete ardealite innocent and process discharge.In completing harmless treatment, phosphogypsum after discharge makes the phosphogypsum of harmless treatment discharge be converted into the phosphogypsum of modification under the effect of continuous hydration reaction, has eliminated impurities in original state phosphogypsum and phosphogypsum has been used to the series of problems bringing as gypsum resource.Effectively discharge phosphogypsum is become to the gypsum resource of regeneration.
For solving the problems of the technologies described above, a kind of phosphogypsum treatment process of the present invention, comprises the steps:
Phosphogypsum modification agent and phosphogypsum are put into extraordinary homogenization stirrer to be stirred;
Described phosphogypsum modification agent is that specific surface area is more than or equal to 300m
2the superfine cement grog micro mist of/kg;
Described extraordinary homogenization stirrer comprises a cylindrical shell that is provided with opening for feed and discharge port, and one is located at vibratile sleeve in cylindrical shell, is located at the mixing mechanism in this sleeve, the driving mechanism that mixing mechanism is connected therewith.Make the silicate minerals generation hydration reaction in terra alba and the properties-correcting agent in phosphogypsum, significantly reduce the content of inorganic fluoride in phosphogypsum, water-soluble phosphorus and water-soluble fluorine, simultaneously by the former phosphogypsum that is acid phosphogypsum and is adjusted into neutrality or meta-alkalescence, make it discharge and reach completely every regulation and the requirement of GB5085.3-2007 " Hazardous wastes judging standard leaches poisonous substance and differentiates " national standard.
Rely on special homogenization stirrer to force fully homogenizing to stir to phosphogypsum and various properties-correcting agent, in described extraordinary homogenization stirrer, vibratile sleeve is separated contained 20 ~ 30% attached water and crystal water in the middle of phosphogypsum, makes contained attached water in the middle of phosphogypsum participate in the hydration reaction of properties-correcting agent and phosphogypsum.So both solved the required water of aquation modification, the segregation of output while having avoided the hydration reaction completely and secondary pollution that causes has also thoroughly solved because phosphogypsum adheres to the use problem that moisture content brings simultaneously.Along with constantly carrying out of hydration reaction, make the phosphorus of solubility and the inorganic fluoride of solubility in phosphogypsum be converted into insoluble Ca
3(PO
4)
2caF with indissoluble
2, Na
2siF
6.Press body is hardened gradually, has certain anti-folding, ultimate compression strength (ultimate compression strength can reach 10Mpa left and right in 28 days).
Further, the mass ratio of described phosphogypsum modification agent and phosphogypsum is 1: 9 ~ 2: 8.
Further, described phosphogypsum modification agent also comprises that specific surface area is more than or equal to 300m
2the calcium carbonate fine powder of/kg; The mass ratio of described superfine cement grog micro mist and calcium carbonate fine powder is 3: 7.Calcium carbonate fine powder is for the pH value of regulation system.
Further, described phosphogypsum modification agent also comprises that concentration is 50% alum solution; Described alum solution quality accounts for 3% ~ 5% of alum solution, superfine cement grog micro mist and calcium carbonate fine powder mixture.
Beneficial effect of the present invention:
1) during phosphogypsum after treatment is, alkalescence, realize harmless treatment, be up to state standards completely;
2) phosphogypsum is converted into reclaimed gypsum, properties excellence, is good engineering materials; Many situations and problem that phosphogypsum runs in building materials industry is used are thoroughly solved, for phosphogypsum fully utilizes, reduces environmental pollution on a large scale, protection of the environment has been started a brand-new road.
3) present method technique is simple, less investment, and processing cost is cheap.
Brief description of the drawings
Fig. 1. process route chart of the present invention.
Embodiment
Fig. 1 is process route chart of the present invention, and wherein, 1# properties-correcting agent is that specific surface area is more than or equal to 300m
2the superfine cement grog micro mist of/kg; 2# properties-correcting agent is that specific surface area is more than or equal to 300m
2the calcium carbonate fine powder of/kg; 3# properties-correcting agent is that concentration is 50% alum solution.
Embodiment 1
The agent of configuration phosphogypsum modification, comprises that specific surface area is 500m
2the superfine cement grog micro mist of/kg, specific surface area are 500m
2the alum solution of the calcium carbonate fine powder of/kg and 50% concentration; Described alum solution quality accounts for 3% of phosphogypsum modification agent; The mass ratio of described superfine cement grog micro mist, calcium carbonate fine powder is 3: 7.
In the construction of phosphogypsum relief outlet, extraordinary homogenization stirrer is installed.Described extraordinary homogenization stirrer comprises a cylindrical shell that is provided with opening for feed and discharge port, one is located at vibratile sleeve in cylindrical shell, be located at the mixing mechanism in this sleeve, the driving mechanism that mixing mechanism is connected therewith, the electric control gear that driving mechanism is connected therewith.
By phosphogypsum modification agent and the mass ratio batching of the original-pack phosphogypsum of just discharging with 1: 9, send into extraordinary homogenization stirrer homogenizing and stir, after repressed moulding, deliver to phosphogypsum slag field and stack.
Phosphogypsum after original state phosphogypsum and modification is delivered to Building Materials In Beijing inspection center company limited tests according to GB5085.3-2007 " Hazardous wastes judging standard leaches poisonous substance and differentiates ".Check data is as shown in table 1.
Table 1
Inspection shows: the phosphogypsum indices of process modification is all far below the specified requirement in national standard.Wherein of paramount importance inorganic fluoride index comparison has reduced more than 90%, full phosphorus index comparison has reduced more than 95%, water miscible Vanadium Pentoxide in FLAKES is compared the phosphogypsum being almost after 100%(modification that declined and is not detected), water-soluble fluorine comparison has declined more than 80%, attached water comparison in phosphogypsum has declined more than 80%, the former phosphogypsum correctability that is acid (pH value is 2 ~ 4) is for neutral and alkaline, reach the emission standard of national regulation completely, truly accomplished harmless discharge.Simultaneously because the modified ardealite of piling up discharge is constantly becoming the hardenite with certain physical strength under hydration reaction condition, just make bulk deposition discharge phosphogypsum in the open not be afraid of wind and weather, avoided the airborne dust bringing due to wind and the pollution problem to Soil Surrounding, surface water, underground water of raining and bringing.
The central residual phosphorus of original state phosphogypsum and fluorine are mainly with H
3pO
4 -, HPO
2 2-, NaF and Na
2siF
6exist etc. form.The slow down reason of hydration and hardening of titanium pigment and soluble fluoride is to form calcium phosphate and Calcium Fluoride (Fluorspan) precipitation covers semi-hydrated gypsum surface at the aquation initial stage, hinders and goes stripping and aquation, causes cement setting slow.On the other hand, the existence of titanium pigment and fluorine has reduced hydrated cementitious generation Ca (OH)
2content, the speed that generates ettringite is slowed down, meanwhile, it is thicker that soluble fluoride makes that hydrated product dihydrate gypsum crystal grows, point of contact between crystal reduces, bonding force slackens, and causes its strength decreased.
According to GB/T23456-2009 " phosphogypsum " standard, original state phosphogypsum and modified ardealite are carried out to comparison and detection, its result shows: original state phosphogypsum meets the two-level index requirement in GB/T23456-2009 " phosphogypsum ", and modified ardealite meets the first class index requirement in GB/T23456-2009 " phosphogypsum ".Wherein water-soluble Vanadium Pentoxide in FLAKES be respectively 0.32% with do not detect, reduced by 100%.Water-soluble fluorine is respectively 0.45% and 0.08%, has reduced more than 80%.Attached water is 12% and 2% respectively, has reduced by 80%.
Utilize natural dihydrate gypsum, original state phosphogypsum, modified ardealite as shown in table 2 as the experimental data of cement setting retarder.
Table 2
Illustrated by upper table:
1) when the phosphogypsum after modification uses as cement setting retarder, keeping under the prerequisite of constructed index, compare significantly and shorten time of coagulation compared with original state phosphogypsum, and basic identical with natural dihydrate gypsum, intensity increases.
2) contrast is found out, while using modified ardealite, usage quantity has improved 1.15% than natural dihydrate gypsum, reach same desirable time of coagulation and intensity index, use modified ardealite can save cement clinker, reduce manufacture of cement cost, the transport of being more convenient for, storage, blanking and metering.
3) when modified ardealite making cement adjustable solidification agent, time of coagulation normal, the good reason of intensity be in modification body bonding component after fine grinding, in the time adding in cement, in cement hydration process, play the effect of intensity crystal seed, the hydration rate that is is accelerated, relatively shift to an earlier date time of coagulation, and then intensity increases while using natural dihydrate gypsum.
In sum: original state phosphogypsum is by the modification of aquation preconditioning technique, and its every physical index can reach the requirement of the material performance index of natural dihydrate gypsum completely, thus effectively change the phosphogypsum of harmless treatment discharge into reclaimed gypsum resource.
Embodiment 2
The agent of configuration phosphogypsum modification, comprises that specific surface area is 300m
2the superfine cement grog micro mist of/kg, specific surface area are 300m
2the alum solution of the calcium carbonate fine powder of/kg and 50% concentration; Described alum solution quality accounts for 5% of phosphogypsum modification agent; The mass ratio of described superfine cement grog micro mist, calcium carbonate fine powder is 1.
In the construction of phosphogypsum relief outlet, extraordinary homogenization stirrer is installed.Described extraordinary homogenization stirrer comprises a cylindrical shell that is provided with opening for feed and discharge port, one is located at vibratile sleeve in cylindrical shell, be located at the mixing mechanism in this sleeve, the driving mechanism that mixing mechanism is connected therewith, the electric control gear that driving mechanism is connected therewith.
By phosphogypsum modification agent and the mass ratio batching of the original-pack phosphogypsum of just discharging with 2: 8, send into extraordinary homogenization stirrer homogenizing and stir, after repressed moulding, deliver to phosphogypsum slag field and stack.
The properties index that detects modified ardealite is better than original state phosphogypsum, and has reached the emission standard of national regulation.
Embodiment 3
In the construction of phosphogypsum relief outlet, extraordinary homogenization stirrer is installed.Described extraordinary homogenization stirrer comprises a cylindrical shell that is provided with opening for feed and discharge port, one is located at vibratile sleeve in cylindrical shell, be located at the mixing mechanism in this sleeve, the driving mechanism that mixing mechanism is connected therewith, the electric control gear that driving mechanism is connected therewith.
Be 400m by specific surface area
2the superfine cement grog micro mist of/kg and the mass ratio batching of the original-pack phosphogypsum of just discharging with 2: 8, send into extraordinary homogenization stirrer homogenizing and stir, and delivers to phosphogypsum slag field and stack after repressed moulding.
The properties index that detects modified ardealite is better than original state phosphogypsum, and has reached the emission standard of national regulation.
Embodiment 4
The agent of configuration phosphogypsum modification, comprises that specific surface area is 500m
2the superfine cement grog micro mist of/kg and specific surface area are 500m
2the calcium carbonate fine powder of/kg; The mass ratio of described superfine cement grog micro mist and calcium carbonate fine powder is 4: 6.In the construction of phosphogypsum relief outlet, extraordinary homogenization stirrer is installed.Described extraordinary homogenization stirrer comprises a cylindrical shell that is provided with opening for feed and discharge port, one is located at vibratile sleeve in cylindrical shell, be located at the mixing mechanism in this sleeve, the driving mechanism that mixing mechanism is connected therewith, the electric control gear that driving mechanism is connected therewith.
By phosphogypsum modification agent and the mass ratio batching of the original-pack phosphogypsum of just discharging with 2: 8, send into extraordinary homogenization stirrer homogenizing and stir, after repressed moulding, deliver to phosphogypsum slag field and stack.
The properties index that detects modified ardealite is better than original state phosphogypsum, and has reached the emission standard of national regulation.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Everyly belong to apparent variation or the still row in protection scope of the present invention of variation that technical scheme of the present invention extends out.
Claims (2)
1. ardealite innocent is processed and a method that changes reclaimed gypsum resource into, it is characterized in that, comprises the steps:
Phosphogypsum modification agent and phosphogypsum are put into extraordinary homogenization stirrer to be stirred;
Described phosphogypsum modification agent comprises that specific surface area is more than or equal to 300m
2the superfine cement grog micro mist of/kg;
Also comprise that specific surface area is more than or equal to 300m
2the calcium carbonate fine powder of/kg; The mass ratio of described superfine cement grog micro mist and calcium carbonate fine powder is 3:7～1;
Also comprise that concentration is 50% alum solution; Described alum solution quality accounts for 3%～5% of phosphogypsum modification agent;
Described extraordinary homogenization stirrer comprises a cylindrical shell that is provided with opening for feed and discharge port, and one is located at vibratile sleeve in cylindrical shell, is located at the mixing mechanism in this sleeve, the driving mechanism that mixing mechanism is connected therewith.
2. method according to claim 1, is characterized in that, the mass ratio of described phosphogypsum modification agent and phosphogypsum is 1:9～2:8.
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| CN105688362A (en) * | 2016-01-18 | 2016-06-22 | 四川大学 | Stabilizing agent for phosphogypsum and method for innocent treatment of phosphogypsum |
| CN110282892B (en) * | 2019-08-13 | 2021-04-27 | 云南磷化集团有限公司 | Pretreatment method for shortening setting time of phosphogypsum for producing gypsum plasterboard |
| CN115849404A (en) * | 2022-12-02 | 2023-03-28 | 贵州大学 | Method for removing sodium and fixing sodium by utilizing crystal form conversion process of phosphogypsum in solution under normal pressure |
| CN116444184A (en) * | 2023-05-04 | 2023-07-18 | 云南吉麟环保科技有限公司 | Disposal method for converting phosphogypsum into high-quality gypsum resource through converting and carding gypsum crystal structure |
Citations (4)
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| CN101164954A (en) * | 2007-09-25 | 2008-04-23 | 中国水利水电第十四工程局 | Method for preparing phosphogypsum retardation setting high efficiency water reducing agent |
| CN101234858A (en) * | 2007-01-31 | 2008-08-06 | 王宝林 | Modification method for phosphogypsum and application thereof |
| CN101306925A (en) * | 2008-07-04 | 2008-11-19 | 昆明理工大学 | Process for preparing modified ardealite by water-free calcining |
| CN101475329A (en) * | 2009-02-09 | 2009-07-08 | 安徽德嘉新型建材有限公司 | Modified phosphogypsum powder and product thereof |
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Patent Citations (4)
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| CN101234858A (en) * | 2007-01-31 | 2008-08-06 | 王宝林 | Modification method for phosphogypsum and application thereof |
| CN101164954A (en) * | 2007-09-25 | 2008-04-23 | 中国水利水电第十四工程局 | Method for preparing phosphogypsum retardation setting high efficiency water reducing agent |
| CN101306925A (en) * | 2008-07-04 | 2008-11-19 | 昆明理工大学 | Process for preparing modified ardealite by water-free calcining |
| CN101475329A (en) * | 2009-02-09 | 2009-07-08 | 安徽德嘉新型建材有限公司 | Modified phosphogypsum powder and product thereof |
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Effective date of registration: 20211223 Address after: 650300 room 407, Qinglong sub district office, Qinglong Town, Anning City, Kunming City, Yunnan Province Patentee after: Yunnan Jilin Environmental Protection Technology Co.,Ltd. Address before: No. 1118, Block E, Huiyuan Apartment, Chaoyang District, Beijing 100101 Patentee before: ZHONGKE CHUANGTOU (BEIJING) TECHNOLOGY Co.,Ltd. |