CN106977123A - A kind of citric acid for being used to remove impurity fluorine in ardealite adds water the process washed - Google Patents
A kind of citric acid for being used to remove impurity fluorine in ardealite adds water the process washed Download PDFInfo
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- CN106977123A CN106977123A CN201710204685.5A CN201710204685A CN106977123A CN 106977123 A CN106977123 A CN 106977123A CN 201710204685 A CN201710204685 A CN 201710204685A CN 106977123 A CN106977123 A CN 106977123A
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- ardealite
- citric acid
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- fluorine
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/745—Preparation from sulfates
Abstract
A kind of citric acid for being used to remove impurity fluorine in ardealite adds water the process washed, including citric acid dissolving, lemon acid elution and washing three process, and the add water preparation process of the process washed of described citric acid includes following three step：First, prepare various concentrations aqueous citric acid solution standby, secondly, with the above-mentioned citric acid solution prepared plus washing process ardealite, finally, utilize lime neutralisation treatment washing waste water, with impurity in ardealite chemical action can occur for citric acid in solution, the impurity such as fluoride and phosphate in ardealite is set to change into washable ease of solubility material, removal of impurities is carried out by washing process again, make after purification, reduce in equipment and dry content of fluoride in flue gas, eliminating the ardealite of fluoride and phosphide can be utilized by ardealite relieving haperacidity joint product cement process, because fluoride is removed, corrosion will not be caused to sulfuric acid and cement production process workshop section equipment again.
Description
Technical field
The present invention relates to the method for removing impurity fluorine in ardealite, belong to industrial solid castoff processing and disposal skill
Art field.
Background technology
From the perspective of ecological environment, containing impurity such as fluorine, phosphorus, silicon in ardealite, because ardealite is stacked, this part
Impurity is through the easy polluted underground water of rain drop erosion and destroys geologic structure, therefore, in recent years, expires it in scientific disposal ardealite
The exploration of the processing method of foot comprehensive utilization target has caused the extensive concern of society research mechanism.Pre- place specific at present
The method of reason ardealite has WATER-WASHING METHOD, lime neutralisation, calcination method etc., and these methods are widely used.Although these are traditional
Processing method disclosure satisfy that the utilizability of ardealite, but there are still limitation, such as WATER-WASHING METHOD water consumption in comprehensive utilization
Big and ardealite treating capacity should not excessively, requirement of the calcination method to fuel it is higher, small to the degree of impurity removal in ardealite etc..
In summary, it is necessary to seek a kind of method that can effectively remove impurity particularly impurity fluorine in ardealite.Therefore, it is understanding
The problem of certainly impurity Oil repellent is big in ardealite, impurity fluorine can effectively be removed in ardealite and make by urgently needing to find one kind
It meets the process of comprehensive utilization and environmental requirement.
According to incompletely statistics, the annual production ardealite 2.12 × 10 in the whole world4~2.97×104T, China's ardealite in 2015
Volume of cargo in storage is more than 3 × 108T, ardealite（Phosphogypsum, PG）It is that the primary solids of wet process phosphoric acid plant and phosphate fertilizer plant give up
Thing, produces 1t phosphoric acid about output 4.5t ~ 5t ardealite, and ardealite is in powdered, and main component is CaSO4·2H2O, phosphorus
Gypsum contains many impurity, such as phosphorus, fluorine, silicon and organic matter etc. compared with the natural gypsum.Phosphorus impurities are comprehensively utilized to ardealite
Characteristic influence is maximum, and the acid feature that ardealite possesses in itself makes it be used as soil in China North China, northwest and the Northeast
Modifying agent, but this ardealite the utilization of resources can not on a large scale, fundamentally solution ardealite Utilizing question, and
Its characteristic can be effectively improved by carrying out pretreatment to ardealite by distinct methods, can be preferably utilized, ardealite
The influence of middle phosphorus is maximum, next to that fluorine and organic matter, they can produce influence to intensity, aquation rate and whiteness of ardealite etc..
Also contain alkali metal salt, silicon, magnesium and radioactive element, such as uranium, radium in ardealite.Phosphorus is primarily present in phosphate, carbonate
Among soluble-salt, phosphogypsum product can be caused to produce scum, efflorescence when meeting water.Silicon is main to be existed in the form of quartz,
Performance impact to ardealite is smaller.Fe2O3、Al2O3, the objectionable impurities such as MgO, cementing material during to preparing II type anhydrous gypsum
Aquation and hardening have certain facilitation, but it is introduced into ardealite can influence the pattern of dihydrate gypsum crystal.And phosphorus stone
People is known from experience and produces harm containing the radioactive element for being difficult to separate again in cream.
Ardealite is the product of Wet-process phosphoric acid (WPPA), in recent years, and domestic ardealite shows the situation of rapid growth, especially
It is larger in the big province's yield of the phosphorus ores such as Yunnan, Guizhou, Hubei, Anhui, Sichuan, Shandong, in terms of ardealite comprehensive utilization, the U.S.,
Germany, Japan, Brazil etc. achieve success in terms of the research, although China rises for the comprehensive utilizating research of ardealite
Step is than later, but development speed is quickly, by the tackling of key scientific and technical problems of development particularly scientific research institutions and enterprise for many years, ardealite
Apply and achieve large development in multiple fields.The ardealite not only economy of relation phosphate fertilizer industry, ecological benefits are comprehensively utilized,
Also it is related to the development of environmental protection and ecological construction, also complies with recycling economy, the economic development theory of Green Development.To 2015
In the end of the year, Chinese ardealite accumulating amount is more than 3 × 108T, but its utilization rate is relatively low（About 10% or so）.
Sulfuric acid is important basic chemical industry raw material, can be widely applied to chemical fertilizer, smelting, gunpowder, petrochemical industry, agriculture（Doctor）Medicine,
The industries such as army's industry.The raw material of traditional mode of production sulfuric acid is sulphur and troilite, accounts for the 70% of sulfuric acid total output, and China is a sulphur
Resource-starved country, is required for meeting demand by imported sulphur every year, imported sulphur 1500t in 2008；Cement is society
The Important building material of construction, applied in the engineerings such as civil construction, waterpower, national defence, the primary raw material of production cement is lime
Stone, can also consume substantial amounts of fuel and electric power, and give off substantial amounts of CO in production2And dust.
China is annual to be needed imported sulphur in production sulfuric acid, cement, exploits substantial amounts of mineral resources, and this behavior is not only
Foreign exchange can be taken, Mineral Resources in China is quickly consumed, and serious pollution can be caused to China's environment.Recycling economy is the epoch
The theme of development, but China rises year by year to the demand of sulfuric acid and cement, and the stacking problems demand of ardealite is solved.Utilize
Ardealite relieving haperacidity co-producing cement, not only solves the demand of Sulphur ressource and cement, it is thus also avoided that mining and environmental pollution,
Achieve many things at one stroke, this will be a kind of following effective way comprehensively utilized of ardealite.
The advantage of gypsum Sulphuric acid co-producing cement is embodied in, and it is, using gypsum as raw material, to be broken down into SO2And CaO,
Dinectly bruning, into clinker, is then milled into cement products together with mixing material after disassembly for CaO and the auxiliary material prepared,
Other impurities in gypsum are also inserted in clinker, and containing SO2Gas be manufactured into sulfuric acid.A kind of raw material can produce two
Product is planted, interests are expanded, while without solid waste, discharge of wastewater, traditional sulfuric acid, manufacture of cement raw material can also be substituted, both
Mining is reduced, the environmental pollution in production is reduced again, but fluorinated volume is big in ardealite, especially by drying workshop section
When in flue gas, fluoride amount is larger, higher to the erosion degree of equipment.
The chemical constituent content of the ardealite of different sources is slightly different, and will come from Guizhou Wengan, Hefei ,Anhui, Yunnan elder brother
Bright ardealite sample takes back laboratory with sealing material, normative reference GB/T5484-2000, GB/T23456-2009,
GC/T2073-2011 is researched and analysed to ardealite sample, and sample is dried 2 hours at 120 DEG C, is cooled to after room temperature and is surveyed
Determine different sources ardealite chemical constituent content, such as table 1.
The different sources ardealite chemical constituent content of table 1
| The place of production | State | CaO | SO3 | SiO2 | P2O5 | F- | Al2O3 | Fe2O3 | MgO | Other |
| Guizhou | Powdery | 30.54 | 42.84 | 2.773 | 0.74 | 0.45 | 0.613 | 0.111 | 0.30 | 21.633 |
| Anhui | Powdery | 32.16 | 44.37 | 4.28 | 2.62 | 0.23 | 0.35 | 0.13 | 0.29 | 15.57 |
| Yunnan | Powdery | 31.94 | 45.38 | 14.52 | 0.94 | 0.12 | 1.66 | 0.15 | 0.17 | 5.12 |
At present, the existing technique using ardealite all needs to pre-process ardealite, in factory's ardealite relieving haperacidity co-producing cement
In technique, ardealite is dried by high-temperature flue gas, and fluorine impurity becomes fluoride by decomposition and is present among drying flue gas, fluorination
Thing causes equipment to be corroded in acidity, so some researchers research is made a return journey except ardealite relieving haperacidity flue gas by appliance arrangement
In fluoride.
Wang Yanjun is in the patent " a kind of ardealite Sulphuric acid gas cleaning diluted acid fluorine removal device " published
（CN205821060U）It is middle to introduce by connecting fluorine removal reactor in pending dilute sulfuric acid storage tank rear end, while in fluorine removal reactor
Entrance sets fluorine removal medicament pipe, pending dilute sulfuric acid and fluorine removal medicament is passed through in fluorine removal reactor simultaneously, in fluorine removal reactor
Middle completion defluorinating process.Small volume, the floor space of fluorine removal reactor are small, without other power agitating devices, react in pressure
Effect is lower to make fluorine removal medicament and diluted acid fully qualitative response by the effect of compressed air, improves reaction speed, saves reaction
Time, and then the removal efficiency of fluorine is improved, set gradually air supporting settler, automatic back-washing surface filtration in fluorine removal reactor rear end
Device and plate and frame filter press, to the further purified treatment of filtrate after fluorine removal, so that the purpose of purification is once reached, this apparatus structure
It is simple and convenient to operate.But it is not that solution ardealite flue gas is fluorine-containing to flue gas fluorine removal in ardealite process of preparing sulfuric acid with apparatus
The high basic plan of amount, while device cleaning is difficult, once serious fluorine leakage problem can be caused by breaking down, exist safety and
Environmental pollution hidden danger.
Some researchers selection carries out fluorine removal pretreatment before ardealite enters drying workshop section to it, and main method includes
Washing ardealite goes the impurity such as fluorine removal, the acid-hatching of young eggs to remove fluorine impurity and citric acid dissolving in ardealite and goes the removal of impurity.While acid wash
Except ardealite is first to carry out acidleach processing to ardealite with sulfuric acid solution, then by filtering, being washed to neutrality, pickle liquor is returned
It is used as decomposing phosphate rock among to Wet Processes of Phosphoric Acid, washing waste liquid can be recycled as the leaching removal of impurities of ardealite by complex acid,
It can avoid causing secondary pollution to environment among process." vitriol lixiviation method removes ardealite to the periodical that Kong Xia, Li Huping etc. are delivered
In the research of middle impurity fluorine "（Chemical Engineering, 2012,40(8):65-68）Point out to find through persulfate solution hot dipping by studying
The clearance of fluorine can reach 84.5% in the ardealite taken, and fluorine-containing mass fraction can be reduced to 0.0350%, draw more satisfactory
Optimal Experimental condition be：Leaching temperature is arranged on 88 DEG C, and leaching time is 45min, and the mass fraction of sulfuric acid is 30%, containing solid
Measure as 0.43g/mL.The ardealite handled by this method improves whiteness, the utilization rate of ardealite is expanded significantly, this side
Method is simple, and effect is good, does not result in secondary pollution.Wang Hong etc. is in periodical " shallow to state ardealite washing filtering technique "（Guizhou
Work, 2013,38(2):42-43）Describing a kind of washing filtering technique can control the free phosphoric acid concentration in ardealite one
In fixed scope, used as raw material supply production ammonium sulfate device, that is, solve ardealite and stack pollution problem, circulation is played again
It is that the progress and development of China's sulphur dioxide of phosphor chemical industry are played a part of actively promoting using economic effect is promoted.Establish an army recklessly in the phase
Print in " phosphogypsum purification water-wash test and technique "（Phosphate fertilizer and compound fertilizer, 2007,22(5):66-67）Using water washing treatment method,
Impurity in ardealite is removed, so that ardealite can be widely used in the production of the building material products such as Thistle board, gypsum block, but
These researchs are that washing removes phosphorus and titanium pigment and soluble fluoride in ardealite, to slightly solubility fluorine such as CaF2、Na2SiF6、
NaF etc. can not be removed, and need that, by processing, secondary pollution not so can be caused simultaneously for washing waste liquid.Soviet Union's fertilizer and deinsectization
Sterilize Science Institute and propose that a kind of method for going fluorine removal, i.e. temperature are heat-treated 30min at 300 DEG C to ardealite, acidity pH exists
1.8 ~ 2.2, humidity is higher than 20%, then can remove in residue phosphogypsum 85 ~ 95% fluorine, but waste liquid shows strong acid obtained by the above method
Property, dealing with improperly can pollute to environment.
In recent years, we disclose a kind of preparation method and application of Treatment of Zinc-containing Wastewater adsorbent, its methods described for pair
Ardealite is modified after carrying out sodium chloride pretreatment using aluminum sulfate modification technology to ardealite, is produced and is obtained aluminium base modification phosphorus
Gypsum adsorbent, Al3+Ardealite interlayer is entered by ion-exchange reactions, and struts interlayer to increase interlamellar spacing and hole
Footpath, the microcellular structure of the adsorbent further increases, so that the porosity and specific surface area of ardealite are improved, with good suction
Attached performance, the ardealite after further handling has higher adsorption capacity, enables to turn into a kind of the excellent of removal zinc ion
Good sorbing material（CN201410690082.7）, hydroxyapatite（HA）To F–With powerful suction-operated, but commonsense method
The HA adsorptivities of synthesis are poor, and we report a kind of synthesis nanometer to micron-sized hydroxyapatite（HA）New method, this
The method of kind can effectively improve HA filters to F–Adsorption efficiency（Environmental Science & Technology,
2014,48(10):5798）, afterwards, some perfect, direct carbon aquations of ardealite are done to the processing of cement plant phosphogypsum slag,
Its carbonating product obtained in calcium cyclic process is set to can be used for CO2Trapping, and utilize useless CaO base adsorbents manufacture water
Mud clinker, and the CO derived from the flue gas of cement plant2The calcium sulfate in ardealite directly can be converted into calcium carbonate, therefore, fortune
Phosphogypsum slag can be not only reclaimed with this method, and the CO in cement plant can be reduced2Discharge（Energy & Fuels,
2016,30(2)）, the recovery to ardealite, we are by using sulphur coal as reducing agent, using thermogravimetric analysis, differential thermal analysis, sweeping
The means such as Electronic Speculum, X-ray diffraction are retouched to characterize decomposable process of the ardealite under the conditions of different atmosphere in nitrogen atmosphere,
Its primary product is calcium sulphoaluminate（Industrial & Engineering Chemistry Research, 2010,49(8):
3597-3602）, in " wet phosphoric acid " chemical fertilizer production, ardealite belongs to a kind of waste by-product, but ardealite is in other necks
But there is purposes in domain greatly, so being just particularly important to its recovery, we report a kind of recovery to ardealite
Method, wherein reducing agent are CO, and additive is calcium chloride, and decomposition temperature is 790 DEG C, and its primary product is calcium sulphoaluminate, but this
It is CO that reducing agent is used in method, belongs to toxic gas, easily produces harm to human body（Industrial & Engineering Chemistry Research, 2012,51(19):6680–6685）, the global demand amount of rare earth element increases sharply,
And the byproduct ardealite of phosphoric acid production is considered as one of source of rare earth element, we report adds in infusion solution
Calcium sulfate anhydrite seed, so that suppress in leachate the degraded of calcium sulfate and reduce calcium concentration, and the leaching efficiency of rare earth
Again relevant with ardealite solubility, i.e., its concentration, which declines, can increase rare earth element leaching content（Industrial & Engineering Chemistry Research, 2016,55, 12309-12316）.
By literature survey, dephosphorization is gone to three kinds in terms of defluorination effect, environmental pollution, financial cost, technical difficulty
Fluorine impurity method is compared in gypsum, and the key property of the ardealite according to research ground, is added using citric acid solution dissolving
The method of washing is pre-processed to ardealite, reaches the purpose for removing fluorine impurity in ardealite.Citric acid purposes widely, is used for
Food, chemical industry, pharmaceuticals industry, food service industry are mainly used as acid and preservative, and chemical industry makees complexing agent using citric acid
And cushioning liquid, pharmaceutical sector mainly makees citric acid radical ion with citric acid, its can be formed with calcium ion it is a kind of be difficult to dissociate can
Solubleness complex, thus calcium ion concentration in blood is reduced, blood clotting is obstructed, be good external anticoagulation.Citric acid
With a large amount of water soluble ingredients of all kinds of impurity reaction generations in ardealite, the reaction equation with fluoride is：
2C6H8O7+3NaF→Na3(C6H5O7)2+3HF
4C6H8O7+3Na2SiF6→2Na3(C6H5O7)2+H3SiF6
2C6H8O7+2Na3AlF6→2Na3(C6H5O7)2+H3AlF6
2C6H8O7+3Na2FeF6→2Na3(C6H5O7)2+H3FeF6
2C6H8O7+3CaF2→Ca3(C6H5O7)2+6HF
It is with phosphate reaction equation：
2C6H8O7+3Ca(H2PO4)2·H2O→Ca3(C6H5O7)2+2H3PO4
2C6H8O7+3CaHPO4·2H2O→Ca3(C6H5O7)2+2H3PO4+2H2O
2C6H8O7+Ca3(PO4)2→Ca3(C6H5O7)2+2H3PO4
From the reaction of above-mentioned citric acid and ardealite, citric acid can be generated with the phosphate in ardealite and fluoride reaction
The readily soluble material that can be washed with water, the effect of removal of impurities can be reached by washing.
In the present invention, we report using citric acid as lytic agent to purify ardealite and make a return journey dephosphorization with reference to washing
The method of impurity fluorine in gypsum.
In recent years, the comprehensive utilizating research of solid waste ardealite causes the interest of each side experts and scholars.In " sulfuric acid life
Liao Qiu realities, Qin Mingwu et al. in production present situation and ardealite Sulphuric acid progress "（Hubei Three Gorges Polytechnic's journal,
2015, (1):98-100）Describe the techniques such as acid production with sulphur, ardealite relieving haperacidity advantage and disadvantage and ardealite comprehensive utilization
Present situation.Lee in 2013 discloses patent of invention after liter et al.（CN201310475824.X）" washing and purifying method of ardealite "
Preparation method.It employs following step：Ardealite is put into water, washed, tiny soluble impurity therein is removed,
Enter ladder pond afterwards and carry out classification washing, ladder pond is divided into 2-5 grades, removes insoluble impurities tiny in ardealite, then enter
Row wet screening is filtered, and removes the quartzy and unreacted impurity of bulky grain in ardealite, is finally neutralized using lime, goes dephosphorization
The acid remained in gypsum.Cao Zhi in 2015 is strong et al. to disclose patent of invention（CN201520404286.X）" one kind removes dephosphorization stone
The application method of the device of organic matter in cream ".This method mainly elaborates a kind of device for removing organic matter in ardealite, passes through
Organic matter in ardealite slurry is taken to overflow in the annular overflow trough on separation cone tank top and collected by air supporting gravitational method with bubble, point
Collected after being cleaned from the remaining slurry in cone tank by cleaning device in discharging opening.It is special that Merka in 2016 et al. discloses invention
Profit（WO2016186527）" Method for complex treatment of phosphogypsum " preparation method.It
Employ following step：After ardealite and sulfuric acid solution reaction, gained mixture is separated into liquid and deposit, deposits owner
Containing calcium sulfate, by deposit and ammoniacal liquor and CO2Gained is precipitated after generating ammonium sulfate and calcium carbonate, filtration drying after reaction
Dissolution of calcium carbonate is separated in nitric acid, then by gained mixture, obtains nitrate solution and fluoride precipitation and silicate is heavy
Form sediment.Konstantin Kovler in 2017 et al. disclose patent of invention (US20170022070) " System and
methods for removing impurities from phosphogypsum and manufacturing gypsum
Binders and products " preparation method.It employs following step：By ardealite under sour environment with chloride
Solution reaction, obtains ardealite sediment, contained in ardealite to remove using electrochemistry and zeolite adsorption after dewatering and filtering
Impurity.E o г а т ы р e в а Е л e н а В л а д и м и р o в н а in 2017 et al. disclose patent of invention (RU0002607862)
“Method of extracting rare-earth metals and producing gypsum plaster from
Anhydrite " preparation method.This method obtains rare earth in mainly elaborating a kind of waste residue for producing sulfuric acid from apatite relieving haperacidity
The method of metal and ardealite plaster of Paris.
Though the above method has many advantages, such as, involved method actual operation difficulty is big in its Part Methods, and fluorine is contained
Amount processing is not thorough enough, and specific aim is poor, it is impossible to tackle the problem at its root, and citric acid adds washing process not only can be to phosphorus stone
Cream is pre-processed, and in ardealite it is fluorine-containing and slightly solubility fluorine with strong points, clearance is high, and follow-up washing waste water is through place
Reason can be recycled.
The content of the invention
Goal of the invention：The weak point existed for currently available technology, the present invention is using citric acid to miscellaneous in ardealite
The difference of matter composition dissolution degree, is converted into soluble washing impurity, and tie to realize by impurity such as fluorides in ardealite
Heshui washing method, designs a kind of citric acid to fluorine impurity in ardealite and adds water and wash away except technique.The method is by contrasting not
The difference for adding water and washing to impurity removal efficiency of flouride in ardealite is dissolved with concentration citric acid, finds a kind of effective to the pre- place of ardealite
Manage the method for complying with ardealite relieving haperacidity joint product cement process standard.
The technical scheme is that：A kind of citric acid for being used to remove impurity fluorine in ardealite adds water the technique side washed
Method, including citric acid dissolving, lemon acid elution and washing three process.It is characterized in that：The citric acid solution can be with phosphorus stone
Chemical action occurs for impurity in cream, the impurity such as fluoride and phosphate in ardealite is changed into washable ease of solubility material,
Removal of impurities is carried out by washing process again, the ardealite after purification is preferably utilized by ardealite relieving haperacidity joint product cement process,
So as to reduce content of fluoride in drying flue gas, while not influenceing sulfuric acid and cement production process, described citric acid, which adds water, to be washed
Process preparation process include following three step：
1.1 first steps are to prepare various concentrations citric acid solution：It is that centesimal electronic balance is accurately weighed respectively with precision
Citric acid 3.00g, 4.00g, 5.00g, 6.00g and 7.00g, match the lemon that mass concentration is 3%, 4%, 5%, 6% and 7% respectively
Aqueous acid is standby, then measures 10mL respectively from the above-mentioned aqueous citric acid solution prepared and be placed in 150mL beakers, each to add
90mL deionized waters, are diluted to the aqueous citric acid solution that mass concentration is 0.3%, 0.4%, 0.5%, 0.6% and 0.7% standby；
1.2 second steps are with citric acid plus washing process ardealite：With precision be centesimal electronic balance weigh 9.00g ~
In six parts of 9.60g ardealite material sample, the glassware for being respectively placed in identical scale and size, then take 10mL's respectively
3%th, 4%, 5%, 6% and 7% aqueous citric acid solution is added in ardealite sample, and 15 ~ 25min of mechanical agitation is until dissolving, dissolving
Mixture afterwards is filtered by filter, and filtrate moves to collecting tank collection, with the and of mass concentration 0.3%, 0.4%, 0.5%, 0.6%
0.7% aqueous citric acid solution carries out ultrasonic disperse to the filter residue after filtering and washs 6 ~ 10min, and in centrifuge with 3000 ~
4000rpm rotating speeds centrifuge 8 ~ 12min, then add the washing of pure water ultrasonic disperse simultaneously rotating centrifugal 2 times, the purification obtained after centrifugation
Ardealite sample 1 afterwards#、2#、3#、4#、5#, then by the ardealite sample after purification by 85 DEG C of electric heating constant-temperature blowing drying box
12h is dried, finished product is obtained；
1.3 the 3rd steps are lime neutralisation treatment washing waste waters：Proportioning mass concentration is added to waste liquid for 0.3 ~ 0.5% limewash
In collecting tank, 8 ~ 12min is stirred, distributed slurry is obtained, the pH value of slurry is determined with pH meter, and it is 85 ~ 95% to add mass concentration
Limewash the pH value of this slurry is adjusted to 7；Alum solution is eventually adding, stirs quiet after 10 ~ 15min in waste water treatment tank
Layering is put, it is 7 sediment for neutralizing water and lower floor's indissoluble to obtain upper strata pH value.
As a further improvement of existing technologies, it is described to add washing process ardealite using citric acid to reach that fluorine removal is imitated
During the method for fruit, ardealite fluorine removal other acid-base property additives are not added in addition to adding citric acid.Described phosphorus
Gypsum is the solid waste of phosphoric acid plant wet production.Described ardealite fluorine removal is contained relative to untreated ardealite fluorine
The relative clearance of amount.Described citric acid, which adds water, to be washed away except fluorine impurity in ardealite, and technological operation is simple, financial cost is closed
Reason, it is with short production cycle.Described ardealite raw material sources are abundant, cost is low, easy acquisition.Ardealite is used as phosphorus after described fluorine removal
Gypsum relieving haperacidity joint product cement process raw material, can reduce ardealite fluoride in the flue gas that drying workshop section produces, it is to avoid to set
It is standby to corrode, with certain environment protection significance.
Relative to the beneficial effect of prior art：
In recent years, the comprehensive utilizating research of solid waste ardealite causes the interest of each side experts and scholars." gas washing in SA production is existing
Liao Qiu realities, Qin Mingwu et al. in shape and ardealite Sulphuric acid progress "（Hubei Three Gorges Polytechnic's journal, 2015,
(1):98-100）Describe the advantage and disadvantage of the techniques such as acid production with sulphur, ardealite relieving haperacidity and the present situation of ardealite comprehensive utilization.
Lee in 2013 discloses patent of invention after liter et al.（CN201310475824.X）The preparation of " washing and purifying method of ardealite "
Method.It employs following step：Ardealite is put into water, washed, tiny soluble impurity therein is removed, afterwards
Classification washing is carried out into ladder pond, ladder pond is divided into 2-5 grades, removes insoluble impurities tiny in ardealite, then carry out wet
Filter is sieved through, the quartzy and unreacted impurity of bulky grain in ardealite is removed, is finally neutralized using lime, ardealite is removed
The acid of middle residual.Cao Zhi in 2015 is strong et al. to disclose patent of invention（CN201520404286.X）" one kind is removed in ardealite
The preparation method of the device of organic matter ".This method mainly elaborates a kind of device for removing organic matter in ardealite, passes through air supporting
Organic matter in ardealite slurry is taken to overflow in the annular overflow trough on separation cone tank top and collected by gravitational method with bubble, separation cone
Remaining slurry in tank is collected after being cleaned by cleaning device in discharging opening.Merka in 2016 et al. discloses patent of invention
(WO2016186527) " Method for complex treatment of phosphogypsum " preparation method.It is adopted
With following step：After ardealite and sulfuric acid solution reaction, gained mixture is separated into liquid and deposit, and deposit is main
Containing calcium sulfate, by deposit and ammoniacal liquor and CO2Gained is precipitated into carbon after generating ammonium sulfate and calcium carbonate, filtration drying after reaction
Sour calcium is dissolved in nitric acid, then gained mixture is separated, and obtains nitrate solution and fluoride precipitation and silicate precipitates.
Konstantin Kovler in 2017 et al. disclose patent of invention（US20170022070）“System and methods
for removing impurities from phosphogypsum and manufacturing gypsum binders
And products " preparation method.It employs following step：By ardealite under sour environment it is anti-with chloride solution
Should, ardealite sediment is obtained, electrochemistry and zeolite adsorption are utilized after dewatering and filtering to remove impurities in ardealite.
E o г а т ы р e в а Е л e н а В л а д и м и р o в н а in 2017 et al. disclose patent of invention（RU0002607862）
“Method of extracting rare-earth metals and producing gypsum plaster from
Anhydrite " preparation method.This method obtains rare earth in mainly elaborating a kind of waste residue for producing sulfuric acid from apatite relieving haperacidity
The method of metal and ardealite plaster of Paris.
Though the above method has many advantages, such as, involved method actual operation difficulty is big in its Part Methods, and fluorine is contained
Amount processing is not thorough enough, and specific aim is poor, it is impossible to tackle the problem at its root, and citric acid adds washing process not only can be to phosphorus stone
Cream is pre-processed, and in ardealite it is fluorine-containing and slightly solubility fluorine with strong points, clearance is high, and follow-up washing waste water is through place
Reason can be recycled.
The present invention is to prepare various concentrations citric acid solution first：It is that centesimal electronic balance difference is accurate with precision
Citric acid 3.00g, 4.00g, 5.00g, 6.00g and 7.00g are weighed, it is 3%, 4%, 5%, 6% and 7% that mass concentration is matched respectively
Aqueous citric acid solution is standby, then measures 10mL respectively from the above-mentioned aqueous citric acid solution prepared and be placed in 150mL beakers, respectively
90mL deionized waters are added, the aqueous citric acid solution that mass concentration is 0.3%, 0.4%, 0.5%, 0.6% and 0.7% is diluted to
It is standby；
Next to that adding washing process ardealite with citric acid：It is that centesimal electronic balance weighs 9.00g ~ 9.60g with precision
Six parts of ardealite material sample, in the glassware for being respectively placed in identical scale and size, then take respectively 10mL 3%, 4%,
5%th, 6% and 7% aqueous citric acid solution is added in ardealite sample, and 15 ~ 25min of mechanical agitation is until dissolving, mixed after dissolving
Compound is filtered by filter, and filtrate moves to collecting tank collection, with mass concentration 0.3%, 0.4%, 0.5%, 0.6% and 0.7%
Aqueous citric acid solution carries out ultrasonic disperse to the filter residue after filtering and washs 6 ~ 10min, and with 3000 ~ 4000rpm in centrifuge
Rotating speed centrifuges 8 ~ 12min, then adds the washing of pure water ultrasonic disperse simultaneously rotating centrifugal 2 times, phosphorus stone after the purification obtained after centrifugation
Cream sample 1#、2#、3#、4#、5#, then by the ardealite sample after purification by being dried in 85 DEG C of electric heating constant-temperature blowing drying box
12h, obtains finished product；
It is finally lime neutralisation treatment washing waste water：Proportioning mass concentration is added to waste collection groove for 0.3 ~ 0.5% limewash
In, 8 ~ 12min is stirred, distributed slurry is obtained, the pH value of slurry is determined with pH meter, and adds the lime that mass concentration is 85 ~ 95%
Water adjusts the pH value of this slurry to 7；Alum solution is eventually adding, stirs to stand after 10 ~ 15min in waste water treatment tank and divides
Layer, it is 7 sediment for neutralizing water and lower floor's indissoluble to obtain upper strata pH value.
In summary, it is a kind of be used for remove impurity fluorine in ardealite citric acid add water the process washed have it is following excellent
Point：
One:Washing method is added water with citric acid to handle phosphoric acid by wet process solid waste ardealite, and the fluorine in ardealite can be made miscellaneous
Matter is substantially removed.
Secondly：Main component is not changed in ardealite after citric acid plus washing process, and phosphorus stone is not influenceed
The progress of cream relieving haperacidity joint product cement process.
Thirdly：Ardealite is the primary solids waste of phosphoric acid by wet process, and its output, accumulating amount are increasing year by year, due to miscellaneous
The problem of easily causing environmental pollution matter composition, the spy of comprehensive utilization is more met by pretreated ardealite more as raw material
Point, with certain environment protection significance.
It four：Citric acid, which adds water, washes waste liquid by collecting using alum and the processing of lime neutralization method, obtained neutral water
It can be used for process cycles to use.
It five：Compared with other ardealite defluorination methods, with simple to operate, cost of investment it is low, be easily achieved and fluorine is miscellaneous
The characteristics of matter removal effect is good.
It six：Ardealite, due to Oil repellent reduction, makes baking as raw material in ardealite relieving haperacidity joint product cement process after processing
Content of fluoride relative reduction in dry flue gas, equipment erosion problem is effectively solved.
It seven：The various concentrations citric acid of use adds the ardealite chemical composition content (m%) after washing process, 5% He
0.5% aqueous citric acid solution coordinates washing best results（P in 3# samples2O5、F-Mass fraction is minimum）, as shown in table 2.
The various concentrations citric acid of table 2 adds ardealite chemical composition content (m%) * after washing process
| Sample | CaO | SO3 | SiO2 | P2O5 | F- | Al2O3 | Fe2O3 | MgO | Other |
| 1# | 29.760 | 38.563 | 2.068 | 0.274 | 0.120 | 0.482 | 0.129 | 0.140 | 28.564 |
| 2# | 30.240 | 40.985 | 1.461 | 0.280 | 0.070 | 0.427 | 0.086 | 0.118 | 26.333 |
| 3# | 30.130 | 41.427 | 2.546 | 0.220 | 0.039 | 0.466 | 0.104 | 0.173 | 24.890 |
| 4# | 29.290 | 40.132 | 1.862 | 0.250 | 0.043 | 0.425 | 0.103 | 0.210 | 27.685 |
| 5# | 29.666 | 39.976 | 2.545 | 0.230 | 0.044 | 0.436 | 0.166 | 0.232 | 26.708 |
*：Chemical composition analysis is carried out to sample after purification using x-ray fluorescence analyzer.
Brief description of the drawings
Fig. 1 is that the citric acid that uses of the present invention adds water and washes before processing（A）After processing（B）Ardealite XRD spectrum.
Fig. 2 be citric acid of the present invention add water wash before processing ardealite SEM figure.
Fig. 3 is ardealite SEM figures under different multiplication factors after citric acid of the present invention plus washing process.
Embodiment is explained further with reference to the accompanying drawings
Fig. 1 is that the citric acid that uses of the present invention adds water and washes before processing（A）After processing（B）Ardealite XRD spectrum, illustration represents
Be collection of illustrative plates feature that ardealite is shown under X-ray.Present invention basis adds washing process phosphorus to various concentrations citric acid
Gypsum compares, and the lemon acid elution that the citric acid dissolving and mass concentration that selection mass concentration is 5% are 0.5% is combined with washing
Method, figure A be before processing ardealite raw material XRD, according to Jade softwares, ardealite main component is CaSO4·2H2O and
SiO2, its PDF card numbering is respectively 33-0311,44-0696, at the same background have it is not of uniform size disperse peak, wherein containing few
The P of amount2O5, its PDF card numbering is 23-1301.It is ardealite raw material XRD after processing to scheme B, according to Jade software analysis, main
Want composition CaSO4·2H2O does not change, but contains a small amount of CaPO in the sample after purification3(OH)·2H2O。
Fig. 2 is that citric acid of the present invention adds water and washes the SEM figures of before processing ardealite, represents that before processing ardealite is brilliant
Shape and impurity situation that body is shown.Show that ardealite particle is plate-like in the parallelogram of rule in figure, single
Grain dense surface is attached with substantial amounts of fine impurities particle.Found out according to scanning electron microscope diagram, the main gray of ardealite,
The platy structure of the parallelogram of comparison rule is integrally presented in ardealite, and most crystalline form is more regular, and surface attachment
There are a large amount of granule foreigns, be titanium pigment, fluorine and organic matter etc..
Fig. 3 is ardealite SEM figures under different multiplication factors, figure after citric acid of the present invention plus washing process
A is that ardealite raw material dissolves by aqueous citric acid solution, and aqueous citric acid solution is washed after dilution, eventually passes water twice
The ardealite sample obtained after washing is compared, impurity is substantially gone under 450 times of multiplication factors with ardealite sample before purification
Remove, overall clean, ardealite entirety parallelogram structure.Figure B is that ardealite raw material dissolves by aqueous citric acid solution,
And aqueous citric acid solution is washed after dilution, the ardealite sample obtained after washing twice is eventually passed in 2200 times of multiplication factors
Under see ester exchange at phosphorus figure, impurity removes clean, and whisker is well arranged, clear-cut, illustrate that the ardealite after purifying is eliminated
Certain Ca (H2PO4)2、CaHPO4、Ca3(PO4)2With the impurity such as organic matter.
Embodiment：A kind of citric acid for being used to remove impurity fluorine in ardealite adds water the process washed, including
Citric acid dissolving, lemon acid elution and washing three process.It is characterized in that：The citric acid solution can be with impurity in ardealite
Generation chemical action, makes the impurity such as fluoride and phosphate in ardealite change into washable ease of solubility material, then pass through water
Wash technique and carry out removal of impurities, the ardealite after purification is preferably utilized by ardealite relieving haperacidity joint product cement process, so as to reduce
The content of fluoride in flue gas is dried, while not influenceing sulfuric acid and cement production process, preparation process of the invention includes as follows
Step：
The first step is to prepare various concentrations citric acid solution：It is that centesimal electronic balance accurately weighs lemon respectively with precision
Sour 3.00g, 4.00g, 5.00g, 6.00g and 7.00g, match the citric acid water that mass concentration is 3%, 4%, 5%, 6% and 7% respectively
Solution for standby, then measure 10mL respectively from the above-mentioned aqueous citric acid solution prepared and be placed in 150mL beakers, respectively add 90mL
Deionized water, is diluted to the aqueous citric acid solution that mass concentration is 0.3%, 0.4%, 0.5%, 0.6% and 0.7% standby；
Second step is with citric acid plus washing process ardealite：With precision be centesimal electronic balance weigh 9.00g ~
In six parts of 9.60g ardealite material sample, the glassware for being respectively placed in identical scale and size, then take 10mL's respectively
3%th, 4%, 5%, 6% and 7% aqueous citric acid solution is added in ardealite sample, and 15 ~ 25min of mechanical agitation is until dissolving, dissolving
Mixture afterwards is filtered by filter, and filtrate moves to collecting tank collection, with the and of mass concentration 0.3%, 0.4%, 0.5%, 0.6%
0.7% aqueous citric acid solution carries out ultrasonic disperse to the filter residue after filtering and washs 6 ~ 10min, and in centrifuge with 3000 ~
4000rpm rotating speeds centrifuge 8 ~ 12min, then add the washing of pure water ultrasonic disperse simultaneously rotating centrifugal 2 times, the purification obtained after centrifugation
Ardealite sample 1 afterwards#、2#、3#、4#、5#, then by the ardealite sample after purification by 85 DEG C of electric heating constant-temperature blowing drying box
12h is dried, finished product is obtained；
3rd step is lime neutralisation treatment washing waste water：Proportioning mass concentration is added to waste collection for 0.3 ~ 0.5% limewash
In groove, 8 ~ 12min is stirred, distributed slurry is obtained, the pH value of slurry is determined with pH meter, and add the stone that mass concentration is 85 ~ 95%
Buck adjusts the pH value of this slurry to 7；Alum solution is eventually adding, stirs to stand after 10 ~ 15min in waste water treatment tank and divides
Layer, it is 7 sediment for neutralizing water and lower floor's indissoluble to obtain upper strata pH value.
Claims (7)
- The process washed 1. a kind of citric acid for removing impurity fluorine in ardealite adds water, including citric acid dissolving, lemon Acid elution and washing three process, it is characterised in that：With impurity in ardealite chemical action can occur for the citric acid solution, make The impurity such as fluoride and phosphate changes into washable ease of solubility material in ardealite, then carries out removal of impurities by washing process, The ardealite after purification is set preferably to be utilized by ardealite relieving haperacidity joint product cement process, so as to reduce fluoride in drying flue gas Content, while do not influence sulfuric acid and cement production process, the add water preparation process of the process washed of described citric acid includes Following three step：1.1 prepare various concentrations citric acid solution：It is that centesimal electronic balance accurately weighs citric acid respectively with precision 3.00g, 4.00g, 5.00g, 6.00g and 7.00g, match mass concentration water-soluble for 3%, 4%, 5%, 6% and 7% citric acid respectively Liquid is standby, then measures 10mL respectively from the above-mentioned aqueous citric acid solution prepared and be placed in 150mL beakers, and each 90mL that adds is gone Ionized water, is diluted to the aqueous citric acid solution that mass concentration is 0.3%, 0.4%, 0.5%, 0.6% and 0.7% standby；1.2 add washing process ardealite with citric acid：It is the phosphorus that centesimal electronic balance weighs 9.00g ~ 9.60g with precision In six parts of gypsum raw material sample, the glassware for being respectively placed in identical scale and size, then 3%, 4%, 5%, the 6% of 10mL is taken respectively Aqueous citric acid solution with 7% is added in ardealite sample, and 15 ~ 25min of mechanical agitation is until dissolving, the mixture after dissolving Filtered by filter, filtrate moves to collecting tank collection, with the lemon of mass concentration 0.3%, 0.4%, 0.5%, 0.6% and 0.7% Aqueous acid carries out ultrasonic disperse to the filter residue after filtering and washs 6 ~ 10min, and with 3000 ~ 4000rpm rotating speeds in centrifuge 8 ~ 12min is centrifuged, the washing of pure water ultrasonic disperse simultaneously rotating centrifugal 2 times, ardealite sample after the purification obtained after centrifugation are then added Product 1#、2#、3#、4#、5#, then the ardealite sample after purification obtained by drying 12h in 85 DEG C of electric heating constant-temperature blowing drying box To finished product；1.3 lime neutralisation treatment washing waste waters：Proportioning mass concentration is added in waste collection groove for 0.3 ~ 0.5% limewash, 8 ~ 12min is stirred, distributed slurry is obtained, the pH value of slurry is determined with pH meter, and adds the limewash that mass concentration is 85 ~ 95% The pH value of this slurry is adjusted to 7；Alum solution is eventually adding, stratification after 10 ~ 15min is stirred in waste water treatment tank, It is 7 sediment for neutralizing water and lower floor's indissoluble to obtain upper strata pH value.
- The process washed 2. a kind of citric acid for removing impurity fluorine in ardealite according to claim 1 adds water, It is characterized in that：Described goes removal of impurity fluorine to be the fluorine in ardealite.
- The process washed 3. a kind of citric acid for removing impurity fluorine in ardealite according to claim 1 adds water, It is characterized in that：Described ardealite is the primary solids waste of Wet-process Phosphoric Acid Production.
- The process washed 4. a kind of citric acid for removing impurity fluorine in ardealite according to claim 1 adds water, It is characterized in that：Described mass concentration is that 3%, 4%, 5%, 6% and 7% aqueous citric acid solution refers to water and citric acid mixing Prepared.
- The process washed 5. a kind of citric acid for removing impurity fluorine in ardealite according to claim 1 adds water, It is characterized in that：The mass concentration of described dilution is that 0.3%, 0.4%, 0.5%, 0.6% and 0.7% aqueous citric acid solution is used for pickling Process.
- The process washed 6. a kind of citric acid for removing impurity fluorine in ardealite according to claim 1 adds water, It is characterized in that：The mass concentration of the alum added in described lime neutralisation treatment washing waste water is 50%, and accounts for the ten of washings / mono-.
- The process washed 7. a kind of citric acid for removing impurity fluorine in ardealite according to claim 1 adds water, It is characterized in that：PH can be again as slurry, lower floor for 7 neutralization water at the middle and upper levels for described lime neutralisation treatment washing waste water Indissoluble thing is mainly CaF2。
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Cited By (9)
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|---|---|---|---|---|
| CN107285652A (en) * | 2017-08-03 | 2017-10-24 | 湖北工业大学 | For preparing the method that the ardealite of high strength gypsum is pre-processed |
| CN108002724A (en) * | 2017-12-06 | 2018-05-08 | 马鞍山拓锐金属表面技术有限公司 | A kind of method that two steps calcining prepares ardealite based cementitious material |
| CN110577375A (en) * | 2019-09-02 | 2019-12-17 | 三峡大学 | phosphogypsum-doped quick-setting and quick-hardening cement matrix, concrete canvas manufactured by same and construction method |
| CN111977677A (en) * | 2020-08-25 | 2020-11-24 | 中国科学院过程工程研究所 | Method for preparing calcium aluminate by using aluminum ash |
| 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 |
| CN114380520A (en) * | 2022-01-29 | 2022-04-22 | 中国建筑材料工业规划研究院 | Method for pretreating phosphogypsum, phosphogypsum crude product and recycled product |
| CN114950347A (en) * | 2022-05-11 | 2022-08-30 | 内蒙古大学 | Defluorination agent prepared from natural gypsum and clay and preparation method thereof |
| CN115092951A (en) * | 2022-07-26 | 2022-09-23 | 一夫科技股份有限公司 | Method for removing phosphorus-containing impurities in phosphogypsum |
| CN115893885A (en) * | 2022-12-02 | 2023-04-04 | 湖北省生态环保有限公司 | Phosphogypsum immersion cleaning agent and phosphogypsum harmless treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107285652A (en) * | 2017-08-03 | 2017-10-24 | 湖北工业大学 | For preparing the method that the ardealite of high strength gypsum is pre-processed |
| CN107285652B (en) * | 2017-08-03 | 2019-10-08 | 湖北工业大学 | It is used to prepare the pretreated method of ardealite of high strength gypsum |
| CN108002724A (en) * | 2017-12-06 | 2018-05-08 | 马鞍山拓锐金属表面技术有限公司 | A kind of method that two steps calcining prepares ardealite based cementitious material |
| CN110577375B (en) * | 2019-09-02 | 2022-01-25 | 三峡大学 | Phosphogypsum-doped quick-setting and quick-hardening cement matrix, concrete canvas manufactured by same and construction method |
| CN110577375A (en) * | 2019-09-02 | 2019-12-17 | 三峡大学 | phosphogypsum-doped quick-setting and quick-hardening cement matrix, concrete canvas manufactured by same and construction method |
| CN111977677A (en) * | 2020-08-25 | 2020-11-24 | 中国科学院过程工程研究所 | Method for preparing calcium aluminate by using aluminum ash |
| 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 |
| CN114380520A (en) * | 2022-01-29 | 2022-04-22 | 中国建筑材料工业规划研究院 | Method for pretreating phosphogypsum, phosphogypsum crude product and recycled product |
| CN114950347A (en) * | 2022-05-11 | 2022-08-30 | 内蒙古大学 | Defluorination agent prepared from natural gypsum and clay and preparation method thereof |
| CN114950347B (en) * | 2022-05-11 | 2023-11-10 | 内蒙古大学 | Defluorinating agent prepared from natural gypsum and clay and preparation method thereof |
| CN115092951A (en) * | 2022-07-26 | 2022-09-23 | 一夫科技股份有限公司 | Method for removing phosphorus-containing impurities in 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 |
| CN115893885A (en) * | 2022-12-02 | 2023-04-04 | 湖北省生态环保有限公司 | Phosphogypsum immersion cleaning agent and phosphogypsum harmless treatment method |
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