CN105983563A - Method for treating phosphate solid wastes - Google Patents
Method for treating phosphate solid wastes Download PDFInfo
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- CN105983563A CN105983563A CN201510070994.9A CN201510070994A CN105983563A CN 105983563 A CN105983563 A CN 105983563A CN 201510070994 A CN201510070994 A CN 201510070994A CN 105983563 A CN105983563 A CN 105983563A
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Abstract
The invention provides a method for treating phosphate solid wastes. The method is mainly used for treating solid wastes produced in the process of producing polyphosphates by using phosphorus containing waste liquid, particularly pesticide production waste liquid with high phosphorus content, as a raw material and/or treating solid wastes produced by the continuous follow-up treatment of the polyphosphates. The method comprises the steps of oxidation treatment, hydrolysis reaction, solid-liquid separation and the like. The treated solid wastes are changed into solid substances with single components, the solid substances return to a phosphate system and are cyclically utilized, phosphate in filtrate can be recycled and made into orthophosphate products, and a novel solution is provided for the phosphate solid wastes.
Description
Technical field
The present invention relates to the processing method of a kind of phosphate solid waste.Producing condensed phosphate process specifically
The processing method of the solid waste that the solid waste of middle generation and the production process with condensed phosphate as raw material produce.
Background technology
Chinese patent 201110310586 disclose a kind of by reclaiming high phosphorous pesticide producing waste material and phosphorous chemical industry
P elements in high P content waste water, prepares the side of condensed phosphate (pyrophosphate, Quadrafos, metaphosphate etc.)
Method.Chinese patent 201210277621.5 discloses one and utilizes condensed phosphate, particularly patent
The method that the condensed phosphate preparing in 201110310586 prepares orthophosphates.Producing these condensed phosphates
And it is solid to produce a small amount of phosphate when being purified to the condensed phosphate of higher quality with them or produce orthophosphates
Useless.
Being mainly composed of of these solid wastes: the phosphate such as sodium pyrophosphate, sodium phosphate, content is 30-70%;Water is not
Molten thing (main component is common for activated carbon, diatomite etc.), content is at 10-30%;A small amount of hydrochloride, content
At 0.1-2%;The iron of trace, calcium, magnesium plasma, content is at 1-1000ppm;Organic matter with trace.Its
In phosphate some be attracted in activated carbon duct with molecular forms, therefore use common process side
Method (being such as dissolved in water) is difficult to remove, and needs corresponding desorption process.Metal ion therein is then and phosphate anion
In conjunction with, presented in complexes or precipitates, equally also there is part to be attracted in activated carbon, needs exist
They could be removed from feed liquid system under specific environment and come with Activated carbon separation.
This solid waste belongs to dangerous solid waste, because which is mixture, and wherein has the phosphate of high-load, therefore not
Can directly fill, burning etc. is processed, and needs, through pretreatment, to be allowed to innoxious, and common pretreatment side
Method does not reaches again requirement.Present invention provides just a kind of method processing this type of solid waste, not only by phosphorus therein
Hydrochlorate reclaims and makes orthophosphates product, and simultaneously by Impurity removals such as metal ion therein, organic matters,
Make the solid waste after process become the more single solid matter of composition, phosphate system can be returned and recycle.
Content of the invention
It is desirable to provide a kind of method processing phosphate solid waste, the method comprises oxidation processes, hydrolysis instead
Should, two or more in solid-liquid separation step, phosphate solid waste after treatment by using the treatment method finally can turn
Turn to recycling solid and phosphate-containing filtrate.
The processing method of phosphate solid waste that the present invention provides is preferably combination or the oxygen of hydrolysis and separation of solid and liquid
Change process and aqua reaction and the combination of separation of solid and liquid, more preferably oxidation processes and hydrolysis and solid-liquid
The combination separating.Actual production can be taken the circumstances into consideration to choose said method according to the impurity situation in phosphate solid waste
Process, and the order processing technique in combination is also determined on a case-by-case basis.
Described phosphate solid waste is preferably and produces contracting with the especially high phosphorous pesticide producing waste liquid of phosphorous waste liquid for raw material
The solid waste producing in the solid waste producing during Quadrafos or the production process with condensed phosphate as raw material.
Described oxidation processes is by soluble in water for phosphate solid waste, and adds oxidant to carry out oxidation reaction, instead
Answering temperature to be 40~300 DEG C, the reaction time is 10min-720min;The addition of oxidant is the 0.1~10 of solid waste amount
Wt%, preferably 0.5~1.0wt%;Described oxidant includes hydrogen peroxide, sodium chlorate, Feton reagent, dioxy
One in change chlorine, potassium permanganate, oxygen, ozone, carbon, preferably hydrogen peroxide or sodium chlorate.
Described oxidation processes is high-temperature oxydation, wet oxidation, Feton oxidation, the one in photochemical catalytic oxidation.
Content of organics < 10ppm in oxidation-treated rear phosphate solid waste.
Described hydrolysis is to add acid in the aqueous solution of phosphate solid waste, and regulation pH is 1.0-9.0, in temperature
Degree is 80-200 DEG C, preferably 100-120 DEG C, is hydrolyzed, makes phosphate become easy under conditions of normal pressure or pressurization
In the ionic species of desorption, and metallic element therein is made again to be present in the form of an ion in feed liquid, during hydrolysis
Between be 30-360min.
Pressure during described pressurization is 0.1-1.0MPa, preferably 0.1-0.4MPa.
The method that described separation of solid and liquid uses include precise microfiltration, barrier film press filtration, in disk centrifuge one
Kind.
The processing method of the phosphate solid waste that the present invention provides, is preferably below scheme:
Scheme is the first, by the water that is dissolved in of phosphate solid waste, and adds acid, and regulation pH is 1.0-9.0, in temperature is
100-120 DEG C, be hydrolyzed under conditions of normal pressure or pressurization reaction, and the reaction time is 30-360min, makes phosphoric acid
Salt becomes the ionic species being easy to desorption, and makes metallic element therein again be present in the form of an ion in feed liquid,
React the feed liquid after terminating through the recycling solid of solid waste isolated and phosphatic filtrate.
Scheme the 2nd, by soluble in water for phosphate solid waste and add hydrogen peroxide or sodium chlorate to carry out oxidation processes, reaction
Temperature is 40~300 DEG C, and the reaction time is 10min-720min;The addition of oxidant is the 0.1~10 of solid waste amount
Wt%, preferably 0.5~1.0wt%;Adding acid in the reactant liquor obtaining after oxidation processes, regulation pH is 1.0-9.0,
Being 100-120 DEG C in temperature, reacting under conditions of normal pressure or pressurization, the reaction time is 30-360min, makes
Phosphate becomes the ionic species being easy to desorption, and makes metallic element therein again be present in material in the form of an ion
In liquid, react the feed liquid after terminating through the recycling solid of solid waste isolated and phosphatic filtrate.
Phosphate-containing filtrate can be through suitable oxidation processes or at 20-100 DEG C, with the flow velocity warp of 0.5-10BV/h
Cross the packed column equipped with exchange adsorbing substance, enter crystallization kettle after removing metal ion and be prepared as phosphate product.
Described exchange adsorbing substance includes the one in ion exchange resin, manganese sand, quartz sand, sial salt.
Described metal ion includes one or more in iron, calcium, magnesium, aluminium, zinc ion.
Detailed description of the invention
Embodiment 1
Take phosphate solid waste 100kg, phosphate content 57%, be dissolved in 400kg water, be warming up to 60 DEG C, add
Enter 5kg hydrogen peroxide, at 60 DEG C, react 30min.The reactant liquor obtaining after oxidation processes add a certain amount of
Phosphoric acid flavouring liquid pH to 7.0, is continuously heating to 120 DEG C, reacts 240min at ambient pressure.By reacted material
Liquid precise microfiltration device filters, and obtains being mainly composed of the wet filter residue of activated carbon and filtrate, and sample analysis is surveyed
Obtaining soluble-salt content in filter residue is 1%, and content of organics is 8ppm, and metal ion content is 4ppm, filter residue
Return phosphate system to recycle.Filtrate flow velocity with 3BV/h at 60 DEG C passes through equipped with cation exchange tree
The clarifier of fat packed column, finally enters crystallization kettle, obtains the sodium orthophosphate that 58.7g content is 94%, phosphate
The rate of recovery 96.8%.
Embodiment 2
Take phosphate solid waste 100kg, phosphate content 57%, be dissolved in 400kg water, add 5kg sodium chlorate,
30min is reacted at 60 DEG C.The reactant liquor obtaining after oxidation processes adds a certain amount of phosphoric acid flavouring liquid pH extremely
Pour feed liquid into autoclave after 4.0, heat up, be passed through air, keep pressure to exist in 0.4-0.6MPa, temperature
155-165 DEG C, the reaction time is 120min.Then reacted feed liquid precise microfiltration device is filtered,
To the wet filter residue being mainly composed of activated carbon and filtrate, it is 1% that sample analysis records soluble-salt content in filter residue,
Content of organics is 6ppm, and metal ion content is 5ppm, and filter residue can return to phosphate system and recycles.
Filtrate can pass through the change device net equipped with cationic ion-exchange resin packed column, by the flow velocity with 3BV/h at 60 DEG C again
Rear entrance crystallization kettle, obtains the sodium orthophosphate that 59g content is 93%, the phosphate rate of recovery 96.3%.
Embodiment 3
Take phosphate solid waste 100kg, phosphate content 52%, be dissolved in 300kg water, add a certain amount of phosphoric acid to adjust
Material liquid pH, to 4.0, is warming up to 95-105 DEG C, and reflux 120~200min at ambient pressure.Reacted feed liquid is used
Diaphragm filter press filters, and obtains being mainly composed of the wet filter residue of activated carbon and filtrate, and sample analysis records in filter residue
Soluble-salt content is 1%, and content of organics is 10ppm, and metal ion content is 9ppm, and filter residue can return to
Phosphate system recycles.Filtrate adds 5kg hydrogen peroxide, 0.1kg nano-TiO2, at 60 DEG C,
With the ultra violet lamp 3-24h of certain wavelength.At 60 DEG C, the flow velocity with 3BV/h passes through equipped with silicon again more afterwards
The clarifier of aluminium salt, finally enters crystallization kettle, obtains the sodium orthophosphate that 53.1g content is 95%, and phosphate reclaims
Rate 97%.
Embodiment 4
Take phosphate solid waste 100kg, phosphate content 60%, be dissolved in 400kg water, be warming up to 60 DEG C, add
Enter 5kg Feton reagent, react 60min at 60 DEG C.The reactant liquor obtaining after oxidation processes add a certain amount of
Hydrochloric acid flavouring liquid pH to 6.0, is continuously heating to 120 DEG C, reacts 180min.Reacted feed liquid is accurate
Millipore filter filters, and obtains being mainly composed of the wet filter residue of activated carbon and filtrate, and sample analysis records in filter residue
Soluble-salt content is 1%, and content of organics is 8ppm, and metal ion content is 10ppm, and filter residue can return to
Phosphate system recycles.Filtrate flow velocity with 1BV/h at 90 DEG C passes through the clarifier equipped with manganese sand again,
Finally enter crystallization kettle, obtain the sodium orthophosphate that 61.9g content is 92%, the phosphate rate of recovery 95%.
Below it is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improve
Also should be regarded as protection scope of the present invention with retouching.
Claims (9)
1. the method processing phosphate solid waste, it is characterised in that described method comprise oxidation processes, hydrolysis,
Two or more in solid-liquid separation step, final obtain recycling solid and phosphate-containing filtrate.
2. the method for claim 1, it is characterised in that the method is preferably hydrolysis and separation of solid and liquid
Combination or the combination of oxidation processes and hydrolysis and separation of solid and liquid, more preferably oxidation processes and hydrolysis are anti-
Should be with the combination of separation of solid and liquid.
3. the method for claim 1, it is characterised in that described phosphate solid waste is for phosphorous waste liquid especially
High phosphorous pesticide producing waste liquid is the solid waste producing during raw material produces condensed phosphate and/or condensed phosphate continues
The solid waste that continuous subsequent treatment produces.
4. method as claimed in claim 1 or 2, it is characterised in that described oxidation processes is by phosphate solid waste
Soluble in water, and add oxidant to carry out oxidation reaction, reaction temperature is 40~300 DEG C, and the reaction time is
10min-720min;The addition of oxidant is 0.1~10wt% of solid waste amount, and described oxidant includes dioxygen
One in water, sodium chlorate, Feton reagent, chlorine dioxide, potassium permanganate, oxygen, ozone, carbon, excellent
Elect hydrogen peroxide or sodium chlorate as.
5. method as claimed in claim 1 or 2, it is characterised in that described hydrolysis is in phosphate solid waste
The aqueous solution in add acid, regulation pH be 1.0-9.0, be 80-200 DEG C in temperature, the condition of normal pressure or pressurization
Under be hydrolyzed, make phosphate become the ionic species being easy to desorption, and make metallic element therein with ion shape
Formula is present in feed liquid again, and hydrolysis time is 30-360min.
6. the method as described in claim 1-5 any one, it is characterised in that comprise the following steps:
Phosphate solid waste being dissolved in water, and adding acid, regulation pH is 1.0-9.0, is 100-120 DEG C in temperature,
Be hydrolyzed under conditions of normal pressure or pressurization reaction, and the reaction time is 30-360min, makes phosphate become and is easy to de-
Attached ionic species, and make metallic element therein again be present in the form of an ion in feed liquid, after reaction terminates
Feed liquid through the recycling solid of solid waste isolated and phosphatic filtrate.
7. the method as described in claim 1-5 any one, it is characterised in that comprise the following steps:
By soluble in water for phosphate solid waste, adding hydrogen peroxide and/or sodium chlorate to carry out oxidation processes, reaction temperature is
40~300 DEG C, the reaction time is 10min-720min;The addition of oxidant is 0.1~10wt% of solid waste amount,
It is preferably 0.5~1.0wt%;Adding acid in the reactant liquor obtaining after oxidation processes, regulation pH is 1.0-9.0,
Being 100-120 DEG C in temperature, reacting under conditions of normal pressure or pressurization, the reaction time is 30-360min, makes
Phosphate becomes the ionic species being easy to desorption, and makes metallic element therein again be present in material in the form of an ion
In liquid, react the feed liquid after terminating through the recycling solid of solid waste isolated and phosphatic filtrate.
8. the method as described in claim the 1st, the 6th, 7 any one, it is characterised in that described phosphate-containing filtrate
The packed column equipped with exchange adsorbing substance can be passed through with the flow velocity of 0.5-10BV/h, removes metal at 20-100 DEG C
Enter crystallization kettle after ion and be prepared as phosphate product.
9. method as claimed in claim 8, it is characterised in that described exchange adsorbing substance include ion exchange resin,
One in manganese sand, quartz sand, sial salt.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107244688A (en) * | 2017-05-16 | 2017-10-13 | 同济大学 | A kind of method that phosphorous solid waste resource recovery is utilized |
CN114289478A (en) * | 2021-12-30 | 2022-04-08 | 连云港职业技术学院 | Resource treatment method for waste salt containing organic matters |
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CN1054753A (en) * | 1991-02-09 | 1991-09-25 | 衡阳市化工研究所 | Utilize the method that the inositol waste residue prepares high-purity phosphoric acid hydrogen calcium of producing |
CN101679038A (en) * | 2007-03-19 | 2010-03-24 | 易开采瑞典有限公司 | phosphorus recovery |
CN102139974A (en) * | 2011-02-21 | 2011-08-03 | 李开明 | Treatment method of phosphorus-containing waste water |
CN102616914A (en) * | 2011-01-31 | 2012-08-01 | 浙江新安化工集团股份有限公司 | Treatment method of phosphorus-containing waste from pesticide production and product obtained thereby |
CN103058156A (en) * | 2011-10-18 | 2013-04-24 | 王军民 | Method for preparing calcium phosphate by utilizing slag charge discharged during sodium hypophosphite preparation |
CN103267734A (en) * | 2013-04-02 | 2013-08-28 | 三峡大学 | Water-quality total phosphor efficient digestion and rapid detection method |
CN103482797A (en) * | 2013-10-14 | 2014-01-01 | 哈尔滨工业大学深圳研究生院 | Process and device for removing hypophosphites and phosphites by advanced oxidation coupling technique |
CN103569981A (en) * | 2012-08-02 | 2014-02-12 | 浙江新安化工集团股份有限公司 | Method for producing orthophosphate products from polyphosphates through hydrolysis |
WO2014178788A1 (en) * | 2013-05-02 | 2014-11-06 | Easymining Sweden Ab | Production of phosphate compounds from materials containing phosphorus and at least one of iron and aluminium |
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2015
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Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1054753A (en) * | 1991-02-09 | 1991-09-25 | 衡阳市化工研究所 | Utilize the method that the inositol waste residue prepares high-purity phosphoric acid hydrogen calcium of producing |
CN101679038A (en) * | 2007-03-19 | 2010-03-24 | 易开采瑞典有限公司 | phosphorus recovery |
CN102616914A (en) * | 2011-01-31 | 2012-08-01 | 浙江新安化工集团股份有限公司 | Treatment method of phosphorus-containing waste from pesticide production and product obtained thereby |
CN102139974A (en) * | 2011-02-21 | 2011-08-03 | 李开明 | Treatment method of phosphorus-containing waste water |
CN103058156A (en) * | 2011-10-18 | 2013-04-24 | 王军民 | Method for preparing calcium phosphate by utilizing slag charge discharged during sodium hypophosphite preparation |
CN103569981A (en) * | 2012-08-02 | 2014-02-12 | 浙江新安化工集团股份有限公司 | Method for producing orthophosphate products from polyphosphates through hydrolysis |
CN103267734A (en) * | 2013-04-02 | 2013-08-28 | 三峡大学 | Water-quality total phosphor efficient digestion and rapid detection method |
WO2014178788A1 (en) * | 2013-05-02 | 2014-11-06 | Easymining Sweden Ab | Production of phosphate compounds from materials containing phosphorus and at least one of iron and aluminium |
CN103482797A (en) * | 2013-10-14 | 2014-01-01 | 哈尔滨工业大学深圳研究生院 | Process and device for removing hypophosphites and phosphites by advanced oxidation coupling technique |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107244688A (en) * | 2017-05-16 | 2017-10-13 | 同济大学 | A kind of method that phosphorous solid waste resource recovery is utilized |
CN114289478A (en) * | 2021-12-30 | 2022-04-08 | 连云港职业技术学院 | Resource treatment method for waste salt containing organic matters |
CN114289478B (en) * | 2021-12-30 | 2023-05-16 | 连云港职业技术学院 | Method for recycling waste salt containing organic matters |
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Effective date of registration: 20170119 Address after: 212152 Zhenjiang Jiangnan Chemical Industry Co., Ltd., Zhenjiang, Zhenjiang New District, Jiangsu, No. 28 Applicant after: ZHENJIANG JIANGNAN CHEMICAL Co.,Ltd. Address before: 311600 Xin''an East Road, Zhejiang, China, No. 555, No. Applicant before: ZHEJIANG WYNCA CHEMICAL INDUSTRY GROUP Co.,Ltd. |
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