CN106915878A - The recovery method of phosphorus in a kind of phosphorus containing sludge - Google Patents
The recovery method of phosphorus in a kind of phosphorus containing sludge Download PDFInfo
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- CN106915878A CN106915878A CN201710186409.0A CN201710186409A CN106915878A CN 106915878 A CN106915878 A CN 106915878A CN 201710186409 A CN201710186409 A CN 201710186409A CN 106915878 A CN106915878 A CN 106915878A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
- C02F11/08—Wet air oxidation
- C02F11/086—Wet air oxidation in the supercritical state
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Environmental & Geological Engineering (AREA)
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- Inorganic Chemistry (AREA)
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- Removal Of Specific Substances (AREA)
Abstract
The embodiment of the invention discloses a kind of recovery method of phosphorus in phosphorus containing sludge, methods described includes：Phosphorus containing sludge is ground, sieve and pulp treatment after, carry out modifier treatment, obtain the sludge that moisture content is 85% 95%；Sludge and excessive oxygen after modifier treatment is passed through into supercritical water oxidation device carries out supercritical water oxidation, stops 10 30 seconds, obtains strong brine and supercritical fluid；Detect the content of beary metal in the strong brine, in the case that content of beary metal in the strong brine is not higher than preset value, the strong brine to alkalescence is adjusted, precipitation process is carried out in addition precipitating reagent to the strong brine, and separated product, obtain phosphorous sediment.Because supercritical water has extremely strong oxidability, phosphorus containing sludge fully reacts in supercritical water oxidation device, and the phosphorus in phosphorus containing sludge can obtain whole releases substantially, greatly improves the organic efficiency of phosphorus in phosphorus containing sludge.
Description
Technical field
The present invention relates to field of sludge treatment, the recovery method of phosphorus in more particularly to a kind of phosphorus containing sludge.
Background technology
Phosphorus is a kind of important nonmetal mineral resource for being difficult to regenerate, and is the essential nutrition unit of the activity of sustaining life
Element.Calculated according to authoritative institution, global phosphor resource can only use 60-130, and phosphorus is listed in China can not meet national warp
One of 20 kinds of mineral resources for development need of helping.On the other hand, water eutrophication is caused with the nutrient such as phosphorus of sewage discharge
The problem of change is increasingly serious, and severe contamination is caused to water body, as current important environmental problem.
The characteristics of having one-way flow due to P elements, therefore during sewage disposal, most phosphorus can only be with
The form of essential elements is stored in organism, is finally discharged in the form of excess sludge, therefore, in realizing phosphorus containing sludge
The recovery of phosphorus is the important method for alleviating water pollution and phosphor resource shortage.
At present, in phosphorus containing sludge in the recovery technology of phosphorus, frequently with acidifying with normal pressure microwave radiating composite, squeeze and filter-
Soak-be aerated again, anaerobism heating etc. method, as far as possible promote sludge in phosphorus discharge to supernatant, to by after separation of solid and liquid
Rich phosphorus supernatant is processed using sedimentation, obtains the phosphorous sediment such as guanite, calcium phosphate crystal, and then realize returning for phosphorus
Receive.But, when carrying out the recycling of phosphorus using these methods, the release concentration of phosphorus is limited in phosphorus containing sludge, makes phosphorus containing sludge
The organic efficiency of middle phosphorus is relatively low.
The content of the invention
The embodiment of the invention discloses a kind of recovery method of phosphorus in phosphorus containing sludge, to realize improving phosphorus in phosphorus containing sludge
The purpose of organic efficiency.Technical scheme is as follows：
A kind of recovery method of phosphorus in phosphorus containing sludge is the embodiment of the invention provides, methods described includes：
Phosphorus containing sludge is ground, sieve and pulp treatment after, carry out modifier treatment, obtain moisture content for 85%-
95% sludge；
Sludge and excessive oxygen after modifier treatment is passed through into supercritical water oxidation device carries out supercritical water oxidation
Reaction, stops 10-30 seconds, obtains strong brine and supercritical fluid, wherein, it is 1.5-2 to cross oxygen quotient；
The content of beary metal in the strong brine is detected, the content of beary metal in the strong brine is not higher than preset value
In the case of, the strong brine to alkalescence is adjusted, precipitation process is carried out in addition precipitating reagent to the strong brine, and product is carried out
Separate, obtain phosphorous sediment, it is preferable that the precipitation process also includes：Addition anion flocculation aid promotes precipitation, described the moon
Ion flocculation aid dosage is the 0.1%-0.3% of the strong brine quality.
Optionally, in the case where the content of beary metal in detecting the strong brine is higher than the preset value, the side
Method also includes：
Addition hydrochloric acid adjusts the pH value of the strong brine to 4-6；
Adsorption treatment is carried out to the strong brine after regulation pH value, the adsorbed product for obtaining is carried out at parsing in alkaline solution
Reason, obtains containing phosphatic desorbed solution；
Addition precipitating reagent containing carrying out precipitation process in phosphatic desorbed solution, and product is separated to described, is obtained
To phosphorous sediment, it is preferable that the precipitation process also includes：Addition anion flocculation aid promotes precipitation, the anionic retention aid
Solidifying agent dosage is the 0.1%-0.3% of the desorbed solution quality.
Optionally, the adsorption treatment includes：
Concussion adsorption treatment is carried out to the strong brine after the regulation pH value using modified aluminas, adsorption time is 0.5-
3 hours, it is preferable that the modified aluminas include：Aluminum sulfate modified aluminas and/or modified with ferric sulfate aluminum oxide.
Optionally, the alkaline solution is NaOH or potassium hydroxide solution that mass fraction is 1%.
Optionally, the precipitating reagent is selected from：In magnesium salts and ammonium salt mixture, aluminium salt, molysite and calcium hydroxide saturated solution
One or more, the mol ratio of the precipitating reagent cationic and phosphate radical is (1-1.5): 1.
Optionally, the anion flocculation aid includes：Polyacrylamide, polyacrylic acid, Sodium Polyacrylate, calcium polyacrylate (CPA)
In one or more.
Optionally, the supercritical water oxidation device includes：Heat exchanger, high-pressure plunger pump and supercritical water oxidation are anti-
Kettle, the heat exchanger, the high-pressure plunger pump and the supercritical water oxidation kettle is answered to be connected in series；
The supercritical water oxidation process includes：
Sludge after modifier treatment is passed through the heat exchanger, after being heated to 320-350 DEG C, by the high-pressure plunger pump
It is forced into 22-30MPa；
By excessive oxygen and by the sludge after high-pressure plunger pump pressurization, the supercritical water oxidation kettle is passed through
Supercritical water oxidation is inside carried out, is stopped 10-30 seconds, obtain strong brine and supercritical fluid.
Optionally, evaporation wall and porous inner tube, the evaporation wall and institute are provided with the supercritical water oxidation kettle
State and fill supercritical water in the cavity between porous inner tube, supercritical water oxidation bottom portion is provided with strong brine and goes out
Mouthful, top is provided with supercritical fluid outlet, liquid oxygen entrance and sludge import.
Optionally, methods described also includes：
The supercritical fluid is passed through the heat exchanger；
By after the supercritical fluid of heat exchanger is cooled down and step-down is processed, after carrying out gas-liquid separation, gaseous state is obtained
Product and aqueous water；
By the liquid Water circulation to the modifier treatment process or directly discharge, the gaseous products are compressed at separation
Reason, reclaims the oxygen in the gaseous products, and the oxygen that will be obtained is back to the supercritical water oxidation device.
Optionally, the pH value of the strong brine to 8.5-9 is adjusted.
In the scheme that the embodiment of the present invention is provided, phosphorus containing sludge is ground, sieve and pulp treatment after, adjusted
Matter treatment, obtains the sludge that moisture content is 85%-95%, is then passed through the sludge and excessive oxygen after modifier treatment overcritical
Water oxidation reaction apparatus carry out supercritical water oxidation, stop 10-30 seconds, obtain strong brine and supercritical fluid, then detect
Content of beary metal in strong brine, in the case that the content of beary metal in strong brine is not higher than preset value, regulation strong brine to
Alkalescence, precipitation process is carried out in addition precipitating reagent to strong brine, and product is separated, and obtains phosphorous sediment, and then return
Receive the phosphorus in phosphorus containing sludge.Because supercritical water has extremely strong oxidability, phosphorus containing sludge is filled in supercritical water oxidation
Interior abundant reaction is put, phosphorus can obtain whole releases substantially in phosphorus containing sludge, make the organic efficiency of phosphorus in phosphorus containing sludge significantly
Improve.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
A kind of flow chart of the recovery method of phosphorus in the phosphorus containing sludge that Fig. 1 is provided by the embodiment of the present invention；
Fig. 2 is the structural representation of supercritical water oxidation device in embodiment illustrated in fig. 1.
Wherein, the corresponding relation in Fig. 2 between each component Name and respective drawings mark is：
Evaporation wall 01, porous inner tube 02, the outlet 04, liquid oxygen entrance 05 of brine outlet 03, supercritical fluid, sludge import
06。
Specific embodiment
The recovery method of phosphorus in a kind of phosphorus containing sludge that the embodiment of the invention provides, as shown in figure 1, the recovery method has
Body is comprised the following steps：
Phosphorus containing sludge is ground, sieve and pulp treatment after, carry out modifier treatment, obtain moisture content for 85%-
95% sludge；
Sludge and excessive oxygen after modifier treatment is passed through into supercritical water oxidation device carries out supercritical water oxidation
Reaction, stops 10-30 seconds, obtains strong brine and supercritical fluid, wherein, it is 1.5-2 to cross oxygen quotient；
The content of beary metal in the strong brine is detected, the content of beary metal in the strong brine is not higher than preset value
In the case of, the strong brine to alkalescence is adjusted, precipitation process is carried out in addition precipitating reagent to the strong brine, and product is carried out
Separate, obtain phosphorous sediment.
Because the quality of phosphorus containing sludge is typically uneven, it is understood that there may be lump or containing phenomenons such as solid impurities, so being
Beneficial to the release of phosphorus in subsequent recovery processing procedure, phosphorus containing sludge can be ground, sieved and pulp treatment, go decontamination
Solid impurity in mud, eliminates caking phenomenon.Can typically be sized to below 20 mesh.Processed in the pulp for carrying out phosphorus containing sludge
When, can be stirred under anaerobic environment, and physics pulp effect and bio-pulpization is acted on association by controlling mixing speed
With playing a role, sludge viscosity is reduced, can also be suitably added demulsifier etc. can eliminate the medicament of emulsification state material, and destruction contains
Emulsification state material in phosphorus sludge, makes the abundant pulp of phosphorus containing sludge, and the specific addition of demulsifier can be by people in the art
Member determines according to the actual emulsified state of phosphorus containing sludge, is not specifically limited herein.
Further, in order to ensure the homogeneous of phosphorus containing sludge, the place of follow-up supercritical water oxidation is not influenceed
Reason effect, pulp treatment after, modifier treatment can also be carried out to phosphorus containing sludge, by phosphorus containing sludge add clear water and/
Or the waste water of phosphorus recovering effect is not influenceed, and be stirred, the moisture content of phosphorus containing sludge is adjusted, and then obtain homogeneous containing
Water rate is the sludge of 85%-95%.In actual applications, it is more conducive to when inventor has found that the moisture content of sludge is 85%-95%
The recycling of phosphorus in sludge, organic efficiency is higher.
It should be noted that above-mentioned grinding, screening, pulp and modifier treatment are processing mode commonly used in the art, this
Art personnel can be in phosphorus containing sludge impurity situation and the factor such as moisture content be determined, do not do specific limit herein
Fixed and explanation.
After modifier treatment, can be anti-for the sludge and excessive oxygen of 85%-95% are passed through supercritical water oxidation by moisture content
Answer in device, carry out super oxidation reaction near water.During supercritical water oxidation is carried out, cross oxygen quotient and be generally 1.5-2,
It is understood that it is to refer to the sludge complete oxidation institute after the oxygen quality of effective supply and modifier treatment in theory to cross oxygen quotient
The ratio between oxygen quality for needing.Stopped 10-30 seconds in supercritical water oxidation device, the sludge after modifier treatment just can be anti-
Should finish, obtain supercritical fluid and rich in phosphatic strong brine.Because the oxidability of supercritical water is strong, by surpassing near water
Phosphorus almost all discharges during oxidation reaction apparatus treatment can make phosphorus containing sludge, strong brine is formed, while can realize that sludge subtracts
Quantify.On the other hand, the product of supercritical water oxidation is generally carbon dioxide, water, nitrogen and inorganic salts, will not produce two
Secondary pollution.
In embodiments of the present invention, the supercritical water oxidation apparatus for being used can include：Heat exchanger, high-pressure plunger pump and
Supercritical water oxidation kettle, heat exchanger, high-pressure plunger pump and supercritical water oxidation kettle are connected in series.In overcritical water oxygen
Change in course of reaction, the sludge after modifier treatment can be passed through in heat exchanger, after being heated to 320-350 DEG C, by high-pressure column
Plug pump is forced into 22-30MPa, then by excessive oxygen and by the sludge after high-pressure plunger pump pressurization, is passed through overcritical water oxygen
Changing carries out supercritical water oxidation in reactor, stop 10-30 seconds, obtains strong brine and supercritical fluid.Wherein, heat exchanger
And high-pressure plunger pump can be herein not specifically limited using corresponding equipment in the prior art.
Above-mentioned supercritical water oxidation kettle can use any supercritical water oxidation kettle in the prior art, herein not
It is specifically limited.Preferably, a kind of supercritical water oxidation kettle is the embodiment of the invention provides, as shown in Fig. 2 this is overcritical
Evaporation wall 01 and porous inner tube 02 are provided with water oxidizing reactor, evaporation wall 01 can be shell structure, with pressure-bearing effect,
Evaporation water is filled in cavity between evaporation wall 01 and porous inner tube 02, supercritical water oxidation bottom portion is provided with strong brine
Outlet 03, top is provided with supercritical fluid outlet 04, liquid oxygen entrance 05 and sludge import 06.Evaporation water evaporation wall 01 with it is many
Annular cascade is formed in cavity between hole inner tube 02, is entered in supercritical water oxidation kettle by porous inner tube 02, many
The inner surface of hole inner tube 02 formed moisture film, make reactant not with supercritical water oxidation kettle inwall directly contact, be prevented effectively from super
Corrosion of the critical oxidation reaction to supercritical water oxidation kettle inwall, damages to supercritical water oxidation kettle.Need
It is noted that above for supercritical water oxidation kettle explanation, it is preferred that emphasis is illustrate its with it is overcritical in the prior art
The difference of water oxidizing reactor, unspecified part may be referred to supercritical water oxidation kettle of the prior art.
In order to avoid the wasting of resources, supercritical water oxidation device is set to carry out from maintenance, can be by supercritical water
The supercritical fluid that oxidation reaction is obtained is passed through above-mentioned heat exchanger, is that the sludge after modifier treatment is heated.Need explanation
It is that, when supercritical water oxidation device carries out supercritical water oxidation treatment for the first time, electric heater pair can be used
Sludge after quenched is heated, the dirt after supercritical fluid that supercritical water oxidation is produced disclosure satisfy that heats quenched
During the demand of mud, just no longer need to use electric heater to heat, and then realize maintaining certainly for supercritical water oxidation device.
Further, can will be cooled down by the supercritical fluid of heat exchanger and step-down treatment, then be carried out gas-liquid
Separating treatment, obtains gaseous products and aqueous water, and aqueous water is back into above-mentioned modifier treatment process, and aqueous water is reclaimed
Utilize, it is to avoid the wasting of resources.Certainly, aqueous water can also be discharged directly.For gaseous products, then it can be pressed
Contracting separating treatment, reclaims the oxygen in gaseous products, and the oxygen that will be obtained is back to supercritical water oxidation device, is super
Critical oxidation reaction provides oxygen, so as to reduce processing cost.And nitrogen in gaseous products etc. does not result in dirt to air
The gas of dye can be discharged into air.
May contain heavy metal in due to processing the strong brine for obtaining by above-mentioned supercritical water oxidation device, so
In order to ensure that the phosphorous sediment for obtaining meets recycling standard, can detect the content of beary metal in strong brine whether be higher than
Preset value.It should be noted that the species and preset value of heavy metal can be determined by those skilled in the art according to purposes is reclaimed,
It is not specifically limited herein.For example, it is used as to make fertilizer if the phosphorous sediment for obtaining will be recycled, then just may be used
Using the heavy metal and content of beary metal threshold value using defined in GB GB/T 23349-2009 as standard, i.e. heavy metal bag
Arsenic, cadmium, lead, chromium and mercury are included, corresponding preset value is respectively：50mg/kg, 10mg/kg, 200mg/kg, 500mg/kg and 5mg/
kg.Wherein, the mode of content of beary metal can use existing any heavy metal analysis mode in detection strong brine, do not do have herein
Body is limited.
In the case that content of beary metal in strong brine is not higher than preset value, strong brine to alkalescence can be first adjusted, added
Plus precipitation process is carried out in precipitating reagent to strong brine, and product is separated, and then obtain phosphorous sediment.Can typically adjust
The pH value of strong brine is saved to 8.5-9, precipitation process effect is more preferable.Wherein, precipitating reagent can be magnesium salts and ammonium salt mixture, aluminium
One or more in salt, molysite and calcium hydroxide saturated solution.
Specifically, magnesium salts and ammonium salt mixture can be according to N with strong brine：P：The mol ratio of Mg is 1:1.05:1.1 are carried out
Addition, more conducively magnesium salts and ammonium salt mixture generate guanite (Mg (NH with the phosphate in strong brine4)PO4·6H2O), improve
Organic efficiency.Aluminium salt, molysite and calcium hydroxide saturated solution then can be with slightly excessive additions, to ensure that the phosphate in strong brine is use up
Possibly generate phosphorous sediment.It is understood that the phosphoric acid in aluminium salt, molysite and calcium hydroxide saturated solution and strong brine
Reactant salt, generates phosphoric acid aluminum precipitation, ferric phosphate precipitation and calcium phosphate precipitation respectively.Wherein, aluminium salt, molysite and calcium hydroxide saturation
The mol ratio of phosphate radical is at (1-1.5) in anions in solution and strong brine: 1, now sedimentation effect is more preferably.
It should be noted that above-mentioned separating treatment is technological means commonly used in the art, for example can be by the side of filtering
Formula is separated product, obtains phosphorous sediment, is not illustrated herein and is limited.
During above-mentioned precipitation process, anion flocculation aid can also be added, to promote precipitation.Wherein, anionic retention aid
Solidifying agent can include：In polyacrylamide, polyacrylic acid, Sodium Polyacrylate, calcium polyacrylate (CPA) one or more, anionic retention aid coagulate
Agent dosage is the 0.1%-0.3% of strong brine quality, now promotes sedimentation effect more preferably.
And in the case that the content of beary metal in strong brine is higher than preset value, in order to ensure to reclaim the phosphorous precipitation for obtaining
Content of beary metal in thing can reach the purpose of purified product without departing from the standard of recovery by absorption and dissection process.Tool
Body, the pH value of hydrochloric acid regulation strong brine can be added to 4-6, adsorption treatment then is carried out to the strong brine after regulation pH value,
The adsorbed product that will be obtained carries out dissection process in alkaline solution, obtains containing phosphatic desorbed solution, and finally addition is precipitated
Agent carries out precipitation process in extremely containing phosphatic desorbed solution, and product is separated, and obtains phosphorous sediment.
The pH value of strong brine is adjusted to 4-6, the carrying out of adsorption treatment can be beneficial to, in adsorption treatment, can used
Modified aluminas carry out concussion adsorption treatment to the strong brine after regulation pH value, and adsorption time is generally 0.5-3 hours.It is preferred that
Ground, modified aluminas can include：Aluminum sulfate modified aluminas and/or modified with ferric sulfate aluminum oxide.In adsorption process, it is modified
Aluminum oxide is very high to phosphatic adsorption rate in strong brine, and to the heavy metal in strong brine, in addition to chromium, adsorption rate is very low, and one
As be less than 10%, and then, in adsorbed product in addition to chromium, other content of beary metal are very low.
After adsorption treatment, adsorbed product can be carried out dissection process in alkaline solution, obtain containing phosphatic solution
Analysis liquid, wherein, alkaline solution can be NaOH or potassium hydroxide solution that mass fraction is 1%.Adsorbed product is in alkalescence
Parsed in solution, obtain the desorbed solution containing sodium phosphate or potassium phosphate, while realizing that modified aluminas regenerate.Finally, to parsing
Liquid carries out precipitation process, just can obtain phosphorous sediment.If containing chromium in adsorbed product, due to CrO4 2-And HCrO4 -Not
With precipitating reagent reaction, so heavy metal chromium is removed in being dissolved in desorbed solution, heavy metal chromium is not contained in phosphorous sediment.
It should be noted that content of beary metal in strong brine higher than the precipitating reagent used in the case of preset value with
The precipitating reagent that above-mentioned content of beary metal is used in the case of being not higher than preset value is identical, will not be repeated here.In strong brine
Content of beary metal higher than in the case of preset value, precipitating reagent cationic is generally with the mol ratio of phosphate radical in desorbed solution
(1-1.5)∶1.Explanation is needed further exist for, the content of beary metal in strong brine is higher than in the case of preset value, it is also possible to
Addition anion flocculation aid promotes precipitation, and specific species and the above-mentioned content of beary metal of anion flocculation aid are not higher than preset value
In the case of the species of anion flocculation aid that is used it is identical, will not be repeated here.Content of beary metal in strong brine is higher than
In the case of preset value, the consumption of anion flocculation aid typically can be the 0.1%-0.3% of desorbed solution quality.
The technical scheme in the embodiment of the present invention is described below in conjunction with the embodiment of the present invention, it is clear that described
Embodiment be only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained under the premise of creative work is not made, belongs to guarantor of the present invention
The scope of shield.
It should be noted that heavy metal includes arsenic, cadmium, lead, chromium and mercury in following examples, preset value is respectively：50mg/
Kg, 10mg/kg, 200mg/kg, 500mg/kg and 5mg/kg.
Embodiment 1：
Phosphorus containing sludge is ground, is sized to below 20 mesh, modifier treatment is carried out after pulp treatment, obtaining moisture content is
85% sludge；
Sludge after modifier treatment is passed through heat exchanger, after being heated to 320 DEG C, 22MPa is forced into by high-pressure plunger pump；
By excessive oxygen and by the sludge after high-pressure plunger pump pressurization, it is passed through in supercritical water oxidation kettle and is surpassed
Critical oxidation reaction, stops 10 seconds, obtains strong brine and supercritical fluid, and it is 1.5 to cross oxygen quotient；
The content of heavy metal arsenic, cadmium, lead, chromium and mercury in detection strong brine is respectively：10mg/kg、6mg/kg、100mg/
Kg, 300mg/kg and 2mg/kg, not higher than preset value, adjust the pH value of strong brine to 8.5, and addition magnesium salts and ammonium salt mixture are extremely
Precipitation process is carried out in strong brine, and product is separated, obtain phosphorous sediment.After testing, weight in the phosphorous sediment
Without departing from preset value, phosphorous recovery is 90.5% to tenor.
Embodiment 2：
Phosphorus containing sludge is ground, is sized to below 20 mesh, modifier treatment is carried out after pulp treatment, obtaining moisture content is
90% sludge；
Sludge after modifier treatment is passed through heat exchanger, after being heated to 330 DEG C, 30MPa is forced into by high-pressure plunger pump；
By excessive oxygen and by the sludge after high-pressure plunger pump pressurization, it is passed through in supercritical water oxidation kettle and is surpassed
Critical oxidation reaction, stops 20 seconds, obtains strong brine and supercritical fluid, and it is 1.8 to cross oxygen quotient；
The content of heavy metal arsenic, cadmium, lead, chromium and mercury in detection strong brine is respectively：10mg/kg、5mg/kg、100mg/
Kg, 200mg/kg and 3mg/kg, not higher than preset value, adjust the pH value of strong brine to 8.8, add molysite and anion flocculation aid
Precipitation process is carried out into strong brine, and product is separated, obtain phosphorous sediment.After testing, in the phosphorous sediment
Without departing from preset value, phosphorous recovery is 96.1% to content of beary metal.
Embodiment 3：
Phosphorus containing sludge is ground, is sized to below 20 mesh, modifier treatment is carried out after pulp treatment, obtaining moisture content is
95% sludge；
Sludge after modifier treatment is passed through heat exchanger, after being heated to 350 DEG C, 27MPa is forced into by high-pressure plunger pump；
By excessive oxygen and by the sludge after high-pressure plunger pump pressurization, it is passed through in supercritical water oxidation kettle and is surpassed
Critical oxidation reaction, stops 25 seconds, obtains strong brine and supercritical fluid, and it is 2.0 to cross oxygen quotient；
Supercritical fluid is passed through heat exchanger, by by the supercritical fluid of heat exchanger cooled down and step-down process after,
Gas-liquid separation treatment is carried out, gaseous products and aqueous water is obtained；
Aqueous water is back to modifier treatment process, gaseous products are compressed into separating treatment, the oxygen that will be obtained is back to
In supercritical water oxidation kettle；
The content of heavy metal arsenic, cadmium, lead, chromium and mercury in detection strong brine is respectively：20mg/kg、2mg/kg、50mg/
Kg, 10mg/kg and 1mg/kg, not higher than preset value, adjust the pH value of strong brine to 9, and addition calcium hydroxide saturated solution is to dense
Precipitation process is carried out in salt solution, and product is separated, obtain phosphorous sediment.After testing, a huge sum of money in the phosphorous sediment
Without departing from preset value, phosphorous recovery is 92.6% to category content.
Embodiment 4：
Phosphorus containing sludge is ground, is sized to below 20 mesh, modifier treatment is carried out after pulp treatment, obtaining moisture content is
85% sludge；
Sludge after modifier treatment is passed through heat exchanger, after being heated to 330 DEG C, 25MPa is forced into by high-pressure plunger pump；
By excessive oxygen and by the sludge after high-pressure plunger pump pressurization, it is passed through in supercritical water oxidation kettle and is surpassed
Critical oxidation reaction, stops 15 seconds, obtains strong brine and supercritical fluid, and it is 1.5 to cross oxygen quotient；
The content of heavy metal arsenic, cadmium, lead, chromium and mercury in detection strong brine is respectively：65mg/kg、12mg/kg、
220mg/kg, 550mg/kg and 10mg/kg, content of beary metal are above preset value, the pH value of addition hydrochloric acid regulation strong brine to
4；
Concussion adsorption treatment, adsorption time are carried out to the strong brine after the regulation pH value using aluminum sulfate modified aluminas
It it is 0.5 hour, the adsorbed product for obtaining carries out dissection process in the sodium hydroxide solution that mass fraction is 1%, is contained
Phosphatic desorbed solution；
Addition aluminium salt carries out precipitation process in extremely containing phosphatic desorbed solution, and product is separated, and obtains phosphorous
Sediment.After testing, in the phosphorous sediment content of beary metal without departing from preset value, phosphorous recovery is 95.0%.
Embodiment 5：
Phosphorus containing sludge is ground, is sized to below 20 mesh, modifier treatment is carried out after pulp treatment, obtaining moisture content is
90% sludge；
Sludge after modifier treatment is passed through heat exchanger, after being heated to 350 DEG C, 28MPa is forced into by high-pressure plunger pump；
By excessive oxygen and by the sludge after high-pressure plunger pump pressurization, it is passed through in supercritical water oxidation kettle and is surpassed
Critical oxidation reaction, stops 20 seconds, obtains strong brine and supercritical fluid, and it is 2 to cross oxygen quotient；
The content of heavy metal arsenic, cadmium, lead, chromium and mercury in detection strong brine is respectively：55mg/kg、10mg/kg、
300mg/kg, 400mg/kg and 8mg/kg, the content of heavy metal arsenic, lead and mercury is higher than preset value, addition hydrochloric acid regulation strong brine
PH value to 5；
Concussion adsorption treatment, adsorption time are carried out to the strong brine after the regulation pH value using modified with ferric sulfate aluminum oxide
It it is 1.5 hours, the adsorbed product for obtaining carries out dissection process in the potassium hydroxide solution that mass fraction is 1%, is contained
Phosphatic desorbed solution；
Addition magnesium salts and ammonium salt mixture and anion flocculation aid carry out precipitation process in extremely containing phosphatic desorbed solution,
And separated product, obtain phosphorous sediment.After testing, in the phosphorous sediment content of beary metal without departing from preset value,
Phosphorous recovery is 93.5%.
Embodiment 6：
Phosphorus containing sludge is ground, is sized to below 20 mesh, modifier treatment is carried out after pulp treatment, obtaining moisture content is
95% sludge；
Sludge after modifier treatment is passed through heat exchanger, after being heated to 330 DEG C, 30MPa is forced into by high-pressure plunger pump；
By excessive oxygen and by the sludge after high-pressure plunger pump pressurization, it is passed through in supercritical water oxidation kettle and is surpassed
Critical oxidation reaction, stops 25 seconds, obtains strong brine and supercritical fluid, and it is 1.7 to cross oxygen quotient；
Supercritical fluid is passed through heat exchanger, by by the supercritical fluid of heat exchanger cooled down and step-down process after,
Gas-liquid separation treatment is carried out, gaseous products and aqueous water is obtained；
Aqueous water is back to modifier treatment process, gaseous products are compressed into separating treatment, the oxygen that will be obtained is back to
In supercritical water oxidation kettle；
The content of heavy metal arsenic, cadmium, lead, chromium and mercury in detection strong brine is respectively：40mg/kg、10mg/kg、
250mg/kg, 550mg/kg and 9mg/kg, the content of heavy metal lead, chromium and mercury is higher than preset value, addition hydrochloric acid regulation strong brine
PH value to 6；
The strong brine after the regulation pH value is shaken using aluminum sulfate modified aluminas and modified with ferric sulfate aluminum oxide
Adsorption treatment is swung, adsorption time is 3 hours, and the adsorbed product for obtaining is carried out in the sodium hydroxide solution that mass fraction is 1%
Dissection process, obtains containing phosphatic desorbed solution；
Addition molysite carries out precipitation process in extremely containing phosphatic desorbed solution, and product is separated, and obtains phosphorous
Sediment.After testing, in the phosphorous sediment content of beary metal without departing from preset value, phosphorous recovery is 96.2%.
Comparative example 1
Phosphorus containing sludge is carried out into centrifugal treating 5 minutes, the salt that mass fraction is 1% is added in the phosphorus containing sludge after centrifugation
Acid, obtains mixed liquor, and the phosphorus containing sludge sludge after centrifugation is 1 with hydrochloric acid volume ratio:10；
Mixed liquor after Heating Water 1 hour, is carried out into centrifugal treating at 70 DEG C, supernatant is obtained；
Use concentration to adjust the pH of supernatant to 10.5 for the NaOH of 5mol/L, add confection, 1-2 is small for precipitation
When, Ca in confection2+、P、NH4+Mol ratio be 1.8：1：1.2；
Precipitated product is dried under the conditions of 40 DEG C, dry phosphorous sediment is obtained.After testing, in the phosphorous sediment
Cadmium content is 26.2mg/kg, and beyond preset value, phosphorous recovery is 70.6%.
Comparative example 2
Phosphorus containing sludge is carried out into gravity concentration treatment, the sludge that concentration is 7000mg/L is obtained；
At room temperature, to concentration to add the hydrochloric acid that concentration is 2.5mol/L in the sludge of 7000mg/L, after regulation acidifying
Sludge pH be 2.0；
Sludge after acidifying is positioned in microwave reactor, microwave frequency is 2.45GHz, at ambient pressure to acidifying after
Sludge carries out microwave, and the sludge outlet temperature of microwave is 95 DEG C；
Sludge after microwave is carried out into separation of solid and liquid in the way of natural subsidence, is collected on the rich phosphorus after separation of solid and liquid
Clear liquid；
According to Ca2+It is 1.8 with the mol ratio of P:1, to adding aqua calcis in supernatant, the pH for adjusting supernatant is
10.5, after reaction 30min, it is filtrated to get phosphorous sediment.After testing, cadmium content is 23.4mg/kg in the phosphorous sediment, is surpassed
Go out preset value, phosphorous recovery is 83.6%.
From above-described embodiment 1-6, using the recovery method of phosphorus in the phosphorus containing sludge that the embodiment of the present invention is provided, contain
The rate of recovery of phosphorus is up to more than 90% in phosphorus sludge, and content of beary metal is low in phosphorous sediment obtained by reclaiming, not over
Preset value.It is phosphorous using the recovery method of phosphorus in phosphorus containing sludge of the prior art from above-mentioned comparative example 1 and comparative example 2
The rate of recovery of phosphorus is relatively low in sludge, and reclaim obtained by phosphorous sediment in content of beary metal easily exceed preset value, influence it is phosphorous
The recycling of sediment.
The recovery method of phosphorus is simple to operation in a kind of phosphorus containing sludge that the embodiment of the present invention is provided, using supercritical water
Oxidation reaction apparatus are processed, and phosphorus containing sludge is fully reacted, and phosphorus can all discharge substantially in phosphorus containing sludge, phosphorus containing sludge
The organic efficiency of middle phosphorus is greatly improved, and can realize sludge reduction.On the other hand, the content of beary metal in strong brine is higher than
In the case of preset value, the purpose of purification of products is realized using absorption and dissection process, so as to get phosphorous sediment in weight
Tenor does not influence the recycling of phosphorous sediment without departing from preset value.
The recovery method to phosphorus in a kind of phosphorus containing sludge provided by the present invention is described in detail above.Herein should
Principle of the invention and implementation method are set forth with specific embodiment, the explanation of above example is only intended to help
Understand the method for the present invention and its central idea.It should be pointed out that for the person of ordinary skill of the art, not departing from this
On the premise of inventive principle, some improvement and modification can also be carried out to the present invention, these are improved and modification also falls into the present invention
The protection of claim.
Claims (10)
1. in a kind of phosphorus containing sludge phosphorus recovery method, it is characterised in that methods described includes：
Phosphorus containing sludge is ground, sieve and pulp treatment after, carry out modifier treatment, obtain moisture content for 85%-95%
Sludge；
Sludge and excessive oxygen after modifier treatment is passed through into supercritical water oxidation device carries out supercritical water oxidation,
Stop 10-30 seconds, obtain strong brine and supercritical fluid, wherein, it is 1.5-2 to cross oxygen quotient；
The content of beary metal in the strong brine is detected, the content of beary metal in the strong brine is not higher than the situation of preset value
Under, the strong brine to alkalescence is adjusted, precipitation process is carried out in addition precipitating reagent to the strong brine, and product is divided
From obtaining phosphorous sediment, it is preferable that the precipitation process also includes：Addition anion flocculation aid promotes precipitation, it is described it is cloudy from
Sub- flocculation aid dosage is the 0.1%-0.3% of the strong brine quality.
2. recovery method as claimed in claim 1, it is characterised in that the content of beary metal in the strong brine is detected is high
In the case of the preset value, methods described also includes：
Addition hydrochloric acid adjusts the pH value of the strong brine to 4-6；
Adsorption treatment is carried out to the strong brine after regulation pH value, the adsorbed product for obtaining carries out dissection process in alkaline solution,
Obtain containing phosphatic desorbed solution；
Addition precipitating reagent containing carrying out precipitation process in phosphatic desorbed solution, and product is separated to described, is contained
Phosphorus sediment, it is preferable that the precipitation process also includes：Addition anion flocculation aid promotes precipitation, the anion flocculation aid
Dosage is the 0.1%-0.3% of the desorbed solution quality.
3. recovery method as claimed in claim 2, it is characterised in that the adsorption treatment includes：
Concussion adsorption treatment is carried out to the strong brine after the regulation pH value using modified aluminas, adsorption time is that 0.5-3 is small
When, it is preferable that the modified aluminas include：Aluminum sulfate modified aluminas and/or modified with ferric sulfate aluminum oxide.
4. recovery method as claimed in claim 2, it is characterised in that the alkaline solution is hydrogen-oxygen that mass fraction is 1%
Change sodium or potassium hydroxide solution.
5. recovery method as claimed in claim 1 or 2, it is characterised in that the precipitating reagent is selected from：Magnesium salts and ammonium salt mix
One or more in thing, aluminium salt, molysite and calcium hydroxide saturated solution, the precipitating reagent cationic and phosphate radical mole
Than being (1-1.5): 1.
6. recovery method as claimed in claim 1 or 2, it is characterised in that the anion flocculation aid includes：Polyacrylamide
In amine, polyacrylic acid, Sodium Polyacrylate, calcium polyacrylate (CPA) one or more.
7. recovery method as claimed in claim 1, it is characterised in that the supercritical water oxidation device includes：Heat exchange
Device, high-pressure plunger pump and supercritical water oxidation kettle, the heat exchanger, the high-pressure plunger pump and the supercritical water oxidation
Reactor is connected in series；
The supercritical water oxidation process includes：
Sludge after modifier treatment is passed through the heat exchanger, after being heated to 320-350 DEG C, is pressurizeed by the high-pressure plunger pump
To 22-30MPa；
By excessive oxygen and by the sludge after high-pressure plunger pump pressurization, it is passed through in the supercritical water oxidation kettle
Row supercritical water oxidation, stops 10-30 seconds, obtains strong brine and supercritical fluid.
8. recovery method as claimed in claim 7, it is characterised in that be provided with evaporation in the supercritical water oxidation kettle
Wall and porous inner tube, fill supercritical water, the overcritical water oxygen in the cavity between the evaporation wall and the porous inner tube
Change reactor bottom and be provided with brine outlet, top is provided with supercritical fluid outlet, liquid oxygen entrance and sludge import.
9. recovery method as claimed in claim 7, it is characterised in that methods described also includes：
The supercritical fluid is passed through the heat exchanger；
By after the supercritical fluid of heat exchanger is cooled down and step-down is processed, after carrying out gas-liquid separation, gaseous products are obtained
And aqueous water；
By the liquid Water circulation to the modifier treatment process or directly discharge, the gaseous products compressed into separating treatment,
The oxygen in the gaseous products is reclaimed, and the oxygen that will be obtained is back to the supercritical water oxidation device.
10. recovery method as claimed in claim 1, it is characterised in that the pH value of the regulation strong brine to 8.5-9.
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| CN109867421A (en) * | 2019-04-08 | 2019-06-11 | 陕西科技大学 | A kind of chromium-bearing sludge processing method and system based on supercritical water oxidation |
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| CN109867421A (en) * | 2019-04-08 | 2019-06-11 | 陕西科技大学 | A kind of chromium-bearing sludge processing method and system based on supercritical water oxidation |
| WO2021204609A1 (en) * | 2020-04-06 | 2021-10-14 | Scfi Limited | Process for the supercritical oxidation of sewage sludge and other waste streams |
| CN111392997A (en) * | 2020-05-19 | 2020-07-10 | 杭州秀澈环保科技有限公司 | Recycling process of organophosphorus sludge |
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