CN110255845A - A kind of resource utilization method of pyrolyzing sludge charcoal - Google Patents
A kind of resource utilization method of pyrolyzing sludge charcoal Download PDFInfo
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- CN110255845A CN110255845A CN201910615263.6A CN201910615263A CN110255845A CN 110255845 A CN110255845 A CN 110255845A CN 201910615263 A CN201910615263 A CN 201910615263A CN 110255845 A CN110255845 A CN 110255845A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
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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
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
Abstract
The invention belongs to pyrolyzing sludge charcoal process fields, disclose a kind of resource utilization method of pyrolyzing sludge charcoal, this method comprises: S1, successively using digestion agent I, digestion agent II and digestion agent III to extract the pyrolyzing sludge charcoal, leaching liquor and solid residue III are obtained；S2, by leaching liquor it is concentrated after carry out ion exchange resin separation, obtain different metal ions and phosphate anion；S3, the source of ammonium using magnesium ion and phosphate anion and being additionally added prepare guanite as raw material；Solid residue III is successively washed, is dried, steam activation and metal ion it is loaded modified, obtain functional adsorbent material.Recycling can be efficiently separated to the metal ion in pyrolyzing sludge charcoal using method provided by the invention, wherein, magnesium ion and phosphate anion are used to prepare guanite, final leaching residue can be used as fertilizers for potted flowers or be made into functional adsorbent material, to realize the resource utilization of pyrolyzing sludge charcoal.
Description
Technical field
The invention belongs to pyrolyzing sludge charcoal process fields, and in particular to a kind of resource utilization side of pyrolyzing sludge charcoal
Method.
Background technique
With the increasingly raising of the urban operating mechanism service level of modern city, the yield of municipal sludge is gradually increased.
In many Sludge resource utilization methods, thoroughly, after processing sludge is steady for rapid, harmless treatment with processing for pyrolyzing sludge
It the advantages that qualitative good and recovering energy source, is paid more and more attention.Whether the content of heavy metal reaches in charcoal obtained by pyrolyzing sludge
Mark and its existing forms, largely affect further applying for pyrolyzing sludge charcoal.Correlative study shows sludge hot
Heavy metal can be enriched in pyrolytic process in solution charcoal.Although pyrolysis itself can play stabilized work to Heavy Metals in Sludge
With also thering are the numerous prior arts to stabilize using modes such as addition curing agent to heavy metal, but for pyrolyzing sludge
The application of charcoal, wherein the limitation of heavy metal is very strict, if pyrolyzing sludge charcoal is applied to soil rashly, not
Come under the action of Soil Microorganism, during long-term soil environmental background value, may result in weight in pyrolyzing sludge charcoal
Metal is converted from stable state to labile state.Therefore, if not being reduced to the total amount of heavy metal in pyrolyzing sludge charcoal
Lower than concerned countries standard, only fixing-stable simply can there are long-term potential pollution risks to environment.
Meanwhile pyrolyzing sludge charcoal is enriched with metal in pyrolytic process, it is a large amount of in addition to existing through detecting
Outside by common metals such as flocculant bring ferro-aluminums, there is also the noble metals such as gold and silver, especially using made from industrial sludge
In pyrolyzing sludge active carbon, therefore the METAL EXTRACTION in pyrolyzing sludge active carbon is particularly important out.
Current research is concentrated mainly on the extraction recycling of Heavy Metals in Sludge, phosphorus and other elements, sludge not yet occurs
Heavy metal, the extraction recycling of phosphorus and other elements and the relevant report of recycling being pyrolyzed in active carbon.
Summary of the invention
The present invention is intended to provide a kind of resource utilization method of new pyrolyzing sludge charcoal, to realize that pyrolyzing sludge is raw
The recycling of object charcoal, this method can solve pyrolyzing sludge charcoal application in heavy metal limitation bottleneck problem while,
So that the resources such as common metal, phosphorus and other elements in sludge organism charcoal are fully used.
Specifically, the present invention provides a kind of resource utilization method of pyrolyzing sludge charcoal, this method includes following
Step:
S1, extraction: by pyrolyzing sludge charcoal using digestion agent I carry out first time extraction, obtain first time leaching liquor and
Solid residue I, then obtained solid residue I is carried out second using digestion agent II and is extracted, obtain second of leaching liquor and solid
The solid residue II is carried out the third leaching using digestion agent III later, obtains the third leaching liquid and solid by residue II
Residue III；The digestion agent I is selected from least one of citric acid, EDTA and sodium hydroxide solution, and the digestion agent II is nothing
Machine acid solution, the digestion agent III are the mixed solution of phosphoric acid and hydrogen peroxide；
The separation of S2, metal ion and phosphate anion: respectively by the first time leaching liquor, second of leaching liquor and
Ion exchange resin separation is carried out after leaching liquor is concentrated three times, obtains different metal ions and phosphate anion；
The preparation of S3, guanite and functional adsorbent material:
The source of ammonium using the obtained magnesium ion of step S2 and phosphate anion and being additionally added prepares guanite as raw material；
The solid residue III is dried using after water washing, and it is living at least partly to dry product progress vapor
Change, the metal ion progress obtained later using step S2 is loaded modified, obtains functional adsorbent material.
Further, in step S1, the condition of the first time extraction, second of extraction and the third leaching is respectively independent
Ground includes that extraction temperature is 25~95 DEG C, and extraction time is 1h~10d, and solid-to-liquid ratio is (5~40) g:1L.
Further, the first time extraction, second of extraction and the third leaching carry out under ultrasound condition, and super
Acoustic frequency is 20~65kHz.
Further, in step S1, the molar concentration of the digestion agent I and digestion agent II is 0.01~5mol/L, described
The molar concentration of phosphoric acid is 0.01~5mol/L in digestion agent III and the volumetric concentration of hydrogen peroxide is 2~20%.
Further, the digestion agent II is selected from least one of sulfuric acid, nitric acid and hydrochloric acid.
Further, in step S2, ion exchange resin used by the ion exchange resin separates is selected from highly acid
In ion exchange resin, weak-acid ion exchange resin, weak-base ion-exchange resin and chelating ion exchange resin extremely
Few one kind.
Further, the resource utilization method of pyrolyzing sludge charcoal provided by the invention further includes handing in the ion
It changes after resin separation, acidification regeneration treatment is carried out to the ion exchange resin of saturation absorption, gained is washed containing heavy metal ion
Alloying metal particle is made in de- liquid after replacing using aluminium scrap, while gained being added at sewage containing aluminum solutions as auxiliary flocculant
Manage factory's secondary settling tank.
Further, in step S3, during preparing guanite, the magnesium ion and phosphate anion and additional
The dosage of the source of ammonium of addition makes the molar ratio of magnesium ion, phosphonium ion and ammonium ion be (1~1.8): (0.8~1.5): (3.5~
4.5)。
Further, in step S3, in the washing process, solid-to-liquid ratio is (5~40) kg:1m3。
Further, in step S3, the condition of the steam activation includes that activation temperature is 700~900 DEG C, vapor
Dosage be 1~5mL/min, activation time be 10~30min.
Further, in step S3, the loaded modified mode is that co-precipitation is modified.
Further, in step S3, this method further includes using remainder drying product as Fertilizer application.
It can be to the metal ion and phosphate anion reality in pyrolyzing sludge charcoal using method provided by the invention
Existing effect separation and recovery utilizes, wherein magnesium ion and phosphate anion are used to prepare guanite, and final leaching residue can be used as
Fertilizer is made into functional adsorbent material, to realize the resource utilization of pyrolyzing sludge charcoal.
Detailed description of the invention
Fig. 1 is a kind of idiographic flow schematic diagram of the resource utilization method of pyrolyzing sludge charcoal provided by the invention.
Specific embodiment
In the present invention, the pyrolyzing sludge charcoal refers to the charcoal made of pyrolysis using sludge as raw material.
Contain the yin such as metal cations and phosphate radical such as magnesium, lead, manganese, copper, zinc, calcium, iron, chromium, aluminium in the pyrolyzing sludge charcoal
Ion.
In the present invention, in step S1, by carrying out classification extraction to pyrolyzing sludge charcoal to realize metal cation
And the recycling of phosphate radical anion.Wherein, the first time extraction is mainly used for recycling phosphate radical, magnesium, lead, manganese plasma,
Second of extraction is mainly used for recycling the metal cations such as copper, zinc, calcium, iron, and the third leaching is mainly used for recycling chromium, iron, aluminium
Equal metal cations.The first time extracts at least one of used digestion agent I in citric acid, EDTA and sodium hydroxide
Kind solution, it is inorganic acid solution, the used extraction of the third leaching that described second, which extracts used digestion agent II,
Agent III is the mixed solution of phosphoric acid and hydrogen peroxide.Wherein, the digestion agent II is preferably selected from sulfuric acid, nitric acid and hydrochloric acid at least
It is a kind of.In addition, the molar concentration of the digestion agent I and digestion agent II is preferably 0.01~5mol/L.Phosphorus in the digestion agent III
The molar concentration of acid is preferably that the volumetric concentration of 0.01~5mol/L and hydrogen peroxide is preferably 2~20%.
There is no particular limitation to the condition extracted three times by the present invention, as long as can be realized the abundant extraction of metal cation
?.A preferred embodiment of the invention, first time extraction, second extraction and the third leaching condition
It is each independently 25~95 DEG C including extraction temperature, extraction time is 1h~10d, and solid-to-liquid ratio is (5~40) g:1L.In addition,
In order to be more advantageous to the dissolution of metal cation and phosphate anion, the first time extraction, second of extraction and third time
Extraction preferably carries out under ultrasound condition, and supersonic frequency is preferably 20~65kHz.
In the present invention, in step S2, the condition of the concentration is so that the volume of leaching liquor is reduced to (the 1/ of original solution
5~1/3) subject to.Ion exchange resin separation is carried out after extraction gained leaching liquor is concentrated three times, not using retention time
With the separation again realized to hybrid ionic contained in each leaching liquor, different retention times obtain single ionic.For example, described
Copper, zinc, calcium, iron these types metal ion are mainly contained in digestion agent II, after separating through ion exchange resin, when due to retaining
Between difference, these types of metal ion can elute from ion exchange resin column and realize separation.Similarly, the digestion agent I
It can also be separated with phosphate radical contained in digestion agent III and metal ion.After the concentration of leaching liquor obtained by extracting three times
The type for carrying out ion exchange resin used by ion exchange resin separates may be the same or different, for example, can be each
From independently selected from strong-acid ion exchange resin, weak-acid ion exchange resin, weak-base ion-exchange resin and chelating type
At least one of ion exchange resin should specifically make a choice according to metal cation type contained therein, as long as energy
It is enough will respectively contained mixed metal ion isolation at single metal ion.
A preferred embodiment of the invention, the resource utilization side of pyrolyzing sludge charcoal provided by the invention
Method further includes carrying out acidification regeneration treatment to the ion exchange resin of saturation absorption after ion exchange resin separation,
Eluent of the gained containing heavy metal ion using being made alloying metal particle after aluminium scrap displacement, while using gained containing aluminum solutions as
Assist flocculant that secondary sedimentation tank of sewage treatment work is added.Wherein, the type of acid solution used by the acidification regeneration treatment should root
It is selected according to the type for the heavy metal ion being adsorbed in ion exchange resin, with can be by these heavy metal ion from ion
Subject to being eluted on exchange resin column.
In the present invention, in step S3, during preparing guanite (ammonium magnesium phosphate), in pyrolyzing sludge active carbon
The magnesium ion and phosphate anion of extraction are as raw material, in the process, need additionally to supplement source of ammonium and are likely to require
Additional supplement magnesium source (in the insufficient situation in magnesium source of recycling).Wherein, each raw material dosage preferably so that magnesium ion, phosphonium ion and
The molar ratio of ammonium ion is (1~1.8): (0.8~1.5): (3.5~4.5).The specific preparation process of the guanite is ability
Known in field technique personnel, therefore not to repeat here.
In the present invention, in step S3, it can be (5~40) kg:1m that the condition of the washing, which generally includes solid-to-liquid ratio,3,
Washing times can be 2~4 times.Sedimentation separation after the washing, solid drying, drying product are used to prepare function adsorption material
Material or a part are used to prepare function adsorbent material and remainder as fertilizer is applied to landscape flower.In the function
In the preparation process of adsorbent material, need that drying product is first carried out steam activation, the metal obtained using step S2 later
Ion (such as at least one of iron ion, calcium ion, magnesium ion, aluminium ion) carries out loaded modified.Wherein, the vapor
The condition of activation includes that activation temperature is preferably 700~900 DEG C, and the dosage of vapor is preferably 1~5mL/min, activation time
Preferably 10~30min.In addition, the loaded modified mode is that co-precipitation is modified, it specifically, will be after steam activation
The metal ion (at least one of iron ion, calcium ion, magnesium ion, aluminium ion) that solid residue III and step S2 are obtained is molten
In solvent, the pH value of system is adjusted to alkalinity so that the above precipitation by metallic ion connects to III surface of solid residue later
Can obtain the function adsorbent material through drying.The function adsorbent material can be used for adsorbing the member of the phosphorus in phosphorus-containing wastewater
Element.
A kind of specific embodiment according to the present invention, as shown in Figure 1, the resource utilization of the pyrolyzing sludge charcoal
Method include by pyrolyzing sludge charcoal using compound digestion agent carry out classification extraction (classification leaching process in, can not
The disconnected optimal extracting technology condition of optimization), solid (solid residue III) and liquid phase after extracting after the isolated extraction of centrifugal filtration
(first time leaching liquor, second of leaching liquor and the third leaching liquid)；Amberlite is carried out after liquid phase is concentrated after extraction
Rouge separation, obtains different metal ions and phosphate anion, wherein gained magnesium ion and phosphate anion are in additionally supplement ammonium
Guanite is made in the case where salt；After ion exchange resin separation, the ion exchange resin of saturation absorption is acidified
Conjunction is made after replacing using aluminium scrap in regeneration treatment, regenerating resin reuse, resin acidification eluent of the gained containing heavy metal ion
Golden metallic particles, which can further be smelted using normal process steps, and gained can be used as containing aluminum solutions
Flocculant is assisted to be added in secondary sedimentation tank of sewage treatment work, and resin acidification gained then can be used as without the eluent of heavy metal ion
Digestion agent reuse is to leach step；The washed rear portion of solid is as flowers and afforestation fertilizer, another portion after extraction
Adsorbent material is made after lease making activation is combined modified.
The present invention will be described in detail by way of examples below.
Embodiment 1
S1, extraction: by pyrolyzing sludge charcoal use digestion agent I (concentration is the aqueous citric acid solution of 0.01mol/L) in
Extract 10d under the conditions of 25 DEG C of temperature, solid-to-liquid ratio 40g:1L, supersonic frequency 65kHz, be centrifugated, obtain first time leaching liquor and
Solid residue I, then by obtained solid residue I use digestion agent II (concentration is the aqueous sulfuric acid of 5mol/L) 75 DEG C of Yu Wendu,
1h is extracted under the conditions of solid-to-liquid ratio 5g:1L, supersonic frequency 20kHz, is centrifugated, obtains second of leaching liquor and solid residue II,
Later by the solid residue II using the (mixed solution of phosphoric acid and hydrogen peroxide, wherein the molar concentration of phosphoric acid is of digestion agent III
The volumetric concentration of 0.01mol/L and hydrogen peroxide is 2%) to soak under the conditions of 40 DEG C of Yu Wendu, solid-to-liquid ratio 5g:1L, supersonic frequency 65kHz
10d is mentioned, is centrifugated, obtains the third leaching liquid and solid residue III.
The separation of S2, metal ion and phosphate anion: by first time leaching liquor be concentrated into original volume a quarter it
Separated afterwards using weak-acid ion exchange resin, wherein eluant, eluent is acetum, using retention time it is different successively
Obtain phosphate anion, magnesium ion and a small amount of lead ion and manganese ion.Highly acid is used after second of leaching liquor is concentrated
Ion exchange resin is separated, wherein eluant, eluent is hydrochloric acid solution, using retention time difference successively obtain copper ion,
Zinc ion, calcium ion and iron ion.The third leaching liquid is concentrated into after a quarter of original volume and is handed over using weakbase ion
It changes resin to be separated, wherein eluant, eluent is ammonia spirit, successively obtains chromium ion and a small amount of using the difference of retention time
Iron ion and aluminium ion.
The preparation of S3, guanite and functional adsorbent material:
The source of ammonium using the obtained magnesium ion of step S2 and phosphate anion and being additionally added prepares guanite as raw material,
Wherein, the dosage of each substance makes the molar ratio of magnesium ion, phosphonium ion and ammonium ion be 1:0.8:3.5.
By the solid residue III using aqueous solvent in solid-to-liquid ratio 5kg:1m3Under the conditions of wash 3 times, sedimentation separation, solid
A part drying product is directly used as fertilizers for potted flowers later by drying, and through steam activation, (steam activation condition includes remainder
Temperature is 800 DEG C, and the dosage of vapor is 2mL/min, activation time 20min), the iron ion obtained later using step S2
It carries out loaded modified, obtains functional adsorbent material, can be used for adsorbing the P elements in phosphorus-containing wastewater.
Embodiment 2
S1, extraction: pyrolyzing sludge charcoal is used into digestion agent I (concentration is the sodium hydrate aqueous solution of 5mol/L) Yu Wen
1h is extracted under the conditions of 95 DEG C of degree, solid-to-liquid ratio 20g:1L, supersonic frequency 65kHz, is centrifugated, obtains first time leaching liquor and solid
Residue I, then obtained solid residue I is used into digestion agent II (concentration is the aqueous solution of nitric acid of 0.01mol/L) 25 DEG C of Yu Wendu, solid
10d is extracted under the conditions of liquor ratio 40g:1L, supersonic frequency 65kHz, is centrifugated, obtains second of leaching liquor and solid residue II,
Later by the solid residue II using the (mixed solution of phosphoric acid and hydrogen peroxide, wherein the molar concentration of phosphoric acid is of digestion agent III
The volumetric concentration of 5mol/L and hydrogen peroxide is 20%) to soak under the conditions of 75 DEG C of Yu Wendu, solid-to-liquid ratio 40g:1L, supersonic frequency 20kHz
1h is mentioned, is centrifugated, obtains the third leaching liquid and solid residue III.
The separation of S2, metal ion and phosphate anion: after first time leaching liquor is concentrated into the one third of original volume
It is separated using strong-acid ion exchange resin, wherein eluant, eluent is hydrochloric acid solution, and different using retention time successively obtain
To phosphate anion and magnesium ion.Second of leaching liquor is concentrated into after original volume a quarter using weak acid ion exchange tree
Rouge is separated, wherein eluant, eluent is acetum, using retention time difference successively obtain copper ion, zinc ion, calcium from
Son and iron ion.The third leaching liquid is concentrated into after original volume 1/5th and is divided using strong basic ion exchange resin
From, wherein eluant, eluent is sodium hydroxide solution, successively obtains chromium ion and aluminium ion using the difference of retention time.
The preparation of S3, guanite and functional adsorbent material:
The source of ammonium using the obtained magnesium ion of step S2 and phosphate anion and being additionally added prepares guanite as raw material,
Wherein, the dosage of each substance makes the molar ratio of magnesium ion, phosphonium ion and ammonium ion be 1.8:1.5:4.5.
By the solid residue III using aqueous solvent in solid-to-liquid ratio 20kg:1m3Under the conditions of wash 3 times, sedimentation separation, solid
A part drying product is directly used as fertilizers for potted flowers later by drying, and through steam activation, (steam activation condition includes remainder
Temperature is 900 DEG C, and the dosage of vapor is 5mL/min, activation time 10min), the calcium ion obtained later using step S2
It carries out loaded modified, obtains functional adsorbent material, can be used for adsorbing the P elements in phosphorus-containing wastewater.
Embodiment 3
S1, extraction: pyrolyzing sludge charcoal is used into digestion agent I (concentration is the EDTA aqueous solution of 2mol/L) Yu Wendu 40
DEG C, extract 5d under the conditions of solid-to-liquid ratio 20g:1L, supersonic frequency 40kHz, be centrifugated, obtain first time leaching liquor and solid residue
I, then obtained solid residue I is used into digestion agent II (concentration is the hydrochloric acid solution of 2mol/L) 25 DEG C of Yu Wendu, solid-to-liquid ratio 20g:
5d is extracted under the conditions of 1L, supersonic frequency 40kHz, is centrifugated, obtains second of leaching liquor and solid residue II, it later will be described
Solid residue II is using (the mixed solution of phosphoric acid and hydrogen peroxide, wherein the molar concentration of phosphoric acid is 2mol/L and double of digestion agent III
To extract 5d under the conditions of 10%) 35 DEG C of Yu Wendu, solid-to-liquid ratio 20g:1L, supersonic frequency 40kHz, centrifugation divides the volumetric concentration of oxygen water
From obtaining the third leaching liquid and solid residue III.
The separation of S2, metal ion and phosphate anion: after first time leaching liquor is concentrated into a quarter of original volume
It is separated using weak-acid ion exchange resin, wherein eluant, eluent is acetum, and different using retention time successively obtain
To phosphate anion, magnesium ion and a small amount of lead ion and manganese ion.By second of leaching liquor be concentrated into original volume five/
Separated after one using chelating ion exchange resin, wherein eluant, eluent is hydrochloric acid solution, using retention time it is different according to
It is secondary to obtain copper ion, zinc ion, calcium ion and iron ion.The third leaching liquid is concentrated into after original volume a quarter and is used
Weak-base ion-exchange resin is separated, wherein eluant, eluent is ammonia spirit, successively obtains chromium using the difference of retention time
Ion and a small amount of aluminium ion.
The preparation of S3, guanite and functional adsorbent material:
The source of ammonium using the obtained magnesium ion of step S2 and phosphate anion and being additionally added prepares guanite as raw material,
Wherein, the dosage of each substance makes the molar ratio of magnesium ion, phosphonium ion and ammonium ion be 1.5:1.2:4.
By the solid residue III using alcohol solvent in solid-to-liquid ratio 40kg:1m3Under the conditions of wash 3 times, sedimentation separation, Gu
A part drying product is directly used as fertilizers for potted flowers later by body drying, and remainder is through steam activation (steam activation condition packet
Including temperature is 900 DEG C, and the dosage of vapor is 5ml/min, activation time 20min), the aluminium obtained later using step S2 from
Son progress is loaded modified, obtains functional adsorbent material, can be used for adsorbing the P elements in phosphorus-containing wastewater.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art are not departing from the principle of the present invention and objective
In the case where can make changes, modifications, alterations, and variations to the above described embodiments within the scope of the invention.
Claims (10)
1. a kind of resource utilization method of pyrolyzing sludge charcoal, which is characterized in that method includes the following steps:
S1, extraction: pyrolyzing sludge charcoal is subjected to first time extraction using digestion agent I, obtains first time leaching liquor and solid
Residue I, then obtained solid residue I is carried out second using digestion agent II and is extracted, obtain second of leaching liquor and solid residue
II, the solid residue II is subjected to the third leaching using digestion agent III later, obtains the third leaching liquid and solid residue
Ⅲ；The digestion agent I is selected from least one of citric acid, EDTA and sodium hydroxide solution, and the digestion agent II is inorganic acid
Solution, the digestion agent III are the mixed solution of phosphoric acid and hydrogen peroxide；
The separation of S2, metal ion and phosphate anion: respectively by the first time leaching liquor, second of leaching liquor and third time
Ion exchange resin separation is carried out after leaching liquor is concentrated, obtains different metal ions and phosphate anion；
The preparation of S3, guanite and functional adsorbent material:
The source of ammonium using the obtained magnesium ion of step S2 and phosphate anion and being additionally added prepares guanite as raw material；
The solid residue III is dried using after water washing, and will at least partly dry product and carry out steam activation, it
The metal ion progress obtained afterwards using step S2 is loaded modified, obtains functional adsorbent material.
2. the resource utilization method of pyrolyzing sludge charcoal according to claim 1, which is characterized in that in step S1,
It is 25~95 DEG C that the condition of the first time extraction, second of extraction and the third leaching includes extraction temperature each independently,
Extraction time is 1h~10d, and solid-to-liquid ratio is (5~40) g:1L；The first time extraction, second of extraction and the third leaching are equal
It is carried out under ultrasound condition, and supersonic frequency is 20~65kHz.
3. the resource utilization method of pyrolyzing sludge charcoal according to claim 1, which is characterized in that in step S1,
The molar concentration of the digestion agent I and digestion agent II is 0.01~5mol/L, and the molar concentration of phosphoric acid is in the digestion agent III
The volumetric concentration of 0.01~5mol/L and hydrogen peroxide is 2~20%；The digestion agent II in sulfuric acid, nitric acid and hydrochloric acid extremely
Few one kind.
4. the resource utilization method of pyrolyzing sludge charcoal according to any one of claims 1 to 3, feature exist
In in step S2, ion exchange resin used by the ion exchange resin separates is selected from strong-acid ion exchange resin, weak
At least one of acid-exchange resin, weak-base ion-exchange resin and chelating ion exchange resin.
5. the resource utilization method of pyrolyzing sludge charcoal according to any one of claims 1 to 3, feature exist
In this method further includes being acidified again after ion exchange resin separation to the ion exchange resin of saturation absorption
Raw processing, alloying metal particle is made in eluent of the gained containing heavy metal ion after replacing using aluminium scrap, while gained is contained aluminium
Secondary sedimentation tank of sewage treatment work is added as auxiliary flocculant in solution.
6. the resource utilization method of pyrolyzing sludge charcoal according to any one of claims 1 to 3, feature exist
In, in step S3, during preparing guanite, the use of the magnesium ion and phosphate anion and the source of ammonium being additionally added
Amount is so that the molar ratio of magnesium ion, phosphonium ion and ammonium ion is (1~1.8): (0.8~1.5): (3.5~4.5).
7. the resource utilization method of pyrolyzing sludge charcoal according to any one of claims 1 to 3, feature exist
In in step S3, in the washing process, solid-to-liquid ratio is (5~40) kg:1m3。
8. the resource utilization method of pyrolyzing sludge charcoal according to any one of claims 1 to 3, feature exist
In, in step S3, the condition of the steam activation includes that activation temperature is 700~900 DEG C, and the dosage of vapor is 1~
5mL/min, activation time are 10~30min.
9. the resource utilization method of pyrolyzing sludge charcoal according to any one of claims 1 to 3, feature exist
In in step S3, the loaded modified mode is that co-precipitation is modified.
10. the resource utilization method of pyrolyzing sludge charcoal according to any one of claims 1 to 3, feature
It is, in step S3, this method further includes using remainder drying product as Fertilizer application.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910615263.6A CN110255845B (en) | 2019-07-09 | 2019-07-09 | Resource utilization method of sludge pyrolytic biochar |
| PCT/CN2019/099328 WO2021003789A1 (en) | 2019-07-09 | 2019-08-06 | Resource utilization method of sludge pyrolysis biochar |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910615263.6A CN110255845B (en) | 2019-07-09 | 2019-07-09 | Resource utilization method of sludge pyrolytic biochar |
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| CN110255845A true CN110255845A (en) | 2019-09-20 |
| CN110255845B CN110255845B (en) | 2020-08-21 |
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| CN113732046A (en) * | 2021-08-26 | 2021-12-03 | 中国科学院烟台海岸带研究所 | Method for removing soil heavy metals by using agriculture and forestry waste leaching liquor |
| CN114177885A (en) * | 2021-11-25 | 2022-03-15 | 华南农业大学 | Magnesium-containing biochar liquid material for recovering phosphorus element in pig farm wastewater and preparation method and application thereof |
| CN114471562A (en) * | 2021-12-28 | 2022-05-13 | 浙江大学 | Metal self-doped sludge carbon-based catalytic material and preparation method and application thereof |
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| CN114471562A (en) * | 2021-12-28 | 2022-05-13 | 浙江大学 | Metal self-doped sludge carbon-based catalytic material and preparation method and application thereof |
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| CN110255845B (en) | 2020-08-21 |
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