CN111892031B - Method and device for recovering and purifying phosphorus from sludge incineration ash - Google Patents
Method and device for recovering and purifying phosphorus from sludge incineration ash Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000010802 sludge Substances 0.000 title claims abstract description 62
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000011574 phosphorus Substances 0.000 title claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 96
- 239000000243 solution Substances 0.000 claims abstract description 92
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 45
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 38
- 239000010452 phosphate Substances 0.000 claims abstract description 38
- 238000000605 extraction Methods 0.000 claims abstract description 33
- 238000000746 purification Methods 0.000 claims abstract description 32
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 238000005341 cation exchange Methods 0.000 claims abstract description 25
- 239000000284 extract Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000005554 pickling Methods 0.000 claims abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 69
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- 229910021645 metal ion Inorganic materials 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- 238000005192 partition Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000004033 plastic Substances 0.000 claims description 16
- 229920003023 plastic Polymers 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- -1 aluminum ions Chemical class 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001424 calcium ion Inorganic materials 0.000 claims description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 12
- 230000009467 reduction Effects 0.000 description 10
- 230000008901 benefit Effects 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000002686 phosphate fertilizer Substances 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
-
- 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
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/2208—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid
-
- 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
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/2208—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid
- C01B25/2212—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid with hydrochloric acid or hydrogen chloride in aqueous medium
-
- 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
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/2208—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid
- C01B25/2216—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid with nitric acid or nitrous vapours in aqueous medium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to the technical field of environmental protection and resource recovery, in particular to a method and a device for recovering and purifying phosphorus from sludge incineration ash. The method comprises the following steps: acid extraction, namely pickling the sludge incineration ash, and filtering to obtain acid extract; and (2) performing electrochemical purification, namely taking the acid extract as anolyte, a nitrate-containing salt solution as catholyte, taking inert electrodes as an anode and a cathode, arranging a cation exchange membrane between the anolyte and the catholyte, and performing electrochemical reaction, wherein the anolyte after the electrochemical reaction is a solution of purified phosphate radical. The method can realize the high-efficiency recovery and high purification of the phosphorus element in the sludge incineration ash, has strong operability and has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of environmental protection and resource recovery, in particular to a method and a device for recovering and purifying phosphorus from sludge incineration ash.
Background
With the acceleration of modern construction and urbanization, China needs to treat a large amount of wastewater every year, and a large amount of municipal sludge is generated. The main treatment means of the municipal sludge is incineration, the sludge incineration technology can effectively meet the requirement of sludge reduction, the pressure on a landfill area is greatly reduced, and the sludge volume is reduced by about 80%. Sludge incineration ash formed after sludge incineration is a main phosphorus-containing waste, but the sludge incineration ash contains about 10% of P2O5In addition, it contains a large amount of metal compounds, and these metal compounds present in a large amount make the sludge incineration ash not directly usable as a raw material for a phosphorus-forming resource.
In order to recover phosphorus from sludge incineration ash, the prior art is mainly carried out by using a pyrogenic process and a wet process. Among them, the reaction conditions of the pyrogenic process are harsh, the energy consumption is large, and only the removal of volatile metals can be realized, but the non-volatile harmful metals (such As, Ni, etc.) cannot be removed. The wet method is more widely used, and mainly extracts phosphorus in the sludge incineration ash through an acid agent. However, the disadvantage is that the pickling solution still contains a large amount of metal ions, and the purity of phosphorus is low, which may prevent the recovery and further use of phosphorus. Nowadays, a large number of methods for recovering phosphorus from sludge incineration ash are limited to laboratory use due to complex equipment, high raw material cost and low usability, so that the industrial popularization and application of the methods are limited, and improvement is needed.
Disclosure of Invention
The invention aims to provide a method and a device for recovering and purifying phosphorus from sludge incineration ash, which aim to solve the problems that the existing method for recovering phosphorus from sludge incineration ash has harsh reaction conditions, low phosphorus purity, complicated equipment for recovering phosphorus and the like and hinders industrial application of the process.
In a first aspect, the present invention provides a method for recovering purified phosphorus from sludge incineration ash, comprising the steps of:
acid extraction: pickling the sludge incineration ash, and filtering to obtain an acid extract;
electrochemical purification: and (2) taking the acid extract as anolyte, taking a nitrate-containing salt solution as catholyte, using inert electrodes as an anode and a cathode, arranging a cation exchange membrane between the anolyte and the catholyte, and carrying out electrochemical reaction, wherein the anolyte after the electrochemical reaction is a solution of purified phosphate radical.
Further, in the acid extraction step, the acid agent used in acid washing is a sulfuric acid solution, a nitric acid solution, a phosphoric acid solution or a hydrochloric acid solution with the concentration of 0.2-1moL/L, the solid-to-liquid ratio of the sludge incineration ash to the acid agent is 1:5-1:20g/mL, the acid washing time is 4-24 hours, insoluble solids are filtered out after acid washing to obtain the acid extraction liquid, and the acid extraction liquid contains phosphate ions and metal ions.
Further, the metal ions in the acid extraction solution include one or more of calcium ions, magnesium ions, aluminum ions, iron ions, copper ions, zinc ions, manganese ions, lead ions, nickel ions and cadmium ions.
Further, in the step of electrochemical purification, electrochemistry is performedApplying a constant current of 15-300mA in the reaction, wherein the electrochemical reaction time is 72-168h, the inert electrode is a platinum sheet electrode, a gold electrode or a graphite electrode, and the area of the electrode is 1-100cm2。
It is understood that the constant current of 15-300mA in the step of electrochemical purification includes any point value within the numerical range of the current, for example, the constant current applied by the electrochemical reaction is 15mA, 20mA, 25mA, 30mA, 50mA, 75mA, 80mA, 100mA, 150mA, 200mA, 250mA, or 300 mA. The electrochemical reaction time of 72-168h includes any point in the time range, for example, the electrochemical reaction time is 72h, 76h, 80h, 96h, 100h, 120h, 144h, 150h or 168 h.
Preferably, the inert electrode is a platinum sheet electrode and the nitrate-containing salt solution is 0.01moL/L of sodium nitrate solution.
Further, in the step of electrochemical purification, the catholyte generates hydroxide precipitates with one or more ions of calcium ions, magnesium ions or aluminum ions.
Further, the method further comprises, after the step of electrochemical purification, a step of cyclic enrichment: and taking the purified phosphate solution as the acid agent in the acid extraction step, and recycling the acid agent for pickling the sludge incineration ash until the concentration of phosphorus in the purified phosphate solution is more than or equal to 450 g/L.
In a second aspect, the present invention provides an apparatus for recovering and purifying phosphorus from sludge incineration ash, the apparatus comprising:
the anode reaction tank is filled with anolyte, and an anode is inserted into the anode reaction tank;
the cathode reaction tank is filled with cathode liquid, and a cathode is inserted into the cathode reaction tank;
cation exchange membrane: the cation exchange membrane is arranged between the anode reaction tank and the cathode reaction tank to separate the anode reaction tank from the cathode reaction tank;
a clapboard: the separator is respectively transversely arranged in the anode reaction tank and the cathode reaction tank, and the anode and the cathode are fixed on the separator;
the device is used for the method for recovering and purifying the phosphorus from the sludge incineration ash.
Furthermore, the partition board is a plastic partition board or a ceramic partition board, the partition board comprises a plurality of transverse strip-shaped boards and a plurality of longitudinal strip-shaped boards, and the transverse strip-shaped boards and the longitudinal strip-shaped boards are intersected to form a plurality of grids; the device also comprises a potentiostat.
Further, the anode reaction tank and the cathode reaction tank are detachable reaction tanks, and the cation exchange membrane is detachably arranged between the anode reaction tank and the cathode reaction tank.
Further, in the acid extraction step, the acid agent used in acid washing is a sulfuric acid solution, a nitric acid solution, a phosphoric acid solution or a hydrochloric acid solution with the concentration of 0.2-1moL/L, the solid-to-liquid ratio of the sludge incineration ash to the acid agent is 1:5-1:20g/mL, the acid washing time is 4-24 hours, insoluble solids are filtered out after acid washing to obtain the acid extraction liquid, and the acid extraction liquid contains phosphate ions and metal ions.
Further, the metal ions in the acid extraction solution include one or more of calcium ions, magnesium ions, aluminum ions, iron ions, copper ions, zinc ions, manganese ions, lead ions, nickel ions and cadmium ions.
Further, in the step of electrochemical purification, the electrochemical reaction is carried out by applying a constant current of 15-300mA for 72-168 h.
It is understood that the constant current of 15-300mA in the step of electrochemical purification includes any point value within the numerical range of the current, for example, the constant current applied by the electrochemical reaction is 15mA, 20mA, 25mA, 30mA, 50mA, 75mA, 80mA, 100mA, 150mA, 200mA, 250mA, or 300 mA. The electrochemical reaction time of 72-168h includes any point in the time range, for example, the electrochemical reaction time is 72h, 76h, 80h, 96h, 100h, 120h, 144h, 150h or 168 h.
Further, in the electrochemical purification step, the inert electrode is a platinum sheet electrode, a gold electrode or a graphite electrode,the electrode area is 1-100cm2。
Preferably, the inert electrode is a platinum sheet electrode and the nitrate-containing salt solution is 0.01moL/L of sodium nitrate solution.
Further, in the step of electrochemical purification, the catholyte generates hydroxide precipitates containing one or more of metal ions such as calcium ions, magnesium ions and aluminum ions.
Further, the method further comprises, after the step of electrochemical purification, a step of cyclic enrichment: and using the purified phosphate solution as the acid agent in the acid extraction step, and recycling the acid agent for acid-washing the sludge incineration ash until the concentration of phosphoric acid in the purified phosphate solution is greater than or equal to 450 g/L.
Firstly, the high purification of phosphorus element in sludge incineration ash is realized. According to the method, firstly, phosphate ions in the sludge incineration ash are extracted along with metal ions through acid extraction, then the metal ions are electrophoresed from an anode to a cathode under the driving force of current through electrolysis, and the phosphate ions are still remained in anolyte due to the obstruction of a cation exchange membrane, so that the separation between the phosphate ions and the metal ions is realized, the purification of the phosphate in the acid extraction solution is further realized, and the separation and purification purposes are achieved.
Secondly, the method has strong operability and good industrial application prospect. Firstly, the method has few steps and simple and convenient operation, can realize the high-efficiency recovery of the phosphorus element through two steps of acid extraction and electrolysis, and has stronger feasibility. Secondly, the method has short period for purifying the phosphorus element, and the solution of the purified phosphate radical can be obtained within 3 to 7 days. Compared with the processes which have longer period and need 14 days to obtain the purified solution, the period is obviously shortened.
And thirdly, the high-concentration enrichment of phosphorus element can be conveniently realized, so that the obtained solution of purified phosphate radical can be more easily applied to practical production. After the electrochemical reaction is carried out, because a large amount of hydrogen ions are generated on one side of the anode, the anode liquor has higher acidity, can be used for pickling new sludge incineration ash again, further carries out electrochemical reaction again to purify phosphate radical, and ensures that the solution of the finally purified phosphate radical contains phosphorus with higher concentration and has less residual metal and other impurities through cyclic reciprocation, thus being applicable to the industries of phosphoric acid and phosphate fertilizer.
The device provided by the invention is not complex, is not easy to cause cation membrane blockage, and further improves the feasibility of industrial application.
Drawings
FIG. 1 is a schematic view showing the structure of an apparatus for recovering purified phosphorus from sludge incineration ash according to an embodiment.
Fig. 2 is a schematic structural diagram of a plastic partition plate in the device of the first embodiment.
FIG. 3 is a graph showing the tendency of the metal ions to decrease during 4 hours of the electrochemical reaction in the second example.
FIG. 4 is an analysis of metal ion remaining during an electrochemical reaction according to the hexagonal method of the embodiment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "comprises" and "comprising," and any variations thereof, of embodiments of the present invention are intended to cover non-exclusive inclusions, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example one
An apparatus for recovering high-purity phosphorus from sludge incineration ash, as shown in fig. 1 and 2, comprises:
a potentiostat 1 for supplying a stabilization current;
an anode 2 and a cathode 3;
an anode reaction tank 4 filled with anolyte, wherein an anode 2 is inserted in the anode reaction tank 4, and the anode reaction tank 4 is a detachable reaction tank;
a cathode reaction tank 5 filled with cathode liquid, wherein a cathode 3 is inserted into the cathode reaction tank 5, and the cathode reaction tank 5 is a detachable reaction tank;
cation exchange membrane 6: the cation exchange membrane 6 is detachably arranged between the anode reaction tank 4 and the cathode reaction tank 5, on one hand, the anode reaction tank 4 and the cathode reaction tank 5 are separated by the cation exchange membrane 6, and on the other hand, the replacement of the cation exchange membrane 6 is facilitated by the detachable installation mode; specifically, the right side wall 41 of the anode reaction tank 4 is hollowed in the middle, the left side wall 51 of the cathode reaction tank 5 is hollowed in the middle, and the cation exchange membrane 6 is sandwiched between the right side wall 41 of the anode reaction tank 4 and the left side wall 51 of the cathode reaction tank 5, so that the anode reaction tank 4 and the cathode reaction tank 5 are separated. In addition, threaded holes (not shown) are respectively formed at the joints of the anode reaction cell 4 and the cathode reaction cell 5, and bolts (not shown) are used to pass through the threaded holes of the anode reaction cell 4 and the threaded holes of the cathode reaction cell 5, so that the anode reaction cell 4 and the cathode reaction cell 5 are screwed and fixed; when the disassembly is needed, the anode reaction tank 4 and the cathode reaction tank 5 can be disassembled by taking out the bolts. Because the cation exchange membrane 6 is clamped between the anode reaction tank 4 and the cathode reaction tank 5, the cation exchange membrane 6 can be detached and replaced after the anode reaction tank 4 and the cathode reaction tank 5 are detached. It is understood that other connection methods can be used to achieve the detachability of the anode reaction cell and the cathode reaction cell in the present invention, such as a snap connection between the anode reaction cell and the cathode reaction cell.
Two plastic partition plates 7: two plastic separators 7 are respectively arranged in the anode reaction tank 4 and the cathode reaction tank 5 along the transverse direction (i.e., the left-right direction in fig. 1) for installing and fixing the electrode positions of the anode 2 and the cathode 3.
In this embodiment, the structure of any plastic partition 7 is as shown in fig. 2, and the plastic partition 7 includes a plurality of transverse strips (strips extending in the up-down direction in fig. 2) and a plurality of longitudinal strips (strips extending in the left-right direction in fig. 2), which are arranged to cross each other to form a plurality of squares. In addition to the plastic separators 7 used to mount the anode 2 and cathode 3, the addition of the plastic separators in the apparatus of this embodiment also facilitates the reduction of precipitation in the catholyte.
The device of this embodiment adopts the structural design who simplifies, can realize electrochemical reaction, is used for the method of retrieving high-purity phosphorus from mud incineration ash with this device, not only can guarantee that electrochemical reaction is easy and simple to handle, easy going, does benefit to the flocculent sediment in the catholyte through the design of plastics baffle moreover for the sediment that arrives can further be recycled.
Example two
The embodiment provides a method for recovering and purifying phosphorus from sludge incineration ash, which comprises the following steps:
acid extraction: using sulfuric acid solution with the concentration of 1moL/L as an acid agent, pickling sludge incineration ash for 24 hours, wherein the solid-to-liquid ratio of the sludge incineration ash to the sulfuric acid solution is 1:5g/mL, filtering out insoluble solids by using a filter membrane after pickling to obtain acid extract, wherein the acid extract contains phosphate ions and a plurality of metal ions, and the metal ions comprise calcium ions, magnesium ions, aluminum ions, iron ions, copper ions, zinc ions, manganese ions, lead ions, nickel ions and cadmium ions.
Electrochemical purification: taking the filtered acid extraction solution as anolyte, 0.01moL/L sodium nitrate solution as catholyte, and making the volumes of the anolyte and the catholyte the same to ensure the hydraulic pressure to be the same, and taking 1cm2The platinum sheet electrodes are an anode and a cathode, a cation exchange membrane is arranged between anolyte and catholyte, electrochemical reaction is carried out for 72 hours under constant current of 100mA, and the anolyte after the electrochemical reaction is a solution of purified phosphate radical.
And (3) cyclic enrichment: replacing a sulfuric acid solution with an acid agent in the acid extraction step by using a solution of purified phosphate radical, carrying out acid washing on the new sludge incineration ash and the solution of the purified phosphate radical for 4 hours according to a solid-to-liquid ratio of 1:20g/mL, and repeating the electrochemical reaction step on the acid extract solution after acid washing and filtering to obtain a final solution of the purified phosphate radical, wherein the solution can be used for industrial production of phosphoric acid and phosphate fertilizer.
The method of the embodiment can perform an electrochemical purification step in the device provided in the first embodiment, and has the advantages of simple operation, strong feasibility and the like. Especially, since the cathode solution gradually forms precipitates, the reduction of the precipitates is facilitated by the plastic partition plate of the device of the embodiment.
Tendency of reduction of Metal ions during 4 hours of electrochemical reaction
In this embodiment, the reduction of metal ions in the anolyte is detected and analyzed in the electrochemical reaction process of the first 4 hours, as shown in fig. 3, in the electrochemical reaction process of the first 4 hours, the concentrations of several metal ions are all reduced to a certain extent, wherein the concentrations of cadmium ions, magnesium ions, lead ions and calcium ions are reduced more significantly, especially cadmium ions and calcium ions, which indicates that the method of the embodiment of the present invention can achieve effective separation of metal ions and phosphate ions, and further achieve the purpose of purifying phosphate ions.
EXAMPLE III
The embodiment provides a method for recovering and purifying phosphorus from sludge incineration ash, which comprises the following steps:
acid extraction: using a sulfuric acid solution with the concentration of 0.2moL/L as an acid agent, pickling sludge incineration ash for 4 hours, wherein the solid-to-liquid ratio of the sludge incineration ash to the sulfuric acid solution is 1:20g/mL, filtering insoluble solids by using a filter membrane after pickling to obtain an acid extract, wherein the acid extract contains phosphate ions and a plurality of metal ions.
Electrochemical purification: taking the filtered acid extraction solution as anolyte, 0.01moL/L sodium nitrate solution as catholyte, and making the volumes of the anolyte and the catholyte the same to ensure the hydraulic pressure to be the same, and taking 100cm2The platinum sheet electrodes are an anode and a cathode, a cation exchange membrane is arranged between anolyte and catholyte, electrochemical reaction is carried out for 168 hours under constant current of 10mA, and the anolyte after the electrochemical reaction is a solution of purified phosphate radical.
And (3) cyclic enrichment: the method comprises the steps of replacing a sulfuric acid solution with an acid agent in an acid extraction step by a solution of purified phosphate radical, carrying out acid washing on new sludge incineration ash and the solution of the purified phosphate radical for 4 hours according to a solid-to-liquid ratio of 1:20g/mL, and repeating the steps of carrying out electrochemical reaction twice on the acid extract solution after acid washing and filtering to obtain a final solution of the purified phosphate radical, wherein the concentration of phosphoric acid in the solution is 450g/L, and the method can be used for industrial production of phosphoric acid and phosphate fertilizers.
The method of the embodiment can perform an electrochemical purification step in the device provided in the first embodiment, and has the advantages of simple operation, strong feasibility and the like. Especially, since the cathode solution gradually forms precipitates, the reduction of the precipitates is facilitated by the plastic partition plate of the device of the embodiment.
Example four
The embodiment provides a method for recovering and purifying phosphorus from sludge incineration ash, which comprises the following steps:
acid extraction: acid-washing sludge incineration ash for 4 hours by using a phosphoric acid solution with the concentration of 1moL/L as an acid agent, wherein the solid-to-liquid ratio of the sludge incineration ash to the phosphoric acid solution is 1:5g/mL, and filtering out insoluble solids by using a filter membrane after acid-washing to obtain an acid extract, wherein the acid extract contains phosphate ions and a plurality of metal ions.
Electrochemical purification: taking the filtered acid extraction solution as anolyte, 0.01moL/L sodium nitrate solution as catholyte, and making the volumes of the anolyte and the catholyte the same to ensure the hydraulic pressure to be the same, and taking 1cm2The platinum sheet electrodes are an anode and a cathode, a cation exchange membrane is arranged between anolyte and catholyte, electrochemical reaction is carried out for 168 hours under constant current of 10mA, and the anolyte after the electrochemical reaction is a solution of purified phosphate radical.
And (3) cyclic enrichment: replacing a phosphoric acid solution with an acid agent in the acid extraction step by using a solution of purified phosphate radical, carrying out acid washing on the new sludge incineration ash and the solution of purified phosphate radical for 4 hours according to the solid-to-liquid ratio of 1:5g/mL, and repeating the electrochemical reaction step on the acid extract solution after acid washing and filtering to obtain a final solution of purified phosphate radical, wherein the solution can be used for industrial production of phosphoric acid and phosphate fertilizer.
The method of the embodiment can perform an electrochemical purification step in the device provided in the first embodiment, and has the advantages of simple operation, strong feasibility and the like. Especially, since the cathode solution gradually forms precipitates, the reduction of the precipitates is facilitated by the plastic partition plate of the device of the embodiment.
EXAMPLE five
The embodiment provides a method for recovering and purifying phosphorus from sludge incineration ash, which comprises the following steps:
acid extraction: acid-washing sludge incineration ash for 24 hours by using a phosphoric acid solution with the concentration of 0.2moL/L as an acid agent, wherein the solid-to-liquid ratio of the sludge incineration ash to the phosphoric acid solution is 1:20g/mL, filtering insoluble solids by using a filter membrane after acid-washing to obtain an acid extract, and the acid extract contains phosphate ions and a plurality of metal ions.
Electrochemical purification: taking the filtered acid extraction solution as anolyte, 0.01moL/L sodium nitrate solution as catholyte, and making the volumes of the anolyte and the catholyte the same to ensure the hydraulic pressure to be the same, and taking 100cm2The platinum sheet electrodes are an anode and a cathode, a cation exchange membrane is arranged between anolyte and catholyte, electrochemical reaction is carried out for 72 hours under constant current of 100mA, and the anolyte after the electrochemical reaction is a solution of purified phosphate radical.
And (3) cyclic enrichment: replacing a phosphoric acid solution with an acid agent in the acid extraction step by using a solution of purified phosphate radical, carrying out acid washing on the new sludge incineration ash and the solution of purified phosphate radical for 4 hours according to the solid-to-liquid ratio of 1:20g/mL, and repeating the electrochemical reaction steps twice on the acid extract solution after acid washing and filtering to obtain a final solution of purified phosphate radical, wherein the solution can be used for industrial production of phosphoric acid and phosphate fertilizer.
The method of the embodiment can perform an electrochemical purification step in the device provided in the first embodiment, and has the advantages of simple operation, strong feasibility and the like. Especially, since the cathode solution gradually forms precipitates, the reduction of the precipitates is facilitated by the plastic partition plate of the device of the embodiment.
EXAMPLE six
The embodiment provides a method for recovering and purifying phosphorus from sludge incineration ash, which comprises the following steps:
acid extraction: acid-washing sludge incineration ash for 12 hours by using nitric acid solution with the concentration of 0.5moL/L as an acid agent, wherein the solid-to-liquid ratio of the sludge incineration ash to phosphoric acid solution is 1:10g/mL, filtering insoluble solids by using a filter membrane after acid-washing to obtain acid extract, wherein the acid extract contains phosphate ions and a plurality of metal ions.
Electrochemical purification: taking the filtered acid extraction solution as anolyte, 0.01moL/L sodium nitrate solution as catholyte, and making the volumes of the anolyte and the catholyte the same to ensure the hydraulic pressure to be the same, and taking 50cm2The platinum sheet electrodes are an anode and a cathode, a cation exchange membrane is arranged between anolyte and catholyte, electrochemical reaction is carried out for 168 hours under constant current of 50mA, and the anolyte after the electrochemical reaction is a solution of purified phosphate radical.
The method of the embodiment can perform an electrochemical purification step in the device provided in the first embodiment, and has the advantages of simple operation, strong feasibility and the like. Especially, since the cathode solution gradually forms precipitates, the reduction of the precipitates is facilitated by the plastic partition plate of the device of the embodiment.
Analysis of residual Metal ions under 168-hour 50mA electrochemical reaction conditions
In the embodiment, in the electrochemical reaction process, the metal ion residue in the anolyte is detected and analyzed, and as a result, as shown in fig. 4, in the electrochemical reaction process of 168 hours under the condition of constant current of 50mA, the concentrations of several metal ions are greatly reduced, and particularly, the concentrations of calcium ions, copper ions, magnesium ions, manganese ions, zinc ions and other ions are reduced more obviously.
The method of the embodiment of the invention has the following advantages:
(1) in the electrochemical reaction process, metal ions in the anolyte can migrate from the anode to the cathode under the drive of current, but phosphate ions cannot enter catholyte due to the arrangement of the cation exchange membrane, so that the effective separation of the phosphate ions and the metal ions is realized, and the purification purpose is achieved. In addition, the catholyte generates OH under the action of electrochemical reaction-Calcium into the catholyteIons, magnesium ions plasma and OH-And combining to generate flocculent precipitate. Since these precipitates are formed in the catholyte, they do not affect the cation exchange membrane, i.e., do not cause clogging of the cation exchange membrane.
(2) Because the anolyte generates a large amount of hydrogen ions under the action of electrochemical reaction, the acidity of the anolyte is stronger, the solution of the purified phosphate radical can be regarded as acid agents such as sulfuric acid or nitric acid and the like and is circularly used in the step of pickling the sludge incineration ash, and the concentration of the phosphate radical in the solution of the purified phosphate radical can be effectively improved because the new sludge incineration ash which is continuously pickled can continuously increase the concentration of the phosphate radical in the acid extraction solution, thereby really and conveniently realizing the enrichment of the phosphate radical. Especially when the concentration of phosphoric acid in the solution enriched with purified phosphate radical is more than or equal to 450g/L, the method can be directly used for producing liquid phosphate fertilizer. The method of the embodiment can perform the electrochemical reaction step in the device provided by the first embodiment, and has the advantages of simple operation, strong feasibility and the like. Especially, since the cathode solution gradually forms precipitates, the reduction of the precipitates is facilitated by the plastic partition plate of the device of the embodiment.
(3) In the invention, the phosphorus in the sludge incineration ash can be effectively purified, and the method mainly researches the current intensity, the reaction time and the electrode area of the electrochemical reaction under optimized conditions, thereby ensuring that the constant current is 15-300mA, the reaction time is 72-168h and the electrode area is 1-100cm2Can realize effective phosphorus purification, and does not need to adopt 14 days to achieve better purification effect.
The method and the device for recovering and purifying phosphorus from sludge incineration ash disclosed by the embodiment of the invention are described in detail, the principle and the implementation mode of the invention are explained by applying specific examples, and the description of the embodiments is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. A method for recovering and purifying phosphorus from sludge incineration ash, characterized in that the method comprises the following steps:
acid extraction: pickling the sludge incineration ash, and filtering to obtain an acid extract; wherein the acid agent used for acid washing is sulfuric acid solution, nitric acid solution, phosphoric acid solution or hydrochloric acid solution with the concentration of 0.2-1 moL/L;
electrochemical purification: and (2) taking the acid extract as anolyte, taking a nitrate-containing salt solution as catholyte, using inert electrodes as an anode and a cathode, arranging a cation exchange membrane between the anolyte and the catholyte, and carrying out electrochemical reaction, wherein the anolyte after the electrochemical reaction is a solution of purified phosphate radical.
2. The method according to claim 1, wherein in the acid extraction step, the solid-to-liquid ratio of the sludge incineration ash to the acid agent is 1:5 to 1:20g/mL, the acid washing time is 4 to 24 hours, and insoluble solids are filtered out after the acid washing to obtain the acid extract, wherein the acid extract contains phosphate ions and metal ions.
3. The method according to claim 2, wherein the metal ions in the acid extract comprise one or more of calcium ions, magnesium ions, aluminum ions, iron ions, copper ions, zinc ions, manganese ions, lead ions, nickel ions and cadmium ions.
4. The method according to any one of claims 1 to 3, wherein in the step of electrochemical purification, the electrochemical reaction is carried out with a constant current of 15 to 300mA for 72 to 168 hours, the inert electrode is a platinum sheet electrode, a gold electrode or a graphite electrode, and the electrode area is 1 to 100cm 2.
5. The method of claim 4, wherein the inert electrode is a platinum sheet electrode and the nitrate-containing salt solution is 0.01moL/L sodium nitrate solution.
6. The method according to any one of claims 2 to 3, characterized in that it further comprises, after said step of electrochemical purification, a step of cyclic enrichment: and using the purified phosphate solution as the acid agent in the acid extraction step, and recycling the acid agent for acid-washing the sludge incineration ash until the concentration of phosphoric acid in the purified phosphate solution is greater than or equal to 450 g/L.
7. A method according to any one of claims 1 to 3, wherein in the step of electrochemical purification, the catholyte produces a hydroxide precipitate of one or more of calcium, magnesium or aluminium ions.
8. An apparatus for recovering and purifying phosphorus from sludge incineration ash, the apparatus comprising:
the anode reaction tank is filled with anolyte, and an anode is inserted into the anode reaction tank;
the cathode reaction tank is filled with cathode liquid, and a cathode is inserted into the cathode reaction tank;
cation exchange membrane: the cation exchange membrane is arranged between the anode reaction tank and the cathode reaction tank to separate the anode reaction tank from the cathode reaction tank;
a clapboard: the separator is respectively transversely arranged in the anode reaction tank and the cathode reaction tank, and the anode and the cathode are fixed on the separator;
the apparatus is used in the method for recovering and purifying phosphorus from sludge incineration ash according to any one of claims 1 to 7.
9. The device according to claim 8, wherein the partition is a plastic partition or a ceramic partition, the partition comprises a plurality of transverse strips and a plurality of longitudinal strips, and the transverse strips and the longitudinal strips are intersected to form a plurality of squares; the device also comprises a potentiostat.
10. The apparatus of claim 8 or 9, wherein the anode reaction cell and the cathode reaction cell are detachable reaction cells, and the cation exchange membrane is detachably arranged between the anode reaction cell and the cathode reaction cell.
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