CN108706991A - A kind of method of phosphoric acid byproduct hydrogen ammonium in high-quality double superphosphate preparation process - Google Patents
A kind of method of phosphoric acid byproduct hydrogen ammonium in high-quality double superphosphate preparation process Download PDFInfo
- Publication number
- CN108706991A CN108706991A CN201810608696.4A CN201810608696A CN108706991A CN 108706991 A CN108706991 A CN 108706991A CN 201810608696 A CN201810608696 A CN 201810608696A CN 108706991 A CN108706991 A CN 108706991A
- Authority
- CN
- China
- Prior art keywords
- ammonium
- filter residue
- parts
- phosphoric acid
- double superphosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
- C05B1/02—Superphosphates
-
- 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
- C01B25/28—Ammonium phosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a kind of methods of phosphoric acid byproduct hydrogen ammonium in high-quality double superphosphate preparation process, and using recessive acid (ammonium chloride) come decomposing rock phosphate with hydrogen, reflection obtains Ca (H2PO4)2The purified high-quality double superphosphate of acquisition, this process obtain ammonium hydrogen phosphate again with sour insoluble slag mixture.The present invention makes recessive acid that rock phosphate in powder be decomposed generation Ca (H in calcium chloride sub-molten salt system2PO4)2With sour insoluble slag mixture, after HCl treatment, and NH is used4The ammonia that Cl decomposing phosphate rock stones generate improves Ca (H after being reacted as raw material2PO4)2Purity, and in the ammonium hydrogen phosphate for obtaining higher value；No waste generates, and realizes recycling for resource, energy conservation and environmental protection, it is cost-effective, it not only solves phosphoric acid by wet process and leads to the problem of a large amount of ardealites, while the ammonium hydrogen phosphate of high value can also be obtained, it realizes that phosphorous chemical industry production process is generated without ardealite, realizes phosphorus chemical industry technological reforger.
Description
Technical field
The invention belongs to secondary in chemical fertilizer production technical field more particularly to a kind of high-quality double superphosphate preparation process
The method for producing ammonium hydrogen phosphate.
Background technology
Ardealite is the industrial residue of generation during Wet-process Phosphoric Acid Production.1 ton of phosphoric acid is often produced (with P2O5Meter), generally
Generate 4~5 tons of ardealites.Since titanium pigment, fluorine and other impurity generate not ardealite building material performance in ardealite
Profit influences, such as extensions of gypsum setting time, hardenite strength reduction, crystal structure are loose, and its water content height, thus
Causing ardealite to prepare, building material poor quality, added value are low, market transportation radius is short.Further, since calcium sulfate and calcium carbonate
Solubility product in ammonium sulfate differs more than 3000 times, therefore calcium sulfate is easy to be converted into solid product by carbonation reaction process
Calcium carbonate and synchronous production ammonium sulfate liquor, ammonium sulfate liquor further inverted can also prepare potassium sulfate and ammonium chloride potassium etc.
Sulfenyl compound fertilizer product.However, on the one hand since the impurity almost all in ardealite enters in solid product, thus lead to gained
Calcium carbonate product particle is tiny, purity and whiteness are poor, added value is low, it is difficult to extensive to utilize；On the other hand, the sulphur in ardealite
Sour calcium, which is converted into after calcium carbonate, needs to consume a large amount of ammonia, and to be eventually converted into ammonium sulfate or ammonium chloride etc. low additional for the ammonia consumed
It is worth product, overall technology economy difficulty is thus caused to reach a standard.
Diammonium hydrogen phosphate is a kind of inorganic compound, English name：Ammonium phosphate, nickname Diammonium phosphate (DAP), work
Industry Diammonium phosphate (DAP), diammonium hydrogen phosphate, chemical formula are (NH4)2HPO4, soluble easily in water【58g/100mL(10℃)】, insoluble in alcohol, third
Ketone, ammonia；Water white transparency monoclinic crystal or white powder are widely used in plate making, medicine, fire prevention, electron tube etc., are a kind of wide
The general concentrated fertilizer for being suitable for veterinary antibiotics, rice and wheat, is industrially used as feed addictive, fire retardant and extinguishing chemical
Dispensing etc..
In existing traditional dihydrate wet phosphoric acid extraction process in terms of a large amount of ardealites of attached production and ardealite processing, or
To the protrusion that in terms of the processing of rock phosphate in powder, economical bad, pollution environment and the added value of product being prepared are low etc.
Problem.As continually strengthening for national environmental protection renovation dynamics deeply promotes with the construction of Guizhou Province conservation culture trial zone, in addition
The appearance of the newly-increased ardealite in Guizhou Province 2018 " with fixed output quota " policy is implemented, and opens phosphorylcholine group phosphorous chemical industry and develops with phosphoric & compound fertilizer industry
Situation tends to be severe.Currently, yet there are no report without ardealite generation, phosphorus chemical industry technological reforger about in phosphorous chemical industry production process
Road.
Invention content
The present invention is in order to solve the above technical problems, provide phosphoric acid byproduct hydrogen in a kind of high-quality double superphosphate preparation process
The method of ammonium.The present invention makes recessive acid that rock phosphate in powder be decomposed generation Ca (H in calcium chloride sub-molten salt system2PO4)2It is insoluble with acid
Slag【Main component is SiO2·nH2O】Mixture the, although Ca (H of reaction gained2PO4)2It can be direct with sour insoluble slag mixture
It is sold as coarse whiting product, but Ca (H in the mixture at this time obtained2PO4)2Purity is not high, and then inventor is to mixing
After object carries out HCl treatment, and use NH4The ammonia that Cl decomposing phosphate rock stones generate further is reacted as raw material, to
Improve Ca (H2PO4)2Purity, and obtain in this reaction process the ammonium hydrogen phosphate of higher value, production process only has
The sour insoluble slag solid that can be used in fields such as building materials, finishing materials generates, and the ammonia that production process generates can return
It receives and utilizes, the carbon dioxide of generation is easily handled.The present invention solves NH4Cl decomposing rock phosphate with hydrogen generates ammonia emission and pollutes environment
The problem of, while ammonia can also be made full use of to prepare the ammonium hydrogen phosphate of higher value, preparing high-quality double superphosphate
It is generated in the process without exhaust gas, waste residue the like waste, realizes recycling for resource, energy conservation and environmental protection is cost-effective, can not only solve
Phosphoric acid by wet process of having determined leads to the problem of a large amount of ardealites, while can also obtain the ammonium hydrogen phosphate of high value, realizes phosphorous chemical industry life
Production process is generated without ardealite, realizes phosphorus chemical industry technological reforger.
In order to reach purpose described above, the present invention uses following technical scheme：
The method of phosphoric acid byproduct hydrogen ammonium, includes the following steps in a kind of high-quality double superphosphate preparation process：
(1) 230~350 parts of water is taken to be placed in reaction vessel, be added 200~260 parts of ammonium chlorides, heating stirring to completely it is molten
Solution, obtains ammonium chloride saturated solution；
(2) 160~250 parts of ground phosphate rock are sent into pulverizer crushing, sieving, the chlorination of step (1) is added under stirring
In ammonium saturated solution, slurrying is stirred, phosphorus ore slurry is obtained；
(3) in the case where phosphorus ore slurry continues stirring, phosphorus ore slurry is added to 300~1000 parts of calcium chloride sub-molten salt bodies
In system, control system temperature stops heating after reacting 3~6h, and 150~300 parts of water are added and continue 25~40min of stirring, collect
The ammonia generated in reaction process, discharging, natural filtration obtain filter residue A；
(4) the filter residue A obtained by step (3) is dissolved in 200~400 parts of 95~100 DEG C of water, is stirred slurrying, controlled
Then 200~300 parts of hydrochloric acid are added dropwise in reaction temperature processed into slurry, after controlling slurries pH value stabilizations, filtrate is collected by filtration 1.；
(5) filtrate obtained by step (4) is 1. placed in 600~800 parts of calcium chloride sub-molten salt systems, stirs simultaneously control volume
It is temperature, filter residue is collected by filtration after reaction, it is dry, obtain filter residue B；
(6) the filter residue B obtained by step (5) is dissolved in 200~300 parts of 95~100 DEG C of water, is placed in calcium chloride sub-molten salt
In system, the reaction temperature of control system is passed through the ammonia obtained by step (3), is separated by solid-liquid separation, is filtered through natural filtration
For liquid 2. with filter residue C, 2. filtrate is the ammonium hydrogen phosphate；
(7) ammonium chloride saturated solution is added into filter residue C obtained by step (6), is placed in 500~700 parts of calcium chloride sub-molten salts
In system, control system temperature is stirred continuously mixing and is reacted, and natural filtration obtains filter residue D, and filter residue D is then sent into drying
It is dry in machine, obtain the double superphosphate.
Further, in step (1), the heating process is to be heated to 55~100 DEG C.
Further, described to crush, be sieved as ground phosphate rock was crushed to 200~300 mesh sieve in step (2).
Further, in step (3), it is to be slowly added to during phosphorus ore slurry is added to calcium chloride sub-molten salt, adds
The time of phosphorus ore slurry >=1h, the reaction was continued 2h or more after the miberal powder that phosphorates is starched.
Further, in step (4), the pH stable numerical value is 2.5~3, and the time of pH stable is at least 1h.
Further, in step (4), the reaction temperature control is 90~99 DEG C；The dropwise addition hydrochloric acid is to be slowly added dropwise.
Further, in step (5), it is to raise the temperature to 140~180 DEG C that the heating, which increases temperature, the reaction
Time be 1~2.5h；The drying process is dry 10~15h under the conditions of filter residue is placed in 160~180 DEG C.
Further, in step (6), ratio=3 of the filter residue B and ammonia:8~10.
Further, in step (7), ratio=1 of the filter residue C and ammonium chloride saturated solution:4~5；The back tender
The temperature of skill is 100~140 DEG C, and the time is 10~14h.
Further, in step (3), step (5), step (6) and step (7), the system temperature controls as 160~
180℃；The calcium chloride sub-molten salt system is stirred evenly after mixing calcium chloride with the water of its weight 50~150%, heating
To 170~180 DEG C, keep stablizing obtained.
P in ground phosphate rock used in the present invention2O5Content is 35.62%, CaO content 50.84%.
The present invention is in calcium chloride sub-molten salt system, using NH4The decalcification principle of Cl (recessive acid), makes NH4Cl is by phosphorus ore
Stone, which decomposes, generates Ca (H2PO4)2With sour insoluble slag mixture fertilizer is can be used as because containing various plants nutrient in sour insoluble slag
Expect beneficial element, main component SiO2·nH2O, therefore the Ca (H obtained by the reaction process2PO4)2It is mixed with sour insoluble slag
Object can be sold directly as double superphosphate product, and P in the double superphosphate product of gained2O5> 40%.
The high-quality double superphosphate preparation method of the present invention, and high value ammonium hydrogen phosphate is obtained during the reaction【(NH4)2HPO4】Related reaction equation it is as follows：
When phosphorus ore ammonium chloride decomposes：
2Ca5(PO4)3F+12NH4Cl=3Ca (H2PO4)2+CaF2+12NH3↑+6CaCl2
(reaction condition：160-180 DEG C, calcium chloride sub-molten salt system)
CaCO3+CaSiO3+2NH4Cl=2NH3↑+H2O+CaCl2+CO2↑+SiO2·2H2O
(reaction condition：160-180 DEG C, calcium chloride sub-molten salt system)
React the Ca (H generated2PO4)2For microsolubility substance, SiO2·2H2O is not acid soluble material, and Ca is obtained by filtration
(H2PO4)2And SiO2·2H2The mixture of O causes the purity of double superhosphate not high, thus using free hydrochloric acid by filter cake into
Row separation, then back reaction is carried out under calcium chloride sub-molten salt system status, to obtain the higher double superhosphate of purity
When double superhosphate purifies：
3Ca(H2PO4)2Sour insoluble slag+2HCl=2H3PO4+CaCl2+ acid insoluble slag ↓
(reaction condition：100 DEG C of <)
2H3PO4+CaCl2=Ca (H2PO4)2+2HCl
(reaction condition：140 DEG C of >, calcium chloride sub-molten salt system)
In the solution, the acidity of HCl is better than H3PO4, therefore H3PO4With CaCl2It can not react, and Ca (H2PO4)2
It can react instead with HCl, generate H3PO4With CaCl2, it is, therefore, usually considered that CaCl2With H3PO4Directly prepare weight peroxophosphoric acid
Calcium is unworkable, Ca (H in the solution2PO4)2It reacts with HCl, generates H3PO4With CaCl2Specific reaction equation
It is as follows：
Ca(H2PO4)2+ 2HCl=2H3PO4+CaCl2
(strong acid occurs in the solution and sets weak acid reaction)
Carry out (NH4)2HPO4Preparation when：
3Ca(H2PO4)2+8NH3=Ca3(PO4)2↓+4(NH4)2HPO4
(reaction condition：160~180 DEG C, calcium chloride sub-molten salt system)
It is passed through Ca (H after ammonia2PO4)2It is reacted with ammonia and generates insoluble Ca3(PO4)2With soluble (NH4)2HPO4, since double superhosphate purification process has been gone out sour insoluble slag (SiO2·2H2O), filtering gained filtrate is phosphoric acid
Hydrogen ammonium, and insoluble Ca3(PO4)2With NH4Cl reactions can obtain the more good Ca (H of higher purity again2PO4)2。
Ca(H2PO4)2Regain reaction it is as follows：
Ca3(PO4)2+4NH4Cl=Ca (H2PO4)2+4NH3↑+2CaCl2
(reaction condition：160~180 DEG C, calcium chloride sub-molten salt system)
Therefore, it is possible to obtain the ammonium hydrogen phosphate of high value during preparing high-quality double superphosphate.
Since present invention employs above technical schemes, have the advantages that：
(1) present invention helps a line experts such as tiger by technical research portion of our company in Chinese Academy Of Sciences Process Engineering Research Institute Lee
Guidance under, the ecological circulation engineering science new theory that research is initiated using Chinese Academy of Sciences's process builds artificial substance closed cycle,
Double superphosphate is prepared using recessive acid combination sub-molten salt technology decomposing phosphate rock stone【Ca(H2PO4)2】, realize phosphorous chemical industry production
Process is generated without ardealite, realizes phosphorus chemical industry technological reforger.
(2) present invention makes recessive acid (NH4Cl) rock phosphate in powder is decomposed in calcium chloride sub-molten salt system and generates Ca
(H2PO4)2With sour insoluble slag mixture, because in sour insoluble slag contain various plants nutrient, can be used as fertilizer beneficial element,
Its main component is SiO2·nH2O, P in the mixture obtained at this time2O5> 40% the, although Ca (H of reaction gained2PO4)2With
Sour insoluble slag【SiO2·nH2O】Mixture can be sold directly as coarse whiting product, but Ca in the mixture at this time obtained
(H2PO4)2Purity is not high, after then inventor carries out HCl treatment to mixture, and uses NH4Cl decomposing phosphate rock stones generate
Ammonia further reacted as raw material, to improve Ca (H2PO4)2Purity, and obtained in this reaction process
The ammonium hydrogen phosphate of higher value【(NH4)2HPO4】, production process only has can be in the acid of the fields such as building materials, finishing material utilization
Insoluble slag【SiO2·nH2O】Solid generates, and the ammonia that production process generates can recycle, and the carbon dioxide of generation is easy
In processing.
(3) present invention solves NH4Cl decomposing rock phosphate with hydrogen leads to the problem of ammonia emission pollution environment, while can also fill
Divide the ammonium hydrogen phosphate for preparing higher value using ammonia, realize resource circulation utilization, reduces the production cost of industry.
(4) present invention generates during preparing high-quality double superphosphate without exhaust gas, waste residue the like waste, realizes resource
Recycle, energy conservation and environmental protection is cost-effective, can not only solve the problems, such as that phosphoric acid by wet process generates a large amount of ardealites, simultaneously
The ammonium hydrogen phosphate of high value can also be obtained【(NH4)2HPO4】。
Description of the drawings
In order to illustrate more clearly of present example or technical solution in the prior art, to embodiment or will show below
Required attached drawing, which is done, in having technology to describe simply introduces, it should be apparent that, the accompanying drawings in the following description is only the present invention
Some examples to those skilled in the art, can also be attached according to these under the premise of not paying creativeness
Figure obtains other attached drawings：
Fig. 1 is high-quality double superphosphate product appearance figure made from the method for the present invention.
Specific implementation mode
Specific embodiments of the present invention will be described in further detail below, but the invention is not limited in these realities
Mode is applied, it is claimed to still fall within the claims in the present invention for any improvement or replacement on the present embodiment essence spirit
Range.
Embodiment 1
The method of phosphoric acid byproduct hydrogen ammonium, includes the following steps in a kind of high-quality double superphosphate preparation process：
(1) it takes 230 parts of water to be placed in reaction vessel, 200 parts of ammonium chlorides is added, heating stirring obtains chlorine to being completely dissolved
Change ammonium saturated solution；The heating process is to be heated to 55 DEG C；
(2) 160 parts of ground phosphate rock are sent into pulverizer crushing, sieving, the ammonium chloride saturation of step (1) is added under stirring
In solution, slurrying is stirred, phosphorus ore slurry is obtained；It is described to crush, be sieved as ground phosphate rock was crushed to 200 mesh sieve；
(3) in the case where phosphorus ore slurry continues stirring, phosphorus ore slurry is added in 300 parts of calcium chloride sub-molten salt systems,
Control system temperature stops heating after reacting 3h, and 150 parts of water are added and continue to stir 25min, collect the ammonia generated in reaction process
Gas, discharging, natural filtration obtain filter residue A；It is to be slowly added to during phosphorus ore slurry is added to calcium chloride sub-molten salt, phosphorate mine
The time of slurry >=1h, the reaction was continued 2h or more after the miberal powder that phosphorates is starched；
(4) the filter residue A obtained by step (3) is dissolved in 200 parts of 95 DEG C of water, is stirred slurrying, controlling reaction temperature,
Then 200 parts of hydrochloric acid are added dropwise into slurry, filtrate is collected by filtration 1. after control slurry pH value is stablized；The pH stable numerical value
It is 2.5, the time of pH stable is at least 1h；The reaction temperature control is 90 DEG C；The dropwise addition hydrochloric acid is to be slowly added dropwise；
(5) filtrate obtained by step (4) is 1. placed in 600 parts of calcium chloride sub-molten salt systems, stirs simultaneously control system temperature
Degree, is collected by filtration filter residue after reaction, dry, obtains filter residue B；It is to raise the temperature to 140 DEG C that the heating, which increases temperature, described
The time of reaction is 1h；The drying process is dry 10h under the conditions of filter residue is placed in 160 DEG C；
(6) the filter residue B obtained by step (5) is dissolved in 200 parts of 95 DEG C of water, is placed in calcium chloride sub-molten salt system, controlled
The reaction temperature of system processed is passed through the ammonia obtained by step (3), is separated by solid-liquid separation through natural filtration, obtains filtrate 2. and filters
2. slag C, filtrate are the ammonium hydrogen phosphate；；
(7) ammonium chloride saturated solution is added into filter residue C obtained by step (6), is placed in 500 parts of calcium chloride sub-molten salt systems
In, control system temperature is stirred continuously mixing and is reacted, and natural filtration obtains filter residue D, and then filter residue D is sent into drying machine
It is dry, obtain the double superphosphate；Ratio=1 of the filter residue C and ammonium chloride saturated solution:4~5；The drying process
Temperature be 100 DEG C, time 10h.
Further, in step (3), step (5), step (6) and step (7), it is 160 that the system temperature, which controls,
℃；The calcium chloride sub-molten salt system is stirred evenly after mixing calcium chloride with the water of its weight 50%, is warming up to 170 DEG C,
It keeps stablizing and be made.
Embodiment 2
The method of phosphoric acid byproduct hydrogen ammonium, includes the following steps in a kind of high-quality double superphosphate preparation process：
(1) it takes 350 parts of water to be placed in reaction vessel, 260 parts of ammonium chlorides is added, heating stirring obtains chlorine to being completely dissolved
Change ammonium saturated solution；The heating process is to be heated to 100 DEG C；
(2) 250 parts of ground phosphate rock are sent into pulverizer crushing, sieving, the ammonium chloride saturation of step (1) is added under stirring
In solution, slurrying is stirred, phosphorus ore slurry is obtained；It is described to crush, be sieved as ground phosphate rock was crushed to 300 mesh sieve；
(3) in the case where phosphorus ore slurry continues stirring, phosphorus ore slurry is added in 1000 parts of calcium chloride sub-molten salt systems,
Control system temperature stops heating after reacting 6h, and 300 parts of water are added and continue to stir 40min, collect the ammonia generated in reaction process
Gas, discharging, natural filtration obtain filter residue A；It is to be slowly added to during phosphorus ore slurry is added to calcium chloride sub-molten salt, phosphorate mine
The time of slurry >=1h, the reaction was continued 2h or more after the miberal powder that phosphorates is starched；
(4) the filter residue A obtained by step (3) is dissolved in 400 parts of 100 DEG C of water, is stirred slurrying, control reaction temperature
Then degree 300 parts of hydrochloric acid is added dropwise into slurry, filtrate is collected by filtration 1. after control slurry pH value is stablized；The pH stable number
Value is 3, and the time of pH stable is at least 1h；The reaction temperature control is 99 DEG C；The dropwise addition hydrochloric acid is to be slowly added dropwise；
(5) filtrate obtained by step (4) is 1. placed in 800 parts of calcium chloride sub-molten salt systems, stirs simultaneously control system temperature
Degree, is collected by filtration filter residue after reaction, dry, obtains filter residue B；It is to raise the temperature to 180 DEG C that the heating, which increases temperature, described
The time of reaction is 2.5h；The drying process is dry 15h under the conditions of filter residue is placed in 180 DEG C；
(6) the filter residue B obtained by step (5) is dissolved in 300 parts of 100 DEG C of water, is placed in calcium chloride sub-molten salt system, controlled
The reaction temperature of system processed is passed through the ammonia obtained by step (3), is separated by solid-liquid separation through natural filtration, obtains filtrate 2. and filters
2. slag C, filtrate are the ammonium hydrogen phosphate；；
(7) ammonium chloride saturated solution is added into filter residue C obtained by step (6), is placed in 700 parts of calcium chloride sub-molten salt systems
In, control system temperature is stirred continuously mixing and is reacted, and natural filtration obtains filter residue D, and then filter residue D is sent into drying machine
It is dry, obtain the double superphosphate；Ratio=1 of the filter residue C and ammonium chloride saturated solution:5；The temperature of the drying process
Degree is 140 DEG C, time 14h.
Further, in step (3), step (5), step (6) and step (7), it is 180 that the system temperature, which controls,
℃；The calcium chloride sub-molten salt system is stirred evenly after mixing calcium chloride with the water of its weight 150%, is warming up to 180 DEG C,
It keeps stablizing and be made.
Embodiment 3
The method of phosphoric acid byproduct hydrogen ammonium, includes the following steps in a kind of high-quality double superphosphate preparation process：
(1) it takes 260 parts of water to be placed in reaction vessel, 220 parts of ammonium chlorides is added, heating stirring obtains chlorine to being completely dissolved
Change ammonium saturated solution；The heating process is to be heated to 65 DEG C；
(2) 180 parts of ground phosphate rock are sent into pulverizer crushing, sieving, the ammonium chloride saturation of step (1) is added under stirring
In solution, slurrying is stirred, phosphorus ore slurry is obtained；It is described to crush, be sieved as ground phosphate rock was crushed to 220 mesh sieve；
(3) in the case where phosphorus ore slurry continues stirring, phosphorus ore slurry is added in 400 parts of calcium chloride sub-molten salt systems,
Control system temperature stops heating after reacting 3.5h, and 180 parts of water are added and continue to stir 30min, collects and is generated in reaction process
Ammonia, discharging, natural filtration obtain filter residue A；It is to be slowly added to during phosphorus ore slurry is added to calcium chloride sub-molten salt, phosphorates
Time >=1h of miberal powder slurry, the reaction was continued 2h or more after the miberal powder that phosphorates is starched；
(4) the filter residue A obtained by step (3) is dissolved in 250 parts of 96 DEG C of water, is stirred slurrying, controlling reaction temperature,
Then 220 parts of hydrochloric acid are added dropwise into slurry, filtrate is collected by filtration 1. after control slurry pH value is stablized；The pH stable numerical value
It is 2.6, the time of pH stable is at least 1h；The reaction temperature control is 92 DEG C；The dropwise addition hydrochloric acid is to be slowly added dropwise；
(5) filtrate obtained by step (4) is 1. placed in 650 parts of calcium chloride sub-molten salt systems, stirs simultaneously control system temperature
Degree, is collected by filtration filter residue after reaction, dry, obtains filter residue B；It is to raise the temperature to 150 DEG C that the heating, which increases temperature, described
The time of reaction is 1.5h；The drying process is dry 11h under the conditions of filter residue is placed in 165 DEG C；
(6) the filter residue B obtained by step (5) is dissolved in 220 parts of 95 DEG C of water, is placed in calcium chloride sub-molten salt system, controlled
The reaction temperature of system processed is passed through the ammonia obtained by step (3), is separated by solid-liquid separation through natural filtration, obtains filtrate 2. and filters
2. slag C, filtrate are the ammonium hydrogen phosphate；；
(7) ammonium chloride saturated solution is added into filter residue C obtained by step (6), is placed in 550 parts of calcium chloride sub-molten salt systems
In, control system temperature is stirred continuously mixing and is reacted, and natural filtration obtains filter residue D, and then filter residue D is sent into drying machine
It is dry, obtain the double superphosphate；Ratio=1 of the filter residue C and ammonium chloride saturated solution:4.2；The drying process
Temperature is 110 DEG C, time 11h.
Further, in step (3), step (5), step (6) and step (7), it is 165 that the system temperature, which controls,
℃；The calcium chloride sub-molten salt system is stirred evenly after mixing calcium chloride with the water of its weight 50~150%, is warming up to
It 173 DEG C, keeps stablizing obtained.
Embodiment 4
The method of phosphoric acid byproduct hydrogen ammonium, includes the following steps in a kind of high-quality double superphosphate preparation process：
(1) it takes 330 parts of water to be placed in reaction vessel, 240 parts of ammonium chlorides is added, heating stirring obtains chlorine to being completely dissolved
Change ammonium saturated solution；The heating process is to be heated to 90 DEG C；
(2) 230 parts of ground phosphate rock are sent into pulverizer crushing, sieving, the ammonium chloride saturation of step (1) is added under stirring
In solution, slurrying is stirred, phosphorus ore slurry is obtained；It is described to crush, be sieved as ground phosphate rock was crushed to 280 mesh sieve；
(3) in the case where phosphorus ore slurry continues stirring, phosphorus ore slurry is added in 800 parts of calcium chloride sub-molten salt systems,
Control system temperature stops heating after reacting 5.5h, and 280 parts of water are added and continue to stir 37min, collects and is generated in reaction process
Ammonia, discharging, natural filtration obtain filter residue A；It is to be slowly added to during phosphorus ore slurry is added to calcium chloride sub-molten salt, phosphorates
Time >=1h of miberal powder slurry, the reaction was continued 2h or more after the miberal powder that phosphorates is starched；
(4) the filter residue A obtained by step (3) is dissolved in 370 parts of 99 DEG C of water, is stirred slurrying, controlling reaction temperature,
Then 280 parts of hydrochloric acid are added dropwise into slurry, filtrate is collected by filtration 1. after control slurry pH value is stablized；The pH stable numerical value
It is 2.9, the time of pH stable is at least 1h；The reaction temperature control is 97 DEG C；The dropwise addition hydrochloric acid is to be slowly added dropwise；
(5) filtrate obtained by step (4) is 1. placed in 750 parts of calcium chloride sub-molten salt systems, stirs simultaneously control system temperature
Degree, is collected by filtration filter residue after reaction, dry, obtains filter residue B；It is to raise the temperature to 170 DEG C that the heating, which increases temperature, described
The time of reaction is 2h；The drying process is dry 14h under the conditions of filter residue is placed in 175 DEG C；
(6) the filter residue B obtained by step (5) is dissolved in 270 parts of 98 DEG C of water, is placed in calcium chloride sub-molten salt system, controlled
The reaction temperature of system processed is passed through the ammonia obtained by step (3), is separated by solid-liquid separation through natural filtration, obtains filtrate 2. and filters
2. slag C, filtrate are the ammonium hydrogen phosphate；；
(7) ammonium chloride saturated solution is added into filter residue C obtained by step (6), is placed in 650 parts of calcium chloride sub-molten salt systems
In, control system temperature is stirred continuously mixing and is reacted, and natural filtration obtains filter residue D, and then filter residue D is sent into drying machine
It is dry, obtain the double superphosphate；Ratio=1 of the filter residue C and ammonium chloride saturated solution:4.8；The drying process
Temperature is 130 DEG C, time 13h.
Further, in step (3), step (5), step (6) and step (7), it is 175 that the system temperature, which controls,
℃；The calcium chloride sub-molten salt system is stirred evenly after mixing calcium chloride with the water of its weight 130%, is warming up to 178 DEG C,
It keeps stablizing and be made.
Embodiment 5
The method of phosphoric acid byproduct hydrogen ammonium, includes the following steps in a kind of high-quality double superphosphate preparation process：
(1) it takes 290 parts of water to be placed in reaction vessel, 230 parts of ammonium chlorides is added, heating stirring obtains chlorine to being completely dissolved
Change ammonium saturated solution；The heating process is to be heated to 80 DEG C；
(2) 200 parts of ground phosphate rock are sent into pulverizer crushing, sieving, the ammonium chloride saturation of step (1) is added under stirring
In solution, slurrying is stirred, phosphorus ore slurry is obtained；It is described to crush, be sieved as ground phosphate rock was crushed to 250 mesh sieve；
(3) in the case where phosphorus ore slurry continues stirring, phosphorus ore slurry is added in 750 parts of calcium chloride sub-molten salt systems,
Control system temperature stops heating after reacting 4.5h, and 225 parts of water are added and continue to stir 33min, collects and is generated in reaction process
Ammonia, discharging, natural filtration obtain filter residue A；It is to be slowly added to during phosphorus ore slurry is added to calcium chloride sub-molten salt, phosphorates
Time >=1h of miberal powder slurry, the reaction was continued 2h or more after the miberal powder that phosphorates is starched；
(4) the filter residue A obtained by step (3) is dissolved in 300 parts of 97 DEG C of water, is stirred slurrying, controlling reaction temperature,
Then 250 parts of hydrochloric acid are added dropwise into slurry, filtrate is collected by filtration 1. after control slurry pH value is stablized；The pH stable numerical value
It is 2.7, the time of pH stable is at least 1h；The reaction temperature control is 95 DEG C；The dropwise addition hydrochloric acid is to be slowly added dropwise；
(5) filtrate obtained by step (4) is 1. placed in 700 parts of calcium chloride sub-molten salt systems, stirs simultaneously control system temperature
Degree, is collected by filtration filter residue after reaction, dry, obtains filter residue B；It is to raise the temperature to 160 DEG C that the heating, which increases temperature, described
The time of reaction is 1.8h；The drying process is dry 13h under the conditions of filter residue is placed in 170 DEG C；
(6) the filter residue B obtained by step (5) is dissolved in 250 parts of 97 DEG C of water, is placed in calcium chloride sub-molten salt system, controlled
The reaction temperature of system processed is passed through the ammonia obtained by step (3), is separated by solid-liquid separation through natural filtration, obtains filtrate 2. and filters
2. slag C, filtrate are the ammonium hydrogen phosphate；；
(7) ammonium chloride saturated solution is added into filter residue C obtained by step (6), is placed in 600 parts of calcium chloride sub-molten salt systems
In, control system temperature is stirred continuously mixing and is reacted, and natural filtration obtains filter residue D, and then filter residue D is sent into drying machine
It is dry, obtain the double superphosphate；Ratio=1 of the filter residue C and ammonium chloride saturated solution:4.5；The drying process
Temperature is 120 DEG C, time 12h.
Further, in step (3), step (5), step (6) and step (7), it is 170 that the system temperature, which controls,
℃；The calcium chloride sub-molten salt system is stirred evenly after mixing calcium chloride with the water of its weight 100%, is warming up to 175 DEG C,
It keeps stablizing and be made.
Method can reach the technique effect in order to further illustrate the present invention, do following experiment：
The powdery double superphosphate product obtained by the embodiment of the present invention 1~5 is detected according to relevant national standard,
Take the average value of 5 embodiment detection the data obtaineds as testing result, present invention gained powdery double superphosphate product testing
The results are shown in Table 1.
1 powdery double superphosphate product testing result of table
As shown in Table 1, fluorine content is 2.16% in the double superphosphate product obtained by the present invention, disclosure satisfy that farmland grade
Product index requirement, in addition, poisonous and harmful heavy metallic residual reaches national related fertilizer index and wants in double superphosphate product
It asks.
In conclusion the present invention helps tiger by technical research portion of our company in Chinese Academy Of Sciences Process Engineering Research Institute Lee waits one
Under the guidance of row expert, the ecological circulation engineering science new theory that research is initiated using Chinese Academy of Sciences's process builds artificial substance and closes
Road recycles, and double superphosphate is prepared using recessive acid combination sub-molten salt technology decomposing phosphate rock stone【Ca(H2PO4)2】, realize phosphatization
Work production process is generated without ardealite, realizes phosphorus chemical industry technological reforger.Make recessive acid (NH4Cl) in calcium chloride sub-molten salt body
Rock phosphate in powder is decomposed in system and generates Ca (H2PO4)2It is first because containing various plants nutrition in sour insoluble slag with sour insoluble slag mixture
Element can be used as fertilizer beneficial element, main component SiO2·nH2O, P in the mixture obtained at this time2O5> 40%, although
React the Ca (H of gained2PO4)2With sour insoluble slag【SiO2·nH2O】Mixture can be sold directly as coarse whiting product, but this
When obtained mixture in Ca (H2PO4)2Purity is not high, after then inventor carries out HCl treatment to mixture, and uses
NH4The ammonia that Cl decomposing phosphate rock stones generate further is reacted as raw material, to improve Ca (H2PO4)2Purity, and
The ammonium hydrogen phosphate of higher value is obtained in this reaction process【(NH4)2HPO4】, production process only can be in building materials, dress
Repair the sour insoluble slag of the fields such as material utilization【SiO2·nH2O】Solid generates, and the ammonia that production process generates can recycle
It utilizes, the carbon dioxide of generation is easily handled.Solves NH4Cl decomposing rock phosphate with hydrogen leads to the problem of ammonia emission pollution environment,
Ammonia can also be made full use of to prepare the ammonium hydrogen phosphate of higher value simultaneously, resource circulation utilization is realized, reduce industry
Production cost.It is generated without exhaust gas, waste residue the like waste during preparing high-quality double superphosphate, realizes the cycle of resource
It utilizes, energy conservation and environmental protection is cost-effective, can not only solve the problems, such as that phosphoric acid by wet process generates a large amount of ardealites, while can also
Obtain the ammonium hydrogen phosphate of high value【(NH4)2HPO4】。
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case of without departing from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, nothing
By from the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended
Claim rather than above description limit, it is intended that the institute in the meaning and scope of the equivalent loins of claim will be fallen
It changes and includes within protection scope of the present invention.
Claims (10)
1. a kind of method of phosphoric acid byproduct hydrogen ammonium in high-quality double superphosphate preparation process, which is characterized in that include the following steps：
(1) take 230~350 parts of water to be placed in reaction vessel, 200~260 parts of ammonium chlorides be added, heating stirring to being completely dissolved,
Obtain ammonium chloride saturated solution；
(2) 160~250 parts of ground phosphate rock are sent into pulverizer crushing, sieving, the ammonium chloride that step (1) is added under stirring is full
In solution, slurrying is stirred, phosphorus ore slurry is obtained；
(3) in the case where phosphorus ore slurry continues stirring, phosphorus ore slurry is added to 300~1000 parts of calcium chloride sub-molten salt systems
In, control system temperature stops heating after reacting 3~6h, and 150~300 parts of water are added and continue 25~40min of stirring, collects anti-
The ammonia that should be generated in the process, discharging, natural filtration obtain filter residue A；
(4) the filter residue A obtained by step (3) is dissolved in 200~400 parts of 95~100 DEG C of water, is stirred slurrying, control is anti-
Temperature is answered, 200~300 parts of hydrochloric acid is then added dropwise into slurry, filtrate is collected by filtration 1. after control slurry pH value is stablized；
(5) filtrate obtained by step (4) is 1. placed in 600~800 parts of calcium chloride sub-molten salt systems, stirs simultaneously control system temperature
Degree, is collected by filtration filter residue after reaction, dry, obtains filter residue B；
(6) the filter residue B obtained by step (5) is dissolved in 200~300 parts of 95~100 DEG C of water, is placed in calcium chloride sub-molten salt system
In, 2. and filter residue control system temperature is passed through the ammonia obtained by step (3), is separated by solid-liquid separation through natural filtration, obtains filtrate
2. C, filtrate are the ammonium hydrogen phosphate；
(7) ammonium chloride saturated solution is added into filter residue C obtained by step (6), is placed in 500~700 parts of calcium chloride sub-molten salt systems
In, control system temperature is stirred continuously mixing and is reacted, and natural filtration obtains filter residue D, and then filter residue D is sent into drying machine
It is dry, obtain the double superphosphate.
2. the method for phosphoric acid byproduct hydrogen ammonium in a kind of high-quality double superphosphate preparation process according to claim 1, special
Sign is：In step (1), the heating process is to be heated to 55~100 DEG C.
3. the method for phosphoric acid byproduct hydrogen ammonium in a kind of high-quality double superphosphate preparation process according to claim 1, special
Sign is：It is described to crush, be sieved as ground phosphate rock was crushed to 200~300 mesh sieve in step (2).
4. the method for phosphoric acid byproduct hydrogen ammonium in a kind of high-quality double superphosphate preparation process according to claim 1, special
Sign is：It is to be slowly added to during phosphorus ore slurry is added to calcium chloride sub-molten salt in step (3), the miberal powder that phosphorates slurry
Time >=1h, the reaction was continued 2h or more after the miberal powder that phosphorates is starched.
5. the method for phosphoric acid byproduct hydrogen ammonium in a kind of high-quality double superphosphate preparation process according to claim 1, special
Sign is：In step (4), the pH stable numerical value is 2.5~3, and the time of pH stable is at least 1h.
6. the method for phosphoric acid byproduct hydrogen ammonium in a kind of high-quality double superphosphate preparation process according to claim 1, special
Sign is：In step (4), the reaction temperature control is 90~99 DEG C；The dropwise addition hydrochloric acid is to be slowly added dropwise.
7. the method for phosphoric acid byproduct hydrogen ammonium in a kind of high-quality double superphosphate preparation process according to claim 1, special
Sign is：In step (5), it is to raise the temperature to 140~180 DEG C that the heating, which increases temperature, time of the reaction is 1~
2.5h；The drying process is dry 10~15h under the conditions of filter residue is placed in 160~180 DEG C.
8. the method for phosphoric acid byproduct hydrogen ammonium in a kind of high-quality double superphosphate preparation process according to claim 1, special
Sign is：In step (6), ratio=3 of the filter residue B and ammonia:8~10.
9. the method for phosphoric acid byproduct hydrogen ammonium in a kind of high-quality double superphosphate preparation process according to claim 1, special
Sign is：In step (7), ratio=1 of the filter residue C and ammonium chloride saturated solution:4~5；The temperature of the drying process is
100~140 DEG C, the time is 10~14h.
10. the method for phosphoric acid byproduct hydrogen ammonium in a kind of high-quality double superphosphate preparation process according to claim 1, special
Sign is：In step (3), step (5), step (6) and step (7), it is 160~180 DEG C that the system temperature, which controls,；It is described
Calcium chloride sub-molten salt system is stirred evenly after mixing calcium chloride with the water of its weight 50~150%, is warming up to 170~180
DEG C, it keeps stablizing obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810608696.4A CN108706991A (en) | 2018-06-13 | 2018-06-13 | A kind of method of phosphoric acid byproduct hydrogen ammonium in high-quality double superphosphate preparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810608696.4A CN108706991A (en) | 2018-06-13 | 2018-06-13 | A kind of method of phosphoric acid byproduct hydrogen ammonium in high-quality double superphosphate preparation process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108706991A true CN108706991A (en) | 2018-10-26 |
Family
ID=63872756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810608696.4A Pending CN108706991A (en) | 2018-06-13 | 2018-06-13 | A kind of method of phosphoric acid byproduct hydrogen ammonium in high-quality double superphosphate preparation process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108706991A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232005A (en) * | 1999-03-30 | 1999-10-20 | 黄孝农 | Process for preparing phosphate fertilizer and soda by circulation of ammonium chloride |
| WO2010043262A1 (en) * | 2008-10-16 | 2010-04-22 | Ecophos Sa | Process for the production of high purity phosphoric acid |
| CN104071818A (en) * | 2013-10-28 | 2014-10-01 | 黔南民族师范学院 | Method for separating calcium, magnesium and phosphorus elements from phosphate tailings by adopting water leaching and ammonium leaching |
| CN107128889A (en) * | 2017-05-12 | 2017-09-05 | 湖北三宁化工股份有限公司 | A kind of decomposing phosphate rock by chlorhydric acid produces the system and technique of calcium hydrophosphate fodder |
| CN107814370A (en) * | 2017-09-29 | 2018-03-20 | 徐州市禾协肥业有限公司 | Prepare environment-friendly cycle process of phosphorus concentrate and products thereof and application |
-
2018
- 2018-06-13 CN CN201810608696.4A patent/CN108706991A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232005A (en) * | 1999-03-30 | 1999-10-20 | 黄孝农 | Process for preparing phosphate fertilizer and soda by circulation of ammonium chloride |
| WO2010043262A1 (en) * | 2008-10-16 | 2010-04-22 | Ecophos Sa | Process for the production of high purity phosphoric acid |
| CN104071818A (en) * | 2013-10-28 | 2014-10-01 | 黔南民族师范学院 | Method for separating calcium, magnesium and phosphorus elements from phosphate tailings by adopting water leaching and ammonium leaching |
| CN107128889A (en) * | 2017-05-12 | 2017-09-05 | 湖北三宁化工股份有限公司 | A kind of decomposing phosphate rock by chlorhydric acid produces the system and technique of calcium hydrophosphate fodder |
| CN107814370A (en) * | 2017-09-29 | 2018-03-20 | 徐州市禾协肥业有限公司 | Prepare environment-friendly cycle process of phosphorus concentrate and products thereof and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107720716B (en) | The technique for preparing battery-level lithium carbonate and ferric phosphate from crude product lithium phosphate recycling lithium phosphorus | |
| CN105367176B (en) | A kind of multielement composite of phosphorus potassium associated minerals utilizes technique | |
| CN105197905B (en) | Extract the production method of phosphorus ore coproduction feed-level calcium biphosphate and technical grade phosphorus ammonium | |
| CN107814370B (en) | Circulating environment-friendly process method for preparing phosphate concentrate, product and application thereof | |
| CN101007626A (en) | Method for producing phosphate by wet method phosphoric acid purification and hydrochloric acid decomposition for phosphate ore | |
| CN101337657A (en) | Process for disassembling phosphate ore by mixed acid and coproducing potassium dihydrogen phosphate, hydrogen phosphate and combined fertilizer | |
| CN106517293B (en) | A kind of method of industrial calcium product coproduction chemical synthesis fertilizer | |
| CN103318863A (en) | Novel acid saving technology for preparing ammonium phosphate from middle-low grade phosphate ore by slurry process | |
| CN104211485A (en) | Method for producing crystalline potassium dihydrogen phosphate and potassium nitrate macroelement water-soluble fertilizer | |
| CN104744175A (en) | Method for producing nitrogen-phosphorus-potassium mixed fertilizer by utilizing phosphorus-potassium associated ore | |
| CN110467168A (en) | The recovery method of titanium pigment in a kind of ardealite | |
| CN101434386A (en) | Method for producing fine phosphate by using dilute acid to decompose middle and low grade phosphate ore using | |
| CN105692668B (en) | A kind of gangue, coal ash for manufacturing for cryolite with high molecular ratio method | |
| CN107827113A (en) | In a kind of industrial monoammonium phosphate and slurry in fluorine recovery method | |
| CN1686816B (en) | Method for multipurpose use of material of acid split phosphate ore and associated production of high purified microsphere nano calcium carbonate | |
| CN110217769B (en) | Method for producing calcium ammonium nitrate byproduct feed-grade DCP | |
| US5035872A (en) | Method of preparing potassium magnesium phosphate | |
| CN108706991A (en) | A kind of method of phosphoric acid byproduct hydrogen ammonium in high-quality double superphosphate preparation process | |
| CN111533099B (en) | Production method of water-soluble monoammonium phosphate | |
| CN111517832B (en) | Separation method of P, Ca in medium-low grade phosphate ore and method for producing fertilizer | |
| CN108821299B (en) | Method for preparing calcium silicate by decomposing phosphate ore by using ammonium chloride | |
| CN108726552B (en) | Method for circularly preparing light calcium carbonate by decomposing phosphate ore by using ammonium chloride | |
| CN103803517B (en) | The method of the low silicon ardealite of high silicon Phosphate Rock acid by-product | |
| CN108502862A (en) | A kind of method that double superphosphate prepares ammonium hydrogen phosphate | |
| CN108455546A (en) | A kind of preparation method of double superphosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Bao Weijun Inventor after: Li Zuohu Inventor after: Wang Yunshan Inventor after: An Xuebin Inventor after: Wang Caiyan Inventor after: Tang Lijun Inventor after: He Runlin Inventor after: He Hua Inventor after: Xiao Xin Inventor after: Liao Jixing Inventor after: Xu Liqin Inventor after: Luo Fulang Inventor after: Han Chaoying Inventor after: Jiang Xuehua Inventor before: Wu Youli Inventor before: Wang Caiyan Inventor before: Tang Lijun Inventor before: Xiang Shuanglong Inventor before: He Runlin Inventor before: Liao Jixing Inventor before: Xu Liqin Inventor before: Luo Fulang Inventor before: Han Chaoying Inventor before: Jiang Xuehua Inventor before: He Hua |
|
| CB03 | Change of inventor or designer information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200813 Address after: Xifeng County in Guizhou Province, Guiyang city town 551109 Applicant after: GUIYANG KAILIN FERTILIZER Co.,Ltd. Applicant after: Institute of Process Engineering, Chinese Academy of Sciences Address before: 551109 xiaozhaiba Town, Xifeng County, Guiyang City, Guizhou Province Applicant before: GUIYANG KAILIN FERTILIZER Co.,Ltd. Applicant before: GUIZHOU KAILIN GROUP Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20220107 |
|
| AD01 | Patent right deemed abandoned |