CN104016323A - Production method for monoammonium phosphate - Google Patents
Production method for monoammonium phosphate Download PDFInfo
- Publication number
- CN104016323A CN104016323A CN201410213411.9A CN201410213411A CN104016323A CN 104016323 A CN104016323 A CN 104016323A CN 201410213411 A CN201410213411 A CN 201410213411A CN 104016323 A CN104016323 A CN 104016323A
- Authority
- CN
- China
- Prior art keywords
- monoammonium phosphate
- reaction
- ureaphil
- production method
- stirring
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical engineering, and particularly relates to a production method for monoammonium phosphate. A monoammonium phosphate product is prepared by directly subjecting high pure urea phosphate and ammonia to a double decomposition reaction and reacting for 20-60 min with stirring by controlling a reaction temperature at 40-80 DEG C and a pH value at a reaction endpoint being 4.2-4.6, and through the steps of cooling for crystallization; separating by centrifugation and drying. Measurements of physical and chemical indexes of the produced product show that the physical and chemical indexes of the produced monoammonium phosphate product meet an industrial first level standard. Specifically, the total nutrient content of monoammonium phosphate is higher than 73%; the content of total nitrogen is 12.01-12.23%; the content of phosphorus pentoxide is 61.05-61.25%; the content of moisture is 0.35-0.52%; a pH value is 4.2-4.6; the content of water insoluble materials is 0.090-0.096%; and the content of fluoride is 0.15-0.19%.
Description
Technical field
The present invention relates to chemical technology field, especially a kind of production method of monoammonium phosphate.
Background technology
Primary ammonium phosphate, is again monoammonium phosphate, along with developing rapidly of industrial or agricultural, in agricultural, is commonly used as efficient nitrogen phosphorus fertilizer, is used for mineral wool agent on timber, paper, fabric etc., fiery paint additive and powder extinguishing agent etc. in industry; In foodstuffs industry, as starter, nutrition agent etc.Visible, the purposes of primary ammonium phosphate is very extensive, and still, for using in industrial or agricultural, the purity requirement of primary ammonium phosphate product is larger, and the production method of PHOSPHORIC ACID TECH.GRADE ammonium dihydrogen mainly contains neutralisation, and raw material phosphoric acid has two kinds of thermal phosphoric acid and phosphoric acid by wet processes; To be yellow phosphorus generate the phosphoric acid of high density through burning, water to the technique of thermal phosphoric acid one ammonium after absorbing, phosphoric acid ammonification, centrifugal, the concentrated crystallisation by cooling of phosphorus ammonium liquid, the dry product industrial grade monoammonium phosphate that to obtain; The method Technology maturation, the advantages such as facility investment is few, constant product quality, but the chief drawback is, thermal phosphoric acid energy consumption is high, pollutes greatly, product cost is high; The technique of preparing industrial grade monoammonium phosphate from wet-process phosphoric acid is that sulfuric acid decomposes ore pulp preparation extraction phosphoric acid by wet process after extraction; After phosphoric acid by wet process purifies, react with ammonia, thereby prepare highly purified industrial grade monoammonium phosphate product.Wet method phosphoric acid manufacture process is all first phosphoric acid by wet process to be purified, then produces with purification acid, and the method technical process is long and complicated, due to the blockade of wet phosphoric acid purifying technology, thereby can not be popularized.
As can be seen here, in prior art, for the production process ubiquity of primary ammonium phosphate product, production energy consumption is high, pollution is large, the material of equipment is had relatively high expectations, and technical process complexity, production cycle is long, and the quality that obtains product is unstable, the technical problem that cost is high.
Summary of the invention
In order to solve the above-mentioned technical problem existing in prior art, the invention provides a kind of production method of directly utilizing production of urea phosphate industrial grade monoammonium phosphate, have that operational path is short, energy consumption is low, constant product quality, by product can be recycled to reclaim and utilize, and cleanliness without any pollution in whole production process, the feature of discharging without " waste gas ", " waste water ", " waste residue ".
Specifically be achieved by the following technical programs:
A production method for monoammonium phosphate, adopts highly purified Ureaphil and ammonia directly to carry out replacement(metathesis)reaction and prepares monoammonium phosphate, and its reaction equation is:
CO(NH
2)
2·H
3PO
4+NH
3=NH
4H
2PO
4+CO(NH
2)
2
Control temperature of reaction is 40-80 DEG C, stirring reaction 20-60min, and reaction end pH value is 4.2-4.6, and by crystallisation by cooling, centrifugation drying step, obtains monoammonium phosphate product.
Specifically comprise the following steps:
(1) preparation of Ureaphil solution: the Ureaphil solid that is 98% by purity adds water and measures in dissolving tank, after being warming up to temperature and being 40-80 DEG C, stirring and dissolving mixes, and to control stirring velocity be 30-50r/min, obtains Ureaphil solution;
(2) monoammonium phosphate is synthetic: Ureaphil solution is adopted in the synthetic groove of transferpump input, and controlling temperature is at 40-80 DEG C, and is (0.99-1.05) according to Ureaphil with the mol ratio of ammonia: 1 ratio adds ammonia to react; Take to add while stirring ammonia, stirring velocity is 60-70r/min, and when stirring reaction 20-60min, when detection pH value is 4.2-4.6, reaction terminating, obtains monoammonium phosphate slip;
(3) crystallization centrifugation: monoammonium phosphate slip is proceeded in crystallizer be cooled to≤40 DEG C at crystallize out, and crystal is proceeded to and in separating centrifuge, carries out centrifugation, obtain filtrate and filter cake, filtrate is urea slip, proceeds to production of urea phosphate technique and carries out Ureaphil raw material production; Filter cake is monoammonium phosphate, and being placed in drying machine, to adopt drying temperature be 80 DEG C, after dry 3-5min, obtains monoammonium phosphate product.
Described temperature of reaction is 50-70 DEG C.
Described temperature of reaction is 60 DEG C.
Described reaction end pH value is 4.3-4.5.
Described reaction end pH value is 4.4.
The time of described stirring reaction is 30-50min.
The time of described stirring reaction is 40min.
In described Ureaphil solution preparation, stirring velocity is 40r/min; During described monoammonium phosphate is synthetic, stirring velocity is 65r/min.
Described monoammonium phosphate product, its physical and chemical index is that monoammonium phosphate total nutrient is greater than 73%, total nitrogen 12.01-12.23%, Vanadium Pentoxide in FLAKES are 61.05-61.25%, and moisture is that 0.35-0.52%, PH are that 4.2-4.6, water-insoluble are that 0.090-0.096%, fluorochemical are 0.15-0.19%.
Described monoammonium phosphate product, its physical and chemical index is that monoammonium phosphate total nutrient is greater than 73%, and total nitrogen 12.07%, Vanadium Pentoxide in FLAKES are 61.15%, and moisture is 0.48%, PH is 4.4, water-insoluble is 0.093%, fluorochemical is 0.17%.
Compared with prior art, technique effect of the present invention is embodied in:
1. by adopting Ureaphil to replace thermal phosphoric acid or purifying phosphoric acid as the raw materials for production of monoammonium phosphate, reduce the energy consumption in production process, simplified the technological process of production, reduced production cost, there is good economic benefit.
2. by the recycling to by product urea slip, avoid the discharge of waste liquid, waste gas and waste residue, reduced environmental pollution, be conducive to the value of environmental protection.
3. by the adjustment of raw material and operational path, the quality product of producing is protected, constant product quality.
4. the product physical and chemical index of producing by detection, the physical and chemical index of the primary ammonium phosphate product of producing of the present invention meets an industrial grade standard, be that monoammonium phosphate total nutrient is greater than 73%, total nitrogen 12.01-12.23%, Vanadium Pentoxide in FLAKES are 61.05-61.25%, and moisture is that 0.35-0.52%, PH are that 4.2-4.6, water-insoluble are that 0.090-0.096%, fluorochemical are 0.15-0.19%.
Brief description of the drawings
Fig. 1 is equipment flowsheet of the present invention.
1-dissolving tank 2-synthesizes groove 3-crystallizer 4-separating centrifuge.
Embodiment
Below in conjunction with accompanying drawing and concrete embodiment, technical scheme of the present invention is done to further restriction, but claimed scope is not only confined to done description.
Noun explanation:
Ureaphil (Urea phosphate, UP), is for No. CAS 4861-19-2, and molecular formula is CH
7n
2o
5p, can be expressed as CO (NH
2)
2h
3pO
4:
It is a kind of fine chemical product that is widely used in the fields such as livestock industry, industry, agricultural, its solid is white crystals or crystalline powder, and soluble in water and alcohol is insoluble to ethers, toluene and tetracol phenixin, it is acid that the aqueous solution is, and starts to decompose to emit carbonic acid gas and ammonia when melting.
Principle explanation:
The present invention adopts pure Ureaphil and ammonia directly to carry out replacement(metathesis)reaction and makes monoammonium phosphate product, and its production principle is as follows:
CO(NH
2)
2·H
3PO
4+NH
3=NH
4H
2PO
4+CO(NH
2)
2
Ureaphil and ammonia generation replacement(metathesis)reaction, generate primary ammonium phosphate, by controlling the pH value of reaction end, obtains monoammonium phosphate product, and this process does not have the discharge of waste gas waste water and refuse, has the significant value of environmental protection; Meanwhile, in production process, produce urea slip, can be used as chemical fertilizers production raw material, also can proceed to production of urea phosphate system and continue to produce Ureaphil product, make technical process reach cyclic production, reduce the consumption of raw material, reduce production costs, there is significant economic benefit.
Be illustrated in figure 1 equipment flowsheet of the present invention, raw material Ureaphil is dissolved in water in dissolving tank 1 or is diluted to the Ureaphil solution that concentration is moderate, and dissolve or dilution in control temperature and reach certain numerical value, proceeded to again in synthetic groove 2, slowly add wherein ammonia simultaneously, being uniformly mixed solution makes it that replacement(metathesis)reaction occur, and control reaction times and temperature of reaction, be adjusted to ph value of reaction one timing simultaneously, reaction reaches terminal, mixed slurry is proceeded to and in crystallizer 3, carries out crystallisation by cooling processing, in the time separating out monoammonium phosphate crystal completely, proceed in separating centrifuge 4, carry out centrifugal treating, obtain filtrate and filter cake, filtrate is urea slip, proceed to chemical fertilizer production process or proceed to production of urea phosphate technique as Ureaphil raw material cyclic production, filter cake is monoammonium phosphate, after dry packing, can obtain industrial grade monoammonium phosphate.
Embodiment 1
A production method for monoammonium phosphate, adopts highly purified Ureaphil and ammonia directly to carry out replacement(metathesis)reaction and prepares monoammonium phosphate, and its reaction equation is:
CO(NH
2)
2·H
3PO
4+NH
3=NH
4H
2PO
4+CO(NH
2)
2
Specifically comprise the following steps:
(1) preparation of Ureaphil solution: the Ureaphil solid that is 98% by purity adds water and measures in dissolving tank, after being heated to temperature and being 40 DEG C, stirring and dissolving mixes, and to control stirring velocity be 30r/min, obtains Ureaphil solution;
(2) monoammonium phosphate is synthetic: Ureaphil solution is adopted in the synthetic groove of transferpump input, and controlling temperature is 40 DEG C, and the ratio that is 0.99:1 with the mol ratio of ammonia according to Ureaphil adds ammonia to react; Take to add while stirring ammonia, stirring velocity is 60-70r/min, and when stirring reaction 20min, detecting pH value is 4.2 o'clock, and reaction terminating obtains monoammonium phosphate slip;
(3) crystallization centrifugation: monoammonium phosphate slip is proceeded to and is cooled to crystallize out at 40 DEG C in crystallizer, and crystal is proceeded to and in separating centrifuge, carries out centrifugation, obtain filtrate and filter cake, filtrate is urea slip, proceeds to production of urea phosphate technique and carries out Ureaphil raw material production; Filter cake is monoammonium phosphate, and being placed in drying machine, to adopt drying temperature be 80 DEG C, after dry 3min, obtains monoammonium phosphate product.
Sampling analysis, the physical and chemical index that this method obtains product is that monoammonium phosphate total nutrient is greater than 73%, total nitrogen 12.01%, Vanadium Pentoxide in FLAKES are 61.15%, and moisture is 0.45%, PH is 4.2, water-insoluble is 0.095%, fluorochemical is 0.18%, reaches PHOSPHORIC ACID TECH.GRADE ammonium dihydrogen acceptable end product standard completely.
Embodiment 2
A production method for monoammonium phosphate, adopts highly purified Ureaphil and ammonia directly to carry out replacement(metathesis)reaction and prepares monoammonium phosphate, and its reaction equation is:
CO(NH
2)
2·H
3PO
4+NH
3=NH
4H
2PO
4+CO(NH
2)
2
Specifically comprise the following steps:
(1) preparation of Ureaphil solution: the Ureaphil solid that is 98% by purity adds water and measures in dissolving tank, after being warming up to temperature and being 80 DEG C, stirring and dissolving mixes, and to control stirring velocity be 50r/min, obtains Ureaphil solution;
(2) monoammonium phosphate is synthetic: Ureaphil solution is adopted in the synthetic groove of transferpump input, and controlling temperature is at 80 DEG C, and the ratio that is 1.05:1 with the mol ratio of ammonia according to Ureaphil adds ammonia to react; Take to add while stirring ammonia, stirring velocity is 70r/min, and when stirring reaction 60min, detecting pH value is 4.6 o'clock, and reaction terminating obtains monoammonium phosphate slip;
(3) crystallization centrifugation: by monoammonium phosphate slip proceed in crystallizer, carry out cooling, while being cooled to 30 DEG C of crystallize outs, and crystal is proceeded to and in separating centrifuge, carries out centrifugation, obtain filtrate and filter cake, filtrate is urea slip, proceeds to production of urea phosphate technique and carries out Ureaphil raw material production; Filter cake is monoammonium phosphate, and being placed in drying machine, to adopt drying temperature be 80 DEG C, after dry 5min, obtains monoammonium phosphate product.
Sampling analysis, the physical and chemical index that this method obtains product is that monoammonium phosphate total nutrient is greater than 73%, total nitrogen 12.23%, Vanadium Pentoxide in FLAKES are 61.25%, and moisture is 0.52%, PH is 4.4, water-insoluble is 0.095%, fluorochemical is 0.17%, reaches PHOSPHORIC ACID TECH.GRADE ammonium dihydrogen acceptable end product standard completely.
Embodiment 3
A production method for monoammonium phosphate, adopts highly purified Ureaphil and ammonia directly to carry out replacement(metathesis)reaction and prepares monoammonium phosphate, and its reaction equation is:
CO(NH
2)
2·H
3PO
4+NH
3=NH
4H
2PO
4+CO(NH
2)
2
Specifically comprise the following steps:
(1) preparation of Ureaphil solution: the Ureaphil solid that is 98% by purity adds water and measures in dissolving tank, after being warming up to temperature and being 60 DEG C, stirring and dissolving mixes, and to control stirring velocity be 40r/min, obtains Ureaphil solution;
(2) monoammonium phosphate is synthetic: Ureaphil solution is adopted in the synthetic groove of transferpump input, and controlling temperature is 60 DEG C, and the ratio that is 1:1 with the mol ratio of ammonia according to Ureaphil adds ammonia to react; Take to add while stirring ammonia, stirring velocity is 65r/min, and when stirring reaction 40min, detecting pH value is 4.4 o'clock, and reaction terminating obtains monoammonium phosphate slip;
(3) crystallization centrifugation: monoammonium phosphate slip is proceeded to and carries out crystallisation by cooling in crystallizer, while being cooled to 45 DEG C, crystal is proceeded in separating centrifuge and carries out centrifugation, obtain filtrate and filter cake, filtrate is urea slip, proceeds to production of urea phosphate technique and carries out Ureaphil raw material production; Filter cake is monoammonium phosphate, and being placed in drying machine, to adopt drying temperature be 80 DEG C, after dry 4min, obtains monoammonium phosphate product.
Sampling analysis, the physical and chemical index that this method obtains product is that monoammonium phosphate total nutrient is greater than 73%, total nitrogen 12.23%, Vanadium Pentoxide in FLAKES are 61.05%, and moisture is 0.35%, PH is 4.6, water-insoluble is 0.090%, fluorochemical is 0.15%, reaches PHOSPHORIC ACID TECH.GRADE ammonium dihydrogen acceptable end product standard completely.
Embodiment 4
A production method for monoammonium phosphate, adopts highly purified Ureaphil and ammonia directly to carry out replacement(metathesis)reaction and prepares monoammonium phosphate, and its reaction equation is:
CO(NH
2)
2·H
3PO
4+NH
3=NH
4H
2PO
4+CO(NH
2)
2
Specifically comprise the following steps:
(1) preparation of Ureaphil solution: the Ureaphil solid that is 98% by purity adds water and measures in dissolving tank, after being heated to temperature and being 50 DEG C, stirring and dissolving mixes, and to control stirring velocity be 40r/min, obtains Ureaphil solution;
(2) monoammonium phosphate is synthetic: Ureaphil solution is adopted in the synthetic groove of transferpump input, and controlling temperature is 50 DEG C, and the ratio that is 1.01:1 with the mol ratio of ammonia according to Ureaphil adds ammonia to react; Take to add while stirring ammonia, stirring velocity is 62r/min, and when stirring reaction 30min, detecting pH value is 4.3 o'clock, and reaction terminating obtains monoammonium phosphate slip;
(3) crystallization centrifugation: monoammonium phosphate slip is proceeded to and is cooled to crystallize out at 33 DEG C in crystallizer, and crystal is proceeded to and in separating centrifuge, carries out centrifugation, obtain filtrate and filter cake, filtrate is urea slip, proceeds to production of urea phosphate technique and carries out Ureaphil raw material production; Filter cake is monoammonium phosphate, is placed in the dry 3.5min of drying machine, and drying temperature is 80 DEG C, obtains monoammonium phosphate product.
Sampling analysis, the physical and chemical index that this method obtains product is that monoammonium phosphate total nutrient is greater than 73%, total nitrogen 12.10%, Vanadium Pentoxide in FLAKES are 61.11%, and moisture is 0.37%, PH is 4.2, water-insoluble is 0.096%, fluorochemical is 0.19%, reaches PHOSPHORIC ACID TECH.GRADE ammonium dihydrogen acceptable end product standard completely.
Embodiment 5
A production method for monoammonium phosphate, adopts highly purified Ureaphil and ammonia directly to carry out replacement(metathesis)reaction and prepares monoammonium phosphate, and its reaction equation is:
CO(NH
2)
2·H
3PO
4+NH
3=NH
4H
2PO
4+CO(NH
2)
2
Specifically comprise the following steps:
(1) preparation of Ureaphil solution: the Ureaphil solid that is 98% by purity adds water and measures in dissolving tank, after being heated to temperature and being 70 DEG C, stirring and dissolving mixes, and to control stirring velocity be 30-50r/min, obtains Ureaphil solution;
(2) monoammonium phosphate is synthetic: Ureaphil solution is adopted in the synthetic groove of transferpump input, and controlling temperature is 70 DEG C, and the ratio that is 1.02:1 with the mol ratio of ammonia according to Ureaphil adds ammonia to react; Take to add while stirring ammonia, stirring velocity is 68r/min, and when stirring reaction 50min, detecting pH value is 4.5 o'clock, and reaction terminating obtains monoammonium phosphate slip;
(3) crystallization centrifugation: monoammonium phosphate slip is proceeded to and is cooled to crystallize out at 37 DEG C in crystallizer, and crystal is proceeded to and in separating centrifuge, carries out centrifugation, obtain filtrate and filter cake, filtrate is urea slip, proceeds to production of urea phosphate technique and carries out Ureaphil raw material production; Filter cake is monoammonium phosphate, is placed in the dry 4.5min of drying machine, and drying temperature is 80 DEG C, obtains monoammonium phosphate product.
Sampling analysis, the physical and chemical index that this method obtains product is that monoammonium phosphate total nutrient is greater than 73%, and total nitrogen 12.07%, Vanadium Pentoxide in FLAKES are 61.15%, and moisture is 0.48%, PH is 4.4, water-insoluble is 0.093%, fluorochemical is 0.17%.
Embodiment 6
A production method for monoammonium phosphate, adopts highly purified Ureaphil and ammonia directly to carry out replacement(metathesis)reaction and prepares monoammonium phosphate, and its reaction equation is:
CO(NH
2)
2·H
3PO
4+NH
3=NH
4H
2PO
4+CO(NH
2)
2
Specifically comprise the following steps:
(1) preparation of Ureaphil solution: the Ureaphil solid that is 98% by purity adds water and measures in dissolving tank, after rising and being heated to temperature and being 75 DEG C, stirring and dissolving mixes, and to control stirring velocity be 45r/min, obtains Ureaphil solution;
(2) monoammonium phosphate is synthetic: Ureaphil solution is adopted in the synthetic groove of transferpump input, and to control temperature be 75 DEG C, the ratio that is 1.03:1 with the mol ratio of ammonia according to Ureaphil adds ammonia to react; Take to add while stirring ammonia, stirring velocity is 66r/min, and when stirring reaction 48min, detecting pH value is 4.2 o'clock, and reaction terminating obtains monoammonium phosphate slip;
(3) crystallization centrifugation: monoammonium phosphate slip is proceeded to and is cooled to crystallize out at 39 DEG C in crystallizer, and crystal is proceeded to and in separating centrifuge, carries out centrifugation, obtain filtrate and filter cake, filtrate is urea slip, proceeds to production of urea phosphate technique and carries out Ureaphil raw material production; Filter cake is monoammonium phosphate, is placed in drying machine, and drying temperature is 80 DEG C, after dry 3.8min, obtains monoammonium phosphate product.
Sampling analysis, the physical and chemical index that this method obtains product is that monoammonium phosphate total nutrient is greater than 73%, and total nitrogen 12.09%, Vanadium Pentoxide in FLAKES are 61.19%, and moisture is 0.50%, PH is 4.5, water-insoluble is 0.095%, fluorochemical is 0.19%.
Embodiment 7
A production method for monoammonium phosphate, adopts highly purified Ureaphil and ammonia directly to carry out replacement(metathesis)reaction and prepares monoammonium phosphate, and its reaction equation is:
CO(NH
2)
2·H
3PO
4+NH
3=NH
4H
2PO
4+CO(NH
2)
2
Specifically comprise the following steps:
(1) preparation of Ureaphil solution: the Ureaphil solid that is 98% by purity adds water and measures in dissolving tank, after being heated to temperature and being 58 DEG C, stirring and dissolving mixes, and to control stirring velocity be 44r/min, obtains Ureaphil solution;
(2) monoammonium phosphate is synthetic: Ureaphil solution is adopted in the synthetic groove of transferpump input, and controlling temperature is 58 DEG C, and the ratio that is 1.04:1 with the mol ratio of ammonia according to Ureaphil adds ammonia to react; Take to add while stirring ammonia, stirring velocity is 61r/min, and when stirring reaction 51min, detecting pH value is 4.6 o'clock, and reaction terminating obtains monoammonium phosphate slip;
(3) crystallization centrifugation: monoammonium phosphate slip is proceeded to and is cooled to crystallize out at 31 DEG C in crystallizer, and crystal is proceeded to and in separating centrifuge, carries out centrifugation, obtain filtrate and filter cake, filtrate is urea slip, proceeds to production of urea phosphate technique and carries out Ureaphil raw material production; Filter cake is monoammonium phosphate, is placed in drying machine, and drying temperature is 80 DEG C, after dry 4.7min, obtains monoammonium phosphate product.
Sampling analysis, the physical and chemical index that this method obtains product is that monoammonium phosphate total nutrient is greater than 73%, and total nitrogen 12.04%, Vanadium Pentoxide in FLAKES are 61.11%, and moisture is 0.47%, PH is 4.3, water-insoluble is 0.091%, fluorochemical is 0.15%.
It is important to point out at this: above embodiment only limits to understand technical scheme of the present invention is further elaborated; and can not be interpreted as technical scheme of the present invention is done to further restriction; those skilled in the art is in the scope of above-described embodiment and technical scheme of the present invention; that makes does not have outstanding substantive distinguishing features and significant progressive improvement with the present invention, still belongs to protection category of the present invention.
Claims (10)
1. a production method for monoammonium phosphate, is characterized in that: adopt highly purified Ureaphil and ammonia directly to carry out replacement(metathesis)reaction and prepare monoammonium phosphate, its reaction equation is:
CO(NH
2)
2·H
3PO
4+NH
3=NH
4H
2PO
4+CO(NH
2)
2
Control temperature of reaction is 40-80 DEG C, stirring reaction 20-60min, and reaction end pH value is 4.2-4.6, and by crystallisation by cooling, centrifugation and drying step, make monoammonium phosphate product.
2. the production method of monoammonium phosphate as claimed in claim 1, its feature comprises the following steps:
(1) preparation of Ureaphil solution: the Ureaphil solid that is 98% by purity adds water and measures in dissolving tank, after being heated to temperature and being 40-80 DEG C, stirring and dissolving mixes, and to control stirring velocity be 30-50r/min, obtains Ureaphil solution;
(2) monoammonium phosphate is synthetic: Ureaphil solution is adopted in the synthetic groove of transferpump input, and control temperature is 40-80 DEG C, and is (0.99-1.05) according to Ureaphil with the mol ratio of ammonia: 1 ratio adds ammonia to react; Take to add while stirring ammonia, stirring velocity is 60-70r/min, and when stirring reaction 20-60min, when detection pH value is 4.2-4.6, reaction terminating, obtains monoammonium phosphate slip;
(3) crystallization centrifugation: by monoammonium phosphate slip proceed in crystallizer, carry out cooling, be cooled to≤40 DEG C crystal is separated out, and crystal is proceeded to and in separating centrifuge, carries out centrifugation, obtain filtrate and filter cake, filtrate is urea slip, proceeds to production of urea phosphate technique and carries out Ureaphil raw material production; Filter cake is monoammonium phosphate, and being placed in drying machine, to adopt drying temperature be 80 DEG C, after dry 3-5min, obtains monoammonium phosphate product.
3. the production method of monoammonium phosphate as claimed in claim 1 or 2, is characterized in that: described temperature of reaction is 50-70 DEG C.
4. the production method of monoammonium phosphate as claimed in claim 1 or 2, is characterized in that: described temperature of reaction is 60 DEG C.
5. the production method of monoammonium phosphate as claimed in claim 1 or 2, is characterized in that: described reaction end pH value is 4.3-4.5.
6. the production method of monoammonium phosphate as claimed in claim 1 or 2, is characterized in that: described reaction end pH value is 4.4.
7. the production method of monoammonium phosphate as claimed in claim 1 or 2, is characterized in that: the time of described stirring reaction is 30-50min.
8. the production method of monoammonium phosphate as claimed in claim 1 or 2, is characterized in that: the time of described stirring reaction is 40min.
9. the production method of monoammonium phosphate as claimed in claim 2, is characterized in that: in described Ureaphil solution preparation, stirring velocity is 40r/min; During described monoammonium phosphate is synthetic, stirring velocity is 65r/min.
10. the production method of monoammonium phosphate as claimed in claim 1 or 2, it is characterized in that: described monoammonium phosphate product, its physical and chemical index is that monoammonium phosphate total nutrient is greater than 73%, total nitrogen 12.01-12.23%, Vanadium Pentoxide in FLAKES are 61.05-61.25%, and moisture is that 0.35-0.52%, PH are that 4.2-4.6, water-insoluble are that 0.090-0.096%, fluorochemical are 0.15-0.19%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410213411.9A CN104016323A (en) | 2014-05-20 | 2014-05-20 | Production method for monoammonium phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410213411.9A CN104016323A (en) | 2014-05-20 | 2014-05-20 | Production method for monoammonium phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104016323A true CN104016323A (en) | 2014-09-03 |
Family
ID=51433387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410213411.9A Pending CN104016323A (en) | 2014-05-20 | 2014-05-20 | Production method for monoammonium phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104016323A (en) |
Cited By (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261372A (en) * | 2014-09-19 | 2015-01-07 | 贵阳中化开磷化肥有限公司 | Production method for preparing ammonium phosphate and coproducing special fertilizer for mulberry |
| CN104261375A (en) * | 2014-09-19 | 2015-01-07 | 贵阳中化开磷化肥有限公司 | Production method for preparing ammonium dihydrogen phosphate and byproduct special fertilizer for radix scutellariae |
| CN104261374A (en) * | 2014-09-19 | 2015-01-07 | 贵阳中化开磷化肥有限公司 | Production method for preparing ammonium dihydrogen phosphate with special astragalus membranaceus fertilizer as byproduct |
| CN104291287A (en) * | 2014-09-19 | 2015-01-21 | 贵阳中化开磷化肥有限公司 | Producing method for preparing ammonium dihydrogen phosphate byproduct as special fertilizer for white gourd |
| CN104291286A (en) * | 2014-09-19 | 2015-01-21 | 贵阳中化开磷化肥有限公司 | Production for preparing special fertilizer for peas from diammonium hydrogen phosphate byproduct |
| CN104291903A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing dendrobium officinale nutrient fertilizer |
| CN104291289A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and byproduct compound fertilizer specially used for tea tree |
| CN104291290A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and co-producing enhancement fertilizer special for onions |
| CN104291291A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Production method for preparing ammonium dihydrogen phosphate byproduct special fertilizer for pumpkin |
| CN104291288A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing monoammonium phosphate and co-producing special compound fertilizer for potatoes |
| CN104291292A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and co-producing compound fertilizer special for blueberries |
| CN104310361A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing potassium dihydrogen phosphate and preparing special fertilizer for peony as byproduct |
| CN104310331A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium phosphate and preparing special fertilizer for longan as byproduct |
| CN104310341A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special composite fertilizer for grapefruit trees as byproduct |
| CN104310336A (en) * | 2014-09-19 | 2015-01-28 | 贵阳中化开磷化肥有限公司 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for ginger as byproduct |
| CN104310330A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special composite fertilizer for orange trees as byproduct |
| CN104311181A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Preparation method of special fertilizer for honey peaches |
| CN104310342A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special composite fertilizer for cabbage as byproduct |
| CN104310338A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for honeysuckle flower as byproduct |
| CN104310333A (en) * | 2014-09-19 | 2015-01-28 | 贵阳中化开磷化肥有限公司 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for corn as byproduct |
| CN104310337A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for sorghum as byproduct |
| CN104310340A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for beet as byproduct |
| CN104310329A (en) * | 2014-09-19 | 2015-01-28 | 贵阳中化开磷化肥有限公司 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for persimmons as byproduct |
| CN104311183A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Preparation method of special fertilizer for grapes |
| CN104310332A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Preparation method of special fertilizer for Celosia cristata |
| CN104310335A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special composite fertilizer for cucumber as byproduct |
| CN104326448A (en) * | 2014-09-19 | 2015-02-04 | 贵阳中化开磷化肥有限公司 | Production method for preparing ammonium dihydrogen phosphate and by-product special fertilizer for sugarcane |
| CN104326452A (en) * | 2014-09-19 | 2015-02-04 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and by-product special compound fertilizer for pineapple |
| CN104326447A (en) * | 2014-09-19 | 2015-02-04 | 贵阳中化开磷化肥有限公司 | Production method for preparing ammonium dihydrogen phosphate and by-product special fertilizer for cucumber |
| CN104326450A (en) * | 2014-09-19 | 2015-02-04 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and by-product special compound fertilizer for lemon |
| CN104326449A (en) * | 2014-09-19 | 2015-02-04 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and by-product special compound fertilizer for eggplant |
| CN104326453A (en) * | 2014-09-19 | 2015-02-04 | 贵州大学 | Production method for preparing ammonium dihydrogen phosphate and by-product special fertilizer for chive |
| CN104326451A (en) * | 2014-09-19 | 2015-02-04 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and by-product special compound fertilizer for soybeans |
| CN104386660A (en) * | 2014-09-19 | 2015-03-04 | 贵阳中化开磷化肥有限公司 | Production method for special watermelon fertilizer as ammonium dihydrogen phosphate preparation byproduct |
| CN104445121A (en) * | 2014-11-21 | 2015-03-25 | 贵阳中化开磷化肥有限公司 | Mono-ammonium phosphate produced by using wet process phosphoric acid and production method of mono-ammonium phosphate |
| CN107746291A (en) * | 2017-10-24 | 2018-03-02 | 贵州大学 | A kind of method of MAP anti-caking |
| CN110304615A (en) * | 2019-06-10 | 2019-10-08 | 四川大学 | Method for preparing industrial grade ammonium dihydrogen phosphate with high-impurity urea phosphate mother liquor as raw material |
| CN117163927A (en) * | 2023-08-15 | 2023-12-05 | 甘肃瓮福化工有限责任公司 | Method for producing powdery monoammonium phosphate by using urea phosphate mother liquor and phosphoric acid slag slurry |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1191635A (en) * | 1966-07-27 | 1970-05-13 | Marchon Products Ltd | Improvements in the manufacture of Orthophosphates |
| DE1767676A1 (en) * | 1968-06-04 | 1971-09-23 | Kalk Chemische Fabrik Gmbh | Process for the production of low-fluorine phosphates |
| CN101519197A (en) * | 2009-04-08 | 2009-09-02 | 四川川恒化工股份有限公司 | Method for producing type I ammonium polyphosphate with high degree of polymerization |
-
2014
- 2014-05-20 CN CN201410213411.9A patent/CN104016323A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1191635A (en) * | 1966-07-27 | 1970-05-13 | Marchon Products Ltd | Improvements in the manufacture of Orthophosphates |
| DE1767676A1 (en) * | 1968-06-04 | 1971-09-23 | Kalk Chemische Fabrik Gmbh | Process for the production of low-fluorine phosphates |
| CN101519197A (en) * | 2009-04-08 | 2009-09-02 | 四川川恒化工股份有限公司 | Method for producing type I ammonium polyphosphate with high degree of polymerization |
Cited By (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310332A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Preparation method of special fertilizer for Celosia cristata |
| CN104291292A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and co-producing compound fertilizer special for blueberries |
| CN104261374A (en) * | 2014-09-19 | 2015-01-07 | 贵阳中化开磷化肥有限公司 | Production method for preparing ammonium dihydrogen phosphate with special astragalus membranaceus fertilizer as byproduct |
| CN104291287A (en) * | 2014-09-19 | 2015-01-21 | 贵阳中化开磷化肥有限公司 | Producing method for preparing ammonium dihydrogen phosphate byproduct as special fertilizer for white gourd |
| CN104291286A (en) * | 2014-09-19 | 2015-01-21 | 贵阳中化开磷化肥有限公司 | Production for preparing special fertilizer for peas from diammonium hydrogen phosphate byproduct |
| CN104291903A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing dendrobium officinale nutrient fertilizer |
| CN104291289A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and byproduct compound fertilizer specially used for tea tree |
| CN104291290A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and co-producing enhancement fertilizer special for onions |
| CN104291291A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Production method for preparing ammonium dihydrogen phosphate byproduct special fertilizer for pumpkin |
| CN104261372A (en) * | 2014-09-19 | 2015-01-07 | 贵阳中化开磷化肥有限公司 | Production method for preparing ammonium phosphate and coproducing special fertilizer for mulberry |
| CN104311183A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Preparation method of special fertilizer for grapes |
| CN104310361A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing potassium dihydrogen phosphate and preparing special fertilizer for peony as byproduct |
| CN104310331A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium phosphate and preparing special fertilizer for longan as byproduct |
| CN104310341A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special composite fertilizer for grapefruit trees as byproduct |
| CN104310336A (en) * | 2014-09-19 | 2015-01-28 | 贵阳中化开磷化肥有限公司 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for ginger as byproduct |
| CN104310330A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special composite fertilizer for orange trees as byproduct |
| CN104311181A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Preparation method of special fertilizer for honey peaches |
| CN104310342A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special composite fertilizer for cabbage as byproduct |
| CN104310338A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for honeysuckle flower as byproduct |
| CN104310333A (en) * | 2014-09-19 | 2015-01-28 | 贵阳中化开磷化肥有限公司 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for corn as byproduct |
| CN104310337A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for sorghum as byproduct |
| CN104310340A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for beet as byproduct |
| CN104261375A (en) * | 2014-09-19 | 2015-01-07 | 贵阳中化开磷化肥有限公司 | Production method for preparing ammonium dihydrogen phosphate and byproduct special fertilizer for radix scutellariae |
| CN104310329A (en) * | 2014-09-19 | 2015-01-28 | 贵阳中化开磷化肥有限公司 | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for persimmons as byproduct |
| CN104291288A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing monoammonium phosphate and co-producing special compound fertilizer for potatoes |
| CN104310335A (en) * | 2014-09-19 | 2015-01-28 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special composite fertilizer for cucumber as byproduct |
| CN104326448A (en) * | 2014-09-19 | 2015-02-04 | 贵阳中化开磷化肥有限公司 | Production method for preparing ammonium dihydrogen phosphate and by-product special fertilizer for sugarcane |
| CN104326452A (en) * | 2014-09-19 | 2015-02-04 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and by-product special compound fertilizer for pineapple |
| CN104326447A (en) * | 2014-09-19 | 2015-02-04 | 贵阳中化开磷化肥有限公司 | Production method for preparing ammonium dihydrogen phosphate and by-product special fertilizer for cucumber |
| CN104326450A (en) * | 2014-09-19 | 2015-02-04 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and by-product special compound fertilizer for lemon |
| CN104326449A (en) * | 2014-09-19 | 2015-02-04 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and by-product special compound fertilizer for eggplant |
| CN104326453A (en) * | 2014-09-19 | 2015-02-04 | 贵州大学 | Production method for preparing ammonium dihydrogen phosphate and by-product special fertilizer for chive |
| CN104326451A (en) * | 2014-09-19 | 2015-02-04 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and by-product special compound fertilizer for soybeans |
| CN104386660A (en) * | 2014-09-19 | 2015-03-04 | 贵阳中化开磷化肥有限公司 | Production method for special watermelon fertilizer as ammonium dihydrogen phosphate preparation byproduct |
| CN104261375B (en) * | 2014-09-19 | 2017-04-19 | 贵阳开磷化肥有限公司 | Production method for preparing ammonium dihydrogen phosphate and byproduct special fertilizer for radix scutellariae |
| CN104261374B (en) * | 2014-09-19 | 2016-04-27 | 贵州开磷集团股份有限公司 | A kind of production method preparing primary ammonium phosphate by-product Radix Astragali special fertilizer |
| CN104291290B (en) * | 2014-09-19 | 2016-07-06 | 贵州大学 | A kind of method preparing the special enhancing fertilizer of ammonium dihydrogen phosphate co-production Bulbus Allii Cepae |
| CN104310331B (en) * | 2014-09-19 | 2016-07-06 | 贵州大学 | A kind of production method preparing ammonium phosphate by-product Arillus Longan special fertilizer |
| CN104291286B (en) * | 2014-09-19 | 2016-08-17 | 贵州开磷集团股份有限公司 | A kind of production method preparing diammonium phosphate by-product Semen Pisi sativi special fertilizer |
| CN104310337B (en) * | 2014-09-19 | 2016-08-31 | 贵州大学 | A kind of method preparing ammonium dihydrogen phosphate by-product Chinese sorghum special fertilizer |
| CN104310333B (en) * | 2014-09-19 | 2016-09-07 | 贵州开磷集团股份有限公司 | A kind of production method preparing ammonium dihydrogen phosphate by-product corn fertilizer |
| CN104310342B (en) * | 2014-09-19 | 2017-02-08 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special composite fertilizer for cabbage as byproduct |
| CN104310335B (en) * | 2014-09-19 | 2017-02-08 | 贵州大学 | Method for preparing ammonium dihydrogen phosphate and preparing special composite fertilizer for cucumber as byproduct |
| CN104445121B (en) * | 2014-11-21 | 2017-02-08 | 贵州开磷集团股份有限公司 | Mono-ammonium phosphate produced by using wet process phosphoric acid and production method of mono-ammonium phosphate |
| CN104445121A (en) * | 2014-11-21 | 2015-03-25 | 贵阳中化开磷化肥有限公司 | Mono-ammonium phosphate produced by using wet process phosphoric acid and production method of mono-ammonium phosphate |
| CN107746291A (en) * | 2017-10-24 | 2018-03-02 | 贵州大学 | A kind of method of MAP anti-caking |
| CN110304615A (en) * | 2019-06-10 | 2019-10-08 | 四川大学 | Method for preparing industrial grade ammonium dihydrogen phosphate with high-impurity urea phosphate mother liquor as raw material |
| CN117163927A (en) * | 2023-08-15 | 2023-12-05 | 甘肃瓮福化工有限责任公司 | Method for producing powdery monoammonium phosphate by using urea phosphate mother liquor and phosphoric acid slag slurry |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104016323A (en) | Production method for monoammonium phosphate | |
| CN104016322A (en) | Production method for diammonium hydrogen phosphate | |
| CN103803518A (en) | Method for preparing monopotassium phosphate by using wet-process phosphoric acid | |
| CN102126738B (en) | Method for producing nitrophosphate fertilizer and co-producing gypsum through decomposing phosphorite with nitric acid | |
| CN103613083B (en) | A kind of phosphoric acid by wet process and high-purity phosphoric acid are in conjunction with the method for manufacture level monoammonium phosphate | |
| CN104003362A (en) | Production method of dipotassium phosphate | |
| CN102992284B (en) | High-magnesium phosphorite de-magging method with by-product magnesium ammonium phosphate | |
| CN103787293A (en) | Method for preparing sodium dihydrogen phosphate by utilizing phosphoric acid by wet process | |
| CN101857210B (en) | Method for producing industrial grade diammonium phosphate from wet-process phosphoric acid | |
| CN111086977B (en) | Method for preparing MCP and MDCP (Madin-Darby Canine phosphate) by using raffinate acid | |
| CN107180999B (en) | A kind of method of comprehensive utilization of waste lithium iron phosphate material | |
| CN105600763B (en) | A kind of method that fluoride salt method of purification produces industrial monoammonium phosphate | |
| CN104016324A (en) | Production method for tripotassium phosphate | |
| CN104445121B (en) | Mono-ammonium phosphate produced by using wet process phosphoric acid and production method of mono-ammonium phosphate | |
| CN103213960A (en) | Method for producing phosphoric acid by decomposing low-grade phosphate rock with wet-process phosphoric acid | |
| CN102126742B (en) | Method for producing chloride-based compound fertilizer and co-producing gypsum through decomposing phosphorite with hydrochloric acid | |
| CN102126740A (en) | Method for producing byproduct gypsum of niter-sulfur-based compound fertilizer by decomposing phosphorite with nitric acid | |
| CN103159195A (en) | Method for preparing potassium dihydrogen phosphate from low-concentration wet-process phosphoric acid | |
| CN103771378A (en) | Method for reversely extracting and co-production of industrial-grade phosphate by using phosphate mother liquor for wet-method purification phosphoric acid | |
| CN102659454B (en) | A method for preparing diammonium phosphate and slow-release fertilizer from high-impurity phosphate rock | |
| CN104016326A (en) | Production method for calcium hydrogen phosphate | |
| CN104557721A (en) | Method for producing 5,5-dimethylhydantoin | |
| CN103539487B (en) | Produce the method for phosphorus ammonium | |
| CN101798074B (en) | Method for using yellow phosphorus-refined dearsenization waste liquid | |
| CN100528743C (en) | Process for preparing high purity phosphoric acid-ammonium by titanium dioxide waste acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140903 |