CN107857604A - A kind of method for handling hydrochloric acid method production calcium monohydrogen phosphate waste water - Google Patents
A kind of method for handling hydrochloric acid method production calcium monohydrogen phosphate waste water Download PDFInfo
- Publication number
- CN107857604A CN107857604A CN201711151220.4A CN201711151220A CN107857604A CN 107857604 A CN107857604 A CN 107857604A CN 201711151220 A CN201711151220 A CN 201711151220A CN 107857604 A CN107857604 A CN 107857604A
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- CN
- China
- Prior art keywords
- waste water
- polyacrylamide
- calcium hydroxide
- ammonium chloride
- mixed liquor
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- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
- C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
- C05B11/12—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using aqueous hydrochloric acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
Abstract
The present invention relates to a kind of method for handling hydrochloric acid method production calcium monohydrogen phosphate waste water, comprise the following steps：1) produced to hydrochloric acid method in calcium monohydrogen phosphate waste water and be passed through ammoniacal liquor, mixed liquor is obtained after reaction；2) flocculant is added into the mixed liquor, obtains calcium hydroxide flocculation sediment, and sediment is delivered to production system and recycled, obtain removing the waste water of calcium hydroxide；3) dried after the waste water of the removal calcium hydroxide is concentrated, obtain finished product ammonium chloride.Calcium chloride transformation in waste water is calcium hydroxide and ammonium chloride by method of the present invention, and calcium hydroxide can continue to participate in the reaction of next step as raw material, and ammonium chloride is a kind of industrial chemicals with high added value, realizes the Comprehensive utilization to waste water.
Description
Technical field
The present invention relates in sulphur dioxide of phosphor chemical industry, the comprehensive utilization of sewage is specially produced during hydrochloric acid method production phosphate fertilizer.
Background technology
The yield ratio of hydrochloric acid method production phosphate fertilizer technique, calcium monohydrogen phosphate and 20% calcium chloride wastewater is 1:1, due to calcium chloride
The yield of waste water is big, concentration is low, and domestic pharmaceutical industry industry same device all using re-dry is first concentrated, eventually becomes calcium chloride substantially
Technique solve the problems, such as contaminated wastewater.But the added value of calcium chloride is low, and market demand is small, most of producers are all
To reduce the yield of calcium monohydrogen phosphate to solve the problems, such as that waste solution of calcium chloride is excessive, this traditional production technology ultimately limit
The yield of phosphate fertilizer.Great potential in terms of based on wastewater utilization and environmental protection considers that the present invention produces to calcium monohydrogen phosphate
During caused waste water comprehensively utilized.
The content of the invention
It is an object of the invention to provide a kind of method for handling hydrochloric acid method production calcium monohydrogen phosphate waste water, comprise the following steps：
1) produced to hydrochloric acid method in calcium monohydrogen phosphate waste water and be passed through ammoniacal liquor, mixed liquor is obtained after reaction；
2) flocculant is added into the mixed liquor, obtains calcium hydroxide flocculation sediment, and sediment is delivered to production system and followed
Ring utilizes, and obtains removing the waste water of calcium hydroxide；
3) dried after the waste water of the removal calcium hydroxide is concentrated, obtain finished product ammonium chloride.
The concentration of the ammoniacal liquor is 25~35%, and the volume ratio of the waste water and ammoniacal liquor is 1:1.5~2.5.Select this
Concentration and volume can make reaction more thoroughly, conversion ratio it is higher；The speed that is passed through of the ammoniacal liquor is 3.5~4m3/h, is selected this
Speed makes course of reaction easily controllable.
During waste water and the ammoniacal liquor reaction, the mixing speed for controlling reactive tank is 12~15 revs/min.Stirring
The power of agitator of device will ensure that reaction liquid is reacted under turbulence state, ensure Reynolds number 1.5 × 104~2.0 ×
104。
The reaction time of the waste water and ammoniacal liquor is 20~30min.The zequin of this time is that ammoniacal liquor has led to it
Afterwards.Select this reaction time both to have realized corresponsively progress completely, will not also be lost time because the reaction time is long.
The flocculant is the polyacrylamide of molecular weight 5,000,000~6,000,000；The addition of the polyacrylamide is hydrogen
The 3~5% of calcium oxide total amount.
During the polyacrylamide flocculation, pH10~11 of the mixed liquor are adjusted.Under the conditions of this pH,
The high conversion rate of reaction, transformation time are shorter, impurity is less in gained precipitation.
The addition manner of the polyacrylamide be polyacrylamide first with water be diluted to percent by volume 55~
60%, it is continuously added to by measuring pump with 0.16~0.22m3/h to reactor, polyacrylamide dilution needs in adition process
Continuously stir.So can more uniformly it add, and course of reaction is more controllable.
After the ammonium chloride is concentrated to 40~50%, ammonium chloride powder is made by spray drying.
Method of the present invention, preferably includes following steps：
1) produced to hydrochloric acid method in calcium monohydrogen phosphate waste water and be passed through ammoniacal liquor, mixed liquor is obtained after reaction；The concentration of the ammoniacal liquor be 25~
35%, the volume ratio of the waste water and ammoniacal liquor is 1:1.5~2.5；The speed that is passed through of ammoniacal liquor is 3.5~4m3/ in course of reaction
H, the mixing speed in reactor is 12~15 revs/min, and the reaction time of the waste water and ammoniacal liquor is 20~30min；
2) flocculant is added into the mixed liquor, obtains calcium hydroxide flocculation sediment, and sediment is delivered to production system and followed
Ring utilizes, and obtains removing the waste water of calcium hydroxide；The flocculant is the polyacrylamide of molecular weight 5,000,000~6,000,000, is added
Dosage is the 3~5% of calcium hydroxide total amount；During the polyacrylamide flocculation, the reacted mixed liquor is adjusted
PH10~11；In the adding procedure of the polyacrylamide, polyacrylamide is first diluted to percent by volume with water
55~60% mixed liquor, it is continuously added to 0.16~0.22m3/h speed into reactor, to polypropylene in adition process
The dilute mixed liquor of acid amides is continuously stirred；
3) dried after the waste water of the removal calcium hydroxide is concentrated, obtain finished product ammonium chloride, the ammonium chloride is concentrated to
After 40~50%, ammonium chloride powder is made by spray drying.
Method of the present invention, has the advantages that：
1) present invention is by selecting optimal ammonia concn, dosage and reaction condition so that calcium ion in waste water fully with
Ammoniacal liquor reacts, and realizes being kept completely separate for calcium ion and chlorion；
2) by selecting suitable flocculant and addition concentration to flocculant, addition manner optimize, generation will be reacted
Calcium hydroxide precipitates completely, obtains more pure ammonium chloride, the quality point of ammonium chloride in the final dried ammonium chloride of gained
Number is >=99%.
In a word, the calcium chloride transformation in waste water is calcium hydroxide and ammonium chloride by method of the present invention, calcium hydroxide
The reaction of next step can be continued to participate in as raw material, ammonium chloride is a kind of industrial chemicals with high added value, is realized to useless
The Comprehensive of water utilizes.
Embodiment
The waste water being related in embodiments of the invention is that hydrochloric acid method is produced caused by phosphate fertilizer technical process, wherein chlorination
The mass percent of calcium is 20%, also water-insoluble 2%, calcium containing compound 0.1%.
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
The present embodiment is related to the method for comprehensive utilization of waste water in calcium monohydrogen phosphate production process, comprises the following steps：
1) in calcium monohydrogen phosphate production process caused by containing 20% calcium chloride wastewater and ammoniacal liquor containing 30% ammonia according to volume ratio 1:
1.5 ratio is reacted in reactive tank, and the speed that is passed through that ammoniacal liquor is controlled in course of reaction is 3.5m3/h, in reactive tank
Mixing speed is 12 revs/min, and the power of agitator of agitator will ensure that reaction liquid is reacted under turbulence state, is ensured
1.5 × 104~2.0 × 104, the reaction time controlled at 20 minutes Reynolds number, generated mixing liquid.
2) mixed liquor from reactive tank enters subsider, the pH value 10~11 of mixed liquor is adjusted with 30% ammoniacal liquor, then add
Enter flocculant polyacrylamide, the molecular weight of polyacrylamide is 500~6,000,000, and in adding procedure, polyacrylamide is first used
Water is diluted to the mixed liquor of percent by volume 55%, then is connected by measuring pump into subsider with 0.16m3/h speed
Continuous to add, the dilute mixed liquor of polyacrylamide need to continuously stir in adition process, and the total amount of adding of polyacrylamide is hydroxide
The 3% of calcium total amount.By calcium hydroxide calcium slurry flocculation to sedimentation trench bottom, conveying is starched by calcium and is pumped to calcium monohydrogen phosphate production system
System recycles, and upper clear supernate enters clarified solution storage tank.
3) concentration is concentrated to 45% by the ammonium chloride weak solution from clarified solution delivery pump by triple effect evaporation by 15%,
Ammonium chloride powder-product is made eventually through ammonium chloride spray drying system, the matter of ammonium chloride in the ammonium chloride powder product
It is 99.5% to measure percentage.
Embodiment 2
1) ammoniacal liquor caused by calcium monohydrogen phosphate production containing 20% calcium chloride wastewater and containing 30% ammonia is according to volume ratio 1:5 ratio
Reacted in reactive tank, the speed that is passed through that ammoniacal liquor is controlled in course of reaction is 3.8m3/h, the mixing speed in reactive tank
For 13 revs/min, the power of agitator of agitator will ensure that reaction liquid is reacted under turbulence state, ensure that Reynolds number exists
1.5 × 104~2.0 × 104, the reaction time was controlled at 25 minutes, generated mixing liquid.
2) mixed liquor from reactive tank enters subsider, and the pH value 10.5 of mixed liquor is adjusted with 30% ammoniacal liquor, is added
Flocculant polyacrylamide, the molecular weight of polyacrylamide is 500~6,000,000, and in adding procedure, polyacrylamide first uses water
Be diluted to the mixed liquor of percent by volume 60%, then by measuring pump with 0.22m3/h speed into subsider it is continuous
Add, the dilute mixed liquor of polyacrylamide need to continuously stir in adition process, and the total amount of adding of polyacrylamide is calcium hydroxide
The 4% of total amount.By calcium hydroxide calcium slurry flocculation to sedimentation trench bottom, conveying is starched by calcium and is pumped to calcium monohydrogen phosphate production system
Recycle, upper clear supernate enters clarified solution storage tank.
3) concentration is concentrated to 40% by the ammonium chloride weak solution from clarified solution delivery pump by triple effect evaporation by 15%,
Ammonium chloride powder-product is made eventually through ammonium chloride spray drying system, the matter of ammonium chloride in the ammonium chloride powder product
It is 99.3% to measure percentage.
Embodiment 3
1) ammoniacal liquor caused by calcium monohydrogen phosphate production containing 20% calcium chloride wastewater and containing 30% ammonia is according to volume ratio 1:2.5 ratio
Example is reacted in reactive tank, and the speed that is passed through that ammoniacal liquor is controlled in course of reaction is 4m3/h, the mixing speed in reactive tank
For 15 revs/min, the power of agitator of agitator will ensure that reaction liquid is reacted under turbulence state, ensure that Reynolds number exists
1.5 × 104~2.0 × 104, the reaction time was controlled at 30 minutes, generated mixing liquid.
2) mixed liquor from reactive tank enters subsider, and the pH value 11 of mixed liquor is adjusted with 30% ammoniacal liquor, adds wadding
Solidifying agent polyacrylamide, the molecular weight of polyacrylamide is 500~6,000,000, and in adding procedure, polyacrylamide is first entered with water
Row is diluted to the mixed liquor of percent by volume 58%, then is continuously added into subsider with 0.2m3/h speed by measuring pump
Enter, the dilute mixed liquor of polyacrylamide need to continuously stir in adition process, and the total amount of adding of polyacrylamide is total for calcium hydroxide
The 5% of amount.By calcium hydroxide calcium slurry flocculation to sedimentation trench bottom, calcium monohydrogen phosphate production system is pumped to by calcium slurry conveying and followed
Ring utilizes, and upper clear supernate enters clarified solution storage tank.
3) concentration is concentrated to 45% by the ammonium chloride weak solution from clarified solution delivery pump by triple effect evaporation by 15%,
Ammonium chloride powder-product is made eventually through ammonium chloride spray drying system, the matter of ammonium chloride in the ammonium chloride powder product
It is 99.1% to measure percentage.
Comparative example 1
Compared with embodiment 1, difference is, the concentration of the ammoniacal liquor is 35%, and the reaction time of ammoniacal liquor and waste water is 12min,
The mass percent of ammonium chloride is 95% in gained ammonium chloride powder product.
Comparative example 2
Compared with embodiment 1, difference is, the speed that is passed through of the ammoniacal liquor is 2.8m3/h, the mixing speed in course of reaction
For 20 revs/min, the mass percent of ammonium chloride is 93% in gained ammonium chloride powder product.
Comparative example 3
Compared with embodiment 1, difference is, does not use polyacrylamide, calcium hydroxide is settled using aluminum sulfate, institute
The mass percent for obtaining ammonium chloride in ammonium chloride powder product is 90%.
Comparative example 4
Compared with embodiment 1, difference is, the addition of polyacrylamide is 2%, chlorination in gained ammonium chloride powder product
The mass percent of ammonium is 92%.
Although above the present invention is made to retouch in detail with general explanation, embodiment and experiment
State, but on the basis of the present invention, it can be made some modifications or improvements, this is aobvious and easy to those skilled in the art
See.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, application claims guarantor is belonged to
The scope of shield.
Claims (9)
- A kind of 1. method for handling hydrochloric acid method production calcium monohydrogen phosphate waste water, it is characterised in that comprise the following steps：1) produced to hydrochloric acid method in the waste water of calcium monohydrogen phosphate and be passed through ammoniacal liquor, mixed liquor is obtained after reaction；2) flocculant is added into the mixed liquor, by calcium hydroxide flocculation sediment, and sediment is delivered to production system and followed Ring utilizes, and obtains removing the waste water of calcium hydroxide；3) dried after the waste water of the removal calcium hydroxide is concentrated, obtain finished product ammonium chloride.
- 2. according to the method for claim 1, it is characterised in that the concentration of the ammoniacal liquor be 25~35%, the waste water with The volume ratio of ammoniacal liquor is 1:1.5~2.5.
- 3. method according to claim 1 or 2, it is characterised in that in course of reaction ammoniacal liquor be passed through speed for 3.5~ 4m3/h, the mixing speed in reactor is 12~15 revs/min, and the power of agitator of agitator will ensure reaction liquid in turbulent flow Reacted under state, Reynolds number is 1.5 × 104~2.0 × 104, reaction time of the waste water and ammoniacal liquor for 20~ 30min。
- 4. according to the method for claim 1, it is characterised in that the flocculant is the poly- of molecular weight 5,000,000~6,000,000 Acrylamide.
- 5. the method according to claim 1 or 4, it is characterised in that the addition of the polyacrylamide is calcium hydroxide The 3~5% of total amount.
- 6. according to the method for claim 5, it is characterised in that during the polyacrylamide flocculation, described in regulation PH10~11 of reacted mixed liquor.
- 7. according to the method for claim 6, it is characterised in that in the adding procedure of the polyacrylamide, polyacrylamide Amine is first diluted to the mixed liquor of percent by volume 55~60% with water, with 0.16~0.22m3/h speed to reactor In be continuously added to, polyacrylamide mixed liquor is continuously stirred in adition process.
- 8. according to the method for claim 1, it is characterised in that after the ammonium chloride is concentrated to 40~50%, pass through spraying Ammonium chloride powder is made in drying.
- 9. according to the method for claim 1, it is characterised in that comprise the following steps：1) produced to hydrochloric acid method in calcium monohydrogen phosphate waste water and be passed through ammoniacal liquor, mixed liquor is obtained after reaction；The concentration of the ammoniacal liquor be 25~ 35%, the volume ratio of the waste water and ammoniacal liquor is 1:1.5~2.5；The speed that is passed through of ammoniacal liquor is 3.5~4m3/ in course of reaction H, the mixing speed in reactor is 12~15 revs/min, and the power of agitator of agitator will ensure reaction liquid in turbulence state Under reacted, for Reynolds number 1.5 × 104~2.0 × 104, the reaction time of the waste water and ammoniacal liquor is 20~30min；2) flocculant is added into the mixed liquor, obtains calcium hydroxide flocculation sediment, and sediment is delivered to production system and followed Ring utilizes, and obtains removing the waste water of calcium hydroxide；The flocculant is the polyacrylamide of molecular weight 5,000,000~6,000,000, is added Dosage is the 3~5% of calcium hydroxide total amount；During the polyacrylamide flocculation, the reacted mixed liquor is adjusted PH10~11；In the adding procedure of the polyacrylamide, polyacrylamide is first diluted to percent by volume with water 55~60% mixed liquor, it is continuously added to 0.16~0.22m3/h speed into reactor, to polypropylene in adition process The dilute mixed liquor of acid amides is continuously stirred；3) dried after the waste water of the removal calcium hydroxide is concentrated, obtain finished product ammonium chloride, the ammonium chloride is concentrated to After 40~50%, ammonium chloride powder is made by spray drying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711151220.4A CN107857604A (en) | 2017-11-18 | 2017-11-18 | A kind of method for handling hydrochloric acid method production calcium monohydrogen phosphate waste water |
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| CN201711151220.4A CN107857604A (en) | 2017-11-18 | 2017-11-18 | A kind of method for handling hydrochloric acid method production calcium monohydrogen phosphate waste water |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445755A (en) * | 2014-10-28 | 2015-03-25 | 中国科学院过程工程研究所 | Method for resourceful treatment of ammonia chloride wastewaters |
| CN107226568A (en) * | 2016-03-25 | 2017-10-03 | 中昊晨光化工研究院有限公司 | It is a kind of to handle the method that hydrochloric acid method produces calcium monohydrogen phosphate waste water |
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- 2017-11-18 CN CN201711151220.4A patent/CN107857604A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445755A (en) * | 2014-10-28 | 2015-03-25 | 中国科学院过程工程研究所 | Method for resourceful treatment of ammonia chloride wastewaters |
| CN107226568A (en) * | 2016-03-25 | 2017-10-03 | 中昊晨光化工研究院有限公司 | It is a kind of to handle the method that hydrochloric acid method produces calcium monohydrogen phosphate waste water |
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Application publication date: 20180330 |
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