CN103539092A - Preparation and applications of wet-process strong phosphoric acid desulfurizing agent - Google Patents
Preparation and applications of wet-process strong phosphoric acid desulfurizing agent Download PDFInfo
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- CN103539092A CN103539092A CN201310449841.6A CN201310449841A CN103539092A CN 103539092 A CN103539092 A CN 103539092A CN 201310449841 A CN201310449841 A CN 201310449841A CN 103539092 A CN103539092 A CN 103539092A
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- phosphoric acid
- sweetening agent
- desulfurizing agent
- milk
- lime
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Abstract
The invention discloses a preparation and applications of a wet-process strong phosphoric acid desulfurizing agent. The desulfurizing agent comprises the following components in percentage by mass: 65%-80% of CaHPO4.2H2O.CaSO4, 3%-10% of Ca(H2PO4)2.H2O, 1%-10% of CaF2, 2%-10% of CaSO4.2H2O, 0.5%-5% of CaCO3, and the balance of impurities. The desulfurizing agent is prepared by the steps of: adding a certain amount of calcium hydroxide at normal temperature according to the quantity of fluorine in waste water, stirring for reacting, filtering, adding calcium hydroxide into a filtrate, drying the secondary filter cake to obtain the desulfurizing agent; mixing the desulfurizing agent and phosphoric acid with mass percentage concentration of P2O5 being15%-30% according to the mass of sulfate radical, forming slurry to be added into phosphoric acid with 40-54% ofP2O5 and 2.5%-6.5% of SO4<2->, carrying out desulfurization reaction at 50-80DEG C, and desulfurizing. The preparation has the characteristics of designing the treatment technology, changing waste water treatment process into a process of preparing a desulfurizing agent mainly containing phosphorus containing calcium salt precipitate, the desulfurizing agent can be used for removing sulfate radicals out of the wet-process strong phosphoric acid, is good in desulfurization effect, the phosphorous resource in the waste water can also be recovered, and the economic benefits and environment-friendly benefits are remarkable.
Description
Technical field
the present invention relates to phosphorous chemical industry field, relate in particular to a kind of preparation and application of wet method strong phosphoric acid sweetening agent.
Background technology
in the process for preparing wet phosphoric acid by dihydrate that China generally adopts, sulfuric acid must be suitably excessive, just can obtain being easy to two water thing gypsum crystallizations of filtration, in the phosphoric acid by wet process therefore obtaining, has a certain amount of sulfate radical.At present, wet phosphoric acid purifying technique generally adopts ground phosphate rock to remove the sulfate radical in strong phosphoric acid at pretreatment stage, use ground phosphate rock to remove sulfate radical, have that phosphorus ore is must be excessive more, phosphorus ore decomposes not exclusively, cross in filter residue that phosphorus content is higher, phosphorus ore decomposes and cause slowly the shortcomings such as the reaction times is long.
present situation based on current wet method strong phosphoric acid pretreatment desulfurizing, need to develop a kind of sweetening effectiveness good, and the obvious sweetening agent of economic benefit and environmental benefit replaces ground phosphate rock.
Summary of the invention
main purpose of the present invention is to overcome above-mentioned shortcoming, and a kind of wet method strong phosphoric acid sweetening agent methods for making and using same is provided, to replace traditional ground phosphate rock sweetening agent.
for achieving the above object, the present invention adopts following technical scheme: the preparation of a kind of wet method strong phosphoric acid sweetening agent and application, and a kind of wet method strong phosphoric acid sweetening agent wherein, its component and quality percentage composition are:
caHPO
4
2H
2
o 65%～80%, Ca (H
2
pO
4
)
2
h
2
o 3%～10%, CaF
2
1%～10%, CaSO
4
2H
2
o 2%～10%, CaCO
3
0.5%～5%, other is impurity; The preparation method of above-mentioned sweetening agent, its step is as follows: (following %, except special instruction, is mass percent)
1. at phosphorus content, be 0.4%～2.4%, fluorine content is 0.4%～2.0%, SO
4
2-
content is that in 0.3%～0.8% waste water, to add CaO mass percentage concentration be 10%～25% milk of lime, milk of lime add-on is that in milk of lime, CaO is 1.5～2.4 times of fluorine in wastewater quality, stirring reaction 0.5～1h, then filters at normal temperatures, is purified liquid and solid phase precipitation slag;
1. in gained scavenging solution, adding CaO concentration is 10%～25% milk of lime, milk of lime add-on is that in milk of lime, CaO is 1.4～1.8 times of phosphorus quality in scavenging solution, stirring reaction 0.5～1.5h at normal temperatures, then filter, filter cake after drying, obtain sweetening agent, filtrate is returned to phosphoric acid production system as process water and is used after purifying.
above-mentioned sweetening agent removes being applied as of sulfate radical in wet method strong phosphoric acid: by sweetening agent and P
2
o
5
be that 15%～30% phosphoric acid mixes 1:1.5～3 in mass ratio, form slip, gained slip is joined to P
2
o
5
be 40%～54%, SO
4
2-
be at 50～80 ℃, to carry out desulphurization reaction 1～3h in 2.5%～6.5% phosphoric acid, doctor solution consumption is SO in phosphoric acid
4
2-
0.9～1.1 times of stoichiometric ratio.
preparation method's step of above-mentioned sweetening agent 2. in filter cake can moistly directly obtain the sweetening agent containing 30%～50% free-water, should be containing the sweetening agent of free-water when the application and P
2
o
5
be that 20%～54% phosphoric acid mixes 1:0.8～2 in mass ratio, form slip, gained slip is joined to P
2
o
5
be 40%～54%, SO
4
2-
be at 50～80 ℃, to carry out desulphurization reaction 1～3h in 2.5%～6.5% phosphoric acid, doctor solution consumption is SO in phosphoric acid
4
2-
0.9～1.1 times of stoichiometric ratio.
the main chemical reactions formula relating in the preparation of above-mentioned sweetening agent is as follows.
?2
→?CaF
2
↓+?2H
2
O
Ca(OH)
2?
+?2H
3
PO
4?
→?Ca(H
2
PO
4
)
2
·H
2
O+?H
2
O
Ca(OH)
2?
+?H
3
PO
4?
→?CaHPO
4
·2H
2
O
Ca(OH)
2?
+?Ca(H
2
PO
4
)
2
·H
2
O+?H
2
O→?2CaHPO
4
·2H
2
O
Ca(OH)
2?
+?H
2
SO
4
→CaSO
4
·2H
2
O
the main chemical reactions formula relating in the application of above-mentioned sweetening agent is as follows.
4
·2H
2
O?+?H
3
PO
4
→Ca(H
2
PO
4
)
2
·H
2
O+?H
2
O
CaCO
3?
+?2H
3
PO
4?
→Ca(H
2
PO
4
)
2
·H
2
O?+?CO
2
↑
Ca(H
2
PO
4
)
2
·H
2
O+H
2
SO
4
→CaSO
4
·0.5H
2
O↓+2H
3
PO
4?
+?0.5H
2
O
CaHPO
4
·2H
2
O?+H
2
SO
4
→CaSO
4
·0.5H
2
O↓+H
3
PO
4
+?1.5H
2
O
tool of the present invention has the following advantages:
(1) cost is low, and environmental benefit is good.The present invention utilizes the composition characteristic of waste water, designing treatment technique, the process of processing waste water is become to preparation and take phosphorous calcium precipitation thing as main sweetening agent process, technique only consumes part lime, just phosphor resource important in waste water is transferred in sweetening agent, finally when for the desulfurization of wet method strong phosphoric acid, this phosphor resource is transferred to phosphoric acid, process costs is low, and economic benefit and environmental benefit are remarkable.
(2) desulfurization is rapid, the reaction times is short.Because sweetening agent is when the desulfurization of wet method strong phosphoric acid is applied, first sweetening agent being mixed to form to slip with a small amount of phosphoric acid makes secondary calcium phosphate in sweetening agent be converted into monocalcium phosphate, while joining so again in wet method strong phosphoric acid desulfurization, react rapider, thereby desulfurization rapidly, thoroughly, shortened the reaction times of technique, sweetening effectiveness is good.
(3) reclamation of phosphorus resource rate is high.Because sweetening agent is when the desulfurization of wet method strong phosphoric acid is applied, sweetening agent easily reacts, decomposes completely, thereby sweetening agent need not be more excessive, and the gypsum deposition slag of generation residual phosphorus content after washing is very low, the phosphor resource overwhelming majority in sweetening agent enters in phosphoric acid, reaches very high reclamation of phosphorus resource rate.
in sum, with the comparison of ground phosphate rock sweetening agent, use sweetening agent desulfurization of the present invention rapider, reaction times is short, because the little phosphorous recovery that makes of phosphorus residual quantity in the complete filter residue of decomposition is high, and sweetening agent makes with low cost from wastewater treatment process, reclaimed the phosphor resource in waste water, economic benefit and environmental benefit are remarkable.
Embodiment
specific embodiment of the invention process is as follows.
the present invention be take waste water as raw material, and its component of sweetening agent and the quality percentage composition that adopt milk of lime processing waste water to prepare are:
caHPO
4
2H
2
o:65%～80%, Ca (H
2
pO
4
)
2
h
2
o:3%～10%, CaF
2
: 1%～10%, CaSO
4
2H
2
o:2%～10%, CaCO
3
: 0.5%～5%, other is impurity.
the preparation method of sweetening agent is:
(1) at phosphorus content, be 0.4%～2.4%, fluorine content is 0.4%～2.0%, SO
4
2-
content is that in 0.3%～0.8% waste water, to add CaO concentration be 10%～25% milk of lime, milk of lime add-on is that in milk of lime, CaO is 1.5～2.4 times of fluorine in wastewater quality, stirring reaction 0.5～1h, then filters at normal temperatures, is purified liquid and solid phase precipitation slag;
(2) in gained scavenging solution, adding CaO concentration is 10%～25% milk of lime, milk of lime add-on is that in milk of lime, CaO is 1.4～1.8 times of phosphorus quality in scavenging solution, stirring reaction 0.5～1.5h at normal temperatures, then filter, filter cake drying obtains sweetening agent, and filtrate is returned to phosphoric acid production system as process water and used after purifying.
sweetening agent removes being applied as of sulfate radical in wet method strong phosphoric acid: by sweetening agent and P
2
o
5
be that 15%～30% phosphoric acid mixes 1:1.5～3 in mass ratio, form slip, gained slip is joined to P
2
o
5
be 40%～54%, SO
4
2-
be at 50～80 ℃, to carry out desulphurization reaction 1～3h in 2.5%～6.5% phosphoric acid, doctor solution consumption is SO in phosphoric acid
4
2-
0.9～1.1 times of stoichiometric ratio.
in the preparation method of sweetening agent, filter cake can moistly directly obtain the sweetening agent containing 30%～50% free-water, should be containing sweetening agent of free-water when the application and P
2
o
5
be that 20%～54% phosphoric acid mixes 1:0.8～2 in mass ratio, form slip, gained slip is joined to P
2
o
5
be 40%～54%, SO
4
2-
be at 50～80 ℃, to carry out desulphurization reaction 1～3h in 2.5%～6.5% phosphoric acid, doctor solution consumption is SO in phosphoric acid
4
2-
0.9～1.1 times of stoichiometric ratio.
for the ease of understanding the present invention, below examples of implementation set forth content of the present invention, content of the present invention is not limited only to the following examples.
embodiment 1
at phosphorus content, be 1.8%, fluorine content is 1.2%, SO
4
2-
content is that in 1 ton of waste water of 0.5%, to add CaO concentration be 20% milk of lime 101kg, and stirring reaction filtered after 40 minutes at normal temperatures, was purified liquid (1002kg, phosphorus content is 1.65%) and solid phase precipitation slag.
in gained scavenging solution, adding CaO concentration is 20% milk of lime 124kg, filters at normal temperatures after stirring reaction 1h, obtains the filter cake containing free-water approximately 40%, and filtrate is returned to phosphoric acid production system as process water and used after purifying.Filter cake drying obtains sweetening agent 105kg, and its component and quality percentage composition are: CaHPO
4
2H
2
o:74%, Ca (H
2
pO
4
)
2
h
2
o:4%, CaF
2
: 3%, CaSO
4
2H
2
o:7%, CaCO
3
: 3%, other is impurity.
by gained 109kg sweetening agent and P
2
o
5
be 20% phosphoric acid in mass ratio 1:2 mix, form slip, gained slip is joined to P
2
o
5
be 46%, SO
4
2-
be, in 4.9% 1130kg phosphoric acid, to carry out desulphurization reaction 1.5h at 75 ℃, doctor solution consumption is SO in phosphoric acid
4
2-
approximately 1.0 times of stoichiometric ratio, desulphurization reaction finishes rear filtration, SO in filtrate phosphoric acid
4
2-
content is 0.24%, and it is only 0.4% that filter residue be take butt phosphorus residual quantity after washing.
embodiment 2
at phosphorus content, be 2.4%, fluorine content is 2.0%, SO
4
2-
content is that in 1 ton of waste water of 0.8%, to add CaO concentration be 25% milk of lime 192kg, and stirring reaction filtered after 1 hour at normal temperatures, was purified liquid (979kg, phosphorus content is 2.0%) and solid phase precipitation slag.
in gained scavenging solution, adding CaO concentration is 25% milk of lime 141kg, filters at normal temperatures after stirring reaction 1.5h, obtains the filter cake containing free-water approximately 50%, and filtrate is returned to phosphoric acid production system as process water and used after purifying.Filter cake drying obtains sweetening agent 123kg, and its component and quality percentage composition are: CaHPO
4
2H
2
o:80%, Ca (H
2
pO
4
)
2
h
2
o:3%, CaF
2
: 1%, CaSO
4
2H
2
o:2%, CaCO
3
: 5%, other is impurity.
by gained 141kg sweetening agent and P
2
o
5
be 30% phosphoric acid in mass ratio 1:1.5 mix, form slip, gained slip is joined to P
2
o
5
be 40%, SO
4
2-
be, in 2.5% 3240kg phosphoric acid, to carry out desulphurization reaction 1h at 50 ℃, doctor solution consumption is SO in phosphoric acid
4
2-
approximately 0.9 times of stoichiometric ratio, desulphurization reaction finishes rear filtration, SO in filtrate phosphoric acid
4
2-
content is 0.26%, and it is only 0.5% that filter residue be take butt phosphorus residual quantity after washing.
embodiment 3
at phosphorus content, be 0.4%, fluorine content is 0.4%, SO
4
2-
content is that in 1 ton of waste water of 0.3%, to add CaO concentration be 10% milk of lime 60kg, and stirring reaction filtered after 0.5 hour at normal temperatures, was purified liquid (1020kg, phosphorus content is 0.35%) and solid phase precipitation slag.
in gained scavenging solution, adding CaO concentration is 10% milk of lime 50kg, filters at normal temperatures after stirring reaction 0.5h, obtains the filter cake containing free-water approximately 30%, and filtrate is returned to phosphoric acid production system as process water and used after purifying.Filter cake drying obtains sweetening agent 22kg, and its component and quality percentage composition are: CaHPO
4
2H
2
o:65%, Ca (H
2
pO
4
)
2
h
2
o:10%, CaF
2
: 10%, CaSO
4
2H
2
o:10%, CaCO
3
: 0.5%, other is impurity.
by gained 22kg sweetening agent and P
2
o
5
be 15% phosphoric acid in mass ratio 1:3 mix, form slip, gained slip is joined to P
2
o
5
be 54%, SO
4
2-
be, in 6.5% 163kg phosphoric acid, to carry out desulphurization reaction 3h at 80 ℃, doctor solution consumption is SO in phosphoric acid
4
2-
approximately 1.1 times of stoichiometric ratio, desulphurization reaction finishes rear filtration, SO in filtrate phosphoric acid
4
2-
content is 0.17%, and it is only 0.7% that filter residue be take butt phosphorus residual quantity after washing.
embodiment 4
in embodiment 2, prepare the filter cake containing free-water approximately 50% obtaining in sweetening process moist, directly as the sweetening agent product containing 50% free-water, by this sweetening agent 282kg and P
2
o
5
be 54% phosphoric acid in mass ratio 1:0.8 mix, form slip, gained slip is joined to P
2
o
5
be 54%, SO
4
2-
be, in 6.5% 1020kg phosphoric acid, to carry out desulphurization reaction 3h at 80 ℃, doctor solution consumption is SO in phosphoric acid
4
2-
approximately 1.1 times of stoichiometric ratio, desulphurization reaction finishes rear filtration, SO in filtrate phosphoric acid
4
2-
content is 0.18%, and it is only 0.6% that filter residue be take butt phosphorus residual quantity after washing.
embodiment 5
in embodiment 3, prepare the filter cake containing free-water approximately 30% obtaining in sweetening process moist, directly as the sweetening agent product containing 30% free-water, by this sweetening agent 31kg and P
2
o
5
be 20% phosphoric acid in mass ratio 1:2 mix, form slip, gained slip is joined to P
2
o
5
be 40%, SO
4
2-
be, in 2.5% 520kg phosphoric acid, to carry out desulphurization reaction 1h at 50 ℃, doctor solution consumption is SO in phosphoric acid
4
2-
approximately 0.9 times of stoichiometric ratio, desulphurization reaction finishes rear filtration, SO in filtrate phosphoric acid
4
2-
content is 0.21%, and it is only 0.4% that filter residue be take butt phosphorus residual quantity after washing.
the above, it is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, any technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the modification above embodiment done according to technical spirit of the present invention, all still belong in the scope of technical solution of the present invention.
Claims (3)
1. a wet method strong phosphoric acid sweetening agent is prepared and application, it is characterized in that a kind of wet method strong phosphoric acid sweetening agent, and its component and quality percentage composition are: CaHPO
42H
2o 65%～80%, Ca (H
2pO
4)
2h
2o 3%～10%, CaF
21%～10%, CaSO
42H
2o 2%～10%, CaCO
30.5%～5%, other is impurity; The preparation method of above-mentioned sweetening agent, its step is as follows: 1. at phosphorus quality percentage composition, be 0.4%～2.4%, fluorine quality percentage composition is 0.4%～2.0%, SO
4 2-quality percentage composition is that in 0.3%～0.8% waste water, to add CaO mass percentage concentration be 10%～25% milk of lime, milk of lime add-on is that in milk of lime, CaO quality is 1.5～2.4 times of fluorine in wastewater quality, stirring reaction 0.5～1h at normal temperatures, then filter, be purified liquid and solid phase precipitation slag; 2. in gained scavenging solution, adding CaO mass percentage concentration is 10%～25% milk of lime, milk of lime add-on is that in milk of lime, CaO quality is 1.4～1.8 times of phosphorus quality in scavenging solution, stirring reaction 0.5～1.5h at normal temperatures, then filter, filter cake after drying, obtain sweetening agent standby, filtrate is returned to phosphoric acid production system as process water and is used after purifying.
2. a kind of wet method strong phosphoric acid sweetening agent preparation according to claim 1 and application, is characterized in that above-mentioned sweetening agent removes being applied as of sulfate radical in wet method strong phosphoric acid: by sweetening agent and P
2o
5mass percentage concentration is 15%～30% phosphoric acid 1:1.5～3 mixing in mass ratio, forms slip, and gained slip is joined to P
2o
5be 40%～54%, SO
4 2-be at 50～80 ℃, to carry out desulphurization reaction 1～3h in 2.5%～6.5% phosphoric acid, doctor solution consumption is SO in phosphoric acid
4 2-0.9～1.1 times of stoichiometric ratio.
3. a kind of wet method strong phosphoric acid sweetening agent preparation according to claim 1 and application, the preparation method's step that it is characterized in that sweetening agent 2. in, filter cake can moistly directly obtain the sweetening agent containing quality percentage composition 30%～50% free-water, should be containing sweetening agent of free-water when the application and P
2o
5be that 20%～54% phosphoric acid mixes 1:0.8～2 in mass ratio, form slip, gained slip is joined to P
2o
5be 40%～54%, SO
4 2-be at 50～80 ℃, to carry out desulphurization reaction 1～3h in 2.5%～6.5% phosphoric acid, doctor solution consumption is SO in phosphoric acid
4 2-0.9～1.1 times of stoichiometric ratio.
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|---|---|---|---|
| CN201310449841.6A CN103539092A (en) | 2013-09-29 | 2013-09-29 | Preparation and applications of wet-process strong phosphoric acid desulfurizing agent |
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|---|---|---|---|
| CN201310449841.6A CN103539092A (en) | 2013-09-29 | 2013-09-29 | Preparation and applications of wet-process strong phosphoric acid desulfurizing agent |
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|---|---|
| CN103539092A true CN103539092A (en) | 2014-01-29 |
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ID=49963016
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|---|---|---|---|
| CN201310449841.6A Pending CN103539092A (en) | 2013-09-29 | 2013-09-29 | Preparation and applications of wet-process strong phosphoric acid desulfurizing agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108692A (en) * | 2014-07-31 | 2014-10-22 | 四川龙蟒钛业股份有限公司 | Wet-process phosphoric acid desulphurization method |
| CN104495771A (en) * | 2014-12-25 | 2015-04-08 | 瓮福（集团）有限责任公司 | Desulfuration method for diluted phosphoric acid |
| CN104591110A (en) * | 2015-01-13 | 2015-05-06 | 四川省汉源化工总厂 | Method for preparing low-sulfur-content calcium dihydrogen phosphate by concentrating wet-process phosphoric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5493694A (en) * | 1977-12-30 | 1979-07-24 | Nissan Chem Ind Ltd | Desulfurization method for wet process phosphoric acid |
| CN101525130A (en) * | 2009-04-10 | 2009-09-09 | 武汉工程大学 | Technique for purifying and producing industrial phosphoric acid by wet-process phosphoric acid |
-
2013
- 2013-09-29 CN CN201310449841.6A patent/CN103539092A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5493694A (en) * | 1977-12-30 | 1979-07-24 | Nissan Chem Ind Ltd | Desulfurization method for wet process phosphoric acid |
| CN101525130A (en) * | 2009-04-10 | 2009-09-09 | 武汉工程大学 | Technique for purifying and producing industrial phosphoric acid by wet-process phosphoric acid |
Non-Patent Citations (2)
| Title |
|---|
| 张翠微等: "湿法磷酸净化脱硫新工艺", 《硫磷设计与粉体工程》, 31 December 2004 (2004-12-31), pages 10 - 13 * |
| 黄燕等: "湿法磷酸的脱硫研究", 《贵州工业大学学报(自然科学版)》, vol. 30, no. 3, 30 June 2001 (2001-06-30), pages 68 - 74 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108692A (en) * | 2014-07-31 | 2014-10-22 | 四川龙蟒钛业股份有限公司 | Wet-process phosphoric acid desulphurization method |
| CN104495771A (en) * | 2014-12-25 | 2015-04-08 | 瓮福（集团）有限责任公司 | Desulfuration method for diluted phosphoric acid |
| CN104591110A (en) * | 2015-01-13 | 2015-05-06 | 四川省汉源化工总厂 | Method for preparing low-sulfur-content calcium dihydrogen phosphate by concentrating wet-process phosphoric acid |
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Application publication date: 20140129 |