CN1176011C - Production process of semiwater-diaquo phosphoric acid - Google Patents
Production process of semiwater-diaquo phosphoric acid Download PDFInfo
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- CN1176011C CN1176011C CNB021281165A CN02128116A CN1176011C CN 1176011 C CN1176011 C CN 1176011C CN B021281165 A CNB021281165 A CN B021281165A CN 02128116 A CN02128116 A CN 02128116A CN 1176011 C CN1176011 C CN 1176011C
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Abstract
The present invention discloses a production method of a semihydrate-dihydrate phosphoric acid. In the essential technical scheme, the calcium emanation rate of a first reaction tank is controlled within 50% to 60% during semi water reaction, and a sulphuric acid is added with two times; part of the sulphuric acid is mixed with a dilute phosphoric acid in an acid mixer, and then the mixture is added into a secondary reaction tank; the other part of the sulphuric acid is added into a dilute phosphoric acid tank, and the concentration of SO4<2-> in the dilute phosphoric acid is controlled within 8% to 10%; part of the dilute phosphoric acid is pumped into the first reaction tank after sulphuric acid is added to the dilute phosphoric acid tank. The rest of the dilute phosphoric acid is added into the acid mixer to mix with the sulphuric acid, and then, the mixture enters the secondary reaction tank; a slurry vacuum flashing vaporization cooler is added into the reaction of the dihydrate. The present invention has the advantages of reasonable technological process, wide adaptability of phosphorite, easy operation, prolonged plug clearing period and high productive efficiency.
Description
Technical field
The present invention relates to a kind of production method of phosphoric acid by wet process, especially relate to a kind of production method of semiwater-diaquo phosphoric acid.
Background technology
The seventies in 20th century, carried out the development research of half water, one or two water thing recrystallize high-concentration wet process phosphoric acid Technologies in the world, the Technology flow process that forms is more, but realizes the Nuo Sike. He Teluo of Fei Sensi company (Norsk-Hydro) flow process of having only Britain of industrialization and the improvement C of the Nissan method flow process of Japan at last.It should be noted that the phosphorus ore that Nuo Sikeheteluo Technology flow process is mainly used aborning is Morocco's phosphorus ore; The phosphorus ore that daily output improvement C method is mainly used aborning is the Florida, US phosphorus ore.(the 1. Wu sesame " phosphoric acid by wet process " of wearing, Chemical Industry Press 1987 chapter 12 P246～291; 2. the Ministry of Chemical Industry's construction coordination department tissue is write " phosphoric acid, phosphorus ammonium, coarse whiting technology and design manual ", and chemical industry is published .1997.P2000).
Yunnan Honglin Chemical Co.,Ltd introduced the Nuo Sikeheteluo patented technology and produces 60000 tons of P per year the beginning of the nineties
2O
5Key equipment, and be constructed and put into operation in Yunnan Honglin Chemical Co.,Ltd (former Yunnan Red River phosphate fertilizer plant) in 94 years.But regrettably, Yunnan Honglin Chemical Co.,Ltd buys the Nuo Sikeheteluo patented technology and produces 60000 tons of P per year
2O
5Key equipment, after going into operation in 94 years, operate by the said firm's patented technology index (being that the CaO eduction rate is 40%) always, up to this device annual production in 98 years only reach 40,000 surplus ton P
2O
s, fail to reach 60,000 tons of P of annual output of design
2O
5Output.
Trace it to its cause, the production of phosphoric acid needs the phosphorus ore supply of stabilised quality, and different phosphorus ores requires to adopt different processing condition and the technical process that adapts when producing phosphoric acid.Though the limited duty of YUNNANHONG phosphorous chemical industry company used Yunnan Province's river and mountain phosphorus ore to do the lab scale evaluation test before introducing the Nuo Sikeheteluo patented technology, and had carried out producing per year 60,000 tons of P according to lab scale evaluation test result
2O
5Design of device, but purchase at the Yunnan multiple spot owing to the raw material phosphorus ore in the actual production, certain variation has taken place in phosphorus ore quality, cause by the semiwater-diaquo phosphoric acid technological process of production of the Nuo Sikeheteluo of external introduction and the production of processing condition incompatibility Chinese yunnan phosphorus ore, plant capacity is very limited, and presses for the more rational production method of research and development.
Summary of the invention
At the deficiencies in the prior art part, the purpose of this invention is to provide a kind of production method of improved semiwater-diaquo phosphoric acid, thereby improve the throughput of existing apparatus effectively.
The present invention is achieved by following technical proposals:
(1) ground phosphate rock and part dilute phosphoric acid are joined first reactive tank, half water material slurry is sent into first reactive tank from second reactive tank after being pumped into the cooling of vacuum flashing water cooler, temperature is 98 ℃～100 ℃ in first reactive tank, and CaO 50%～60% reaction of being brought into by phosphorus ore in the first reactive tank inner control forms CaSO
40.5H
2O, all the other CaO are dissolved in the slip with the mono-calcium phosphate form;
Second reactive tank is gone in the overflow of (2) half water materials slurry, sulfuric acid and remaining dilute phosphoric acid are added second reactive tank, the temperature of controlling second reactive tank is 100 ℃～103 ℃, and the free sulphur acid group is 2.0%～2.4%, generates CaSO to guarantee the CaO total overall reaction that phosphorus ore is brought into
40.5H
2O, and form thick, even, stable crystallization;
(3) slip again overflow go into medial launder, after pump into half water thing filter, partly filtrate is sent into sour storehouse as finished product phosphoric acid, all the other filtrates and a washing lotion are sent into the dilute phosphoric acid groove, sulfate radical content is 8%～10% in the adding sulfuric acid control dilute phosphoric acid in the dilute phosphoric acid groove, filter cake washs the filtrate of sending here with two water thing filtering systems for the last time through countercurrent washing; The washing lotion that half water thing filter cake after the washing is sent here with two water thing filtering systems is washed into two water thing conversion tanks;
(4) add sulfuric acid and go into two water things and transform the A groove, control two water things and transform that sulfate concentration is 8%～12% in the A groove.Two water materials slurry transforms the B groove by two water things and pumps into the vacuum flashing water cooler, and the back flows into two water things and transforms the A groove, and temperature is 60～70 ℃ in the control A groove, medial launder is gone in the slip overflow, be pumped into two water thing filters again, filter cake process water countercurrent washing, the phosphogypsum dihydrate after cleaning is discharged system.
Compared with prior art the present invention has following outstanding feature:
(1) CaO that is brought into by phosphorus ore in the control of half water part, first reactive tank has 50%～60% reaction to generate CaSO
4.0.5H
2O, all the other CaO of 40%～50% are dissolved in the slip with the form of mono-calcium phosphate, that is to say that the calcium eduction rate at half water part first reactive tank (1A groove) should be controlled at 50%～60%, be different from Nuo Sikeheteluo technology calcium eduction rate and be controlled at 40%, also be different from daily output improvement C method calcium eduction rate and be controlled at 70%;
(2) be to be divided into two places to add at half water part sulfuric acid; After adding acid mixing device and dilute phosphoric acid mixes, a part of sulfuric acid joins second reactive tank; Another part sulfuric acid joins the dilute phosphoric acid groove, and sulfate concentration is 8%～10%SO in the control dilute phosphoric acid
4 2-Sulfuric acid all joins second reactive tank in Nuo Sikeheteluo and daily output improvement C method technology;
(3) in the dilute phosphoric acid groove, behind the adding sulfuric acid, with pump the part dilute phosphoric acid is delivered to first reactive tank (1A groove) again, so that the CaO eduction rate of regulating and control in first reactive tank with the circulation slip is 50%～60%; All the other part dilute phosphoric acids are sent to acid mixing device and mix adding second reactive tank in back with sulfuric acid; And in Nuo Sikeheteluo technology, dilute phosphoric acid is all delivered to acid mixing device and is mixed adding second reactive tank in back with sulfuric acid; Dilute phosphoric acid all joins the premix groove and is used for wetting ground phosphate rock in daily output improvement C method technology.
(4) partly have additional a slime vacuum flash cooler in the reaction of two water things, so that be controlled at the temperature of reaction of two water thing conversion tanks is 60 ℃～70 ℃, at two water the slip refrigerating unit is not set all partly in Nuo Sikeheteluo technology and daily output improvement C method technology.
(5) in the present invention's half water-two water thing phosphoric acid process, phosphoric acid extraction concentration is 40-48%, phosphoric acid total phosphorus yield 〉=97%.
Just because production method of the present invention has These characteristics, so technical process of the present invention is more reasonable, and to the wide adaptability of phosphorus ore, turndown ratio is big, the block clearing cycle stretch-out, the production efficiency height has effectively improved the throughput of existing apparatus.
Description of drawings
Fig. 1 is the Nuo Sikeheteluo half water-two water recrystallize strong phosphoric acid process flow diagram of Britain;
Fig. 2 is the daily output improvement C method half water-two water recrystallize strong phosphoric acid process flow diagram of Japan;
Fig. 3 is half water-two a water recrystallize strong phosphoric acid process flow diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing prior art and technical process of the present invention are done concrete contrast, thereby content of the present invention is made more detailed description, but content of the present invention is not limited to shown in the accompanying drawing.
As shown in Figure 1, according to Nuo Sike two He Teluo technical process, ground phosphate rock adds the 1st groove, and the volume of the 1st groove is bigger, is the twice of the 2nd groove; Sulfuric acid and dilute phosphoric acid add the 2nd groove, and slip flows into the 1st groove from the 2nd groove with being pumped into vacuum flashing water cooler 7 backs.The CaO that control is brought into by phosphorus ore in the 1st groove has 40% to form CaSO
4.0.5H
2O, and remaining 60%CaO with mono-calcium phosphate form exist in the slip, this is the technical characterstic of Nuo Sikeheteluo technical process.Go into the 2nd groove in the slip overflow that the 1st groove forms, the CaO in this slip and the sulfuric acid of adding fully react, and generate CaSO
4.0.5H
2O, half water material slurry go into medial launder 3 by the 2nd groove overflow again, after starch filter 8 with being pumped into half water material again.Through the filtering filtrate of half water thing filter, partly pump into the finished acid storehouse as finished product phosphoric acid, remaining partly the mixing with a washing lotion sent into dilute phosphoric acid groove 6, again with being pumped into the 2nd reactive tank.Half water thing filter cake is through three countercurrent washings, and the filtrate of sending here with two water thing filtering systems is washed for the last time.The washing lotion that half water thing filter cake after the washing is sent here with two water thing filtering systems pours two water thing conversion tanks 4, adds sulfuric acid in groove, makes CaSO
4.0.5H
2O transforms to recrystallize into and is CaSO
4.2H
2O.Two water material stock pumps after the conversion are sent into two water thing filters 9, and the filter cake after the filtration discharges after countercurrent washing.
As shown in Figure 2, according to one or the two water thing recrystallize strong phosphoric acid technical process of the improvement C of Japanese Nissan company method half water, ground phosphate rock and dilute phosphoric acid add the less premix groove 11 of volume, and the residence time is 5～10 minutes in the groove, make ground phosphate rock surface wettability and partly dissolved at this.Slip overflows to two placed in-line reactive tanks 1,2 behind the premix, and sulfuric acid then joins 1,2 reactive tanks according to a certain percentage respectively.Reacted slip is pumped into slip divider 12 from medial launder 3 usefulness, and some is delivered to half water thing filter 8, and another partly sends into reactive tank 1 as overfall.Slip is 1～2.5 hour in the residence time of reactive tank 1,2, and the overfall amount is 1～2 times of finished product slip amount.The sulfuric acid that joins reactive tank 1 makes the CaO that is brought into by phosphorus ore have 70% reaction to form CaSO
4.0.5H
2O, and remaining 30% CaO is present in the slip with the form of mono-calcium phosphate.Remaining sulfuric acid joins reactive tank 2, and makes slip in the groove maintain 2%～3% free sulfuric acid.The CaO that control is brought into by phosphorus ore in reactive tank 2 has 70% reaction to form CaSO
4.0.5H
2O, this is the technical characterstic of daily output improvement C method technical process.
The filtering filtrate of half water thing filter is partly sent into sour storehouse as finished acid, and a remaining filtrate and a washing lotion merge returns premix groove 11 as dilute phosphoric acid, and filter cake is sent into two water thing conversion tanks 4 after the part filtrate washing once that two water thing filtering systems are sent here.
The dilute phosphoric acid of two water thing filtering systems adds two water thing conversion tanks 4 with half water thing filter cake, and sulfuric acid concentration is 10%～15% in the adding sulfuric acid control flume 4, and the residence time is 2 hours, and transforming Tc is 50 ℃～80 ℃.Two water materials slurry is with being pumped into filter 9, and filter cake washs back discharge system with clear water.
As shown in Figure 3, by the technical process of the present invention's half water-two water thing recrystallize strong phosphoric acid, ground phosphate rock and part dilute phosphoric acid join reactive tank 1, half water material slurry and send into groove 1 after reactive tank 2 usefulness are pumped into 7 coolings of vacuum flashing water cooler.At groove 1 interior reaction temperature is 98 ℃～100 ℃, and the CaO that control is brought into by phosphorus ore has 50%～60% reaction to form CaSO
4.0.5H
2O, all the other CaO are dissolved in the slip with the mono-calcium phosphate form.Half water material slurry is gone into reactive tank 2 from reactive tank 1 overflow, and sulfuric acid and remaining dilute phosphoric acid add reactive tank 2, and the temperature of reaction of control flume 2 is 100 ℃～103 ℃, and the free sulphur acid group is 2%～2.4%, generates CaSO to guarantee the CaO total overall reaction that phosphorus ore is brought into
4.0.5H
2O, and form thick, even, stable crystallization.Slip overflow is again gone into medial launder 3, after pump into half water thing filter 8, partly filtrate is sent into sour storehouse as finished product phosphoric acid, all the other filtrates and a washing lotion are sent into dilute phosphoric acid groove 6, in groove 6, add sulfuric acid and be controlled at sulfate radical content 8%～10% in the dilute phosphoric acid, filter cake washs through second adverse current, the filtrate that last washing is sent here with two water thing filtering systems.The washing lotion that half water thing filter cake after the washing is sent here with two water thing filtering systems pours two water thing conversion tank 4A.Add sulfuric acid and go into the 4A groove, sulfate concentration is 8～12% in the control 4A groove.Two water materials slurry pumps into vacuum flashing water cooler 7 backs by the 4B groove and flows into the 4A groove, temperature is 60～70 ℃ in the control flume, and medial launder 5 is gone in the slip overflow, sends into two water thing filters 9 with pump 10 again, filter cake process water countercurrent washing, the phosphogypsum dihydrate after cleaning is discharged system
Yunnan Honglin Chemical Co.,Ltd has bought Nuo Sikeheteluo half water one phosphate dihydrate technology patent and 60kt/aP in early 1990s
2O
5The a complete set of production equipment of/a put into production in 1994, only was ton P surplus producing 40000 per year to the actual capacity of device in 1999
2O
5The back undergoes technological transformation by the Nuo Sikeheteluo production equipment of new technical process provided by the invention to original introduction, the examination running continuously through 120 hours, and the throughput of transforming the back device reaches 70kt/aP
2O
5Up to now, work well by the improved production equipment of novel technique, throughput is also constantly increasing.
Claims (1)
1. the production method of a semiwater-diaquo phosphoric acid, this method comprises the following steps:
(1) ground phosphate rock and part dilute phosphoric acid join first reactive tank, half water material slurry is sent into first reactive tank from second reactive tank after being pumped into the cooling of vacuum flashing water cooler, the degree that overflows in first reactive tank is 98 ℃～100 ℃, and CaO50%～60% reaction of being brought into by phosphorus ore in the first reactive tank inner control forms CaSO
4.0.5H
2O, all the other CaO are dissolved in the slip with the mono-calcium phosphate form;
Second reactive tank is gone in the overflow of (2) half water materials slurry, sulfuric acid and remaining dilute phosphoric acid are added second reactive tank, the temperature of controlling second reactive tank is 100 ℃～103 ℃, and the free sulphur acid group is 2.0%～2.4%, generates CaSO to guarantee the CaO total overall reaction that phosphorus ore is brought into
4.0.5H
2O, and form thick, even, stable crystallization;
(3) slip again overflow go into medial launder, after pump into half water thing filter, partly filtrate is sent into sour storehouse as finished product phosphoric acid, all the other filtrates and a washing lotion are sent into the dilute phosphoric acid groove, in the dilute phosphoric acid groove, add sulfuric acid and be controlled at that sulfate radical content is 8%～10% in the dilute phosphoric acid, filter cake washs the filtrate of sending here with two water thing filtering systems for the last time through countercurrent washing; The washing lotion that half water thing filter cake after the washing is sent here with two water thing filtering systems is washed into two water thing conversion tanks;
(4) add sulfuric acid and go into two water things conversion A groove, control two water things and transform that sulfate concentration is 8%～12% in the A groove, two water materials slurry transforms the B groove by two water things and pumps into the vacuum flashing water cooler, the back flows into two water things and transforms the A groove, temperature is 60 ℃～70 ℃ in the control A groove, and medial launder is gone in the slip overflow, is pumped into two water thing filters again, filter cake process water countercurrent washing, the phosphogypsum dihydrate after cleaning is discharged system;
(5) phosphoric acid extraction concentration is 40%～48%, phosphoric acid total phosphorus yield 〉=97%.
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| CNB021281165A CN1176011C (en) | 2002-12-25 | 2002-12-25 | Production process of semiwater-diaquo phosphoric acid |
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| CNB021281165A CN1176011C (en) | 2002-12-25 | 2002-12-25 | Production process of semiwater-diaquo phosphoric acid |
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| CN1176011C true CN1176011C (en) | 2004-11-17 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674279B (en) * | 2012-06-08 | 2014-05-07 | 贵州川恒化工有限责任公司 | Method for producing phosphoric acid by hemihydrate technique |
| CN103086335B (en) * | 2013-02-05 | 2014-06-18 | 瓮福（集团）有限责任公司 | Method for production of phosphoric acid and combined production of a-hemihydrate gypsum through dehydrate-hemihydrate wet phosphoric acid technology |
| CN103641094B (en) * | 2013-11-28 | 2016-03-16 | 贵州开磷集团股份有限公司 | A kind of use ground phosphate rock that wets produces the method for double superhosphate |
| CN105036101B (en) * | 2015-08-11 | 2017-07-21 | 中国五环工程有限公司 | Hemi-dihydrate process wet method phosphoric acid manufacture process and its system |
| CN105217590B (en) | 2015-09-18 | 2017-05-10 | 金正大诺泰尔化学有限公司 | Method for production of wet process phosphoric acid and byproducts alpha-hemihydrated gypsum and high purity and high whiteness alpha-hemihydrated gypsum |
| CN105253867B (en) | 2015-09-18 | 2017-10-17 | 金正大生态工程集团股份有限公司 | A kind of production method of phosphoric acid by wet process by-product αsemiwatergypsum |
| CN106006697B (en) * | 2016-05-19 | 2017-09-08 | 湖北六国化工股份有限公司 | The pilot-plant and technique of a kind of phosphorus mine tailing acidolysis |
| CN110510590B (en) * | 2019-10-08 | 2024-06-14 | 中化重庆涪陵化工有限公司 | Stable and efficient wet-process phosphoric acid production system and process |
| CN111732086A (en) * | 2020-07-31 | 2020-10-02 | 天宝动物营养科技股份有限公司 | Process for preparing phosphoric acid and co-producing high-purity gypsum by semi-water-dihydrate method |
| CN112194109B (en) * | 2020-09-30 | 2022-06-21 | 湖北宜化松滋肥业有限公司 | Method for producing phosphoric acid and coproducing gypsum by semi-water-dihydrate wet-process phosphoric acid process |
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