CN110371938A - A method of passing through calcium sulfate crystal form during impurity content control phosphoric acid by wet process - Google Patents
A method of passing through calcium sulfate crystal form during impurity content control phosphoric acid by wet process Download PDFInfo
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- CN110371938A CN110371938A CN201910677237.6A CN201910677237A CN110371938A CN 110371938 A CN110371938 A CN 110371938A CN 201910677237 A CN201910677237 A CN 201910677237A CN 110371938 A CN110371938 A CN 110371938A
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 116
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 98
- 239000012535 impurity Substances 0.000 title claims abstract description 69
- 239000013078 crystal Substances 0.000 title claims abstract description 67
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 63
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 62
- 208000021302 gastroesophageal reflux disease Diseases 0.000 claims abstract description 36
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims abstract description 26
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims abstract description 26
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 26
- 235000019691 monocalcium phosphate Nutrition 0.000 claims abstract description 26
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims description 136
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910003638 H2SiF6 Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229960005069 calcium Drugs 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 11
- 230000002572 peristaltic effect Effects 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000011777 magnesium Substances 0.000 description 36
- 235000011132 calcium sulphate Nutrition 0.000 description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 239000011734 sodium Substances 0.000 description 26
- 239000001175 calcium sulphate Substances 0.000 description 24
- 239000002253 acid Substances 0.000 description 16
- 239000011574 phosphorus Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000002367 phosphate rock Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- -1 metals cation Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000186216 Corynebacterium Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention provides a kind of methods for controlling phosphoric acid by wet process process calcium sulfate crystal form by impurity content, by phosphoric acid, obtain acid reflux solution after sulfuric acid and water mixing, acid reflux solution and a water calcium dihydrogen phosphate and impurity are mixed and are used as material 1；Material 2 is used as after water is mixed with sulfuric acid；Material 1 and material 2 are added in reactor, react the product obtained after 2-5h at being 50-90 DEG C in temperature and extract out also by peristaltic pump, extraction rate is identical as the sum of the addition rate of two kinds of solution.The present invention is by investigating the influence of single impurity such as Si/Al/Fe/Mg/K/Na and the collaboration of more impurity to crystal of calcium sulfate process, specify the control range of impurity, realize the regulation to calcium sulfate crystal form, to improve by-product ardealite activity and phosphoric acid quality, the effective rate of utilization of phosphor resource constantly can be improved, the promotion of ardealite quality also provides good condition to its comprehensive utilization.
Description
Technical field
The present invention relates to the crystalline substances that the content by impurity in product low level phosphorus ore in control controls phosphoric acid by wet process process calcium sulfate
Type regulation.
Background technique
Currently, China's phosphorus ore is largely mid low grade phosphate rock, impurity content is higher.Part during phosphoric acid by wet process
Impurity can be dissolved into liquid phase, influence the quality of phosphoric acid.On the other hand, the crystal form of undissolved impurity effect calcium sulfate, thus
Reduce P2O5Yield, influence calcium sulfate in the integrated application of every profession and trade.Therefore, shadow of the research impurity to phosphogypsum crystal process
Sound is of great significance.
200610022562 .1 of patent " a method of high-concentration phosphoric acid is prepared using mid low grade phosphate rock " it is then that will wash
After water sufficiently washs ardealite, part washing lotion is used to produce precipitate phosphoric acid salt, and rest part returns in extraction tank, although
Reduce phosphoric acid loss, but increases the phosphatic process of production.201610511259 .1 of patent is " a kind of to utilize phosphorus ore system
The method of standby purifying phosphoric acid " be the direct extracting metals cation purification of wet process phosphoric acid from phosphoric acid by wet process method, extraction process
In, the cation only in diluted acid enters in organic phase, but pertains only to a kind of impurity, and other impurities problem does not solve.Patent
201610936085 .3 are " a kind of to utilize metal ion controlling party in slag acid caused by mid low grade phosphate rock production ammonium phosphate salt
Method " it is using precipitating reagent removal sodium, potassium and magnesium alkali metal ion；Then the rate of settling is improved using settling agent；Finally using cold
But method removes aluminium, iron ion.
The industrial process of phosphoric acid by wet process mainly has two water laws, half water law and Ban Shui-two water law.Phosphorus ore acid hydrolysis process
In, by-product calcium sulphate dihydrate stable crystal form, thus the fluctuation of operating condition is small to device influence on system operation, to charging phosphorus ore mineral
Adaptable, production capacity accounts for 95% or more of Chinese phosphoric acid aggregated capacity；But the technique phosphrus reagent is relatively low, extraction acid concentration is low, energy consumption
Height, solid waste phosphogypsum activity in production is poor, resource utilization difficulty is big.Half water law production technology can directly obtain
The phosphoric acid of higher concentration, and SO in product acid3, the impurity contents such as Al and F it is low, acid is high-quality；But the technique is for the suitable of phosphorus ore
Answering property is poor, P2O5Yield is lower, while by-product ardealite P2O5Content is high, is unfavorable for comprehensively utilizing.Based on above two technique road
Line, the developing focus of phosphoric acid by wet process switchs to-two wet technology of half water in recent years.The process energy consumption is lower, and a step obtains in phosphoric acid
P2O5For 42%~45% phosphoric acid, and P2O5The rate of recovery is high, few up to dissolved impurity in 98%~98.5% acid, the matter of product acid
It measures；By-product gypsum is high-quality, is conducive to comprehensive utilization.But its production process is more difficult to control, and more sensitive to impurity.
Under existing wet method phosphoric acid manufacture process, the ardealite granular size of generation is different, and pattern is different, leads to its mistake
Filtering velocity rate is slow, is unfavorable for washing, and reduces the activity of ardealite and the yield of phosphoric acid.It is blocked up in addition, the presence of impurity will lead to pipeline
Plug, causes certain economic loss.Research shows that by the content and mutual ratio of control phosphoric acid by wet process Process Impurity, it is raw
At coarse uniform calcium sulphate crystal, the rate of recovery of its filtering rate and phosphorus is improved.
Summary of the invention
In order to solve the problems, such as calcium sulfate crystal polymorph control during phosphoric acid by wet process, the present invention provides one kind and passes through impurity content
The method for controlling phosphoric acid by wet process process calcium sulfate crystal form.
To achieve this purpose, the present invention adopts the following technical scheme:
A method of phosphoric acid by wet process process calcium sulfate crystal form is controlled by impurity content, the specific steps are as follows:
Present invention Ca (H2PO4)2 ▪H2O addition substitution phosphorus ore, the content by controlling impurity investigate it to crystal of calcium sulfate mistake
The influence of journey.
(1) by phosphoric acid, acid reflux solution is obtained after sulfuric acid and water mixing, by acid reflux solution and a water calcium dihydrogen phosphate and impurity
It is mixed and is used as material 1；The mass concentration of the phosphoric acid is 85% or more；The mass concentration of the sulfuric acid be 98% and
More than；The phosphoric acid, sulfuric acid, water mass ratio be 12-15:1:18-20.The quality of acid reflux solution and a water calcium dihydrogen phosphate
Than for 1.2-1.8:1.
(2) material 2 is used as after mixing water with sulfuric acid；The mass concentration of sulfuric acid is higher than 95% in the material 2；Wherein,
The mass ratio of water and sulfuric acid is 0.8-1.5:1.
(3) material 1 and material 2 are added in reactor by the flow of 7:3-6, and the product obtained after being reacted is also by compacted
Dynamic pumping goes out, and extraction rate is identical as the sum of the addition rate of two kinds of solution, is remained unchanged with the volume guaranteed in crystallizer.
Material 1 and material 2 are added in reactor by the flow of 7:5, reach 3h when the residence time, product passes through wriggling at this time
Pump is extracted out with same rate.After reaching stable state, separated in time sampling, to avoid that partial size point occurs in sampling process
Grade, using the sampling mode of fast intermittent.
Impurity includes any one or more compound containing Si, Al, Fe, Mg, K, Na element in the material 1.
The impurity includes H2SiF6、SiO2、AlPO4、Fe2O3, any one in MgO, KOH, NaOH.
Each impurity content is as follows:
The Si additional amount is Si/Ca=0.004 to 0.06；
The Al additional amount is Al/Ca=0.01 to 0.16；
The Fe additional amount is Fe/Ca=0.01 to 0.14；
The Mg additional amount is Mg/Ca=0.01 to 0.16；
The K additional amount is K/Ca=0.022 to 0.1；
The Na additional amount is Na/Ca=0.022 to 0.1.
It is individually added into any one compound impurities containing Si, Al, Fe, Mg, K, Na element in reaction system, reaches control
The purpose of calcium sulfate crystal form, impurity content are as follows:
The Si additional amount is Si/Ca=0.01 to 0.05；
The Al additional amount is Al/Ca=0.01 to 0.05；
The Fe additional amount is Fe/Ca=0.01 to 0.10；
The Mg additional amount is Mg/Ca=0.01 to 0.05；
The K additional amount is K/Ca=0.01 to 0.05；
The Na additional amount is Na/Ca=0.01 to 0.05.
The multiple compounds impurity containing Si, Al, Fe, Mg, K, Na element, preferably the following two kinds side are added in reaction system
Case, wherein impurity content is as follows:
Si, Mg, Al, Na are added while described, additional amount is Si/Ca=0.01 to 0.05, Mg/Ca=0.01 to 0.05, Al/Ca
=0.01 to 0.05, Na/Ca=0.01 to 0.04；
Si, Al, Fe, Mg, Na are added while described, additional amount is Si/Ca=0./1 to 0.05, Mg/Ca=0.01 to 0.05,
Al/Ca=0.01 is to 0.0.04, Fe/Ca=0.01 to 0.03, Na/Ca=0.01 to 0.04.
50-90 DEG C of the reaction temperature of material 1 and material 2 in the reactor, reaction time 2-5h.
In preferred embodiment, the reaction temperature of material 1 and material 2 in the reactor is 70 DEG C, 75 DEG C or 80 DEG C, the reaction time
2h and 3h.
The present invention investigates influence of the impurity content to calcium sulfate crystal form using phosphoric acid by wet process, by investigating different impurities not
With the influence under content to crystal of calcium sulfate process, objectionable impurities in apparent phosphorus ore is screened and is regulated and controled by phosphorus ore early period, is controlled
The content of objectionable impurities processed makes it be stablized in practical Wet-process Phosphoric Acid Production, is coarse, uniform neat gypsum crystal,
The comprehensive utilization of the quality and ardealite that improve phosphoric acid has realistic meaning.
Detailed description of the invention
Fig. 1 is the shape appearance figure of calcium sulphate crystal that difference Si/Ca ratio obtains in embodiment 1, wherein A for Si/Ca=
0.01, B is Si/Ca=0.02, and C is Si/Ca=0.03, and D is Si/Ca=0.04.
Fig. 2 is the shape appearance figure of calcium sulphate crystal that difference Al/Ca ratio obtains in embodiment 2, wherein A for Al/Ca=
0.01, B is Al/Ca=0.02, and C is Al/Ca=0.03, and D is Al/Ca=0.04.
Fig. 3 is the shape appearance figure of calcium sulphate crystal that difference Fe/Ca ratio obtains in embodiment 3, wherein A for Fe/Ca=
0.01, B is Fe/Ca=0.02, and C is Fe/Ca=0.06, and D is Fe/Ca=0.10.
Fig. 4 is the shape appearance figure of calcium sulphate crystal that difference Mg/Ca ratio obtains in embodiment 4, wherein A for Mg/Ca=
0.01, B is Mg/Ca=0.02, and C is Mg/Ca=0.03, and D is Mg/Ca=0.04.
Fig. 5 is the shape appearance figure for the calcium sulphate crystal that difference K/Ca ratio obtains in embodiment 5, and wherein A is K/Ca=0.01, B
It is K/Ca=0.03 for K/Ca=0.02, C, D is K/Ca=0.04.
Fig. 6 is the shape appearance figure for the calcium sulphate crystal that poly-doped impurity obtains under different proportion in embodiment 6, and wherein A is Si/
Ca=0.01, Mg/Ca=0.01,Al/Ca=0.01, Na/Ca=0.01；B be Si/Ca=0.02, Mg/Ca=0.02, Al/Ca=
0.01, Na/Ca=0.01；C is i/Ca=0.02, Mg/Ca=0.02, Al/Ca=0.03, Na/Ca=0.03；D be Si/Ca=0.03,
Mg/Ca=0.03、Al/Ca=0.02、Na/Ca=0.02。
Fig. 7 is the shape appearance figure for the calcium sulphate crystal that poly-doped impurity obtains under different proportion in embodiment 7, and wherein A is Si/
Ca=0.03,Mg/Ca=0.02,Al/Ca= 0.02,Fe/Ca= 0.04,Na/Ca=0.02；B be Si/Ca=0.03, Mg/Ca=
0.02,Al/Ca= 0.02,Fe/Ca=0.05,Na/Ca=0.02；C be Si/Ca=0.03, Mg/Ca=0.03, Al/Ca=0.03,
Fe/Ca=0.06,Na/Ca=0.03；D be Si/Ca=0.03, Mg/Ca=0.03, Al/Ca=0.02, Fe/Ca=0.06, Na/Ca=
0.02。
Specific embodiment
Embodiment 1
First by phosphoric acid, obtain acid reflux solution after sulfuric acid and water mixing, phosphoric acid, sulfuric acid, water mass ratio be 12-15:1:18-
20, this example presses 85%H3PO4The ratio of 60.9g, 98% concentrated sulfuric acid 4.3g, water 84.8g prepare a certain amount of acid reflux solution, will return
Acid solution and a water calcium dihydrogen phosphate and impurity, which are mixed, is used as material 1, the quality of acid reflux solution and a water calcium dihydrogen phosphate
Than for 1.2-1.8:1, this example is prepared in 60g acid reflux solution/mono- water calcium dihydrogen phosphate of 41.3g ratio.
Be used as material 2 after water is mixed with sulfuric acid, the mass ratio of water and 98% sulfuric acid is 0.8-1.5:1, this example according to
The ratio of 98% concentrated sulfuric acid of 36g water and 33.2g is pre-mixed as material 2.
Influence of the fluosilicic acid to calcium sulphate crystal, the additive amount of the impurity are Si/Ca=0.01,0.02,0.03,0.04.
Material 1 and material 2 are added to respectively with the flow velocity of 2.8L/min and 2.0L/min to the flask of 2L by peristaltic pump
In, it is stirred to react 3h at 80 DEG C, is deducted with 4.73ml/min(reaction process air-loss by 0.07 ml/min) rate starts
Extraction liquid is sampled using interval, is sampled every 1 and a half hours, filtering.Increase the flat of calcium sulphate crystal with Si/Ca
Equal partial size is gradually reduced, and the increase of fluosilicic acid content is on crystal morphology substantially without influence.When Si/Ca=0.03, calcium sulphate crystal is raw
Long best, the shape appearance figure of crystal is shown in Fig. 1.
Embodiment 2
First by phosphoric acid, obtain acid reflux solution after sulfuric acid and water mixing, phosphoric acid, sulfuric acid, water mass ratio be 12-15:1:18-
20, this example presses 85%H3PO4The ratio of 60.9g, 98% concentrated sulfuric acid 4.3g, water 84.8g prepare a certain amount of acid reflux solution, will return
Acid solution and a water calcium dihydrogen phosphate and impurity, which are mixed, is used as material 1, the quality of acid reflux solution and a water calcium dihydrogen phosphate
Than for 1.2-1.8:1, this example is prepared in 60g acid reflux solution/mono- water calcium dihydrogen phosphate of 41.3g ratio.
Be used as material 2 after water is mixed with sulfuric acid, the mass ratio of water and 98% sulfuric acid is 0.8-1.5:1, this example according to
The ratio of 98% concentrated sulfuric acid of 36g water and 33.2g is pre-mixed as material 2.
AlPO4Influence to calcium sulphate crystal, the impurity additive amount be Al/Ca=0.01,0.02,0.03,0.04.
Material 1 and material 2 are added to respectively with the flow velocity of 2.8L/min and 2.0L/min to the flask of 2L by peristaltic pump
In, it is stirred to react 3h at 80 DEG C, is deducted with 4.73ml/min(reaction process air-loss by 0.07 ml/min) rate starts
Extraction liquid was sampled every 1 and a half hours later, filtering.As Al/Ca increases, the average grain diameter of calcium sulphate crystal is gradually
Increase, crystal morphology becomes corynebacterium from slender rod shaped.When Al/Ca=0.02, calcium sulphate crystal growth is best, the pattern of crystal
Figure is shown in Fig. 2.
Embodiment 3
First by phosphoric acid, obtain acid reflux solution after sulfuric acid and water mixing, phosphoric acid, sulfuric acid, water mass ratio be 12-15:1:18-
20, this example presses 85%H3PO4The ratio of 60.9g, 98% concentrated sulfuric acid 4.3g, water 84.8g prepare a certain amount of acid reflux solution, will return
Acid solution and a water calcium dihydrogen phosphate and impurity, which are mixed, is used as material 1, the quality of acid reflux solution and a water calcium dihydrogen phosphate
Than for 1.2-1.8:1, this example is prepared in 60g acid reflux solution/mono- water calcium dihydrogen phosphate of 41.3g ratio.
Be used as material 2 after water is mixed with sulfuric acid, the mass ratio of water and 98% sulfuric acid is 0.8-1.5:1, this example according to
The ratio of 98% concentrated sulfuric acid of 36g water and 33.2g is pre-mixed as material 2.
Fe2O3Influence to calcium sulphate crystal, the impurity additive amount be Fe/Ca=0.01,0.02,0.06,0.10.
Material 1 and material 2 are added to respectively with the flow velocity of 2.8L/min and 2.0L/min to the flask of 2L by peristaltic pump
In, it is stirred to react 3h at 80 DEG C, is deducted with 4.73ml/min(reaction process air-loss by 0.07 ml/min) rate starts
Extraction liquid was sampled every 1 and a half hours later, filtering.As Fe/Ca increases, the average grain diameter of calcium sulphate crystal is gradually
Increase, there is slender rod shaped generation.The Al and Fe of similar concentration are to CaSO4Crystal growth has similar influence.When Fe/Ca=0.06,
Calcium sulphate crystal growth is best, and the shape appearance figure of crystal is shown in Fig. 3.
Embodiment 4
First by phosphoric acid, obtain acid reflux solution after sulfuric acid and water mixing, phosphoric acid, sulfuric acid, water mass ratio be 12-15:1:18-
20, this example presses 85%H3PO4The ratio of 60.9g, 98% concentrated sulfuric acid 4.3g, water 84.8g prepare a certain amount of acid reflux solution, will return
Acid solution and a water calcium dihydrogen phosphate and impurity, which are mixed, is used as material 1, the quality of acid reflux solution and a water calcium dihydrogen phosphate
Than for 1.2-1.8:1, this example is prepared in 60g acid reflux solution/mono- water calcium dihydrogen phosphate of 41.3g ratio.
Be used as material 2 after water is mixed with sulfuric acid, the mass ratio of water and 98% sulfuric acid is 0.8-1.5:1, this example according to
The ratio of 98% concentrated sulfuric acid of 36g water and 33.2g is pre-mixed as material 2.
Influence of the MgO to calcium sulphate crystal, the impurity additive amount be Mg/Ca=0.01,0.02,0.03,0.04.
Material 1 and material 2 are added to respectively with the flow velocity of 2.8L/min and 2.0L/min to the flask of 2L by peristaltic pump
In, it is stirred to react 3h at 80 DEG C, is deducted with 4.73ml/min(reaction process air-loss by 0.07 ml/min) rate starts
Extraction liquid was sampled every 1 and a half hours later, filtering.Impurity Mg the size of crystal is influenced it is smaller, on pattern influence compared with
Greatly.When Mg content is low, there is acicular crystal generation, as Mg/Ca increases, acicular crystal is gradually converted into rodlike.When Mg/Ca=
0.02, calcium sulphate crystal growth is best, and the shape appearance figure of crystal is shown in Fig. 4.
Embodiment 5
First by phosphoric acid, obtain acid reflux solution after sulfuric acid and water mixing, phosphoric acid, sulfuric acid, water mass ratio be 12-15:1:18-
20, this example presses 85%H3PO4The ratio of 60.9g, 98% concentrated sulfuric acid 4.3g, water 84.8g prepare a certain amount of acid reflux solution, will return
Acid solution and a water calcium dihydrogen phosphate and impurity, which are mixed, is used as material 1, the quality of acid reflux solution and a water calcium dihydrogen phosphate
Than for 1.2-1.8:1, this example is prepared in 60g acid reflux solution/mono- water calcium dihydrogen phosphate of 41.3g ratio.
Be used as material 2 after water is mixed with sulfuric acid, the mass ratio of water and 98% sulfuric acid is 0.8-1.5:1, this example according to
The ratio of 98% concentrated sulfuric acid of 36g water and 33.2g is pre-mixed as material 2.
Influence of the KOH to calcium sulphate crystal, the impurity additive amount be K/Ca=0.01,0.02,0.03,0.04.
Material 1 and material 2 are added to respectively with the flow velocity of 2.8L/min and 2.0L/min to the flask of 2L by peristaltic pump
In, it is stirred to react 3h at 80 DEG C, is deducted with 4.73ml/min(reaction process air-loss by 0.07 ml/min) rate starts
Extraction liquid was sampled every 1 and a half hours later, filtering.K has little effect crystal habit, with the increasing of K content
Add, crystalline size is gradually increased and tended towards stability, and due to the increase of nucleation rate, forms little particle, the shape appearance figure of crystal is shown in
Fig. 5.
Embodiment 6
First by phosphoric acid, obtain acid reflux solution after sulfuric acid and water mixing, phosphoric acid, sulfuric acid, water mass ratio be 12-15:1:18-
20, this example presses 85%H3PO4The ratio of 60.9g, 98% concentrated sulfuric acid 4.3g, water 84.8g prepare a certain amount of acid reflux solution, will return
Acid solution and a water calcium dihydrogen phosphate and impurity, which are mixed, is used as material 1, the quality of acid reflux solution and a water calcium dihydrogen phosphate
Than for 1.2-1.8:1, this example is prepared in 60g acid reflux solution/mono- water calcium dihydrogen phosphate of 41.3g ratio.
Be used as material 2 after water is mixed with sulfuric acid, the mass ratio of water and 98% sulfuric acid is 0.8-1.5:1, this example according to
The ratio of 98% concentrated sulfuric acid of 36g water and 33.2g is pre-mixed as material 2.
It investigates while Si(H is added2SiF6), Mg(MgO), Al(AlPO4), Na(NaOH) influence to calcium sulphate crystal, institute
Stating impurity additive amount is Si/Ca=0.01 to 0.05, Mg/Ca=0.01 to 0.05, Al/Ca=0.01 to 0.05, Na/Ca=0.01
To 0.04；
Material 1 and material 2 are added in the flask of 2L with the flow velocity of 2.8L/min and 2.0L/min respectively by peristaltic pump,
It is stirred to react 3h at 80 DEG C, is deducted with 4.73ml/min(reaction process air-loss by 0.07 ml/min) rate starts to extract out
Reaction solution was sampled every 1 and a half hours later, filtering, by the observation to crystalline growth and crystal form, as Si/Ca=0.02, Mg/
Calcium sulphate crystal growth is best when Ca=0.02, Al/Ca=0.01, Na/Ca=0.01, and the shape appearance figure of crystal is shown in Fig. 6.
Embodiment 7
First by phosphoric acid, obtain acid reflux solution after sulfuric acid and water mixing, phosphoric acid, sulfuric acid, water mass ratio be 12-15:1:18-
20, this example presses 85%H3PO4The ratio of 60.9g, 98% concentrated sulfuric acid 4.3g, water 84.8g prepare a certain amount of acid reflux solution, will return
Acid solution and a water calcium dihydrogen phosphate and impurity, which are mixed, is used as material 1, the quality of acid reflux solution and a water calcium dihydrogen phosphate
Than for 1.2-1.8:1, this example is prepared in 60g acid reflux solution/mono- water calcium dihydrogen phosphate of 41.3g ratio.
Be used as material 2 after water is mixed with sulfuric acid, the mass ratio of water and 98% sulfuric acid is 0.8-1.5:1, this example according to
The ratio of 98% concentrated sulfuric acid of 36g water and 33.2g is pre-mixed as material 2.
It investigates while Si(SiO is added2), Al(AlPO4), Fe(Fe2O3), Mg(MgO), Na(NaOH), to calcium sulphate crystal
Influence, the impurity additive amount be Si/Ca=0.01 to 0.05, Mg/Ca=0.01 to 0.05, Al/Ca=0.01 to 0.04,
Fe/Ca=0.01 to 0.10, Na/Ca=0.01 to 0.04.
Material 1 and material 2 are added to respectively with the flow velocity of 2.8L/min and 2.0L/min to the flask of 2L by peristaltic pump
In, it is stirred to react 3h at 80 DEG C, is deducted with 4.73ml/min(reaction process air-loss by 0.07 ml/min) rate starts
Extraction liquid was sampled every 1 and a half hours later, filtering, by the observation to crystalline growth and crystal form, when Si/Ca=
Calcium sulphate crystal growth is best when 0.03, Mg/Ca=0.02, Al/Ca=0.02, Fe/Ca=0.05, Na/Ca=0.02, crystal
Shape appearance figure is shown in Fig. 7.
Claims (10)
1. a kind of method for controlling calcium sulfate crystal form during phosphoric acid by wet process by impurity content, which is characterized in that specific as follows:
(1) by phosphoric acid, acid reflux solution is obtained after sulfuric acid and water mixing, acid reflux solution and a water calcium dihydrogen phosphate and impurity are mixed
Stirring is used as material 1；
(2) material 2 is used as after mixing water with sulfuric acid；
(3) material 1 and material 2 are added in reactor, react the product obtained after 2-5h also by compacted at being 50-90 DEG C in temperature
Dynamic pumping goes out, and extraction rate is identical as the sum of the addition rate of two kinds of solution.
2. the method for controlling calcium sulfate crystal form during phosphoric acid by wet process by impurity content as described in claim 1, feature exist
In the mass ratio of acid reflux solution and a water calcium dihydrogen phosphate is 1.2-1.8:1, P in material 12O5Mass fraction 25wt%, SO3Contain
Amount is 30-35g/L.
3. the method for controlling calcium sulfate crystal form during phosphoric acid by wet process by impurity content as described in claim 1, feature exist
In the mass concentration of phosphoric acid as described in step (1) is 85% or more；The mass concentration of the sulfuric acid is 98% or more；
The phosphoric acid, sulfuric acid, water mass ratio be 12-15:1:18-20；
The mass concentration of sulfuric acid is higher than 95% in material 2 described in step (2)；Wherein, the mass ratio of water and sulfuric acid is 0.8-
1.5:1。
4. the method for controlling calcium sulfate crystal form during phosphoric acid by wet process by impurity content as described in claim 1, feature exist
In impurity includes any one or more compound containing Si, Al, Fe, Mg, K, Na element in the material 1.
5. the method for controlling calcium sulfate crystal form during phosphoric acid by wet process by impurity content as claimed in claim 4, feature exist
In the impurity includes H2SiF6、SiO2、AlPO4、Fe2O3, any one or more in MgO, KOH, NaOH.
6. the method for controlling calcium sulfate crystal form during phosphoric acid by wet process by impurity content as claimed in claim 4, feature exist
In each impurity content is as follows:
The Si additional amount is Si/Ca=0.001 to 0.06；
The Al additional amount is Al/Ca=0.01 to 0.16；
The Fe additional amount is Fe/Ca=0.01 to 0.14；
The Mg additional amount is Mg/Ca=0.01 to 0.16；
The K additional amount is K/Ca=0.01 to 0.1；
The Na additional amount is Na/Ca=0.01 to 0.1.
7. the method for controlling calcium sulfate crystal form during phosphoric acid by wet process by impurity content as claimed in claim 6, feature exist
In being individually added into any one compound impurities containing Si, Al, Fe, Mg, K, Na element in reaction system, reach control sulfuric acid
The purpose of calcium crystal form, impurity content are as follows:
The Si additional amount is Si/Ca=0.01 to 0.05；
The Al additional amount is Al/Ca=0.01 to 0.05；
The Fe additional amount is Fe/Ca=0.01 to 0.10；
The Mg additional amount is Mg/Ca=0.01 to 0.05；
The K additional amount is K/Ca=0.01 to 0.05；
The Na additional amount is Na/Ca=0.01 to 0.05.
8. the method for controlling calcium sulfate crystal form during phosphoric acid by wet process by impurity content as claimed in claim 6, feature exist
In, the multiple compounds impurity containing Si, Al, Fe, Mg, K, Na element, preferably the following two kinds scheme are added in reaction system, wherein
Impurity content is as follows:
While described be added Si, Mg, Al, K, additional amount be Si/Ca=0.01 to 0.05, Mg/Ca=0.01 to 0.05, Al/Ca=
0.01 to 0.05, Na/Ca=0.01 to 0.04；
Si, Al, Fe, Mg, Na are added while described, additional amount is Si/Ca=0./1 to 0.05, Mg/Ca=0.01 to 0.05,
Al/Ca=0.01 is to 0.0.04, Fe/Ca=0.01 to 0.03, Na/Ca=0.01 to 0.04.
9. the method for controlling calcium sulfate crystal form during phosphoric acid by wet process by impurity content as described in claim 1, feature exist
In the flow of material 1 and material 2 is 7:3-6.
10. the method for controlling calcium sulfate crystal form during phosphoric acid by wet process by impurity content as described in claim 1, feature exist
In the reaction temperature of material 1 and material 2 in the reactor is 70 DEG C, 75 DEG C or 80 DEG C, reaction time 2h and 3h.
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