CN105197939A - Acid pickling and waste acid treatment process for improving purity of powdery quartz sand - Google Patents
Acid pickling and waste acid treatment process for improving purity of powdery quartz sand Download PDFInfo
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- CN105197939A CN105197939A CN201510626781.XA CN201510626781A CN105197939A CN 105197939 A CN105197939 A CN 105197939A CN 201510626781 A CN201510626781 A CN 201510626781A CN 105197939 A CN105197939 A CN 105197939A
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- acid
- quartz sand
- pickling
- calcium
- sand powder
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000006004 Quartz sand Substances 0.000 title claims abstract description 74
- 238000005554 pickling Methods 0.000 title claims abstract description 64
- 239000002253 acid Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002699 waste material Substances 0.000 title abstract 4
- 238000010306 acid treatment Methods 0.000 title abstract 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000001556 precipitation Methods 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- -1 iron ions Chemical class 0.000 claims abstract description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011575 calcium Substances 0.000 claims abstract description 26
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 26
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 49
- 235000021110 pickles Nutrition 0.000 claims description 37
- 239000012065 filter cake Substances 0.000 claims description 24
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 239000008399 tap water Substances 0.000 claims description 6
- 235000020679 tap water Nutrition 0.000 claims description 6
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract 1
- 238000010979 pH adjustment Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 239000010433 feldspar Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000010786 composite waste Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- NOMZRECDBIBSDZ-UHFFFAOYSA-L potassium;sodium;oxalate Chemical compound [Na+].[K+].[O-]C(=O)C([O-])=O NOMZRECDBIBSDZ-UHFFFAOYSA-L 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention provides an acid pickling and waste acid treatment process for improving purity of powdery quartz sand. The process includes the steps: putting the powdery quartz sand in an acid pickling purification device, and using an acid pump for pumping acid pickling solution into the acid pickling purification device, wherein the acid pickling solution is composed of hydrofluoric acid, fluorosilicic acid, oxalic acid and water or composed of fluorosilicic acid, oxalic acid and water; removing the acid pickling solution after acid pickling, and collecting; delivering the powdery quartz sand to a washing device by clear water after acid pickling, washing to neutral, and dewatering to obtain a finished product of powdery quartz sand; transferring waste acid into a neutralization tank for neutralization, delivering into a sedimentation tank by the pump, and allowing calcium fluosilicate and calcium oxalate to precipitate; delivering the clear water into a regulation tank after precipitation to realize pH adjustment for precipitation of iron ions; using oxalic acid or fluorosilicic acid to adjust pH, precipitating calcium fluosilicate and calcium oxalate again, filtering to obtain clear water, and delivering the clear water to a workshop for recycling. The acid pickling and waste acid treatment process for improving purity of the powdery quartz sand has the advantages of remarkable purity improvement and impurity reduction and simplicity and convenience in subsequent treatment.
Description
Technical field
The invention provides a kind of improve quartz sand powder purity pickling and useless acid-treated technique, relate to the formula of pickle solution, after pickling purifying technique and pickling, the treatment process of waste water, belongs to nonmetalliferous ore deep processing and environmental technology field.
Background technology
Quartz sand is one of a kind of important ceramic, and it is widely used in the industries such as glass, pottery, cement, refractory materials; The height of quartz sand grade (purity) and the size of value depend primarily on the number of the metallic impurity mineral content of quartz sand self, especially with impurity iron for the content representing metalliferous mineral is how many, decide self-value and the use value of quartz sand.In order to effectively reduce the content of the irony element in quartz sand, usual people are preparing the way deironing mostly adopting high intensity magnetic separation in quartz sand process, and its effect is not very desirable, is difficult to the requirement reaching expection; For this reason, the general way deironing just adopting chemical pickling in this area, although the way deironing of pickling can reach and exceed the requirement of expection, can produce a large amount of acid-bearing wastewaters in acid cleaning process needs process.This just brings a series of environmental issue.Present people to be used for the acid solution of quartz sand purifying and mostly to adopt strong acid as acid solution and composite acid solutions thereof such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid; What these acid solutions produced wants to accomplish complete recycle containing sour spent acid process (sulfuric acid outer), needs to drop into huge environment friendly system and equipment, and this, for the large enterprise of turnout, is very difficult.
Acid solution composite is in the art as hydrofluoric acid, silicofluoric acid and sulfuric acid; Hydrofluoric acid, silicofluoric acid and nitric acid; Composite acid solutions such as hydrofluoric acid, silicofluoric acid and hydrochloric acid or dioxide-containing silica can be improved, but deironing does not reach requirement; Be that deironing reaches requirement, and the purity of silicon-dioxide can not be improved; Can reach requirement and calcium ion concn after follow-up acid-bearing wastewater process in water exceeds standard and cause the saltiness in the quartz sand after washing too high, the purity of last silicon-dioxide does not still reach the object of expection.
For this reason, the enterprise being engaged in purifying quartz sand in this area urgently wishes to study a kind of acid formula that can either improve quartz sand purity, this acid-bearing wastewater can be processed very well again, acid-bearing wastewater after process all can also be recycled and is not affected the processing method of quality product, and the method also needs to possess: environmental protection facility drops into the technical requirementss such as little, running cost is low, easy to operate, it is also one of brand-new problem of of quartz sand powder purification domain engineering technician.
Summary of the invention
The invention solves the deficiency in background technology, provide a kind of improve quartz sand powder purity pickling and useless acid-treated technique, the present invention can improve the purity of the silicon-dioxide in quartz sand significantly and significant reduce in quartz sand the impure minerals such as aluminium sesquioxide, basic metal, ferric oxide, titanium dioxide, meanwhile, the waste water that subsequent handling of the present invention produces easily processes cleaning.
Realizing the technical scheme that above-mentioned purpose of the present invention adopts is:
A kind of improve quartz sand powder purity pickling and useless acid-treated technique, comprise the following steps: (1), quartz sand powder to be purified is put in pickling purifying plant, pickle solution to be pumped in pickling purifying plant and the negative pressure water absorption system opened in pickling purifying plant with sour pump, described pickle solution is made up of 1 ~ 10% hydrofluoric acid, 5 ~ 20% silicofluoric acid, 3 ~ 20% oxalic acid and 50 ~ 90% water, or is made up of 10 ~ 20% silicofluoric acid, 5 ~ 20% oxalic acid and 60 ~ 85% water;
(2), by heating temperatures to 60 ~ 85 DEG C in pickling purifying plant, and ON cycle system makes the pickle solution of heat circulate dynamic acid-washed quartz sand powder, and pickling removes pickle solution after 3 ~ 6 hours and collects;
(3), deliver in water washing device with clear water by the quartz sand powder after pickling in pickling purifying plant, by quartz sand powder washing to neutrality, dehydration i.e. obtained finished product quartz sand powder;
(4), the pickle solution collected in step (2) is transferred in neutralization tank with after lime slurry neutralization to pH=6 ~ 7, generate calcium silicofluoride and calcium oxalate precipitation, by the pickle solution after neutralization with being pumped in settling tank, in settling tank under calcium silicofluoride and calcium oxalate precipitation, reclaim after the material pressure filter of collecting precipitation is pressed into filter cake and use;
(5), by the clear water after calcium silicofluoride and calcium oxalate precipitation send in equalizing tank again and regulate pH=8.5 ~ 9, with precipitated iron ion, the iron ion material pressure filter after precipitation is pressed into filter cake and reclaims use;
(6), by the clear water after precipitation of iron ions send into equalizing tank again, after regulating pH=6 ~ 7, again precipitate caoxalate with oxalic acid, the calcium ion concn in the clear water obtained after filtering with quartz filter is identical with tap water, can deliver to workshop and recycle.
The dilute sulphuric acid reaction of equivalent with it of described calcium silicofluoride and caoxalate filter cake, the silicofluoric acid of generation and oxalic acid deliver to workshop recycle again, and the calcium sulfate of generation can be made byproduct and sell.
Described iron ion filter cake is sold as the raw material preparing ferrous sulfate.
Because it is a thermopositive reaction that hydrofluoric acid and quartz sand and feldspar react in the present invention, and generation silicon tetrafluoride gas, namely this gas is dissolved in the water of system is silicofluoric acid; And the reaction of silicofluoric acid and quartz sand and feldspar is slow, it can fast decoupled feldspar and molten except quartz sand powder in case of heating; In this system, hydrofluoric acid and quartz sand powder react liberated heat that oxalic acid can be impelled to accelerate complexing are molten except the irony element in quartz sand and feldspar, thus reach can feldspar in fast decoupled quartz sand, reduce again the ferric oxide content in quartz sand fast, thus arrive the object of purifying quartz sand powder purity.
To compare prior art, adopt the composite acid solution of hydrofluoric acid, silicofluoric acid and oxalic acid can improve the purity of the silicon-dioxide in quartz sand significantly and significant reduce in quartz sand the impure minerals such as aluminium sesquioxide, basic metal, ferric oxide, titanium dioxide in the present invention, achieve unexpected effect.But also finding that the composite waste water of other acid solutions of waste water ratio that its subsequent handling produces will easily process and clean a lot, its Economic model is very remarkable.
In addition, the present invention is in the technique processed spent acid, and the calcium sulfate of generation can make byproduct, or is used for producing the products such as Sodium Silicofluoride (potassium) and sodium oxalate (potassium) with produced silicofluoric acid and oxalic acid.The iron ion be settled out can be used as produces ferrous sulfate raw material.Its whole production process does not have waste water, spent acid and waste gas to arrange outward, is the green production process of energy-saving and environmental protection.
Embodiment
Below in conjunction with specific embodiment, detailed specific description is done to the present invention, but protection scope of the present invention is not limited to following examples.
The pickling purifying plant adopted in following examples is the patent No.: the device provided in ZL201110247061.4, the authorized announcement date of this patent: on November 7th, 2012.
Embodiment 1
The step provided in the present embodiment is as follows: (1), put in pickling purifying plant by quartz sand powder to be purified, to be pumped into by pickle solution in pickling purifying plant and the negative pressure water absorption system opened in pickling purifying plant with sour pump, described pickle solution is made up of 10 ~ 20% silicofluoric acid, 5 ~ 20% oxalic acid and 60 ~ 85% water.The quartz sand powder that the quartz sand powder to be purified used in this embodiment produces for Anhui silica sand company, after testing following (massfraction): the SiO of its composition
2: 99.52%, Al
2o
3: 1460ppm, Fe
2o
3: 201ppm, TiO
2: 49.2ppm, Na
20:50.2ppm, K
20:522.8ppm.
(2), by the heating temperatures to 60 DEG C in pickling purifying plant, and ON cycle system makes the pickle solution of heat circulate dynamic acid-washed quartz sand powder, and pickling removes pickle solution after 6 hours and collects.
(3), deliver in water washing device with clear water by the quartz sand powder after pickling in pickling purifying plant, by quartz sand powder washing to neutrality, dehydration i.e. obtained finished product quartz sand powder.Product is after testing: SiO
2: 99.87%, Al
2o
3: 348.6ppm, Fe
2o
3: 23ppm, TiO
2: 14ppm, Na
20:15.6ppm, K
20:65ppm.
(4), the pickle solution collected in step (2) is transferred in neutralization tank with after lime slurry neutralization to pH=6, generate calcium silicofluoride and calcium oxalate precipitation, by the pickle solution after neutralization with being pumped in settling tank, in settling tank under calcium silicofluoride and calcium oxalate precipitation, reclaim after the material pressure filter of collecting precipitation is pressed into filter cake and use;
The dilute sulphuric acid reaction of equivalent with it of described calcium silicofluoride and caoxalate filter cake, the silicofluoric acid of generation and oxalic acid deliver to workshop recycle again, and the calcium sulfate of generation can be made byproduct and sell.
(5), by the clear water after calcium silicofluoride and calcium oxalate precipitation send in equalizing tank again and regulate pH=8.5, with precipitated iron ion, the iron ion material pressure filter after precipitation is pressed into filter cake and reclaims use; The raw material that described iron ion filter cake can be used as preparing ferrous sulfate is sold.
(6), by the clear water after precipitation of iron ions send into equalizing tank again, after regulating pH=6.5, again precipitate caoxalate with oxalic acid, the calcium ion concn in the clear water obtained after filtering with quartz filter is identical with tap water, can deliver to workshop and recycle.
Embodiment 2
The step provided in the present embodiment is as follows: (1), put in pickling purifying plant by quartz sand powder to be purified, to be pumped into by pickle solution in pickling purifying plant and the negative pressure water absorption system opened in pickling purifying plant with sour pump, described pickle solution is made up of 1 ~ 10% hydrofluoric acid, 5 ~ 20% silicofluoric acid, 3 ~ 20% oxalic acid and 50 ~ 90% water.The quartz sand powder that the quartz sand powder to be purified used in this embodiment produces for Anhui silica sand company, after testing following (massfraction): the SiO of its composition
2: 99.52%, Al
2o
3: 1460ppm, Fe
2o
3: 201ppm, TiO
2: 49.2ppm, Na
20:50.2ppm, K
20:522.8ppm.
(2), by the heating temperatures to 80 DEG C in pickling purifying plant, and ON cycle system makes the pickle solution of heat circulate dynamic acid-washed quartz sand powder, and pickling removes pickle solution after 3 hours and collects.
(3), deliver in water washing device with clear water by the quartz sand powder after pickling in pickling purifying plant, by quartz sand powder washing to neutrality, dehydration i.e. obtained finished product quartz sand powder.Product is after testing: SiO
2: 99.91%, Al
2o
3: 196.6ppm, Fe
2o
3:, 14ppm, TiO
2: 9.6ppm, Na
20:7.8ppm, K
20:28ppm.
(4), the pickle solution collected in step (2) is transferred in neutralization tank with after lime slurry neutralization to pH=7, generate calcium silicofluoride and calcium oxalate precipitation, by the pickle solution after neutralization with being pumped in settling tank, in settling tank under calcium silicofluoride and calcium oxalate precipitation, reclaim after the material pressure filter of collecting precipitation is pressed into filter cake and use;
The dilute sulphuric acid reaction of equivalent with it of described calcium silicofluoride and caoxalate filter cake, the silicofluoric acid of generation and oxalic acid deliver to workshop recycle again, and the calcium sulfate of generation can be made byproduct and sell.
(5), by the clear water after calcium silicofluoride and calcium oxalate precipitation send in equalizing tank again and regulate pH=9, with precipitated iron ion, the iron ion material pressure filter after precipitation is pressed into filter cake and reclaims use; The raw material that described iron ion filter cake can be used as preparing ferrous sulfate is sold.
(6), by the clear water after precipitation of iron ions send into equalizing tank again, after regulating pH=7, again precipitate caoxalate with oxalic acid, the calcium ion concn in the clear water obtained after filtering with quartz filter is identical with tap water, can deliver to workshop and recycle.
Embodiment 3
The step provided in the present embodiment is as follows: (1), put in pickling purifying plant by quartz sand powder to be purified, to be pumped into by pickle solution in pickling purifying plant and the negative pressure water absorption system opened in pickling purifying plant with sour pump, described pickle solution is made up of 1 ~ 10% hydrofluoric acid, 5 ~ 20% silicofluoric acid, 3 ~ 20% oxalic acid and 50 ~ 90% water.The quartz sand powder that the quartz sand powder to be purified used in this embodiment produces for Shandong silica sand company, after testing following (massfraction): the SiO of its composition
2: 98.69%, Al
2o
3: 5800ppm, Fe
2o
3: 1510ppm, TiO
2: 230ppm, Na
20:20.5ppm, K
20:1200ppm.
(2), by the heating temperatures to 70 DEG C in pickling purifying plant, and ON cycle system makes the pickle solution of heat circulate dynamic acid-washed quartz sand powder, and pickling removes pickle solution after 3 hours and collects.
(3), deliver in water washing device with clear water by the quartz sand powder after pickling in pickling purifying plant, by quartz sand powder washing to neutrality, dehydration i.e. obtained finished product quartz sand powder.Product is after testing: SiO
2: 99.84%, Al
2o
3: do not detect, Fe
2o
3: 49ppm, TiO
2: 100ppm, Na
20: do not detect, K
20: do not detect.
(4), the pickle solution collected in step (2) is transferred in neutralization tank with after lime slurry neutralization to pH=6.5, generate calcium silicofluoride and calcium oxalate precipitation, by the pickle solution after neutralization with being pumped in settling tank, in settling tank under calcium silicofluoride and calcium oxalate precipitation, reclaim after the material pressure filter of collecting precipitation is pressed into filter cake and use;
The dilute sulphuric acid reaction of equivalent with it of described calcium silicofluoride and caoxalate filter cake, the silicofluoric acid of generation and oxalic acid deliver to workshop recycle again, and the calcium sulfate of generation can be made byproduct and sell.
(5), by the clear water after calcium silicofluoride and calcium oxalate precipitation send in equalizing tank again and regulate pH=8.5, with precipitated iron ion, the iron ion material pressure filter after precipitation is pressed into filter cake and reclaims use; The raw material that described iron ion filter cake can be used as preparing ferrous sulfate is sold.
(6), by the clear water after precipitation of iron ions send into equalizing tank again, after regulating pH=6.4, again precipitate caoxalate with oxalic acid, the calcium ion concn in the clear water obtained after filtering with quartz filter is identical with tap water, can deliver to workshop and recycle.
Embodiment 4
The step provided in the present embodiment is as follows: (1), put in pickling purifying plant by quartz sand powder to be purified, to be pumped into by pickle solution in pickling purifying plant and the negative pressure water absorption system opened in pickling purifying plant with sour pump, described pickle solution is made up of 10 ~ 20% silicofluoric acid, 5 ~ 20% oxalic acid and 60 ~ 85% water.The quartz sand powder that the quartz sand powder to be purified used in this embodiment produces for Shandong silica sand company, after testing following (massfraction): the SiO of its composition
2: 98.76%, Al
2o
3: 6000ppm, Fe
2o
3: 580ppm, TiO
2: 260ppm, Na
20:10ppm, K
20:1300ppm.
(2), by the heating temperatures to 60 DEG C in pickling purifying plant, and ON cycle system makes the pickle solution of heat circulate dynamic acid-washed quartz sand powder, and pickling removes pickle solution after 6 hours and collects.
(3), deliver in water washing device with clear water by the quartz sand powder after pickling in pickling purifying plant, by quartz sand powder washing to neutrality, dehydration i.e. obtained finished product quartz sand powder.Product is after testing: SiO
2: 99.86%, Al
2o
3: do not detect, Fe
2o
3: 76ppm, TiO
2: 180ppm, Na
20: do not detect, K
20: do not detect.
(4), the pickle solution collected in step (2) is transferred in neutralization tank with after lime slurry neutralization to pH=6, generate calcium silicofluoride and calcium oxalate precipitation, by the pickle solution after neutralization with being pumped in settling tank, in settling tank under calcium silicofluoride and calcium oxalate precipitation, reclaim after the material pressure filter of collecting precipitation is pressed into filter cake and use;
The dilute sulphuric acid reaction of equivalent with it of described calcium silicofluoride and caoxalate filter cake, the silicofluoric acid of generation and oxalic acid deliver to workshop recycle again, and the calcium sulfate of generation can be made byproduct and sell.
(5), by the clear water after calcium silicofluoride and calcium oxalate precipitation send in equalizing tank again and regulate pH=8.5, with precipitated iron ion, the iron ion material pressure filter after precipitation is pressed into filter cake and reclaims use; The raw material that described iron ion filter cake can be used as preparing ferrous sulfate is sold.
(6), by the clear water after precipitation of iron ions send into equalizing tank again, after regulating pH=6.5, again precipitate caoxalate with oxalic acid, the calcium ion concn in the clear water obtained after filtering with quartz filter is identical with tap water, can deliver to workshop and recycle.
Claims (3)
1. one kind is improved the pickling of quartz sand powder purity and useless acid-treated technique, it is characterized in that comprising the following steps: (1), quartz sand powder to be purified is put in pickling purifying plant, pickle solution to be pumped in pickling purifying plant and the negative pressure water absorption system opened in pickling purifying plant with sour pump, described pickle solution is made up of 1 ~ 10% hydrofluoric acid, 5 ~ 20% silicofluoric acid, 3 ~ 20% oxalic acid and 50 ~ 90% water, or is made up of 10 ~ 20% silicofluoric acid, 5 ~ 20% oxalic acid and 60 ~ 85% water;
(2), by heating temperatures to 60 ~ 85 DEG C in pickling purifying plant, and ON cycle system makes the pickle solution of heat circulate dynamic acid-washed quartz sand powder, and pickling removes pickle solution after 3 ~ 6 hours and collects;
(3), deliver in water washing device with clear water by the quartz sand powder after pickling in pickling purifying plant, by quartz sand powder washing to neutrality, dehydration i.e. obtained finished product quartz sand powder;
(4), the pickle solution collected in step (2) is transferred in neutralization tank with after lime slurry neutralization to pH=6 ~ 7, generate calcium silicofluoride and calcium oxalate precipitation, by the pickle solution after neutralization with being pumped in settling tank, in settling tank under calcium silicofluoride and calcium oxalate precipitation, reclaim after the material pressure filter of collecting precipitation is pressed into filter cake and use;
(5), by the clear water after calcium silicofluoride and calcium oxalate precipitation send in equalizing tank again and regulate pH=8.5 ~ 9, with precipitated iron ion, the iron ion material pressure filter after precipitation is pressed into filter cake and reclaims use;
(6), by the clear water after precipitation of iron ions send into equalizing tank again, after regulating pH=6 ~ 7 with oxalic acid, precipitation caoxalate, the calcium ion concn in the clear water obtained after filtering with quartz filter is identical with tap water, can deliver to workshop and recycle.
2. the pickling of raising quartz sand powder purity according to claim 1 and useless acid-treated technique, it is characterized in that: the dilute sulphuric acid reaction of equivalent with it of described calcium silicofluoride and caoxalate filter cake, the silicofluoric acid generated and oxalic acid deliver to workshop recycle again, and the calcium sulfate of generation can be made byproduct and sell.
3. the pickling of raising quartz sand powder purity according to claim 1 and useless acid-treated technique, is characterized in that: described iron ion filter cake is sold as the raw material preparing ferrous sulfate.
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