CN115028170A - Method for producing low-iron siliceous raw material by combined scrubbing of fluoride-free alkali and acid - Google Patents
Method for producing low-iron siliceous raw material by combined scrubbing of fluoride-free alkali and acid Download PDFInfo
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- CN115028170A CN115028170A CN202210711693.XA CN202210711693A CN115028170A CN 115028170 A CN115028170 A CN 115028170A CN 202210711693 A CN202210711693 A CN 202210711693A CN 115028170 A CN115028170 A CN 115028170A
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- 239000002253 acid Substances 0.000 title claims abstract description 163
- 238000005201 scrubbing Methods 0.000 title claims abstract description 161
- 239000003513 alkali Substances 0.000 title claims abstract description 118
- 239000002994 raw material Substances 0.000 title claims abstract description 98
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000243 solution Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 6
- 239000011737 fluorine Substances 0.000 claims 6
- 229910052731 fluorine Inorganic materials 0.000 claims 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 37
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 14
- 239000006004 Quartz sand Substances 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 41
- 239000004576 sand Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000007885 magnetic separation Methods 0.000 description 16
- 239000012141 concentrate Substances 0.000 description 15
- 229960002050 hydrofluoric acid Drugs 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 239000002210 silicon-based material Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000009991 scouring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011044 quartzite Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention belongs to the technical field of purification and deep processing of nonmetallic ores, and particularly relates to a method for producing a low-iron siliceous raw material by combined scrubbing of fluorine-free alkali and acid. The method provided by the invention comprises the following steps: (1) continuously mixing the siliceous raw material with alkali liquor to carry out alkali scrubbing, and carrying out solid-liquid separation to obtain an alkali-scrubbed siliceous raw material, wherein the alkali liquor is an aqueous solution of inorganic strong alkali and/or alkali carbonate; (2) continuously mixing the alkali washing siliceous raw material with a fluorine-free acid solution to carry out acid scrubbing, and carrying out solid-liquid separation to obtain the low-iron siliceous raw material, wherein the fluorine-free acid solution is an aqueous solution of inorganic strong acid and/or oxalic acid. The method provided by the invention adopts series alkali scrubbing and acid scrubbing, and realizes continuous and dynamic reduction of Fe in siliceous raw materials on the basis of not using hydrofluoric acid 2 O 3 、Al 2 O 3 The content of the low-iron silicon raw material quartz sand can be used for producing the low-iron silicon raw material quartz sand. Moreover, the invention adopts a fluoride-free alkali-acid combined scrubbing method, has low environmental-friendly admission condition and environmental-friendly treatmentIs easy to reach the standard.
Description
Technical Field
The invention belongs to the technical field of purification and deep processing of nonmetallic ores, and particularly relates to a method for producing a low-iron siliceous raw material by combined scrubbing of fluorine-free alkali and acid.
Background
Along with the rapid development of industries such as semiconductor, electron, photovoltaic new energy and the like, the silicon material (SiO) 2 ) The quality requirement of (2) is higher and higher, especially the content of the siliceous raw material is concerned, the low iron content is required, and the Fe is generally required 2 O 3 A content of less than 0.010%, and high silicidation, generally requiring SiO 2 The content is more than 99.50 percent.
At present, the methods for producing low-iron siliceous raw materials mainly comprise the following two methods: 1. the conventional physical method treatment process comprises the following steps: for high-quality siliceous raw materials including high-quality vein quartz, quartzite or imported high-quality sea sand and the like, the processing method mainly comprises physical processes of grinding, grading, magnetic separation, gravity separation and the like, and the processing method mainly utilizes the quality of high silicon and low iron of the high silicon and low iron to produce and process; 2. acid leaching process: for common or poor-quality siliceous raw materials, including common vein quartz, quartzite, quartz sandstone, quartz sand and the like, after the treatment in the step 1, the quality is difficult to reach the standard, and an acid leaching process is required to be added: namely, the siliceous raw material treated in the step 1 is soaked in hydrofluoric acid and oxalic acid at a temperature of 50-95 ℃, undergoes a long-time (4-48 h) chemical dissolution reaction, and is washed with water to remove iron and extract silicon.
The method 1 needs to use siliceous resources with excellent quality, but the siliceous raw material resources have small reserves and high raw ore cost, and the requirements of sustainable development of the industry are difficult to meet along with the gradual shortage of domestic resources. The method 2 is intermittent production in hydrofluoric acid environment, utilizes heating for long-time reaction to leach and remove iron, has high cost and F - Environmental pollution of ions, and the like.
Disclosure of Invention
In view of this, the invention provides a method for producing low-iron siliceous materials by combined scrubbing of fluoride-free alkali and acid. The invention adopts a fluoride-free alkali-acid combined scrubbing method, has low environmental protection admittance conditions and simple environmental protection standard-reaching treatment; and the low-iron siliceous raw material treated by the method provided by the invention has obviously reduced treatment cost on the premise of reaching the chemical index standard.
In order to solve the technical problem, the invention provides a method for continuously producing low-iron siliceous raw materials by combined scrubbing of fluoride-free alkali and acid, which comprises the following steps:
(1) continuously mixing the siliceous raw material with alkali liquor to carry out alkali scrubbing, and carrying out solid-liquid separation to obtain an alkali-scrubbed siliceous raw material, wherein the alkali liquor is an aqueous solution of inorganic strong alkali and/or alkali carbonate;
(2) continuously mixing the alkali washing siliceous raw material with a fluorine-free acid solution to carry out acid scrubbing, and carrying out solid-liquid separation to obtain the low-iron siliceous raw material, wherein the fluorine-free acid solution is an aqueous solution of inorganic strong acid and/or oxalic acid.
Preferably, the mass percentage of the alkali liquor is 10-25%.
Preferably, the ratio of the feeding mass of the siliceous raw material to the volume of the alkali liquor in unit time is 25t (1.5-2) m 3 。
Preferably, the fluorine-free acid solution is an aqueous solution of inorganic strong acid and oxalic acid, the mass percentage of the inorganic strong acid in the fluorine-free acid solution is 10-25%, and the mass percentage of the oxalic acid in the fluorine-free acid solution is 5-8%.
Preferably, the volume percentage content of the raw material particles with the particle size distribution of 0.71-0.125 mm of the siliceous raw material is more than or equal to 95%.
Preferably, the alkaline scrubbing and the acid scrubbing are carried out independently in a scrubbing machine, the linear velocity of the scrubbing impellers of the scrubbing machine being independently > 15m/s for the alkaline scrubbing and the acid scrubbing.
Preferably, the alkali scrubbing and the acid scrubbing are independently performed under the ultrasonic wave auxiliary condition, the working frequency of the ultrasonic wave is independently 20-100 kHz, and the power of the ultrasonic wave is independently 80-120W.
Preferably, the temperature of the alkali scrubbing and the acid scrubbing is independently 50 to 120 ℃.
Preferably, in the step (1), scrubbing alkali liquor is obtained through solid-liquid separation, the scrubbing alkali liquor is circularly used for alkali scrubbing, and the alkali scrubbing is carried outThe alkali liquor used for washing comprises circularly entered scrubbing alkali liquor and continuously supplemented newly added alkali liquor, and the flow velocity of the newly added alkali liquor is 0.3-0.8 m when the alkali is scrubbed 3 And h, the mass percentage of the newly added alkali liquor is 15-30%.
Preferably, in the step (2), the solid-liquid separation further obtains a scrubbing fluoride-free acid solution, the scrubbing fluoride-free acid solution is circularly scrubbed by the acid, the fluoride-free acid solution used for scrubbing by the acid comprises the circularly-entered scrubbing fluoride-free acid solution and continuously-supplemented newly-added fluoride-free acid solution, and when scrubbing by the acid is performed, the flow rate of the newly-added fluoride-free acid solution is 0.5-1.2 m 3 And h, the newly added fluorine-free acid solution is an aqueous solution of inorganic strong acid and oxalic acid, the mass percentage of the inorganic strong acid in the newly added fluorine-free acid solution is 10-25%, and the mass percentage of the oxalic acid in the newly added fluorine-free acid solution is 5-8%.
The invention provides a method for continuously producing low-iron siliceous raw materials by combined scrubbing of fluoride-free alkali and acid, which comprises the following steps: (1) continuously mixing the siliceous raw material with alkali liquor to carry out alkali scrubbing, and carrying out solid-liquid separation to obtain an alkali scrubbing siliceous raw material, wherein the alkali liquor is an aqueous solution of inorganic strong alkali and/or alkali carbonate; (2) continuously mixing the alkali washing siliceous raw material with a fluorine-free acid solution to carry out acid scrubbing, and carrying out solid-liquid separation to obtain the low-iron siliceous raw material, wherein the fluorine-free acid solution is an aqueous solution of inorganic strong acid and/or oxalic acid. The method provided by the invention adopts series alkali scrubbing and acid scrubbing, firstly, the siliceous raw material is subjected to alkali scrubbing in alkali liquor, and the alkali liquor and SiO in the siliceous raw material are utilized 2 Reaction to dissolve the surface of silicon material and expose the same SiO in the surface and gap of silicon material 2 Intergrowth of Fe 2 O 3 、Al 2 O 3 Minerals, and simultaneously realizes Fe in gaps of siliceous raw materials in the continuous and dynamic alkali liquor scrubbing process 2 O 3 、Al 2 O 3 The mineral is rapidly stripped from the gap and is fully exposed on the surface of the siliceous raw material; then in the process of scrubbing without fluorine-free acid solution, the water solution of inorganic strong acid and/or oxalic acid and Fe 2 O 3 、Al 2 O 3 Mineral reaction, stripping from the surface of siliceous material during continuous dynamic scrubbing with a fluoride-free acid solutionRemoving Fe in siliceous raw material 2 O 3 、Al 2 O 3 The purpose of (1). In conclusion, the method provided by the invention adopts the series connection of alkali scrubbing and acid scrubbing, and realizes the continuous dynamic reduction of Fe in the siliceous raw material on the basis of not using hydrofluoric acid 2 O 3 、Al 2 O 3 The content of the iron-silicon-based raw material can be used for producing low-iron silicon-based raw materials. Moreover, the invention adopts a fluoride-free alkali-acid combined scrubbing method, so that the environmental protection admittance condition is low, and the environmental protection standard-reaching treatment is easy; the treatment cost of the low-iron siliceous raw material treated by the method provided by the invention is obviously reduced on the premise of meeting the chemical index standard, and the results of the embodiment show that the method for continuously producing the low-iron siliceous raw material by jointly scrubbing the fluorine-free alkali and the acid has the following warehousing quality: SiO 2 2 ≥99.40％，Al 2 O 3 ≤0.11％，Fe 2 O 3 Less than or equal to 96ppm, the quality of the concentrate meets the requirement, the concentrate yield is 550t/d, and the treatment cost is reduced by about 50 percent compared with the hydrofluoric acid pickling process.
Drawings
FIG. 1 is a flow chart of a process for continuously producing a low-iron siliceous material by using a fluorine-free alkaline-acid combined scrubbing method according to an embodiment of the present invention.
Detailed Description
The invention provides a method for continuously producing low-iron siliceous raw materials by combined scrubbing of fluoride-free alkali and acid, which comprises the following steps:
(1) continuously mixing the siliceous raw material with alkali liquor to carry out alkali scrubbing, and carrying out solid-liquid separation to obtain an alkali-scrubbed siliceous raw material, wherein the alkali liquor is an aqueous solution of inorganic strong alkali and/or alkali carbonate;
(2) continuously mixing the alkali washing siliceous raw material with a fluorine-free acid solution to carry out acid scrubbing, and carrying out solid-liquid separation to obtain the low-iron siliceous raw material, wherein the fluorine-free acid solution is an aqueous solution of inorganic strong acid and/or oxalic acid.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art unless otherwise specified.
The invention continuously mixes siliceous raw materials with alkali liquor (hereinafter referred to as first mixing) to carry out alkali scrubbing, and carries out solid-liquid separation (hereinafter referred to as first solid-liquid separation) to obtain alkali scrubbing siliceous raw materials, wherein the alkali liquor is an aqueous solution of inorganic strong base and/or alkali carbonate.
In the present invention, the method for producing the siliceous raw material preferably comprises the steps of:
sequentially carrying out crushing, grinding, medium-strength magnetic separation, primary high-strength magnetic separation, secondary high-strength magnetic separation and classification on the quartz sandstone ore to obtain the siliceous raw material.
The invention has no special requirements on the specific implementation process of crushing and grinding.
In the present invention, the magnetic field strength at the time of the medium-intensity magnetic separation is preferably 0.5T.
In the present invention, the magnetic field strength in the first-level high-intensity magnetic separation is preferably 1.3T.
In the present invention, the magnetic field strength at the time of the second-stage high-intensity magnetic separation is preferably 1.5T.
The present invention has no particular requirement for the specific implementation of the classification.
In the invention, the siliceous raw material is siliceous raw material sand, which is named as quartz raw sand.
In the invention, the volume percentage content of the raw material particles with the particle size distribution of 0.71-0.125 mm of the siliceous raw material is more than or equal to 95%.
In the present invention, the chemical composition of the siliceous material is preferably: SiO 2 2 ：98.85％，Al 2 O 3 ：0.38％，Fe 2 O 3 ：0.041％。
In the present invention, the yield of the siliceous material was 20 t/h.
In the present invention, the aqueous solution of the inorganic strong base and/or the alkali metal carbonate is used.
In the present invention, the inorganic strong base is preferably sodium hydroxide and/or potassium hydroxide, and more preferably sodium hydroxide.
In the present invention, the alkali metal carbonate is preferably sodium carbonate and/or potassium carbonate, more preferably sodium carbonate.
In a particular embodiment of the invention, the inorganic strong base is preferably sodium hydroxide.
In the invention, the alkali liquor is preferably 10-25% by mass, and more preferably 12-25% by mass.
In the invention, the ratio of the feeding mass of the siliceous raw material to the volume of the alkali liquor is preferably 25t (1.5-2) m in unit time 3 Preferably 25t (1.6-1.8) m 3 。
In the present invention, the continuous feeding rate of the siliceous material is preferably 25t/h at the time of the alkali scouring.
In the present invention, the first mixing is preferably carried out in a scouring machine.
In the present invention, the alkali scouring is preferably performed in a scouring machine.
In an embodiment of the invention, the scrubber is purchased from mechanical equipment technologies, Inc. of Yikay, Jiangsu.
As a specific embodiment of the present invention, the alkaline scrubbing was performed in 3 tandem double-tank scrubbers.
As an embodiment of the invention, the double tank scrubber has a charge volume of 2m 3 。
In the invention, the linear speed of the scrubbing impeller of the scrubbing machine is preferably more than 15m/s, and more preferably 15.5-18 m/s during alkaline scrubbing.
In the invention, the alkali scrubbing is preferably carried out under the auxiliary condition of ultrasonic waves, and the working frequency of the ultrasonic waves is preferably 20-100 kHz, and more preferably 25-80 Hz.
In the present invention, the power of the ultrasonic wave is preferably 80 to 120W, and more preferably 100W.
In the present invention, the acid scrubbing is preferably carried out under ultrasonic assistance, and the ultrasonic device is preferably an ultrasonic sonification device attached to the scrubbing machine, and the ultrasonic device is preferably an indirect contact type ultrasonic sonification device.
In the invention, the temperature of the alkali scrubbing is preferably 50-120 ℃, more preferably 60-110 ℃, and further preferably 65-85 ℃.
In the present invention, the first solid-liquid separation is preferably performed in a dehydrator.
The present invention does not require any particular embodiment of the first solid-liquid separation.
In the present invention, the first solid-liquid separation also results in a scrubbing lye.
In the present invention, the scrubbing lye is preferably circulated for the alkali scrubbing.
In the present invention, the scrubbing lye is preferably pre-treated before it is recycled. In the present invention, the pretreatment preferably includes: standing and separating; the invention preferably separates the argillaceous substances removed from the surface of the siliceous raw material in the scrubbing alkali liquor by standing separation.
In the present invention, the pre-treatment preferably further comprises heating the scrub lye after the standing separation. In the invention, the heating is preferably to heat the scrubbing alkali liquor after standing and separating to 50-120 ℃, more preferably to 60-110 ℃, and further preferably to 65-85 ℃.
In the invention, the muddy water obtained by the washing alkaline water standing separation enters an environment-friendly water treatment system, and is discharged after reaching the standard or recycled after being treated.
In the present invention, the lye used in the alkali scrubbing preferably comprises scrubbing lye which is recycled and added continuously.
In the invention, the flow rate of the newly added alkali liquor is preferably 0.3-0.8 m during the alkali scrubbing 3 More preferably 0.5 to 0.6 m/h 3 /h。
In the invention, the mass percentage of the newly added alkali liquor is preferably 10-25%, and more preferably 15-25%.
In the present invention, the newly added lye is preferably used after heating. In the invention, the temperature of the newly added alkali liquor is preferably 50-120 ℃, more preferably 60-110 ℃, and further preferably 65-85 ℃.
After obtaining the alkali washing siliceous raw material, the invention continuously mixes the alkali washing siliceous raw material with a fluorine-free acid solution (hereinafter referred to as second mixing) for acid scrubbing, and performs solid-liquid separation (hereinafter referred to as second solid-liquid separation) to obtain the low-iron siliceous raw material, wherein the fluorine-free acid solution is an aqueous solution of inorganic strong acid and/or oxalic acid.
In the invention, the fluorine-free acid solution is an aqueous solution of inorganic strong acid and/or oxalic acid.
In the present invention, the inorganic strong acid is preferably one or more of hydrochloric acid, sulfuric acid, and nitric acid.
In a specific embodiment of the present invention, the strong inorganic acid is particularly preferably sulfuric acid.
In the invention, the fluorine-free acid solution is preferably an aqueous solution of inorganic strong acid and oxalic acid, and the mass percentage content of the inorganic strong acid in the fluorine-free acid solution is preferably 10-25%, and more preferably 15-25%.
In the invention, the mass percentage of oxalic acid in the fluorine-free acid solution is preferably 5-8%, and more preferably 5.5-8%.
In the present invention, the alkali scrubbing and the acid scrubbing are performed in series.
In the present invention, the second mixing is preferably carried out in a scouring machine.
In the present invention, the acid scrubbing is preferably carried out in a scrubber.
In an embodiment of the invention, the scrubber is purchased from mechanical equipment technologies, Inc. of Yikay, Jiangsu.
As an embodiment of the present invention, the acid scrubbing was performed in 3 tandem double tank scrubbers.
As an embodiment of the invention, the double tank scrubber has a charge volume of 2m 3 。
In the invention, the linear speed of the scrubbing impeller of the scrubbing machine is preferably more than 15m/s, and more preferably 15.5-18 m/s during acid scrubbing.
In the invention, the acid scrubbing is preferably carried out under the auxiliary condition of ultrasonic waves, and the working frequency of the ultrasonic waves is preferably 20-100 kHz, and more preferably 25-80 Hz.
In the present invention, the power of the ultrasonic wave is preferably 80 to 120W, and more preferably 100W.
In the present invention, the acid scrubbing is preferably carried out under ultrasonic assistance, and the ultrasonic device is preferably an ultrasonic sonification device attached to the scrubbing machine, and the ultrasonic device is preferably an indirect contact type ultrasonic sonification device.
In the invention, the acid scrubbing temperature is preferably 50-120 ℃, more preferably 60-110 ℃, and further preferably 65-85 ℃.
In the present invention, the second solid-liquid separation is preferably performed in a dehydrator.
The present invention does not require a particular embodiment of the second solid-liquid separation.
In the present invention, the second solid-liquid separation also results in a scrub fluoride-free acid solution.
In the present invention, the scrubbing fluoride-free acid solution is preferably circulated to perform the acid scrubbing.
In the present invention, the scrub acid free solution is preferably pre-treated before being recycled. In the present invention, the pretreatment preferably includes: standing for separation. The present invention preferably separates iron and aluminum salts from the scrubbed fluoride-free acid solution by standing separation.
In the present invention, the pretreatment preferably further comprises heating the scrub non-fluorinated acid solution after the standing separation. In the invention, the heating preferably heats the scrubbing fluoride-free acid solution after standing separation to 50-120 ℃, more preferably 60-110 ℃, and further preferably 65-85 ℃.
In the invention, the precipitate obtained by standing and separating the scrubbing acid water enters an environment-friendly water treatment system, and is discharged after reaching the standard or recycled after being treated.
In the present invention, the fluorine-free acid solution used in the acid scrubbing preferably comprises a scrubbing fluorine-free acid solution which is circulated and added continuously.
In the invention, the flow rate of the newly added fluorine-free acid solution is preferably 0.5-1.2 m during acid scrubbing 3 More preferably 0.8 to 1.0m 3 /h。
In the invention, the newly added fluorine-free acid solution is preferably an aqueous solution of an inorganic strong acid and oxalic acid, the inorganic strong acid is preferably one or more of hydrochloric acid, sulfuric acid and nitric acid, and more preferably sulfuric acid.
In the invention, the mass percentage of the inorganic strong acid in the newly added fluorine-free acid solution is 10-25%, and more preferably 12-25%.
In the invention, the mass percentage content of oxalic acid in the newly added fluorine-free acid liquid is preferably 5-8%, and more preferably 5.5-8%.
In the invention, the newly added fluorine-free acid solution is preferably used after being heated. In the invention, the temperature of the newly added fluorine-free acid solution is preferably 50-120 ℃, more preferably 60-110 ℃, and further preferably 65-85 ℃.
In the invention, the second solid-liquid separation is carried out to obtain an acid scrubbing solid product, and the invention preferably carries out post-treatment on the acid scrubbing solid product to obtain the iron-removing siliceous raw material. In the present invention, the post-treatment preferably comprises: and carrying out neutralization cleaning and solid-liquid separation in sequence. In the invention, the neutralization cleaning is preferably carried out by mixing the acid scrubbing solid product with water for neutralization cleaning, and the low-iron siliceous raw material is obtained by solid-liquid separation after the neutralization cleaning; and the neutralized cleaning water obtained by the solid-liquid separation enters a cleaning water circulating system, and the neutralized cleaning water is recycled after precipitation.
Compared with the traditional acid soaking (static) method, the method provided by the invention has the advantages that the total purification time is relatively short, the product quality of the low-iron siliceous raw material is stable, the labor intensity is low, the cost is relatively low, and the method is favorable for large-scale industrial production.
The method provided by the invention replaces hydrofluoric acid (HF) by serially connecting alkali scrubbing and acid scrubbing, realizes fluorine-free production of low-iron siliceous raw materials, and has the advantages of simple water treatment and obvious environmental protection benefit.
The method provided by the invention can realize normal-temperature purification, has better purification effect in a heating state, and has the characteristics of lower purification temperature, less medicament consumption and shorter time.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
The deposited quartz sandstone ore is subjected to crushing, grinding, medium-intensity magnetic separation (0.5T magnetic field), high-intensity magnetic separation (1.3T magnetic field), high-intensity magnetic separation (1.5T magnetic field) and classification in sequence to obtain quartz sand serving as the siliceous raw material sand in the embodiment; the yield is 20t/h, and the chemical components of the siliceous raw material are as follows: SiO 2 2 ：98.85％，Al 2 O 3 ：0.38％，Fe 2 O 3 : 0.041 percent; the volume percentage content of raw material particles with the particle size distribution of 0.71-0.125 mm of the siliceous raw material is more than or equal to 95 percent.
Adding siliceous raw material sand into 3 series-connected 2m sand at a speed of 25t/h by using the conventional quantitative belt feeder 3 In the double-groove scrubbing machine, circularly scrubbing alkali liquor (NaOH liquor, 50 ℃) and newly added alkali liquor (NaOH liquor, 50 ℃) are added simultaneously, and the addition amount is 0.6m 3 Adding NaOH aqueous solution with the mass percentage of 25% of alkali liquor; the linear speed of a scrubbing impeller of the scrubbing machine is 18m/s, and the alkali scrubbing temperature is 50 ℃;
alkali liquor is removed from the alkali-scrubbed siliceous raw material sand on a dehydrator to obtain scrubbing alkali liquor and alkali-scrubbed siliceous raw material sand, and the scrubbing alkali liquor is directly recycled without being heated after standing to remove muddy water;
the alkaline washing siliceous material sand flows into 3 series-connected 2m sand 3 In a double-groove scrubbing machine, the fluorine-free acid solution (50 ℃) and the newly added fluorine-free acid solution (50 ℃) are added at the same time, and the addition amount of the newly added fluorine-free acid solution is 1.0m 3 H; the new fluorine-free acid solution comprises the following components: the mass content is 25 percent of H 2 SO 4 And 8% by mass of H 2 C 2 O 4 An aqueous solution; the linear speed of a scrubbing impeller of the scrubbing machine is 18m/s, and the alkali scrubbing temperature is 50 ℃;
removing the non-fluoric acid solution from the acid-scrubbed siliceous raw material sand on a dehydrator to obtain the scrubbing non-fluoric acid solution and an acid scrubbing solid product, standing the scrubbing non-fluoric acid solution to remove ferric salt and aluminum salt, and directly recycling the scrubbing non-fluoric acid solution without heating;
adding water into the acid scrubbing solid product for neutralization and cleaning, and then dehydrating to obtain iron-silicon raw material concentrate, wherein the quality of the concentrate in a warehouse is as follows: SiO 2 2 ：99.40％，Al 2 O 3 ：0.11％，Fe 2 O 3 : 0.0096% (96ppm), particle distribution: 0.71 mm-0.125 mm is more than or equal to 95 percent (volume content); the quality of the concentrate meets the requirements, and the concentrate yield is 550 t/d.
Example 2
The deposited quartz sandstone ore is subjected to crushing, grinding, medium-intensity magnetic separation (0.5T magnetic field), high-intensity magnetic separation (1.3T magnetic field), high-intensity magnetic separation (1.5T magnetic field) and classification in sequence to obtain quartz sand serving as the siliceous raw material sand in the embodiment; the yield is 20t/h, and the chemical components of the siliceous raw material are as follows: SiO 2 2 ：98.85％，Al 2 O 3 ：0.38％，Fe 2 O 3 : 0.041 percent; the volume percentage content of raw material particles with the particle size distribution of 0.71-0.125 mm of the siliceous raw material is more than or equal to 95 percent.
Adding siliceous raw material sand into 3 series-connected 2m sand at a speed of 25t/h by using the conventional quantitative belt feeder 3 In the double-groove scrubbing machine, circularly scrubbing alkali liquor (NaOH liquor, 75 ℃) and newly added alkali liquor (NaOH liquor, 75 ℃) are added simultaneously, and the addition amount of the newly added alkali liquor is 0.6m 3 H, newly adding an alkali solution which is a NaOH aqueous solution with the mass percentage of 25%; the linear speed of a scrubbing impeller of the scrubbing machine is 18m/s, and the alkali scrubbing temperature is 75 ℃;
alkali liquor is removed from the siliceous raw material sand subjected to alkali scrubbing on a dehydrator to obtain scrubbing alkali liquor and alkaline washing siliceous raw material sand, the scrubbing alkali liquor is kept stand to remove muddy water, and then the mixture is heated to 75 ℃ for recycling;
the alkaline washing siliceous material sand flows into 3 series-connected 2m sand 3 In a double-groove scrubbing machine, circularly scrubbing fluorine-free acid liquid (75 ℃) and newly added fluorine-free acid liquid (75 ℃) are added at the same time, and the addition amount of the newly added fluorine-free acid liquid is 1.0m 3 H; the new fluorine-free acid solution comprises the following components: the mass content is 25 percent of H 2 SO 4 And 8% by mass of H 2 C 2 O 4 An aqueous solution; the linear speed of a scrubbing impeller of the scrubbing machine is 18m/s, and the alkaline scrubbing temperature is (75 ℃);
removing the non-fluoric acid solution from the acid-scrubbed siliceous raw material sand on a dehydrator to obtain the scrubbing non-fluoric acid solution and an acid scrubbing solid product, standing the scrubbing non-fluoric acid solution to remove ferric salt and aluminum salt, and heating to 75 ℃ for recycling;
adding water into the acid scrubbing solid product for neutralization and cleaning, and then dehydrating to obtain iron-silicon raw material concentrate, wherein the quality of the concentrate in a warehouse is as follows: SiO 2 2 ：99.55％，Al 2 O 3 ：0.089％，Fe 2 O 3 : 0.0090% (90ppm), particle distribution: 0.71 mm-0.125 mm is more than or equal to 95 percent (volume content); the quality of the concentrate meets the requirement, and the concentrate yield is 550 t/d.
Example 3
The preparation method is basically the same as that of example 1, except that: the alkali scrubbing and the acid scrubbing are carried out under the ultrasonic wave auxiliary condition at the same time, and when the alkali scrubbing is carried out, the ultrasonic wave is in an indirect contact type, the working frequency is 40KHZ, and the power is 100W; when acid scrubbing is carried out, the ultrasonic wave is in an indirect contact mode, the working frequency is 40KHZ, and the power is 100W.
Example 4
The preparation method is basically the same as that of the example 2, except that: the alkali scrubbing and the acid scrubbing are simultaneously carried out under the ultrasonic wave auxiliary condition, when in alkali scrubbing, the ultrasonic wave is in an indirect contact type, the working frequency is 40KHZ, and the power is 100W; when acid scrubbing is carried out, the ultrasonic wave is in an indirect contact mode, the working frequency is 40KHZ, and the power is 100W.
Comparative example 1
The deposited quartz sandstone ore is subjected to crushing-grinding-medium-strength magnetic separation (0.5T magnetic field) -high-strength magnetic separation (1.3T magnetic field) -high-strength magnetic separation (1.5T magnetic field) -classification in sequence to obtain quartz sand serving as siliceous raw material sand of the comparative example; the yield is 20t/h, and the chemical components of the siliceous raw material are as follows: SiO 2 2 ：98.85％，Al 2 O 3 ：0.38％，Fe 2 O 3 : 0.041 percent; the volume percentage content of raw material particles with the particle size distribution of 0.71-0.125 mm of the siliceous raw material is more than or equal to 95 percent.
Adopting 12 phi 3500 x 6500mm acid soaking tanks for production, wherein the adding amount of siliceous raw material sand is 50 t/tank; using hydrofluoric acid (HF acid) and oxalic acid (H) 2 C 2 O 4 ) Soaking with 30m of fluorine-free acid solution 3 A/tank; the acid stock solution comprises the following components: 2500kg of 40% HF acid and 2500kg of oxalic acid; the acid soaking temperature is 80 ℃, and the soaking time is 7 h; according to the steps of feeding for 1h, acid soaking for 7h and acid discharging2 h-sand washing and 1 h' are circularly and repeatedly produced, and the total time of the total acid leaching production work is 12 h/time. Considering the recycling of the fluorine-free acid solution, the consumption (the new acid addition) is about 20 percent of the acid stock solution (mass ratio) each time.
Adding water into the acid-soaked solid product for neutralization and cleaning, and then dehydrating to obtain iron-silicon raw material concentrate, wherein the quality of the concentrate in a warehouse is as follows: SiO 2 2 ：99.45％，Al 2 O 3 ：0.098％，Fe 2 O 3 : 0.0093% (93ppm), particle size: 0.71 mm-0.125 mm is more than or equal to 95 percent (volume content); the quality of the concentrate meets the requirement, and the concentrate yield is 500 t/d.
The invention makes an economic comparison of the hydrofluoric acid immersion schemes of example 1(50 deg.C), example 2(75 deg.C) and comparative example 1, with the results shown in Table 1:
table 1 economic comparison results of the inventive example 1, the inventive example 2 and the comparative example 1
As can be seen from the comparison in table 1, the chemical index of the low-iron siliceous raw material sand (quartz concentrate) treated by the method for continuously producing the low-iron siliceous raw material by combined scrubbing with the fluorine-free alkaline acid provided in the embodiments 1 and 2 of the present invention satisfies the quality requirement of the low-iron siliceous raw material, and the cost is reduced by about 50%. And the invention adopts a fluoride-free process, has low environmental protection admission condition, and is easy to reach the standard in environmental protection treatment.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A method for continuously producing low-iron siliceous raw materials by combined scrubbing of fluorine-free alkali and acid comprises the following steps:
(1) continuously mixing the siliceous raw material with alkali liquor to carry out alkali scrubbing, and carrying out solid-liquid separation to obtain an alkali-scrubbed siliceous raw material, wherein the alkali liquor is an aqueous solution of inorganic strong alkali and/or alkali carbonate;
(2) continuously mixing the alkali washing siliceous raw material with a fluorine-free acid solution to carry out acid scrubbing, and carrying out solid-liquid separation to obtain the low-iron siliceous raw material, wherein the fluorine-free acid solution is an aqueous solution of inorganic strong acid and/or oxalic acid.
2. The method according to claim 1, characterized in that the alkali liquor is 10-25% by mass.
3. The method according to claim 1 or 2, wherein the ratio of the feed mass of the siliceous raw material to the volume of the lye per unit time is 25t (1.5-2) m 3 。
4. The method according to claim 1, wherein the fluorine-free acid solution is an aqueous solution of inorganic strong acid and oxalic acid, the mass percentage of the inorganic strong acid in the fluorine-free acid solution is 10-25%, and the mass percentage of the oxalic acid in the fluorine-free acid solution is 5-8%.
5. The method according to claim 1, wherein the volume percentage of the raw material particles with the particle size distribution of the siliceous raw material of 0.71-0.125 mm is not less than 95%.
6. The method of claim 1, wherein the alkaline scrubbing and the acid scrubbing are independently performed in a scrubber machine having a linear velocity of a scrubber impeller independently > 15m/s for the alkaline scrubbing and the acid scrubbing.
7. The method according to claim 6, wherein the alkali scrubbing and the acid scrubbing are independently performed under ultrasonic assistance, the ultrasonic operating frequency is independently 20 to 100kHz, and the ultrasonic power is independently 80 to 120W.
8. The method of claim 1, wherein the temperature of the alkaline scrubbing and the acid scrubbing is independently 50 to 120 ℃.
9. The method as claimed in claim 1, wherein in step (1), the solid-liquid separation further obtains scrubbing alkali liquor, the scrubbing alkali liquor circulates for the alkali scrubbing, the alkali liquor used in the alkali scrubbing comprises scrubbing alkali liquor which circulates in and continuously supplemented additional alkali liquor, and the flow rate of the additional alkali liquor during the alkali scrubbing is 0.3-0.8 m 3 And h, the mass percentage of the newly added alkali liquor is 15-30%.
10. The method as claimed in claim 1, wherein in the step (2), the solid-liquid separation further obtains scrubbing non-fluorine acid liquid, the scrubbing non-fluorine acid liquid is circularly subjected to the acid scrubbing, the non-fluorine acid liquid used in the acid scrubbing comprises circularly-entering scrubbing non-fluorine acid liquid and continuously supplemented additional non-fluorine acid liquid, and the flow rate of the additional non-fluorine acid liquid during the acid scrubbing is 0.5-1.2 m 3 And h, the newly added fluorine-free acid solution is an aqueous solution of inorganic strong acid and oxalic acid, the mass percentage of the inorganic strong acid in the newly added fluorine-free acid solution is 10-25%, and the mass percentage of the oxalic acid in the newly added fluorine-free acid solution is 5-8%.
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