CN109592693A - A kind of method that acid leaching residue produces waterglass - Google Patents
A kind of method that acid leaching residue produces waterglass Download PDFInfo
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- CN109592693A CN109592693A CN201811395956.0A CN201811395956A CN109592693A CN 109592693 A CN109592693 A CN 109592693A CN 201811395956 A CN201811395956 A CN 201811395956A CN 109592693 A CN109592693 A CN 109592693A
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- Prior art keywords
- white clay
- waterglass
- leaching residue
- acid leaching
- wet processing
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 235000019353 potassium silicate Nutrition 0.000 title claims abstract description 88
- 239000002253 acid Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000002386 leaching Methods 0.000 title claims abstract description 40
- 239000004927 clay Substances 0.000 claims abstract description 102
- 239000002994 raw material Substances 0.000 claims abstract description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000009854 hydrometallurgy Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 37
- 239000010881 fly ash Substances 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000004062 sedimentation Methods 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 239000002699 waste material Substances 0.000 abstract description 7
- 241001274660 Modulus Species 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 90
- 235000011121 sodium hydroxide Nutrition 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000010883 coal ash Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 235000020097 white wine Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Glass Compositions (AREA)
Abstract
The method that the technical field more particularly to a kind of acid leaching residue utilized the invention belongs to Ash Utilization produces waterglass includes the following steps: that the acid leaching residue to generate in acid hydrometallurgical processes as raw material, prepares waterglass using wet processing；The wet processing are as follows: the white clay is contacted with soda bath and carries out hydro-thermal reaction, the waterglass can be obtained after filtering.The present invention is not only able to achieve acid leaching residue waste utilization using wet processing, can also produce the waterglass of various moduluses, reduces production cost.
Description
Technical field
The technical field more particularly to a kind of acid leaching residue utilized the invention belongs to Ash Utilization produces waterglass
Method.
Background technique
Waterglass is a kind of metal silicate object that water can be dissolved in as made of alkali metal oxide and silica composition
Matter, molecular formula are represented by Na2O·mSiO2(m is known as modulus, is one of waterglass important parameter), purposes is very extensive.?
Chemical field is used to manufacture silica gel, white carbon black, molecular sieve, sodium metasilicate, silica solution, layer silicon and instant powdery sodium silicate, silicic acid
The various silicates products such as potassium sodium, are the base stocks of silicon compound.In light industry, it is that washing powder, soap etc. are washed
Wash indispensable raw material and water softener, settling agent in agent.It can be used for assisting-dyeing, bleaching and slurry in textile industry
Yarn.In machinery industry, it is widely used in casting, grinding wheel manufacture and anticolodal etc..In building trade, it is used to manufacture quick-drying
Cement, acid-resistant cement dubbin, soil-solidified-agent, refractory material etc..Agriculturally it can manufacture silicon element fertilizer material.In addition, water
Glass also act as the silica-alumina catalyst of catalytic cracking, the binder of corrugated paper and mine ore dressing, waterproof, leak stopping,
Iron slip casting, fire retarding wood protection, food antiseptic etc..
The production technology of waterglass is divided to two kinds of dry and wet.Dry method is using quartz sand and soda ash as raw material, at high temperature
(1400~1600 DEG C) frit reaction (4~6h), can producing high mode, (m >=2.6 reach as high as 3.7) waterglass；This method makes
With extensive, market occupancy volume is up to 90% or more；But the energy consumption of this method is higher, and product quality is poor.Wet process is with quartz sand and burning
Alkali (~30%) is raw material, reacts (4~6h) under (150~170 DEG C) pressurizations (0.5~0.8MPa) of heating, produces low modulus
The waterglass of (m < 2.6)；This method is relatively easy to control product quality, lower production costs；But this method low efficiency.
Because impurity content is more in the silicon resources such as flyash or gangue and its acid leaching residue, wet processing system is generallyd use
Water intaking glass.For example, the patent document of Publication No. CN101259965A discloses a kind of side of preparing soluble glass from coal gangue
Method, disclosing gangue granularity is 60-80 mesh, carries out acidleach after roasting to it, and maturing temperature is 750 ± 50 DEG C, concentration of hydrochloric acid
It is 25~36%, liquid-solid ratio is (200~300)/(70~130)；Acid leaching residue and 5~6% caustic soda liquid-solid ratio (80~120)/
0.5~1h is reacted at 100,80~105 DEG C, obtains waterglass.The patent document of Publication No. CN102583417A discloses one
The method of kind preparing soluble glass from coal gangue, carries out acidleach, concentration of hydrochloric acid 20%, liquid-solid ratio (ml/g) after gangue is roasted
It is 6/1；Concentration of caustic soda is 1.8mol/L (~6.5%), and the liquid-solid ratio (ml/g) with acid leaching residue is 10/1,70 DEG C of reaction 2h, is obtained
The waterglass of modulus m=2.32, meets national standard.The patent document of Publication No. CN102344148A discloses a kind of coal
The method that spoil acid leaching residue produces soluble glass of high modulus, takes Al2O3≤ 8%, SiO2>=75% acid leaching residue is raw material, is first produced
Low modulus (m=2) waterglass, then acid gangue phase analysis is added in low modulus water glass and carries out mentioning film reaction, it is final that height is made
Modulus (m is up to 4.6) waterglass.The patent document of Publication No. CN105540602A discloses a kind of coal ash for manufacturing water intaking glass
The method of glass, flyash react 4~8h at 260~320 DEG C with 90~98% concentrated sulfuric acids after low-temperature bake, obtain acidleach
Slag；18~20% caustic soda are contacted with acid leaching residue, liquid-solid ratio 2:1~1:1, and 4~6h is reacted at 160~180 DEG C, obtains m=2.2's
- 5 type waterglass of liquid.The patent document of Publication No. CN101993087A discloses a kind of method of coal ash for manufacturing water intaking glass,
Flyash granularity≤100 mesh, concentration of hydrochloric acid 20~38%, liquid-solid ratio (150~200)/100 react 2~6h at 70~95 DEG C；
Concentration of caustic soda 8~20%, liquid-solid ratio (100~120)/100 are 130~200 DEG C, 0.4~4h is reacted under 0.25~1.6MPa, dilute
Waterglass is obtained after releasing filtering.
The studies above needs first activated, acidleach processing step to obtain using gangue or coal-powder boiler flyash as raw material
Acid leaching residue, then again using acid leaching residue as waste low modulus water glass.At present using quartz sand as raw material, using wet processing
Waterglass is produced, modulus of water glass obtained is not high；To improve modulus using wet processing, then need to increase to quartz sand
Activation procedure, production cost can be greatly increased and generate more waste residue.
So, the modulus that waterglass how can be improved while cost is reduced is urgently to be solved one big at this stage
Problem.
Summary of the invention
It is an object of the present invention to it is existing prepare waterglass aiming at the problem that, in line with the original to flyash " eating dry bleed "
Then, a kind of method that acid leaching residue produces various modulus waterglass is provided, is not only able to achieve using wet processing to flyash acidleach
The waste utilization of gained acid leaching residue afterwards, can also produce the waterglass of various moduluses, reduce production cost.
To achieve the goals above, technical scheme is as follows:
A kind of method that acid leaching residue produces waterglass, includes the following steps:
Using the acid leaching residue generated in acid hydrometallurgical processes as raw material, waterglass is prepared using wet processing；
The wet processing are as follows: the acid leaching residue is contacted with soda bath and carries out hydro-thermal reaction, can be obtained after filtering
The waterglass.
The method provided according to the present invention, the acid leaching residue can be gained acid leaching residue after flyash acidleach.Preferably,
The acid leaching residue is the white clay generated in flyash acid oxidation aluminium process system.
For example, in some instances, the acid leaching process condition of flyash acid oxidation aluminium are as follows: pickling agent be 25wt%~
The hydrochloric acid solution of 27wt%, hydrochloric acid solution actual amount/theoretical amount molar ratio be 0.85~0.90, extraction temperature be 120~
160 DEG C, leaching pressure is 450~500kPa, and extraction time is 2~3h.The leaching rate of aluminium generates after 85% or more, acidleach
Stripping slurry.
It is highly preferred that the stripping slurry generated in flyash acid oxidation aluminium process system to be separated by solid-liquid separation and be washed
It washs, it is preferred to use after sedimentation or plate-frame filtering separation and washing, obtain the white clay.For example, the flyash acid system of Shenhua Group
In alumina technology system (for example, the patent document of Publication No. CN102145905A disclose it is a kind of using fluid bed powder coal
Ash is the method that raw material prepares metallurgical-grade aluminum oxide；The patent document of Publication No. CN103755060A discloses a kind of fine coal
The method of dissolved mineral slurry separating, washing in grey acid system production alumina process；The patent document of Publication No. CN105016368A
Disclose a kind of method of iron content removing iron from solution of aluminum chloride) generate white clay.The white clay is circulating fluid bed coal ash through hydrochloric acid
Product after corrosion, SiO therein2Content is high and activity is good, can be used as excellent waterglass raw materials for production, is subject to weight
It is new to utilize, it " can not only turn waste into wealth ", realize the principle of flyash " eating dry bleed ", be expected to produce using wet processing
Soluble glass of high modulus out.
In some instances, the separation of solid and liquid and the process of washing use sedimentation separation or plate-frame filtering separating technology,
And multi-stage countercurrent pulping and washing technique, it is as follows to obtain the white clay physicochemical property:
The real density average value about 1.64g/cm of the white clay3, bulk density about 0.61g/cm3；
The average grain diameter of the white clay is 5~6 μm, and 5 μm of particles below account for about 60%；
Specific surface area >=90m of the white clay2/ g is 5~6 times of flyash specific surface area；
The white clay has porous structure, and aperture is 2~50nm；
90wt% the above white clay is amorphous structure.
The method provided according to the present invention, it is preferable that SiO in the white clay2Content be more than or equal to 68wt%, Fe2O3
Content be less than or equal to 0.28wt%.By stripping slurry be separated by solid-liquid separation and carrying out washing treatment after, the additional loss chlorine of gained white clay from
Sub- content≤9kg/t, additional loss aluminium composition≤2.1 kg/t, pH=6~9.Present inventor's discovery, the SiO in white clay2
Content is very high and Fe2O3Under conditions of content is very low, prepares and be just avoided that during waterglass and generate excessive waste residue.
Preferably, the white clay has porous structure, and aperture is 2~50nm；And 90wt% the above white clay is non-
Crystalline structure；Average grain diameter≤6 μm of the white clay, more preferably 5-6 μm, wherein 5 μm of particles below account for white clay total amount
60wt%；Specific surface area >=90m of the white clay2/ g is 5 times or more of flyash.Present inventor's discovery, use are excellent
The white clay of choosing, pore structure and amorphous structure, lesser partial size that white clay particle has and the high-specific surface area having are lived
Property it is higher than quartz sand, be excellent waterglass wet production raw material, be conducive to that the water glass of high mode (m be less than or equal to 2.6) is made
Glass.
So, it using white clay as reaction raw materials, not only may be implemented to produce various modulus water glass using wet processing
Glass, and the waterglass for having high mode can be made." soluble glass of high modulus " of the present invention refers to wet processing for preparation
The waterglass that means are produced, modulus m, which is more than or equal to 2.6, just can be described as soluble glass of high modulus.
The method provided according to the present invention, it is preferable that the mass concentration of the soda bath is 5~30 wt%, more preferably
For 10~25wt%；It is 1:1~3:1, more preferably 1:1~2:1 that the liquid of the soda bath and acid leaching residue, which consolidates mass ratio,.
The method provided according to the present invention, it is preferable that the process conditions of the wet processing include: that reaction temperature is 60
~200 DEG C, more preferably 90~180 DEG C；Reaction pressure is 0.1~1.6MPa, more preferably 0.1~0.6MPa；Reaction time
For 0.5~6h, more preferably 1~3h.
Compared with the existing technology, the beneficial effect of technical solution of the present invention is:
(1) using the acid leaching residue generated in acid hydrometallurgical processes as raw material, the waterglass of various moduluses can be produced
(wherein containing the waterglass of high mode), realizes waste utilization, and production cost is suitable with traditional handicraft；
(2) it using white clay as reaction raw materials in preferred embodiment, not only realizes in flyash acid oxidation aluminium technique and gives up
The recycling of object, and in the various modulus waterglass for using wet processing to produce, soluble glass of high modulus is further comprised, and raw
Cost is relatively low for production；
(3) the resulting waterglass of the present invention is best in quality, can meet the requirement of national standard high-class product.
Detailed description of the invention
Figures 1 and 2 show that SEM of the white clay sample used in each embodiment under the different visuals field schemes according to the present invention；
Fig. 3 shows white clay sample XRD diagram used in each embodiment according to the present invention.
Specific embodiment
In order to which technical characteristic and content of the invention is understood in detail, it is described in more detail below of the invention
Preferred embodiment.Although describing the preferred embodiment of the present invention in embodiment, however, it is to be appreciated that can be with various
Form realizes the present invention without that should be limited by the embodiments set forth herein.
In some examples of the invention, the method that acid leaching residue produces various modulus waterglass includes the following steps: with acid
Property hydrometallurgical processes in the acid leaching residue that generates be raw material, waterglass is prepared using wet processing；
The wet processing are as follows: the acid leaching residue is contacted with soda bath and carries out hydro-thermal reaction, can be obtained after filtering
The waterglass.
In the preferred embodiment, the acid leaching residue is the white clay generated in flyash acid oxidation aluminium process system.Example
Such as, in some instances, using the white clay generated in flyash acid oxidation aluminium process system as the original for preparing waterglass
Material, the acid leaching process condition of flyash acid oxidation aluminium are as follows: pickling agent is 25wt%~27wt% hydrochloric acid solution, hydrochloric acid solution
Actual amount/theoretical amount molar ratio be 0.85~0.90, extraction temperature be 120~160 DEG C, leach pressure be 450~
500kPa, extraction time are 2~3h；Stripping slurry can be obtained after 85% or more, acidleach processing in the leaching rate of aluminium.
The stripping slurry generated in flyash acid oxidation aluminium process system is separated by solid-liquid separation and is washed；Preferred
In embodiment, after separating and wash using sedimentation or plate-frame filtering, the white clay is obtained.For example, in some instances, institute
The process for being separated by solid-liquid separation washing is stated using sedimentation separation or plate-frame filtering separating technology and multi-stage countercurrent pulping and washing technique, is obtained
It is as follows to the white clay physicochemical property:
The real density average value about 1.64g/cm of the white clay3, bulk density about 0.61g/cm3；
The average grain diameter of the white clay is 5~6 μm, and 5 μm of particles below account for about the 60% of white clay total amount；
Specific surface area >=90m of the white clay2/ g, for example, being 91.67m2/g；Than the specific surface area of flyash
(16.2m2/ g) it is much larger, for example, being 5~6 times of flyash specific surface area；
The white clay has porous structure, and aperture is 2~50nm；
90wt% the above white clay is amorphous structure.
After stripping slurry is separated by solid-liquid separation, before gained filter cake does not wash, be additional loss chloride ion 183.2~
The extra dry white wine mud of 248kg/t；After gained filter cake carries out carrying out washing treatment, the extra dry white wine that additional loss chloride ion is 4.36~8.98kg/t is obtained
Mud.SiO in the white clay2Content be more than or equal to 68wt%, Fe2O3Content be less than or equal to 0.28wt%.
In some preferred embodiments, the mass concentration of the soda bath is 10~25%, for example, 11%,
12%, 17%, 19%, 20%, 22%, 24%；The liquid-solid ratio of the soda bath and white clay is 1:1~3:1, for example, 2:1.
The process conditions of the wet processing include: reaction temperature are as follows: 60~200 DEG C, preferably 90~180 DEG C, example
Such as, 93 DEG C, 97 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C；Reaction pressure is 0.1~1.6MPa, for example,
0.2MPa, 0.4MPa, 0.7MPa, 0.9 MPa, 1.0MPa, 1.2MPa, 1.4MPa, preferably 0.1~0.6MPa；Reaction time
For 0.5~6 h, for example, 1h, 2h, 3.5h, 4h, 4.5h, 5h, preferably 1~3h.
Raw material sources:
In flyash acid oxidation aluminium process system, it is 27% that leaching process, which generates pickling agent used when stripping slurry,
Aqueous hydrochloric acid solution, aqueous hydrochloric acid solution actual amount/theoretical amount molar ratio be 0.86, extraction temperature be 160 DEG C, leach pressure
Power is 450~500kPa, extraction time about 2h.Under this condition, the leaching rate of aluminium reaches 85% or more.
Stripping slurry is handled in such a way that plate-frame filtering separates and washs, the primary chemical composition of gained white clay
As shown in table 1, main physical and chemical is as shown in table 2.
1 white clay primary chemical of table forms (wt%)
2 white clay main physical and chemical of table
There are four types of models for national standard liquid soluble glass, as shown in table 3.
3 national standard liquid soluble glass model of table
Following embodiments will (composition and performance be shown in Tables 1 and 2 using white clay as described above；Its SEM figure and XRD diagram are shown in
Shown in Fig. 1-Fig. 3, wherein Fig. 1 can be seen that the pore diameter range of white clay, Fig. 2 can be seen that the average particle size range of white clay), lead to
Cross the waterglass that wet processing produces different moduluses.
Embodiment 1:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 25wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.4:1, reaction temperature is 90 DEG C, reaction pressure 0.1MPa, reaction time 1.5h.Waterglass is made after reaction.
After measured, SiO in white clay2Dissolution rate is 85%；Gained modulus of water glass m=2.2, iron-content 0.016%,
Meet -1 high-class product of state's standard liquid.
Embodiment 2:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 23wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.4:1, reaction temperature is 90 DEG C, reaction pressure 0.1MPa, reaction time 1.5h.After reaction, water glass is made
Glass.
After measured, SiO in white clay2Dissolution rate is 85%；Modulus of water glass m=2.4, iron-content 0.016% meet
- 1 high-class product of state's standard liquid.
Embodiment 3:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 20wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.4:1, reaction temperature is 95 DEG C, reaction pressure 0.1MPa, reaction time 1.5h.After reaction, water glass is made
Glass.
After measured, SiO in white clay2Dissolution rate is 84%；Modulus of water glass m=2.6, iron-content 0.016% meet
- 2 high-class product of state's standard liquid.
Embodiment 4:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 18wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid-solid ratio of NaOH aqueous solution and white clay is
1.4:1, reaction temperature are 95 DEG C, reaction pressure 0.1MPa, reaction time 1.5h.After reaction, waterglass is made.
After measured, SiO in white clay2Dissolution rate is 83%；Modulus of water glass m=2.9, iron-content 0.015% meet
- 2 high-class product of state's standard liquid.
Embodiment 5:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 16wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.5:1, reaction temperature is 95 DEG C, reaction pressure 0.1MPa, reaction time 2h.After reaction, waterglass is made.
After measured, SiO in white clay2Dissolution rate is 82%；Modulus of water glass m=3.1, iron-content 0.015% meet
- 3 high-class product of state's standard liquid.
Embodiment 6:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 15wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.5:1, reaction temperature is 95 DEG C, reaction pressure 0.1MPa, reaction time 2h.After reaction, waterglass is made.
After measured, SiO in white clay2Dissolution rate is 82%；Modulus of water glass m=3.3, iron-content 0.015% meet
- 3 high-class product of state's standard liquid.
Embodiment 7:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 14wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.5:1, reaction temperature is 100 DEG C, reaction pressure 0.1MPa, reaction time 2h.After reaction, waterglass is made.
After measured, SiO in white clay2Dissolution rate is 81%；Modulus of water glass m=3.4, iron-content 0.014% meet
- 3 high-class product of state's standard liquid.
Embodiment 8:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 15wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
1.3:1, reaction temperature are 100 DEG C, reaction pressure 0.1MPa, reaction time 2h.After reaction, waterglass is made.
After measured, SiO in white clay2Dissolution rate is 78%；Modulus of water glass m=3.5, iron-content 0.013% meet
- 4 high-class product of state's standard liquid.
Embodiment 9:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 13wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.5:1, reaction temperature is 100 DEG C, reaction pressure 0.1MPa, reaction time 2h.After reaction, waterglass is made.
After measured, SiO in white clay2Dissolution rate is 78%；Modulus of water glass m=3.6, iron-content 0.013% meet
- 4 high-class product of state's standard liquid.
Embodiment 10:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 12wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.5:1, reaction temperature is 100 DEG C, reaction pressure 0.1MPa, reaction time 2.5h.After reaction, water glass is made
Glass.
After measured, SiO in white clay2Dissolution rate is 77%；Modulus of water glass m=3.8, iron-content 0.013% meet
- 4 high-class product of state's standard liquid.
Embodiment 11:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 20wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.6:1, reaction temperature is 160 DEG C, reaction pressure 0.5MPa, reaction time 1h.After reaction, waterglass is made.
After measured, white clay SiO2Dissolution rate is 86%；Modulus of water glass m=2.3, iron-content 0.016%, meets state
- 1 high-class product of standard liquid.
Embodiment 12:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 13wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.6:1, reaction temperature is 160 DEG C, reaction pressure 0.5MPa, reaction time 3h.After reaction, waterglass is made.
After measured, SiO in white clay2Dissolution rate is 83%；Modulus of water glass m=3.6, iron-content 0.016% meet
- 4 high-class product of state's standard liquid.
Embodiment 13:
Using above-mentioned white clay as raw material (composition and performance is shown in Tables 1 and 2), waterglass is produced using wet processing: by white clay
It is that 13wt%NaOH aqueous solution mixes, and stirs and reacted with mass concentration；The liquid of NaOH aqueous solution and white clay consolidates mass ratio
For 1.6:1, reaction temperature is 180 DEG C, reaction pressure 0.6MPa, reaction time 3h.After reaction, waterglass is made.
After measured, SiO in white clay2Dissolution rate is 85%；Modulus of water glass m=3.6, iron-content 0.016% meet
- 4 high-class product of state's standard liquid.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is also not necessarily limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this
Many modifications and changes are obvious for the those of ordinary skill of technical field.
Claims (8)
1. a kind of method that acid leaching residue produces waterglass, which comprises the steps of:
Using the acid leaching residue generated in acid hydrometallurgical processes as raw material, waterglass is prepared using wet processing；
The wet processing are as follows: the acid leaching residue is contacted with soda bath and carries out hydro-thermal reaction, can be obtained after filtering described
Waterglass.
2. the method according to claim 1, wherein the acid leaching residue is flyash acid oxidation aluminium process system
The white clay of middle generation.
3. according to the method described in claim 2, it is characterized in that, molten by being generated in flyash acid oxidation aluminium process system
Slurry is separated by solid-liquid separation and is washed out, it is preferred to use after sedimentation or plate-frame filtering separation and washing, obtains the white clay.
4. according to the method described in claim 2, it is characterized in that, SiO in the white clay2Content be more than or equal to 68wt%,
Fe2O3Content be less than or equal to 0.28wt%.
5. according to the method in claim 2 or 3, which is characterized in that the white clay have porous structure, aperture be 2~
50nm；And 90wt% the above white clay is amorphous structure.
6. according to the method in claim 2 or 3, which is characterized in that average grain diameter≤6 μm of the white clay；The white clay
Specific surface area >=90m2/g。
7. method according to claim 1 or 2, which is characterized in that the mass concentration of the soda bath be 5~
30wt%；
It is 1:1~3:1 that the liquid of the soda bath and acid leaching residue, which consolidates mass ratio,.
8. method according to claim 1-7, which is characterized in that the process conditions of the wet processing include:
Reaction temperature is 60~200 DEG C；Reaction pressure is 0.1~1.6MPa；Reaction time is 0.5~6h.
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| CN113772686A (en) * | 2021-10-22 | 2021-12-10 | 北京润捷浩达科技有限公司 | Method for preparing water glass and co-producing metal salt crystals by using silicon-rich clay |
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