CN106925594A - A kind of processing method of flyash acid dissolution slag - Google Patents
A kind of processing method of flyash acid dissolution slag Download PDFInfo
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- CN106925594A CN106925594A CN201511016148.5A CN201511016148A CN106925594A CN 106925594 A CN106925594 A CN 106925594A CN 201511016148 A CN201511016148 A CN 201511016148A CN 106925594 A CN106925594 A CN 106925594A
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- acid
- flyash
- solid
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- dissolution slag
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- 239000002253 acid Substances 0.000 title claims abstract description 93
- 239000010881 fly ash Substances 0.000 title claims abstract description 76
- 238000004090 dissolution Methods 0.000 title claims abstract description 58
- 239000002893 slag Substances 0.000 title claims abstract description 55
- 238000003672 processing method Methods 0.000 title claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 20
- 239000012265 solid product Substances 0.000 claims abstract description 15
- 239000007790 solid phase Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 5
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 claims description 3
- 235000021360 Myristic acid Nutrition 0.000 claims description 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 2
- 229940070765 laurate Drugs 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000012263 liquid product Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 241000370738 Chlorion Species 0.000 description 13
- 239000000843 powder Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000007885 magnetic separation Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 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
- 230000032050 esterification Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000006148 magnetic separator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- SUQAQYSGRRAOLJ-UHFFFAOYSA-N CC(C)=O.CCCCCCCCCCCC(O)=O Chemical compound CC(C)=O.CCCCCCCCCCCC(O)=O SUQAQYSGRRAOLJ-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- -1 but now Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- KYIDJMYDIPHNJS-UHFFFAOYSA-N ethanol;octadecanoic acid Chemical compound CCO.CCCCCCCCCCCCCCCCCC(O)=O KYIDJMYDIPHNJS-UHFFFAOYSA-N 0.000 description 1
- IWMXCBIQIXXGFK-UHFFFAOYSA-N ethanol;tetradecanoic acid Chemical compound CCO.CCCCCCCCCCCCCC(O)=O IWMXCBIQIXXGFK-UHFFFAOYSA-N 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000002977 hyperthermial effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of processing method of flyash acid dissolution slag, comprise the following steps：Slurrying：Flyash acid dissolution slag is uniformly mixed with water；It is modified：Step a gained slurries are uniformly mixed with aliphatic acid, is reacted；Separate：Step b gained modified products are carried out into separation of solid and liquid, solid product and liquid product is obtained；Chloride ion content, environmental protection in flyash acid dissolution slag can efficiently be reduced by the method for the present invention.
Description
Technical field
The invention belongs to Solid state fermentation field, more particularly to a kind of processing method of flyash acid dissolution slag.
Background technology
With being rooted in the hearts of the people for " Mode of Circular " theory, flyash is administered and also existed using technology
Reach its maturity, especially for aluminous fly-ash, (such as aluminium content in terms of aluminum oxide exists in flyash
30wt%, 40wt% even more than 50wt%), the technology of aluminum oxide is extracted therefrom increasingly perfect,
The acid extracting flyash as disclosed in alkali fusion flyash produces alumina technology, CN 102145905A
Produce alumina technology etc.；But these techniques can all produce a large amount of residues.
In acid extracting flyash produces alumina technology, acid is carried out to flyash using hydrochloric acid solution
Molten treatment to extract aluminum oxide in flyash, it is necessary to carry out separation of solid and liquid after sour molten treatment terminates,
Wherein, the solution isolated can further refine purification, and the solid residue isolated, i.e. fine coal
Grey acid dissolution slag.In actual production, aluminium effect is put forward in order to improve the sour molten of flyash, flyash exists
Generally need to carry out pulverization process before acid is molten, however, the flyash acid dissolution slag of exquisiteness is in above-mentioned solid-liquid
But become a huge unfavorable factor in separation process, cause separation of solid and liquid it is difficult (for example,
Flyash acid dissolution slag by after press filtration, its solid content is only about 53wt%, and even across 18 months
Natural air drying, its solid content still only have about 84.7wt%.), and separate after solid residue in
Also contain substantial amounts of aluminium chloride, this not only results in the aluminium for extracting and largely loses, and therein
Chlorion can also cause serious threat to environment.
In order to reduce the environmental hazard of residue, conventional method has washing process.Although washing can
Part chloride ion content is reduced to reach, but should not industrially use the method, on the one hand reason is
Washing will expend substantial amounts of cleaning water source, and chloride ion content is still higher in acid dissolution slag after washing；
On the other hand, due to also containing the acid solution for being largely difficult to separate, substantial amounts of washings sheet in residue
Body is also a kind of pollution sources, and directly discharge still can bring environmental pollution.
The content of the invention
It is an object of the invention to provide a kind of processing method of flyash acid dissolution slag, to solve fine coal
The serious higher problem of chloride ion content in grey acid dissolution slag.To achieve the above object, the present invention is used
Following technical scheme：
A kind of processing method of flyash acid dissolution slag, comprises the following steps：
A, slurrying：Flyash acid dissolution slag is uniformly mixed with the water for adding, slurry is obtained；
It is b, modified：Step a gained slurries are uniformly mixed with aliphatic acid, is reacted, obtain modified product；
C, separation：Step b gained modified products are carried out into separation of solid and liquid, solid product and liquid is obtained
Phase product.
The method according to the invention, step a is uniformly to mix flyash acid dissolution slag with water, to make
Into slurry.Wherein, the flyash acid dissolution slag is that (a such as step acid is molten in sour molten treatment for flyash
Method) to extract in flyash after aluminum oxide, solid residue obtained from separation of solid and liquid is carried out, this is consolidated
Body residue because by crushing and acid is molten, specific surface area is big and activity is high, therefore it is particularly preferred that
Flyash acid dissolution slag used in step a is that flyash is aoxidized in the molten treatment of acid with extracting flyash
After aluminium, the solid residue for carrying out separation of solid and liquid and directly obtaining, without carrying out any pretreatment (ratio
Such as traditional washing or alkali neutralisation treatment), to ensure follow-up good modified effect.
The flyash processes to extract the work of aluminum oxide in flyash through sour molten (such as hydrochloric acid acid is molten)
For known in the art, such as sour molten disclosed in CN102145905A puies forward aluminium technique to skill, and it is logical
The mode quoted is crossed to be incorporated into the application.Specifically, the preparation method of the flyash acid dissolution slag
May comprise steps of：
1), magnetically separating and removing ion from fly ash:Flyash is size-reduced to be reached below 100 mesh, and add water to be made into contains admittedly
The slurry for 20~40wt% is measured, magnetic separation, magnetic separation field intensity 1.0~2.0 are carried out on vertical ring magnetic separator
Ten thousand GS；Slurry after magnetic separation obtains the filter cake that solid content is 25~50wt% after separation of solid and liquid；
2), acid is molten:Filter cake after magnetic separation is placed in acid-resistant reacting kettle carries out that hydrochloric acid acid is molten, and hydrochloric acid is dense
It is 20~35wt% to spend, and HCl and the mol ratio of aluminum oxide in flyash are 4 in hydrochloric acid:1~9:1, it is molten
It is 100 DEG C~200 DEG C to go out temperature, and dissolution 0.1~2.5MPa of pressure, dissolution time is 0.5h~4h；It is excellent
Selection of land, concentration of hydrochloric acid is 20~30wt%, and HCl is with the mol ratio of aluminum oxide in flyash in hydrochloric acid
4.5:1~9:1, leaching temperature is 130 DEG C~150 DEG C, dissolution 0.3~1.0MPa of pressure, dissolution time
It is 1.5h~2.5h；The molten rear product of acid obtains the flyash acid dissolution slag through separation of solid and liquid.
For step 2), during separation of solid and liquid, type, operation according to the equipment for carrying out separation of solid and liquid
The difference of parameter, the flyash acid dissolution slag also includes the water that content is not waited, those skilled in the art
Understand, difficult due to separating, its water content is not less than 40wt% substantially.The flyash acid dissolution slag
After drying and dehydrating, its each component is counted in the form of an oxide, comprising：The SiO of 41.0~56.0wt%2、
The Al of 16.0~32.0wt%2O3, 2.0~3.9wt% TiO2, 0.4~0.9wt% Fe2O3。
The method according to the invention, in step a, the consumption of the water it is excessive or it is very few be unfavorable for after
Continuous modification.Preferably, by weight, in step a, in the flyash acid dissolution slag
Solid phase is 1 with the mass ratio of the water for being added:1~1:10, more preferably 1:1.5~1:8, more preferably
1:1.5~4；Wherein, in the flyash acid dissolution slag solid phase quality (i.e. solid phase dry weight) can lead to
Cross to dry weigh after flyash acid dissolution slag and obtain, be known in the art, repeat no more here.
The method according to the invention, in step a, the hybrid mode of material is not particularly limited, example
Such as by the uniform mixing of the existing material of mechanical agitation, naturally it is also possible to be that other can mix material
Uniform mode.
The method according to the invention, step b is uniformly to mix slurry obtained above with aliphatic acid,
To be modified reaction.Inventor is through the discovery that studies for a long period of time, the solid in flyash acid dissolution slag sludge
Powder particle surface has substantial amounts of surface hydroxyl, and surface hydroxyl is formed with the hydrone in acid solution with hydrogen bond formation
Conjunction relation, this is a kind of weaker chemical bonds relation, and dissolving with hydrochloric acid is in water, so that shape
Into acid, separate relation is difficult between water and solid powder/particle；In addition, the chlorination in being dissolved in acid solution
Aluminium, then preservation, in wherein, there is certain flocculation to solid particle in the form of dimer or polymer
Effect；Additionally, the research to the electro kinetic potential of solid powder/particle shows, its isoelectric pH value=2 is said
Bright H+Concentration is especially high, and the H of its surface hydroxyl can dissociate, and make surface negatively charged, to
Material of the cation form preservation in sludge has adsorptivity, and these factors are even more and increase acid dissolution slag
The separating difficulty of sludge each component.Therefore, the present invention utilizes aliphatic acid in flyash acid dissolution slag
Solid powder/particle carries out hydrophobically modified, it is changed into hydrophobic surface by water-wetted surface, so that suitable
Profit reduces the chloride ion content in solid phase after separating.
Method in accordance with the invention it is preferred that aliphatic acid described in step b is saturated fatty acid；It is excellent
Selection of land, the fatty chain length of the saturated fatty acid is 12~18；It is further preferred that described full
It is selected from aliphatic acid one or more in stearic acid, palmitic acid, laurate and myristic acid.On
The hydrophobically modified treatment that preferably aliphatic acid is particularly suitable for flyash acid dissolution slag of the invention is stated, is had
Beneficial to raising modified effect.
One of the invention is preferred embodiment, in step b, the aliphatic acid with slurry
Before mixing, the aliphatic acid is dissolved in organic solvent that can be miscible with water first, to be made into fat
Acid solution, then mixes with the slurry again.It is highly preferred that aliphatic acid in the adipic acid solution
Concentration be 10g/L~100g/L, more preferably 20g/L~80g/L, such as 30g/L, 40g/L or
60g/L etc..Wherein, it is comprehensive from cost, environmental protection and with the slurry mixed effect from the point of view of,
The organic solvent is preferably but not limited to ethanol, glacial acetic acid or acetone.
One of the invention preferred embodiment, and the modified-reaction in step b is in normal temperature (ratio
Such as 5~40 DEG C) under carry out.Need further to improve the tradition that temperature can just be carried out compared to most of
Modified-reaction, it is surprising that slurry of the invention is with modifying agent (aliphatic acid) at normal temperatures
Modified-reaction can be smoothly completed.By further further investigation, inventor has found：By fine coal
The surface hydroxyl of grey acid dissolution slag powder and the esterification of fatty acid molecule c-terminus, by aliphatic chain with
Covalent bond form is combined in solid powder particle surface, this to inspire so as to reach hydrophobic purpose
Heterogeneous esterification reaction on solid-liquid interface, it usually needs carry out hyperthermic treatment.However, in this hair
Lucky preservation has aluminium chloride in bright flyash acid dissolution slag, although as it was previously stated, the presence of aluminium chloride
It is unfavorable for the separation of solid and liquid of flyash acid dissolution slag, but now, aluminium chloride is sour as a kind of strong Lewis,
Al3+The carbonyl of outer layer unoccupied orbital and carboxylic acid can form relatively stable complex compound, the complex compound again with
Silicon (aluminium) alcoholic extract hydroxyl group on acid dissolution slag solid powder/particle surface is reacted, and its activation energy can be substantially reduced,
And reaction efficiency is greatly improved, such that it is able to as the catalyst of normal temperature esterification, be catalyzed foregoing
Esterification.Its catalytic mechanism is as follows：
This point is very significant, because flyash acid dissolution slag yield is huge and also contains acid
Liquid, it is therefore not necessary to heat temperature raising can not only reduce a large amount of energy consumptions, but also can be pre- well
The volatilization of acid-resistance gas (HCl), environmental protection and energy saving.
In the present invention, due to aluminium chloride catalytic effect well, the modification time is shorter, example
Such as it is no less than 10min, more preferably preferably 10~45min, 15~30min.
The method according to the invention, in step b, the consumption of the aliphatic acid can be according to powder in slurry
The surface hydroxyl quantity of coal ash acid dissolution slag and accordingly adjust, such as slightly excess 0.2wt%.Preferably,
The consumption of aliphatic acid described in step b is the 0.4wt%~3wt% of solid phase in the slurry, preferably 0.8
Wt%~2.8wt%, more preferably 1.2wt%~2.6wt%.Equally, in step b, can be stirred by machinery
The uniform mixing for realizing material such as mix.
The method according to the invention, step c is that step b gained modified products are carried out into separation of solid and liquid,
Obtain solid product and liquid product.Wherein, the liquid product can further return to flyash
Molten section of acid is with recycling, it is also possible to which return to step a is reused.In step c, described consolidates
Liquid separate can use solid-liquid separation means commonly used in the art, such as centrifugation, pressure filtration or
Vacuum filtration etc..
Preferably, the particle diameter of flyash acid dissolution slag described in step a for 100 mesh (can be by 100 mesh
Standard Tyler screen) or smaller szie, such as 150 mesh, 200 mesh or 250 mesh.
Compared with prior art, the present invention has advantages below：
1) because flyash acid dissolution slag specific surface area is big, chemism is high after sour molten treatment, uses
Aliphatic acid is modified treatment to flyash acid dissolution slag and is also easier to carry out；Further, since flyash is sour
The catalytic action of remaining aluminium chloride in molten slag, such that it is able to use normal temperature esterification, completes powder
Expect that the surface of particle is modified, and with the uniform (2853cm in the infrared spectrum of Fig. 1 of grafting-1、2923
cm-1Place-CH3、-CH2- c h bond characteristic absorption peak be solid particles surface aliphatic chain indication),
Industrial equipment is simple, be easy to amplify the advantage of production；
2) it is solid residue of the flyash by salt Ore Leaching, institute for flyash acid dissolution slag of the invention
Stating residue can not wash, calcine and directly processed through the method for the present invention, without in other
Between process, such that it is able to save great amount of cost；
3) after in the present invention, being processed through the method for the present invention, water content reduces 10wt% in solid product
Left and right, but the chloride ion content remained in solid product can but reduce 10-15 times, this is ability
Field technique personnel are unexpected, not only contribute to environmental protection, while also recyclable a large amount of useful
Aluminium chloride.
4) after being processed through the method for the present invention, the water content of solid product not only can be effectively reduced,
Even if water content is identical, the solid product after modification compared with unmodified solid product,
Drying time can substantially shorten, such as and the 2/3 of not enough the latter's drying time, so as to be conducive to solid phase
Product follow-up treatment or utilization.
Brief description of the drawings
Fig. 1 be embodiment 5 in before modified after flyash acid dissolution slag infrared spectrum comparison diagram.
Specific embodiment
More detailed description is made to the present invention by the following examples, but the present invention is not limited in
These embodiments.
The preparing raw material of flyash acid dissolution slag
The preparing raw material of the molten residue of flyash acid is the recirculating fluidized bed coal powder of certain steam power plant's output,
Its chemical composition is as shown in table 1.
The circulating fluid bed coal ash chemical composition (wt%) of table 1
| SiO2 | Al2O3 | TiO2 | CaO | MgO | Fe2O3 | FeO | K2O | Na2O | LOS | SO2 | Summation |
| 34.70 | 46.28 | 1.48 | 3.61 | 0.21 | 1.54 | 0.22 | 0.39 | 0.17 | 7.17 | 1.32 | 95.77 |
Embodiment 1
Above-mentioned fluidization bed fly ash (table 1) is taken, 200 mesh (Taylor standard sieve), the system of adding water are crushed to
It is the slurry of 33wt% into solid content, using vertical-ring magnetic separator (referring to Chinese patent
CN102145905A, and entire contents are incorporated herein), the magnetic separation in the case where field intensity is 1.5 ten thousand GS
Twice, the filter cake that solid content is 37.5wt% is obtained after plate and frame filter press press filtration；To in the filter cake
Add concentration carries out sour molten reaction for the technical hydrochloric acid of 28wt%, in the HCl in hydrochloric acid and flyash
Aluminum oxide mol ratio be 6:1,150 DEG C of reaction temperature, reaction pressure 0.6MPa, reaction time
2h, product (grinds refined filtration environmental protection equipment Co., Ltd XMY2-450 through filter press in the Xiangyang of Hubei
Type) separation of solid and liquid (pressure is 18MPa, pressurising time 3min, time of filter pressing 5min), obtain
Flyash acid dissolution slag G1, its water content is determined to 47.5wt%.
Take the molten residue G1 of above-mentioned flyash acid to be placed in 80 DEG C of air dry oven, dry to water and contain
Amount is not more than 0.1wt%, obtains desciccate G2.
Chlorine ion content determination in desciccate：It is 1 by solid-liquid mass ratio:3 ratio does 100g
Dry product G2 mixes washing, filtering with deionized water, collects filtrate；Repeat above-mentioned washing, filtering
Process, until chlorine ion concentration is not more than 0.01mol/L (silver nitrate titration detection) in filtrate.Meter
The total amount of chlorion in all filtrates is calculated, the content for obtaining chlorion in desciccate G2 is
14.4wt%.
Embodiment 2
Take flyash acid dissolution slag G1 obtained by a certain amount of embodiment 1 (dry solid weight is about 20kg)
Add water preparation slurry, puts into stirred tank, and institute's amount of water is 9 times of dry solid weight, stirs equal
It is even；
The stearic acid ethanol solution 7L of 4kg/100L is taken, in addition stirred tank；Continue to stir 12min,
Stop stirring, obtain modified product；
By above-mentioned modified product through filter press separation of solid and liquid (separation condition is ibid), solid product is obtained
A1, its water content is determined to 37.9wt%.
Take above-mentioned solid phase product A1 to be placed in 80 DEG C of air dry oven, drying is little to water content
In 0.1wt%, desciccate A2 is obtained.
Method according to chloride ion content in desciccate is determined in embodiment 1 determines desciccate A2
The content of middle chlorion, the content for obtaining chlorion in desciccate A2 is 0.046wt%.
Embodiment 3
Take flyash acid dissolution slag G1 obtained by a certain amount of embodiment 1 (dry solid weight is about 40kg)
Add water preparation slurry, puts into stirred tank, and institute's amount of water is 3 times of dry solid weight, stirs equal
It is even；
The palmitic acid glacial acetic acid solution 14L of 4kg/100L is taken, in addition stirred tank；Continue to stir
22min, stops stirring, obtains modified product；
By above-mentioned modified product through filter press separation of solid and liquid (separation condition is ibid), solid product is obtained
B1, its water content is determined to 37.8wt%.
Take above-mentioned solid phase product B1 to be placed in 80 DEG C of air dry oven, drying is little to water content
In 0.1wt%, desciccate B2 is obtained.
Method according to chloride ion content in desciccate is determined in embodiment 1 determines desciccate B2
The content of middle chlorion, the content for obtaining chlorion in desciccate B2 is 0.047wt%.
Embodiment 4
Take flyash acid dissolution slag G1 obtained by a certain amount of embodiment 1 (dry solid weight is about 60kg)
Add water preparation slurry, puts into stirred tank, and institute's amount of water is 1.5 times of dry solid weight, stirs equal
It is even；
The laurate acetone soln 24L of 4kg/100L is taken, in addition stirred tank；Continue to stir 18min,
Stop stirring, obtain modified product；
By above-mentioned modified product through filter press separation of solid and liquid (separation condition is ibid), solid product is obtained
C1, its water content is determined to 37.5wt%.
Take above-mentioned solid phase product C1 to be placed in 80 DEG C of air dry oven, drying is little to water content
In 0.1wt%, desciccate C2 is obtained.
Method according to chloride ion content in desciccate is determined in embodiment 1 determines desciccate C2
The content of middle chlorion, the content for obtaining chlorion in desciccate C2 is 0.045wt%.
Embodiment 5
Take flyash acid dissolution slag G1 obtained by a certain amount of embodiment 1 (dry solid weight is about 80kg)
Add water preparation slurry, puts into stirred tank, and institute's amount of water is 1.5 times of dry solid weight, stirs equal
It is even；
The myristic acid ethanol solution 32L of 4kg/100L is taken, in addition stirred tank；Continue to stir
25min, stops stirring, obtains modified product；
By above-mentioned modified product through filter press separation of solid and liquid (separation condition is ibid), solid product is obtained
D1, its water content is determined to 36.4wt%.
Take above-mentioned solid phase product D1 to be placed in 80 DEG C of air dry oven, drying is little to water content
In 0.1wt%, desciccate D2 is obtained.
Method according to chloride ion content in desciccate is determined in embodiment 1 determines desciccate D2
The content of middle chlorion, the content for obtaining chlorion in desciccate D2 is 0.04wt%.
Meanwhile, detection is sampled to above-mentioned flyash acid dissolution slag G1 and solid product D1, to survey
Infrared spectrogram (the test equipment of the flyash acid dissolution slag after making before modified：U.S. Nicolet
AVATAR360 examination of infrared spectrum instrument), referring specifically to Fig. 1.
As shown in Figure 1：For with respect to D1 white clays, the infrared spectrum of modified G1 white clays exists
2960~2852cm-1Between occur in that new peak, belong to CH3、CH2C h bond it is flexible
Vibration, is the characteristic absorption peak of aliphatic chain；1468cm-1、1382cm-1The new peak occurred at two is then
It is CH3、CH2C h bond deformation vibration characteristic peak, illustrate that fatty acid molecule has been connected to
The surface of solid particulate matter.
Comparative example 1
Take flyash acid dissolution slag G1 obtained by a certain amount of embodiment 1 (dry solid weight is about 80kg)
Add water preparation slurry, puts into stirred tank, and institute's amount of water is 5 times of dry solid weight, stirs equal
Continue to stir 25min after even；Then through filter press separation of solid and liquid (separation condition is ibid), consolidate
Phase product E1, its water content is determined to 46.2wt%.
Take above-mentioned solid phase product E1 to be placed in 80 DEG C of air dry oven, dry to water content and be not more than
0.1wt%, obtains desciccate E2；Compared with solid product D1 is dried, the time required to drying E1 about
It is 1.5~2 times of D1.
Method according to chloride ion content in desciccate is determined in embodiment 1 determines desciccate E2
The content of middle chlorion, the content for obtaining chlorion in desciccate E2 is 0.75wt%.
Claims (10)
1. a kind of processing method of flyash acid dissolution slag, comprises the following steps：
A, slurrying：Flyash acid dissolution slag is uniformly mixed with the water for adding；
It is b, modified：Step a gained slurries are uniformly mixed with aliphatic acid, is reacted；
C, separation：Step b gained modified products are carried out into separation of solid and liquid, solid product and liquid is obtained
Phase product.
2. processing method according to claim 1, it is characterised in that fat described in step b
Acid is saturated fatty acid；Preferably, the fatty chain length of the saturated fatty acid is 12~18.
3. processing method according to claim 1 and 2, it is characterised in that in step b, institute
One or more during saturated fatty acid is selected from stearic acid, palmitic acid, laurate and myristic acid is stated,
Preferably myristic acid.
4. the processing method according to any one of claim 1-3, it is characterised in that step b
In, the aliphatic acid is dissolved in organic solvent that can be miscible with water, after being made into adipic acid solution
Mix with the slurry again；Preferably, fatty acid concentration is 10~100g/L in the adipic acid solution.
5. the processing method according to any one of claim 1-4, it is characterised in that step b
In modified-reaction carry out at normal temperatures.
6. the processing method according to any one of claim 1-5, it is characterised in that step b
In the modified-reaction time be 10~45min.
7. the processing method according to any one of claim 1-6, it is characterised in that with weight
Count, the solid phase described in step a in flyash acid dissolution slag is with the mass ratio of the water for being added
1:1~1:15, preferably 1:1.5~1:10.
8. the processing method according to any one of claim 1-7, it is characterised in that step b
Described in aliphatic acid consumption be solid phase in the slurry 0.4wt%~3wt%, preferably described slurry
0.8wt%~the 2.8wt% of solid phase in material.
9. the processing method according to any one of claim 1-8, it is characterised in that step a
Described in flyash acid dissolution slag particle diameter be 100 mesh or smaller szie.
10. the processing method according to any one of claim 1~9, it is characterised in that institute
State flyash acid dissolution slag and carry out the molten treatment of acid for flyash to extract in flyash after aluminum oxide, carry out
Solid residue obtained from separation of solid and liquid；It is further preferred that the flyash acid dissolution slag is through drying
After dehydration, its each component is counted in the form of an oxide, comprising：The SiO of 41.0~56.0wt%2、
The Al of 16.0~32.0wt%2O3, 2.0~3.9wt% TiO2, 0.4~0.9wt% Fe2O3。
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