CN109675523A - A kind of yellow phosphorus furnace slag prepares the method and application of chromium adsorbent - Google Patents
A kind of yellow phosphorus furnace slag prepares the method and application of chromium adsorbent Download PDFInfo
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- CN109675523A CN109675523A CN201811553226.9A CN201811553226A CN109675523A CN 109675523 A CN109675523 A CN 109675523A CN 201811553226 A CN201811553226 A CN 201811553226A CN 109675523 A CN109675523 A CN 109675523A
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- yellow phosphorus
- chromium
- furnace slag
- phosphorus furnace
- solid
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- 239000011651 chromium Substances 0.000 title claims abstract description 66
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 32
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002893 slag Substances 0.000 title claims abstract description 28
- 239000003463 adsorbent Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 44
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000011343 solid material Substances 0.000 claims abstract description 17
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 22
- NGHMEZWZOZEZOH-UHFFFAOYSA-N silicic acid;hydrate Chemical compound O.O[Si](O)(O)O NGHMEZWZOZEZOH-UHFFFAOYSA-N 0.000 claims description 20
- 239000007790 solid phase Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 18
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 16
- 239000001099 ammonium carbonate Substances 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 8
- VIGMAPZYSWAUDT-UHFFFAOYSA-N N[SiH2]O Chemical compound N[SiH2]O VIGMAPZYSWAUDT-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002699 waste material Substances 0.000 abstract description 12
- 238000012545 processing Methods 0.000 abstract description 11
- 239000000377 silicon dioxide Substances 0.000 abstract description 11
- 229910052681 coesite Inorganic materials 0.000 abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229940088417 precipitated calcium carbonate Drugs 0.000 abstract description 3
- 238000001802 infusion Methods 0.000 abstract description 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012876 carrier material Substances 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- PWKQWSBUJOHVID-UHFFFAOYSA-N OC.CO[SiH](OC)OC Chemical compound OC.CO[SiH](OC)OC PWKQWSBUJOHVID-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- YICOVXASQKWWDU-UHFFFAOYSA-N ethanol;3-triethoxysilylpropan-1-amine Chemical compound CCO.CCO[Si](OCC)(OCC)CCCN YICOVXASQKWWDU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- -1 metallurgy Substances 0.000 description 1
- KXHFTXJPJMEXKR-UHFFFAOYSA-N methanol 3-trimethoxysilylpropan-1-amine Chemical compound OC.CO[Si](OC)(OC)CCCN KXHFTXJPJMEXKR-UHFFFAOYSA-N 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses method and application that a kind of yellow phosphorus furnace slag prepares chromium adsorbent, this method is leached using nitric acid solution decomposes yellow phosphorus furnace slag, and decomposition solid material is washed, dry, obtains high activity and porous SiO2Then powder carrier material obtains SiO by infusion process covered composite yarn2Base chromium adsorbent powder body material；It decomposes leachate to convert through ammonium carbonate salts, obtains precipitated calcium carbonate and ammonium nitrate solution product；By SiO2Base chromium adsorbent powder body material is applied in chromate waste water processing, which has good adsorption properties to chromium in waste water；The method of the present invention process equipment is simple, operation is easy, is safe, and yellow phosphorus furnace slag resource utilization is high, is a kind of processing technology routine having using trade waste production compared with high value added product, it can reach secondary resource comprehensive utilization, realize circular economy, energy-saving and emission-reduction purpose.
Description
Technical field
The invention belongs to industrial solid castoffs to utilize field, and in particular to the preparation of chromium adsorbent in a kind of chromate waste water
And its application.
Background technique
With the fast development of industrial or agricultural and urbanization, the water pollution problems as caused by heavy metal ion is gradually aggravated.?
In heavy metal contaminants, chromium (Cr) is one of common and most toxic heavy metal contaminants, and the chromium in chromate waste water is main
From industries such as plating, process hides, chemical industry, pigment, metallurgy, refractory materials, it exists in the form of trivalent and sexavalence compound.
Due to the highly dissoluble and its high carcinogenic and mutagenesis type of Cr VI, toxicity is most strong, about the 100 of trivalent chromium times, than three
Valence chromium has more bio-toxicity.Various countries are to the waste water of discharge, fisheries water water quality, field irrigation water quality, the surface water and drink
The chromium content of water, there are strict requirements.China is defined as Cr VI to implement one of the index of overall control, and provides industry
Cr VI maximum concentration is 0.5mg/L in the waste water of discharge, and the maximum concentration of total chromium is 1.5mg/L, and not handy dilution method generation
For necessary processing.
The key of processing waste water containing chrome is to reduce the content of Cr VI, can generally be realized by two kinds of approach: (1) led to
Crossing chemical reaction makes Cr VI be changed into the trivalent chromium that low toxicity easily precipitates, and further removes trivalent chromium；(2) by Cr VI chemical combination
Object is separated from water.Currently, a variety of physico-chemical process include ion exchange, chemical precipitation, electrochemical treatments, absorption and UF membrane
Etc. the processing for having been used for heavy metal wastewater thereby, wherein absorption method is due to having low cost, high efficiency, easy to operate and without secondary dirt
The features such as dye, it is considered to be a method of efficient removal Cr (VI).
When yellow phosphorus furnace slag is that electric furnace process produces yellow phosphorus using raw materials such as rock phosphate in powder, silica, coke, in 1400~1600 DEG C of height
The lower molten mass formed of temperature contains a large amount of SiO through having amorphous, high activity solid waste obtained by water quenching chilling2With
CaO；Report same as the present invention is had no at present.
Summary of the invention
The purpose of the present invention is to provide a kind of yellow phosphorus furnace slags to prepare SiO2Base Cr(VI) adsorbent powder body material method,
This method be using trade waste production can be used for Cr(VI in chromate waste water) adsorption and separation material process route, it is reachable
It comprehensively utilizes, realizes waste treatment and waste, circular economy, energy-saving and emission-reduction purpose to secondary resource.
In the method for the present invention yellow phosphorus furnace slag use acidleach, can be obtained porous, high activity, high-specific surface area it is amorphous
SiO2, with this SiO2It, using amino silane as starting material, is handled, can be obtained by surface recombination, drying etc. by infusion process for matrix
There must be the SiO of good Cr absorption property2Based composite adsorption material.
The method that yellow phosphorus furnace slag of the present invention prepares chromium adsorbent is as follows:
(1) consolidate the ratio that mass ratio is 8~12:1 in liquid, Yellow phosphorus furnace is added into the nitric acid solution of mass concentration 10~15%
Slag leaches 0.5 ~ 2.0h under room temperature, stirring condition, is separated by filtration to obtain silicic acid hydrate solid-phase material and leachate；
(2) use water washing silicic acid hydrate solid-phase material for 3 times of step (1) yellow phosphorus furnace slag quality 50~80%, then in 120~
It is 3~5 hours dry at 150 DEG C；
(3) under room temperature, stirring condition, by the silicic acid hydrate solid-phase material of step (2) after dry be added to mass concentration 5~
In 10% amino silane -ol solution, it is stirred to react 2.0~5.0 hours, then mixture is placed under ultrasound condition at dispersion
1.0 ~ 2.0h, still aging 3.0 ~ 6.0h are managed, is separated by filtration to obtain complex solid material and filtrate, wherein amino silane -ol is molten
It is 15~20:1 that the liquid of silicic acid hydrate solid-phase material, which consolidates mass ratio, after liquid and drying；
(4) the isolated complex solid material of step (3), dry 5 ~ 8h, obtains SiO under the conditions of 60~100 DEG C2Base chromium is inhaled
Attached dose of powder body material；
Under room temperature, stirring condition, it is gradually added into ammonium carbonate or ammonium hydrogen carbonate in the leachate isolated to step (1),
NO in middle leachate3 -It is 1:1.0~2.2 with the molar ratio of ammonium carbonate or ammonium hydrogen carbonate, is then stirred to react 1~2h, filters
Isolated solid sediment and precipitation filtrates wash solid sediment, and then dry 2.0 ~ 3.0h at 100 ~ 120 DEG C, obtains
To light calcium carbonate product；
(6) precipitation filtrates that step (5) is isolated, are concentrated by evaporation, cooling, obtain ammonium nitrate solution product.
Alcohol in the amino silane -ol solution is methanol, ethyl alcohol, isopropanol or their aqueous solution etc., their water
Solution is that one kind obtained, the amino silane -ol of mass concentration 5~10% is mixed by any ratio in methanol, ethyl alcohol or isopropyl alcohol and water
Solution is concentration of the amino silane in alcoholic solution.
The amino silane can be 3- aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, polyamino
Alkyltrialkoxysilaneand (isopropanol), N- β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane, N- β (aminoethyl)-
γ-aminopropyltriethoxy dimethoxysilane etc..
The step (1), (3), the speed of agitator in (5) are 300~500rpm.
The present invention another object is that by chromium adsorbent made from the above method apply chromate waste water processing in, room temperature,
Under stirring condition, SiO is added in chromate waste water2Base chromium adsorbent powder material processing 5.0~8.0 hours, every 100mL contain chromium
Waste water adds 100~150mgSiO2Base chromium adsorbent powder body material, is separated by filtration to obtain chromium purified solution.
The present invention has following advantages and effect:
(1) silica and calcium oxide in the present invention effectively extraction and application yellow phosphorus furnace slag, preparing has compared with high added value
Product provides a new technology for the utilization of yellow phosphorus furnace slag；
(2) in the method for the present invention process flow, the light calcium carbonate product of calcium oxide preparation high-quality in recycling yellow phosphorus furnace slag
While, pass through the compound SiO being prepared2Based composite powder material can be used for the absorption point of heavy metals in industrial wastewater chromium
From achieving the purpose that the treatment of wastes with processes of wastes against one another；
(3) the features such as present invention has process equipment simple, and operation is easy, is safe.
The solid slag preparation that the present invention is generated using phosphorus production has the compound of good adsorption properties to chromium in waste water
Sorbent material can adequately and reasonably utilize resource, turn waste into wealth, and reduce environmental pollution, economize on resources, reach environmentally protective
Purpose is of great significance to the recycling of resource.
Specific embodiment
Below by embodiment, invention is further described in detail, but the scope of the present invention is not limited in described
Hold.
The main component of yellow phosphorus furnace slag raw material used in following embodiments are as follows: yellow phosphorus furnace slag contains SiO2 41.62%, CaO
49.72%；Electrogalvanizing is passivated chrome waste liquid and contains Cr (VI) 35mg/L.
Embodiment 1
(1) 600 grams of nitric acid solution that mass concentration is 10% are added in the reactor, consolidates mass ratio by the liquid of 12:1, yellow phosphorus is added
50 grams of clinker, 1.0h, isolated leachate and hydration are reacted in leaching under conditions of room temperature, mixing speed are 400rpm
Silicic acid solid material；
(2) the silicic acid hydrate solid-phase material that step (1) obtains uses the water washing 3 of step (1) yellow phosphorus furnace slag material quality 50%
It is secondary, it is then 3 hours dry under the conditions of 150 DEG C；
(3) under room temperature, 300rpm stirring condition, it is dense that the silicic acid hydrate solid-phase material of step (2) after dry is added to quality
In 3- aminopropyl triethoxysilane-ethanol solution that degree is 5%, it is stirred to react 3.0 hours, is then placed in mixture
Decentralized processing 1.0h under ultrasound condition, still aging 5.0h are separated by filtration to obtain complex solid material and filtrate, wherein 3- ammonia third
It is 15:1 that the liquid of ethyl triethoxy silicane alkane-ethanol solution and dry silicic acid hydrate solid-phase material, which consolidates mass ratio,；
(4) the isolated complex solid material of step (3), dry 6h, obtains SiO under the conditions of 70 DEG C2Base chromium adsorbent powder
Body material；
(5) under room temperature, stirring condition, it is gradually added into ammonium carbonate in the leachate isolated to step (1), wherein leachate
In NO3 -Molar ratio with ammonium carbonate is 1:1.0, is then stirred to react 1h, is separated by filtration to obtain solid sediment and precipitating filter
Liquid washs solid sediment, and then the dry 2.0h at 120 DEG C, obtains light calcium carbonate product；Through analyzing, precipitated calcium carbonate
Products C aCO3Content is 98.24%, and appearance is white；
(6) precipitation filtrates that step (5) is isolated, are concentrated by evaporation to ammonium nitrate (NH4NO3) mass concentration be greater than 65%
When, it is cooling, obtain ammonium nitrate solution product；Through analyzing, which reaches 4523-2013 ammonium nitrate solution product technology of HG/T
It is required that.
It takes and is passivated waste liquid 100mL containing Cr (VI) electrogalvanizing, step (4) are added under room temperature, 400rpm stirring condition and obtain
SiO2Base chromium adsorbent powder body material 100mg, stir process 8.0 hours, is separated by filtration to obtain chromium purified solution；Through analyzing,
The adsorbing and removing rate of Cr (VI) is 95%.
Embodiment 2
(1) 400 grams of nitric acid solution that mass concentration is 15% are added in the reactor, consolidates mass ratio by the liquid of 8:1, yellow phosphorus is added
50 grams of clinker, 0.5h, isolated leachate and hydration are reacted in leaching under conditions of room temperature, mixing speed are 500rpm
Silicic acid solid material；
(2) the silicic acid hydrate solid-phase material that step (1) obtains uses the water washing 3 of step (1) yellow phosphorus furnace slag material quality 80%
It is secondary, it is then 5 hours dry under the conditions of 120 DEG C；
(3) under room temperature, 400rpm stirring condition, it is dense that the silicic acid hydrate solid-phase material of step (2) after dry is added to quality
In polyamino alkyltrialkoxysilaneand-aqueous isopropanol that degree is 7%, it is stirred to react 5.0 hours, is then placed in mixture
Decentralized processing 1.5h under ultrasound condition, still aging 3.0h are separated by filtration to obtain complex solid material and filtrate, wherein polyamino
It is 18:1 that the liquid of alkyltrialkoxysilaneand-aqueous isopropanol and dry silicic acid hydrate solid-phase material, which consolidates mass ratio,；
(4) the isolated complex solid material of step (3), dry 5h, obtains SiO under the conditions of 100 DEG C2Base chromium adsorbent powder
Body material；
(5) under room temperature, stirring condition, it is gradually added into ammonium hydrogen carbonate in the leachate isolated to step (1), wherein leaching
NO in liquid3 -Be 1:2.0 with the molar ratio of ammonium hydrogen carbonate, be then stirred to react 2.0h, be separated by filtration to obtain solid sediment and
Precipitation filtrates wash solid sediment, and then the dry 3.0h at 100 DEG C, obtains light calcium carbonate product；Through analyzing, lightweight
Calcium carbonate product CaCO3Content is 97.82%, and appearance is white；
(6) precipitation filtrates that step (5) is isolated, are concentrated by evaporation to ammonium nitrate (NH4NO3) mass concentration be greater than 65%
When, it is cooling, obtain ammonium nitrate solution product；Through analyzing, which reaches 4523-2013 ammonium nitrate solution product technology of HG/T
It is required that；
It takes and is passivated waste liquid 100mL containing Cr (VI) electrogalvanizing, addition step (4) obtains under room temperature, 300rpm stirring condition
SiO2Base chromium adsorbent powder body material 120mg, stir process 6.0 hours, is separated by filtration to obtain chromium purified solution；Through analyzing, Cr
(VI) adsorbing and removing rate is 97%.
Embodiment 3
(1) 500 grams of nitric acid solution that mass concentration is 12% are added in the reactor, consolidates mass ratio by the liquid of 10:1, yellow phosphorus is added
50 grams of clinker, 2.0h, isolated leachate and hydration are reacted in leaching under conditions of room temperature, mixing speed are 300rpm
Silicic acid solid material；
(2) the silicic acid hydrate solid-phase material that step (1) obtains washs 3 using the water of step (1) yellow phosphorus furnace slag material quality 60%
It is secondary, it is then 4 hours dry under the conditions of 130 DEG C；
(3) under room temperature, 500rpm stirring condition, it is dense that the silicic acid hydrate solid-phase material of step (2) after dry is added to quality
In γ-aminopropyltrimethoxysilane-methanol solution that degree is 10%, it is stirred to react 4.0 hours, is then placed in mixture super
Decentralized processing 1.5h under the conditions of sound, still aging 4.0h are separated by filtration to obtain complex solid material and filtrate, wherein γ-ammonia third
It is 20:1 that the liquid of base trimethoxy silane-methanol solution and dry silicic acid hydrate solid-phase material, which consolidates mass ratio,；
(4) the isolated complex solid material of step (3), dry 8h, obtains SiO under the conditions of 60 DEG C2Base chromium adsorbent powder
Body material；
(5) under room temperature, stirring condition, it is gradually added into ammonium hydrogen carbonate in the leachate isolated to step (1), wherein leaching
NO in liquid3 -Be 1:2.2 with the molar ratio of ammonium hydrogen carbonate, be then stirred to react 1.5h, be separated by filtration to obtain solid sediment and
Precipitation filtrates wash solid sediment, and then the dry 2.5h at 110 DEG C, obtains light calcium carbonate product, through analyzing, lightweight
Calcium carbonate product CaCO3Content is 98.06%, and appearance is white；
(6) precipitation filtrates that step (5) is isolated, are concentrated by evaporation to ammonium nitrate (NH4NO3) mass concentration be greater than 65%
When, it is cooling, obtain ammonium nitrate solution product；Through analyzing, which reaches 4523-2013 ammonium nitrate solution product technology of HG/T
It is required that；
It takes and is passivated waste liquid 100mL containing Cr (VI) electrogalvanizing, addition step (4) obtains under room temperature, 500rpm stirring condition
SiO2Base chromium adsorbent powder body material 150mg, stir process 5.0 hours, is separated by filtration to obtain chromium purified solution；Through analyzing, Cr
(VI) adsorbing and removing rate is 98%.
Embodiment 4
(1) 550 grams of nitric acid solution that mass concentration is 11% are added in the reactor, consolidates mass ratio by the liquid of 11:1, yellow phosphorus is added
50 grams of clinker, 1.5h, isolated leachate and hydration are reacted in leaching under conditions of room temperature, mixing speed are 500rpm
Silicic acid solid material；
(2) the silicic acid hydrate solid-phase material that step (1) obtains uses the water washing 3 of step (1) yellow phosphorus furnace slag material quality 70%
It is secondary, it is then 3.5 hours dry under the conditions of 140 DEG C；
(3) under room temperature, 400rpm stirring condition, it is dense that the silicic acid hydrate solid-phase material of step (2) after dry is added to quality
In N- β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane-ethanol water (ethyl alcohol 75%, water 25%) that degree is 8%, stir
Reaction 4.5 hours is mixed, mixture is then placed in decentralized processing 2.0h under ultrasound condition, still aging 6.0h is separated by filtration
To complex solid material and filtrate, wherein N- β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane-ethanol water and dry
It is 16:1 that the liquid of dry silicic acid hydrate solid-phase material, which consolidates mass ratio,；
(4) the isolated complex solid material of step (3), dry 7h, obtains SiO under the conditions of 90 DEG C2Base chromium adsorbent powder
Body material；
(5) under room temperature, stirring condition, it is gradually added into ammonium carbonate in the leachate isolated to step (1), wherein leachate
In NO3 -Molar ratio with ammonium carbonate is 1:1.2, is then stirred to react 2h, is separated by filtration to obtain solid sediment and precipitating filter
Liquid washs solid sediment, and then the dry 3.0h at 100 DEG C, obtains light calcium carbonate product, through analyzing, precipitated calcium carbonate
Products C aCO3Content is 98.36%, and appearance is white；
(6) precipitation filtrates that step (5) is isolated, are concentrated by evaporation to ammonium nitrate (NH4NO3) mass concentration be greater than 65%
When, it is cooling, obtain ammonium nitrate solution product；Through analyzing, which reaches 4523-2013 ammonium nitrate solution product technology of HG/T
It is required that；
(5) it takes and is passivated waste liquid 100mL containing Cr (VI) electrogalvanizing, addition step (4) obtains under room temperature, 400rpm stirring condition
SiO2Base chromium adsorbent powder body material 140mg, stir process 7.0 hours, is separated by filtration to obtain chromium purified solution；Through analyzing, Cr
(VI) adsorbing and removing rate is 97%.
Claims (5)
1. a kind of method that yellow phosphorus furnace slag prepares chromium adsorbent, it is characterised in that sequentially include the following steps:
(1) consolidate the ratio that mass ratio is 8~12:1 in liquid, Yellow phosphorus furnace is added into the nitric acid solution of mass concentration 10~15%
Slag leaches 0.5 ~ 2.0h under room temperature, stirring condition, is separated by filtration to obtain silicic acid hydrate solid-phase material and leachate；
(2) use water washing silicic acid hydrate solid-phase material for 3 times of step (1) yellow phosphorus furnace slag quality 50~80%, then in 120~
It is 3~5 hours dry at 150 DEG C；
(3) under room temperature, stirring condition, by the silicic acid hydrate solid-phase material of step (2) after dry be added to mass concentration 5~
In 10% amino silane -ol solution, it is stirred to react 2.0~5.0 hours, then mixture is placed under ultrasound condition at dispersion
1.0 ~ 2.0h, still aging 3.0 ~ 6.0h are managed, is separated by filtration to obtain complex solid material and filtrate, wherein amino silane -ol is molten
It is 15~20:1 that the liquid of silicic acid hydrate solid-phase material, which consolidates mass ratio, after liquid and drying；
(4) the isolated complex solid material of step (3), dry 5 ~ 8h, obtains SiO under the conditions of 60~100 DEG C2Base chromium is inhaled
Attached dose of powder body material；
(5) under room temperature, stirring condition, it is gradually added into ammonium carbonate or ammonium hydrogen carbonate in the leachate isolated to step (1),
The wherein NO in leachate3 -It is 1:1.0~2.2 with the molar ratio of ammonium carbonate or ammonium hydrogen carbonate, is then stirred to react 1~2h, mistake
Isolated solid sediment and precipitation filtrates are filtered, solid sediment is washed, then dry 2.0 ~ 3.0h at 100 ~ 120 DEG C,
Obtain light calcium carbonate product；
(6) precipitation filtrates that step (5) is isolated, are concentrated by evaporation, cooling, obtain ammonium nitrate solution product.
2. the method that yellow phosphorus furnace slag according to claim 1 prepares chromium adsorbent, it is characterised in that: amino silane -ol is molten
Alcoholic solution in liquid is methanol, ethyl alcohol, isopropanol or their aqueous solution.
3. the method that yellow phosphorus furnace slag according to claim 1 prepares chromium adsorbent, it is characterised in that: amino silane is 3- ammonia
Propyl-triethoxysilicane, γ-aminopropyltrimethoxysilane, polyamino alkyltrialkoxysilaneand, N- β (aminoethyl)-
γ-aminopropyltriethoxy diethoxy silane or N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane.
4. the method that yellow phosphorus furnace slag according to claim 1 prepares chromium adsorbent, it is characterised in that: it is characterized by: stirring
It mixes and is carried out at 300~500rpm of revolving speed.
5. yellow phosphorus furnace slag of any of claims 1-4 prepares chromium adsorbent made from the method for chromium adsorbent containing chromium
Application in wastewater treatment, it is characterised in that: under room temperature, stirring condition, SiO is added in chromate waste water2Base chromium adsorbent
Powder body material is handled 5.0~8.0 hours, and every 100mL chromate waste water adds 100~150mgSiO2Base chromium adsorbent powder body material,
It is separated by filtration to obtain chromium purified solution.
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