CN112093878B - Cyanogen removing agent and preparation method thereof - Google Patents
Cyanogen removing agent and preparation method thereof Download PDFInfo
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- CN112093878B CN112093878B CN202010864256.2A CN202010864256A CN112093878B CN 112093878 B CN112093878 B CN 112093878B CN 202010864256 A CN202010864256 A CN 202010864256A CN 112093878 B CN112093878 B CN 112093878B
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000010881 fly ash Substances 0.000 claims abstract description 90
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 26
- 150000001879 copper Chemical class 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 15
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 35
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 18
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 21
- 230000000052 comparative effect Effects 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- -1 photographic offset Substances 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a cyanogen removing agent and a preparation method thereof. The cyanogen removing agent comprises the following components in parts by weight: 40-50 parts of modified fly ash, 15-25 parts of inorganic copper salt and 2-3 parts of polymeric iron; the modified fly ash is obtained by mixing fly ash with inorganic acid, and sequentially carrying out microwave treatment, hydrothermal treatment and inorganic ferric salt treatment. The cyanide remover provided by the invention has a good treatment effect on high-concentration cyanide-containing wastewater, can reduce the cyanide concentration in the cyanide-containing wastewater to below 0.5mg/L, and meets the requirements of GB 8978-1996 comprehensive wastewater discharge Standard; when the cyanide remover provided by the invention is used for treating high-concentration cyanide-containing wastewater, the dosage is small, and the cost is reduced.
Description
Technical Field
The invention relates to the technical field of cyanide-containing wastewater treatment, in particular to a cyanide remover and a preparation method thereof.
Background
Cyanide refers to compounds containing cyano groups (CN), including organic and inorganic cyanides. Among them, common inorganic cyanides are sodium cyanide (NaCN), potassium cyanide (KCN), etc.; common organic cyanides are acrylonitrile, ethanedinitrile, and the like. Cyanide has wide application in industrial production, and a large amount of cyanide-containing wastewater is also produced. The main sources of cyanide-containing wastewater are: mining and refining of minerals, photographic offset, coke oven wastewater, electroplating plants, metal surface treatment plants, gas plants, dye plants, leather plants, plastic plants, synthetic fibers, surface quenching of steel ingots, industrial gas washing, and the like.
In cyanide-containing wastewater, inorganic cyanide is added with CN - Or complex ion forms, sometimes the cyanide-containing complex ion is the predominant form present. In gold smelting, gold is extracted by adopting a gold leaching mode of sodium cyanide, and then partial discharge of a displacement lean solution is generated during zinc displacement, wherein the displacement lean solution mainly contains NaCN and [ Zn (CN) 4 ]] 2- 、[Fe(CN) 6 ] 4- 、[Cu(CN) 4 ] 2- 、Cu 2 (CN) 2 Cyanide compounds such as NaCNS; in coking wastewaterThe ratio of simple cyanide is about 16% -24%, and the rest is complex cyanide, including [ Zn (CN) 4 ] 2- 、[CdCN) 4 ] 2- 、[Cu(CN) 4 ] 2- 、[Fe(CN) 6 ] 3- 、[Fe(CN) 6 ] 4- Etc. Complex cyanide increases the difficulty of wastewater treatment and increases the treatment cost.
Methods for treating cyanide-containing wastewater are reported in literature to be mainly physical, chemical and biochemical. The physical method has high cost, low practical value, good treatment effect of the chemical method, too high addition amount, large wastewater treatment amount of the upgrading method, low cost and poor treatment effect.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a cyanide remover and a preparation method thereof, which solve the technical problem of poor treatment effect of the existing cyanide-containing wastewater treatment method in the prior art.
To achieve the technical purpose, the first aspect of the invention provides a cyanogen removing agent, which comprises the following components in parts by weight: 40-50 parts of modified fly ash, 15-25 parts of inorganic copper salt and 2-3 parts of polymeric iron;
the modified fly ash is obtained by mixing fly ash with inorganic acid, and sequentially carrying out microwave treatment, hydrothermal treatment and inorganic ferric salt treatment.
Further, the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid; the concentration of the inorganic acid is 1-3 mol/L; the mass ratio of the fly ash to the inorganic acid is 1: (5-10).
Further, the conditions of the microwave treatment are as follows: the microwave power is 100-300W, the microwave temperature is 80-90 ℃, and the microwave time is 15-30 min;
further, the conditions of the hydrothermal treatment are: the hydrothermal temperature is 80-100 ℃, and the hydrothermal time is 4-8 h.
Further, the inorganic ferric salt is one or more of ferrous chloride, ferric sulfate and ferrous sulfate; the concentration of the inorganic ferric salt is 3-5 mol/L; the mass ratio of the fly ash to the inorganic ferric salt is 1: (1-3).
Further, the inorganic ferric salt treatment conditions are as follows: the temperature is 40-50 ℃ and the time is 10-20 min.
Further, the inorganic copper salt is one or two of copper sulfate and copper chloride; the polymeric iron is one or more of polymeric ferric chloride, polymeric ferric sulfate, polymeric ferric nitrate and polymeric ferrosilicon.
Further, the mass ratio of the inorganic copper salt to the polymeric iron is 8:1.
The second aspect of the invention provides a method for preparing a cyanogen removing agent, comprising the following steps:
s1: mixing the fly ash with inorganic acid, and carrying out microwave treatment, hydrothermal treatment and inorganic ferric salt treatment to obtain modified fly ash;
s2: and uniformly mixing the modified fly ash, the inorganic copper salt and the polymeric iron to obtain the cyanogen removing agent.
The preparation method of the cyanogen removing agent provided by the second aspect of the invention is used for preparing the cyanogen removing agent provided by the first aspect of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the cyanide remover provided by the invention has a good treatment effect on high-concentration cyanide-containing wastewater, can reduce the cyanide concentration in the cyanide-containing wastewater to below 0.5mg/L, and meets the requirements of GB 8978-1996 comprehensive wastewater discharge Standard;
when the cyanide remover provided by the invention is used for treating high-concentration cyanide-containing wastewater, the dosage is small, and the cost is reduced;
the method has the advantages of wide sources of raw materials and simple preparation process, and can be suitable for process production.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The first aspect of the invention provides a cyanogen removing agent, which comprises the following components in parts by weight: 40-50 parts of modified fly ash, 15-25 parts of inorganic copper salt and 2-3 parts of polymeric iron. The modified fly ash is obtained by mixing fly ash with inorganic acid, and performing microwave treatment, hydrothermal treatment and inorganic ferric salt treatment.
The main component of the fly ash is SiO 2 、Al 2 O 3 、FeO、Fe 2 O 3 CaO is generally obtained through physical and chemical processes such as high temperature, melting, cooling and the like, has high specific surface area, can act with adsorbates in a form of complexation, ion exchange, chemical bonding, physical adsorption and the like, and has good adsorption performance.
In the invention, after microwave treatment, the disintegration of the glass network polymer in the fly ash can be promoted, and the SiO is accelerated 2 -Al 2 O 3 Bond cleavage; after hydrothermal treatment, the internal structure of the fly ash can be further destroyed, the specific surface area is increased, and the adsorption activity is improved; after being treated by inorganic ferric salt, the internal pore canal and the surface of the fly ash can improve the loading capacity on the iron ions, thereby facilitating the complexing of the iron ions and cyanide ions and further improving the cyanide removal effect; the surface of the modified fly ash also contains abundant hydroxyl groups, and can be compounded with metal ions to improve flocculation sedimentation effect. Meanwhile, the polymeric iron also has better flocculation capability, and when the polymeric iron is used together with the modified fly ash, the synergistic capability of the polymeric iron and the modified fly ash can be fully exerted, so that the flocculation effect is further improved. Copper ions in the inorganic copper salt can be complexed with cyanide ions to form a precipitate, and the precipitate is compounded with the modified fly ash and the polymeric ferric sulfate, so that the cyanide removal effect is more remarkable.
In the present embodiment, the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, and the concentration thereof is 1 to 3mol/L, preferably 1.5 to 2.5mol/L, and further 2mol/L; the mass ratio of the fly ash to the inorganic acid is 1: (5-10), preferably 1: (6-9), and further 1:7. The conditions of the microwave treatment are as follows: the microwave power is 100-300W, the microwave temperature is 80-90 ℃, and the microwave time is 15-30 min; preferably, it is: the microwave power is 150-250W, the microwave temperature is 83-87 ℃, the microwave time is 20-25 min, and the method further comprises the following steps: the microwave power is 200W, the microwave temperature is 85 ℃, and the microwave time is 20min. The conditions of the hydrothermal treatment are as follows: the hydrothermal temperature is 80-100 ℃, and the hydrothermal time is 4-8 hours; preferably, it is: the hydrothermal temperature is 85-95 ℃, the hydrothermal time is 5-7 h, and the method further comprises the following steps: the hydrothermal temperature is 90 ℃, and the hydrothermal time is 6 hours. The inorganic ferric salt is one or more of ferrous chloride, ferric sulfate and ferrous sulfate, and the concentration of the inorganic ferric salt is 3-5 mol/L, preferably 4mol/L; the mass ratio of the fly ash to the inorganic ferric salt is 1: (1-3), preferably 1:2. The inorganic ferric salt treatment conditions are as follows: the temperature is 40-50 ℃ and the time is 10-20 min, preferably: the temperature is 45 ℃ and the time is 15min. According to the invention, the raw material addition amount, microwave treatment, hydrothermal treatment and inorganic ferric salt treatment conditions are strictly controlled, so that the obtained modified fly ash, inorganic copper salt and polymeric iron are compounded, and the obtained cyanogen removing agent has a better cyanogen removing effect.
In this embodiment, the inorganic copper salt is one or both of copper sulfate and copper chloride; the polymeric iron is one or more of polymeric ferric chloride, polymeric ferric sulfate, polymeric ferric nitrate and polymeric ferrosilicon. Further, the mass ratio of the inorganic copper salt to the polymeric iron is 8:1. In the proportion range, the obtained cyanogen removing agent has better cyanogen removing effect.
The second aspect of the invention provides a method for preparing a cyanogen removing agent, comprising the following steps:
s1: mixing the fly ash with inorganic acid, and carrying out microwave treatment, hydrothermal treatment and inorganic ferric salt treatment to obtain modified fly ash;
s2: and uniformly mixing the modified fly ash, the inorganic copper salt and the polymeric iron to obtain the cyanogen removing agent.
The preparation method of the cyanogen removing agent provided by the second aspect of the invention is used for preparing the cyanogen removing agent provided by the first aspect of the invention.
Example 1
(1) Mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 6h at 90 ℃, adding 10g of ferric sulfate with the molar concentration of 4mol/L, and stirring for 15min at 45 ℃ to obtain modified fly ash;
(2) 45g of modified fly ash, 20g of copper sulfate and 2.5g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Example 2
(1) Mixing 5g of fly ash with 50g of dilute sulfuric acid with the molar concentration of 1mol/L, carrying out microwave treatment for 15min under the conditions of 100W of microwave power and 80 ℃ of microwave temperature, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 6h at 90 ℃, adding 10g of ferric sulfate with the molar concentration of 4mol/L, and stirring for 15min at 45 ℃ to obtain modified fly ash;
(2) 45g of modified fly ash, 20g of copper sulfate and 2.5g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Example 3
(1) Mixing 5g of fly ash and 25g of dilute nitric acid with the molar concentration of 3mol/L, carrying out microwave treatment for 30min under the conditions of the microwave power of 300W and the microwave temperature of 90 ℃, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 6h at the temperature of 90 ℃, adding 10g of ferric sulfate with the molar concentration of 4mol/L, and stirring for 15min at the temperature of 45 ℃ to obtain modified fly ash;
(2) 45g of modified fly ash, 20g of copper sulfate and 2.5g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Example 4
(1) Mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 8h at 80 ℃, adding 10g of ferric sulfate with the molar concentration of 4mol/L, and stirring for 15min at 45 ℃ to obtain modified fly ash;
(2) 45g of modified fly ash, 20g of copper sulfate and 2.5g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Example 5
(1) Mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 4h at 100 ℃, adding 10g of ferric sulfate with the molar concentration of 4mol/L, and stirring for 15min at 45 ℃ to obtain modified fly ash;
(2) 45g of modified fly ash, 20g of copper sulfate and 2.5g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Example 6
(1) Mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 6h at 90 ℃, adding 5g of ferric sulfate with the molar concentration of 3mol/L, and stirring for 15min at 45 ℃ to obtain modified fly ash;
(2) 45g of modified fly ash, 20g of copper sulfate and 2.5g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Example 7
(1) Mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 6h at 90 ℃, adding 15g of ferric sulfate with the molar concentration of 5mol/L, and stirring for 15min at 45 ℃ to obtain modified fly ash;
(2) 45g of modified fly ash, 20g of copper sulfate and 2.5g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Example 8
(1) Mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 6h at 90 ℃, adding 10g of ferric sulfate with the molar concentration of 4mol/L, and stirring for 15min at 45 ℃ to obtain modified fly ash;
(2) 40g of modified fly ash, 24g of copper sulfate and 3g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Example 9
(1) Mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 6h at 90 ℃, adding 10g of ferric sulfate with the molar concentration of 4mol/L, and stirring for 15min at 45 ℃ to obtain modified fly ash;
(2) 50g of modified fly ash, 16g of copper sulfate and 2g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Example 10
(1) Mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 6h at 90 ℃, adding 10g of ferric sulfate with the molar concentration of 4mol/L, and stirring for 15min at 45 ℃ to obtain modified fly ash;
(2) 45g of modified fly ash, 25g of copper sulfate and 2g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Example 11
(1) Mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, transferring the reaction liquid into a reaction kettle, carrying out hydrothermal treatment for 6h at 90 ℃, adding 10g of ferric sulfate with the molar concentration of 4mol/L, and stirring for 15min at 45 ℃ to obtain modified fly ash;
(2) 45g of modified fly ash, 15g of copper sulfate and 3g of polymeric ferric sulfate are uniformly mixed to obtain the cyanogen removing agent.
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 was obtained by uniformly mixing only 20g of copper sulfate and 2.5g of polymeric ferric sulfate, to obtain a cyanogen-removing agent.
Comparative example 2
Comparative example 2 was different from example 1 in that only 45g of modified fly ash and 2.5g of polymeric ferric sulfate were uniformly mixed in comparative example 2 to obtain a cyanogen removing agent.
Comparative example 3
Comparative example 3 differs from example 1 in that comparative example 3 was obtained by uniformly mixing only 45g of modified fly ash and 20g of copper sulfate, thereby obtaining a cyanogen-removing agent.
Comparative example 4
Comparative example 4 differs from example 1 in that comparative example 4 was obtained by uniformly mixing 30g of modified fly ash, 8g of copper sulfate, and 1g of polymeric ferric sulfate, to obtain a cyanogen-removing agent.
Comparative example 5
Comparative example 5 differs from example 1 in that comparative example 5 was obtained by uniformly mixing 20g of modified fly ash, 20g of copper sulfate, and 2.5g of polymeric ferric sulfate, to obtain a cyanogen-removing agent.
Comparative example 6
Comparative example 6 differs from example 1 only in that the modified fly ash obtained was prepared as follows:
5g of fly ash and 35g of dilute hydrochloric acid with the molar concentration of 2mol/L are mixed, the reaction solution is transferred into a reaction kettle, the reaction kettle is subjected to hydrothermal treatment for 6 hours at 90 ℃, then 10g of ferric sulfate with the molar concentration of 4mol/L is added, and the mixture is stirred for 15 minutes at 45 ℃ to obtain the modified fly ash.
Comparative example 7
Comparative example 7 differs from example 1 only in that the modified fly ash obtained was prepared as follows:
mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, then adding 10g of ferric sulfate with the molar concentration of 4mol/L into the reaction solution, and stirring for 15min at 45 ℃ to obtain the modified fly ash.
Comparative example 8
Comparative example 8 differs from example 1 only in that the modified fly ash obtained was prepared as follows:
mixing 5g of fly ash with 35g of dilute hydrochloric acid with the molar concentration of 2mol/L, carrying out microwave treatment for 20min under the conditions of 200W of microwave power and 85 ℃ of microwave temperature, transferring the reaction solution into a reaction kettle, and carrying out hydrothermal treatment for 6h at 90 ℃ to obtain the modified fly ash.
Preparation of cyanide-containing waste water
Weighing 0.5g of potassium ferricyanide K 3 [Fe(CN) 6 ]Adding the mixture into 20L of tap water, and uniformly stirring to obtain cyanide-containing wastewater containing about 12.76mg/L cyanide ions.
Cyanide detection method
Weighing different weights of the cyanogen removing agents of the examples 1-11 and the comparative examples 1-8, adding the cyanogen removing agents into 1L cyanide-containing wastewater, stirring for 10min, standing, filtering with quantitative filter paper, and collecting filtrate; weighing 200ml of filtrate, adding 500ml of filtrate into the filtrate, putting the filtrate into explosion-proof beads, continuously adding 10ml of EDTA-2Na solution with the mass concentration of 100g/L and 10ml of phosphoric acid with the mass fraction of 85%, covering a bottle stopper, and keeping the distillate heated at the speed of 2-4 ml/min; in this process, the distillate was absorbed by 10ml of sodium hydroxide solution as an absorbing solution (typically sodium hydroxide solution with a mass fraction of 10g/L, 4% sodium hydroxide was used when sodium sulfite and sodium carbonate were present in the sample), and when the solution in the receiving flask was nearly 100ml (distillate + absorbing solution), distillation was stopped, the distillate in the receiving measuring cylinder was transferred to a conical flask, the condenser was rinsed with a small amount of water, the receiving measuring cylinder was rinsed, and the washing liquid was collected to the conical flask where the distillate was discharged.
In a conical flask of distillate was added dropwise 0.2ml of a silvered indicator (0.02 g of p-dimethylaminobenzylidene rhodanine, dissolved in 100ml of acetone) and the solution was titrated from yellow to orange with a silver nitrate standard of mass concentration 0.01003mol/L, and reading V was recorded 1 Cyanide content C with CN - mg/L.
Wherein:
c' — concentration mol/L of silver nitrate standard solution;
V 1 measuring the dosage of the sample distillate titrating silver nitrate solution, and measuring ml;
V 0 titration of silver nitrate solution dosage, ml, of blank sample distillate
V-volume of solution measured in the distillation flask, ml;
52.04-2 cyanide ions (2 CN) - ) Molar mass g/mol.
Test group 1
The cyanide-removing agents obtained in examples 1 to 11 and comparative examples 1 to 8 were weighed out separately, and the cyanide-removing effect is shown in Table 1.
As can be seen from Table 1, the cyanide removing agents obtained in examples 1 to 11 of the present invention all had a good cyanide removing effect. In comparison with example 1, the modified fly ash, the inorganic copper salt and the polymeric iron are not added in comparative examples 1 to 3, respectively, and the synergistic effect among the modified fly ash, the inorganic copper salt and the polymeric iron cannot be exerted, so that the obtained cyanide remover is inferior to that in example 1. Compared with example 1, the modified fly ash in comparative example 4 is added more, so that the contents of inorganic copper salt and polymeric iron in the formula are less, and the synergistic effect of the inorganic copper salt and polymeric iron is poor, so that the obtained cyanide remover is poorer than that of example 1. Compared with example 1, the modified fly ash in comparative example 5 is added to a small amount, so that the contents of inorganic copper salt and polymeric iron in the formula are large, and the synergistic effect of the inorganic copper salt and polymeric iron is poor, so that the obtained cyanide remover is poorer than that of example 1. Compared with example 1, the modified fly ash of comparative example 6 is not treated by microwaves, and the glass network polymer and the disintegration effect inside the fly ash are poor, so that the specific surface area is large, the adsorption of iron ions and cyanide ions is unfavorable, and the cyanide removal effect is poor. The modified fly ash of comparative example 7, compared with example 1, was not subjected to hydrothermal treatment, and it was impossible to further increase the specific surface area and increase the surface hydroxyl group content, resulting in poor cyanide removal effect. The modified fly ash of comparative example 8, which was not treated with inorganic iron salt, had a low surface iron content and had poor complexing effect with cyanide ions, resulting in poor cyanide removal effect, as compared with example 1.
Test group 2
The cyanide-removing agents obtained in the examples were weighed in different amounts and the cyanide-removing effect is shown in Table 2.
TABLE 2
| Concentration of drug added mg/L | Standing time | Residual cyanide amount mg/L | |
| Group 1 | 50 | 15 | 2.583 |
| Group 2 | 200 | 15 | 0.462 |
| Group 3 | 500 | 15 | 0.134 |
| Group 4 | 800 | 15 | 0.097 |
| Group 5 | 1000 | 15 | 0.074 |
| Group 6 | 1200 | 15 | 0.068 |
As can be seen from Table 2, the cyanide remover obtained in example 1 of the present invention can have a good cyanide removing effect at a low dosing concentration. When the dosing concentration is 200mg/L and the standing time is 15min, the residual cyanide content in cyanide-containing wastewater can meet the requirement of GB 8978-1996 comprehensive wastewater discharge Standard of less than 0.5 mg/L. After that, as the dosing concentration increases, the residual cyanide content in the cyanide-containing wastewater gradually decreases, and when the dosing concentration increases to 800mg/L, the dosing concentration continues to increase, and the decrease of the residual cyanide content in the cyanide-containing wastewater tends to be gentle.
Compared with the prior art, the invention has the beneficial effects that:
the cyanide remover provided by the invention has a good treatment effect on high-concentration cyanide-containing wastewater, can reduce the cyanide concentration in the cyanide-containing wastewater to below 0.5mg/L, and meets the requirements of GB 8978-1996 comprehensive wastewater discharge Standard;
when the cyanide remover provided by the invention is used for treating high-concentration cyanide-containing wastewater, the dosage is small, and the cost is reduced;
the method has the advantages of wide sources of raw materials and simple preparation process, and can be suitable for process production.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (4)
1. The cyanide remover is characterized by comprising the following components in parts by weight: 40-50 parts of modified fly ash, 15-25 parts of inorganic copper salt and 2-3 parts of polymeric iron;
the modified fly ash is obtained by mixing fly ash with inorganic acid, and sequentially carrying out microwave treatment, hydrothermal treatment and inorganic ferric salt treatment; the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid; the concentration of the inorganic acid is 1-3 mol/L; the mass ratio of the fly ash to the inorganic acid is 1: (5-10); the microwave treatment conditions are as follows: the microwave power is 100-300W, the microwave temperature is 80-90 ℃, and the microwave time is 15-30 min; the conditions of the hydrothermal treatment are as follows: the hydrothermal temperature is 80-100 ℃, and the hydrothermal time is 4-8 hours; the inorganic ferric salt is one or more of ferrous chloride, ferric sulfate and ferrous sulfate; the concentration of the inorganic ferric salt is 3-5 mol/L; the mass ratio of the fly ash to the inorganic ferric salt is 1: (1-3); the inorganic ferric salt treatment conditions are as follows: the temperature is 40-50 ℃ and the time is 10-20 min.
2. The cyanide remover according to claim 1, wherein the inorganic copper salt is one or both of copper sulfate and copper chloride; the polymeric iron is one or more of polymeric ferric chloride, polymeric ferric sulfate, polymeric ferric nitrate and polymeric ferrosilicon.
3. The cyanide remover of claim 2, wherein the mass ratio of inorganic copper salt to polymeric iron is 8:1.
4. A method for preparing the cyanogen removing agent according to any one of claims 1 to 3, comprising the steps of:
mixing the fly ash with inorganic acid, and carrying out microwave treatment, hydrothermal treatment and inorganic ferric salt treatment to obtain modified fly ash;
and uniformly mixing the modified fly ash, the inorganic copper salt and the polymeric iron to obtain the cyanogen removing agent.
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