CN109607599A - A method of thallous bromide is prepared using smeltery's acid waste water containing thallium as raw material - Google Patents
A method of thallous bromide is prepared using smeltery's acid waste water containing thallium as raw material Download PDFInfo
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- CN109607599A CN109607599A CN201910098363.6A CN201910098363A CN109607599A CN 109607599 A CN109607599 A CN 109607599A CN 201910098363 A CN201910098363 A CN 201910098363A CN 109607599 A CN109607599 A CN 109607599A
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- waste water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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Abstract
The invention belongs to metal product production fields, and in particular to a method of thallous bromide is prepared using smeltery's acid waste water containing thallium as raw material.Present invention finds molybdenum-rhenium recycling, dedicated ion exchange resin --- RCX-5143 resin has the function of special selective absorption to trivalent thallium complex anion, using RCX-5143 resin under highly acidity pH < 1 direct adsorbing and extracting thallium, it does not need with alkali neutralization acidity, raw material is smeltery's acid waste water, the adsorbent material being added in entire technical process is commercially available RCX-5143 resin, not only simple process, inexpensive, and the rate of recovery of thallium is up to 84.6%~89.5%.
Description
Technical field
The invention belongs to metal product production fields, and in particular to a kind of to prepare by raw material of smeltery's acid waste water containing thallium
The method of thallous bromide.
Background technique
Thallous bromide (TlBr) is a kind of industrial chemicals with specific use, for manufacturing indoor temperature nucleus radiation detector
(indoor temperature nucleus radiation detector, which refers to, to work at room temperature, while having higher detection efficient and preferable energy resolution to X-ray again
Detector), have in fields such as nuclear medicine, safety check, environmental monitoring, space flight and aviation, industrial flaw detection and high-energy physics very wide
Wealthy application prospect.TlBr raw material is usually to use chemical reagent TlNO3A kind of synthesis (crystal growth TlBr is reacted with HBr
The solution synthesis method of powder, application number CN200910273160.2, publication date 2010-11-03).And TlNO3Again by thallium
It is prepared by powder and dilute nitric acid reaction.The stock number of thallium is extremely limited, more than ten ton of world's annual output, therefore is prepared using this method
TlBr is expensive.
Thallium is typically found in some mineral resources (such as non-ferrous metal sulfide mine).Needed in non-ferrous metal metallurgy into
Row desulfurization with roasting technique, roasting process generate a large amount of SO2Flue gas dilute acid wash Sulphuric acid, the acid waste water after washing are commonly called as waste acid.
Contain various heavy in waste acid, thallium cumulative amount is up to tens of mg/L.Acid waste water generallys use in lime and sedimentation removes
Heavy metal generates a large amount of solid wastes, and thallium mainly exists with monovalent ion, and hydroxide (TlOH) is dissolved in water, as with regard to this row
It puts, thallium pollution will be caused.On the one hand, waste water containing thallium will seriously pollute environment as handled not in time；On the other hand, thallium resource
Extremely limited, the content in the earth's crust is very low, and average abundance only has 0.8mg/kg, in smelting process without recycling be to thallium
The waste of resource.
The application for a patent for invention of Publication No. CN103833068A discloses one kind and produces protobromide with lead-zinc smelting wastewater
Pb-Zn deposits melting waste slag and lime are first added in lead-zinc smelting wastewater, collects the bed mud of precipitating, then past for the method for thallium, this method
Pb-Zn deposits smelting wastewater is added in bed mud and sulfuric acid obtains thallium extracting solution, potassium bromide then is added toward thallium extracting solution and obtains sediment
Thallous bromide.Although the scheme of above-mentioned patent application has the advantages that " treatment of wastes with processes of wastes against one another ", the rate of recovery of thallium is relatively low.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art, it is acid containing thallium with smeltery that the purpose of the present invention is to provide one kind
Waste water is the method that raw material prepares thallous bromide, and the side of thallous bromide is especially prepared using the acid waste water containing thallium of pH < 1 as raw material
Method, this method have the advantages that the heavy metal thallium rate of recovery is high.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A method of thallous bromide is prepared using smeltery's acid waste water containing thallium as raw material, comprising the following steps:
(1) pretreatment of resin
It is rinsed with water after RCX-5143 anion exchange resin is impregnated with sodium hydroxide solution to neutrality, then with salt acidleach
Bubble is transformed into chlorine type, is then rinsed with water to neutrality, obtains pretreated resin；
(2) preparation of thallous bromide
Smeltery's acid waste water containing thallium is taken, insoluble matter is filtered out, dropwise addition bromine water to waste water is in orange-yellow under stirring conditions,
And keep 10min colour-fast, make monovalence thallium (Tl+) fully oxidized and form trivalent thallium complex anion, pre- place is added into waste water
The resin of reason, stirring are adsorbed, and are filtered, and are collected resin, are used Na2SO3Solution elutes resin, obtains rich Tl+Filtrate,
Potassium bromide (KBr) is added to richness Tl+Bromide ion concentration is 0.05~0.08mol/L in filtrate, and precipitating collects sediment, is dried,
Obtain the thallous bromide (TlBr).
Preferably, the method for the present invention for preparing thallous bromide uses the acid waste water containing thallium of pH < 1 for raw material.
Preferably, RCX-5143 anion exchange resin mesh granularity described in step (1) is -100 mesh~+150 mesh, i.e.,
RCX-5143 anion exchange resin of the partial size between 100 mesh~150 mesh.
Preferably, the condition of soaking with sodium hydroxide described in step (1) is the 1mol/L sodium hydroxide with 4 times of volumes
Solution impregnates 40~60min of resin.
Preferably, it is 1~2mol/L salt that the condition of salt acid soak described in step (1), which is with the concentration of 4 times of volumes,
Acid solution impregnates 40~60min of resin.
Preferably, the mass percentage concentration of bromine water described in step (2) is 3%.
Preferably, when pretreated resin being added into waste water described in step (2), the solid-to-liquid ratio of resin and waste water is
0.005~0.01g/ml.
Preferably, Na described in step (2)2SO3The mass percentage concentration of solution is 0.5~1%.
Preferably, Na is used described in step (2)2SO3When solution elutes resin, resin and Na2SO3Solution
Solid-to-liquid ratio is 1:2g/ml.
Preferably, when a length of 40~60min that stirring described in step (2) is adsorbed.
Preferably, Na is used described in step (2)2SO3When a length of 30~50min that solution elutes resin.
Since smelting industry acid waste water contains SO4 2-、Cl-Equal anion, therefore trivalent thallium described in step (2) is with yin
Ion includes TlBr4 -、TlBr5 2-、TlBr6 3-、TlCl4 -、Tl(SO4)2 -Equal complex anions.
The key reaction process of the method for the invention is briefly described below:
1. in acid waste water containing thallium plus bromine water makes Tl+Oxidation is shaped to trivalent thallium complex anion；
Tl+(acid waste water containing thallium)+bromine water → trivalent thallium complex anion (1),
2. RCX-5143 resins exchange adsorbs trivalent thallium complex anion；
Resin-Cl-+ trivalent thallium complex anion → resin-trivalent thallium complex anion+Cl-(2),
3. with reducing agent Na2SO3Desorption elution, by the Tl in resin3+It is reduced into Tl+Destroy trivalent thallium complex anion；
Resin-trivalent thallium complex anion+SO3 2-→ resin-SO4 2-+Tl+(3),
4. eluent adds bromide ion (potassium bromide), thallium is made to precipitate recycling in the form of TlBr；
Tl++Br-→TlBr↓ (4)。
Compared with the prior art, the invention has the following advantages and beneficial effects:
Present invention finds molybdenum-rhenium recycling, dedicated ion exchange resin --- RCX-5143 resin is to trivalent thallium complex anion
Have the function of special selective absorption, using RCX-5143 resin under highly acidity pH < 1 direct adsorbing and extracting thallium, do not need
With alkali neutralization acidity, raw material is smeltery's acid waste water, and the adsorbent material being added in entire technical process is commercially available RCX-
5143 resins, not only simple process, inexpensive, and also the rate of recovery of thallium is up to 84.6%~89.5%.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
For not specifically specified technological parameter, routine techniques progress can refer to.
Embodiment 1
The present embodiment provides a kind of methods and its comparison that thallous bromide is prepared using smeltery's acid waste water containing thallium as raw material
Test, acid waste water used come from Guangdong smeltery, thallium-containing quantity 76mg/L, pH < 1.
1, the preparation of thallous bromide
(1) taking 25g mesh granularity is -100 mesh~+150 mesh RCX-5143 resin (commercially available Du sheng, a reed pipe wind instrument RCX-5143 resin) with 4
The 1mol/L sodium hydroxide solution of times volume impregnates 60min, is rinsed with water to neutrality, then with the 2mol/L's of 4 times of volumes
Hydrochloric acid solution impregnates 60min, is rinsed with water to neutrality, obtains pretreated resin；
(2) 2.5L of acid waste water containing thallium is taken, insoluble matter is filtered out, it is 3% that mass percentage concentration is added dropwise under stirring conditions
Bromine water to waste water solution in orange-yellow, and 10min is colour-fast；Acid waste water containing thallium, stirring is added in pretreated resin
60min is filtered and is collected resin；The Na that 100ml mass percentage concentration is 1% is added2SO3Solution stirs 50min, filters and receive
Collect filtrate；It is 0.08mol/L that potassium bromide to bromide ion concentration, which is added, and precipitating collects sediment, is dried to get thallous bromide
(TlBr)0.23g。
2, the detection of thallous bromide purity
Use atomic absorption spectrophotometry detect thallous bromide purity for 99.5%.
3, the rate of recovery of thallium calculates:
The thallium rate of recovery for being calculated as follows to obtain this example the method is 86.5%.
Comparative experiments 1
The 2.5L of acid waste water containing thallium (thallium-containing quantity 76mg/L) for taking above-mentioned Guangdong smeltery, by Publication No.
1 the method for application for a patent for invention embodiment of CN103833068A obtains the thallous bromide (TlBr) that purity is 99.2%
0.17g, the rate of recovery for being calculated thallium is 63.7%.
Embodiment 2
The present embodiment provides a kind of methods and its comparison that thallous bromide is prepared using smeltery's acid waste water containing thallium as raw material
Test, acid waste water containing thallium used come from Guangxi smeltery, thallium-containing quantity 71mg/L, pH < 1.
1, the preparation of thallous bromide
(1) taking 20g mesh granularity is -100 mesh~+150 mesh RCX-5143 resin (commercially available Du sheng, a reed pipe wind instrument RCX-5143 resin) with 4
The 1mol/L sodium hydroxide solution of times volume impregnates 50min, is rinsed with water to neutrality, then with the 2mol/L's of 4 times of volumes
Hydrochloric acid solution impregnates 50min, is rinsed with water to neutrality, obtains pretreated resin；
(2) 2.5L of acid waste water containing thallium is taken, insoluble matter is filtered out, it is 3% that mass percentage concentration is added dropwise under stirring conditions
Bromine water to waste water solution in orange-yellow, and 10min is colour-fast.Above-mentioned waste water is added in pretreated resin, stirs 50min,
It filters and collects resin；Adding 80ml mass percentage concentration is 0.8%Na2SO3Solution stirs 40min, filters and collect filter
Liquid, being eventually adding potassium bromide bromide ion concentration into filtrate is 0.07mol/L, and precipitating collects sediment, is dried to get bromination
Sub- thallium (TlBr) 0.21g.
2, the detection of thallous bromide purity
Use atomic absorption spectrophotometry detect thallous bromide purity for 99.6%.
3, the rate of recovery of thallium calculates:
It is calculated using the method for embodiment 1, the thallium rate of recovery of this example the method is 84.6%.
4, comparative experiments
The above-mentioned Guangxi smeltery 2.5L of acid waste water containing thallium (thallium-containing quantity 71mg/L) is taken, by Publication No.
2 the method for application for a patent for invention embodiment of CN103833068A obtains the thallous bromide (TlBr) that purity is 99.4%
0.16g, the rate of recovery for being calculated thallium is 64.4%.
Embodiment 3
The present embodiment provides a kind of methods and its comparison that thallous bromide is prepared using smeltery's acid waste water containing thallium as raw material
Test, acid waste water containing thallium used come from Hunan smeltery, thallium-containing quantity 64mg/L, pH < 1.
1, the preparation of thallous bromide
(1) taking 15g mesh granularity is -100 mesh~+150 mesh RCX-5143 resin (commercially available Du sheng, a reed pipe wind instrument RCX-5143 resin) with 4
The 1mol/L sodium hydroxide solution of times volume impregnates 50min, is rinsed with water to neutrality, then with the 1mol/L's of 4 times of volumes
Hydrochloric acid solution impregnates 50min, is rinsed with water to neutrality, obtains pretreated resin；
(2) 2.5L of acid waste water containing thallium is taken, insoluble matter is filtered out, it is 3% that mass percentage concentration is added dropwise under stirring conditions
Bromine water to waste water solution in orange-yellow, and 10min is colour-fast.Pretreated resin is added in waste water, 50min, mistake are stirred
It filters and collects resin；Addition 60ml mass percentage concentration is 1%Na2SO3Solution stirs 40min, filters and collect filtrate.Finally
It is 0.06mol/L that potassium bromide to bromide ion concentration, which is added, and precipitating collects sediment, is dried to get thallous bromide (TlBr)
0.20g。
2, the detection of thallous bromide purity
Use atomic absorption spectrophotometry detect thallous bromide purity for 99.7%.
3, the rate of recovery of thallium calculates:
It is calculated using the method for embodiment 1, the thallium rate of recovery of this example the method is 89.5%.
4, comparative experiments
The 2.5L of acid waste water containing thallium (thallium-containing quantity 64mg/L) for taking above-mentioned Hunan smeltery, by Publication No.
3 the method for application for a patent for invention embodiment of CN103833068A obtains the thallous bromide (TlBr) that purity is 99.3%
0.15g, the rate of recovery for being calculated thallium is 66.8%.
Embodiment 4
The present embodiment provides a kind of methods and its comparison that thallous bromide is prepared using smeltery's acid waste water containing thallium as raw material
Test, acid waste water used come from Henan smeltery, thallium-containing quantity 52mg/L, pH < 1.
1, the preparation of thallous bromide
(1) taking 12.5g mesh granularity is -100 mesh~+150 mesh RCX-5143 resin (commercially available Du sheng, a reed pipe wind instrument RCX-5143 resin)
40min is impregnated with the 1mol/L sodium hydroxide solution of 4 times of volumes, is rinsed with water to neutrality, then with the 1mol/L of 4 times of volumes
Hydrochloric acid solution impregnate 40min, be rinsed with water to neutrality, obtain pretreated resin；
(2) 2.5L of acid waste water containing thallium is taken, insoluble matter is filtered out, it is 3% that mass percentage concentration is added dropwise under stirring conditions
Bromine water to waste water solution in orange-yellow, and 10min is colour-fast.Above-mentioned waste water is added in pretreated resin, stirs 40min,
It filters and collects resin；Adding 50ml mass percentage concentration is 0.5%Na2SO3Solution stirs 30min, filters and collect filter
Liquid；Being eventually adding bromide ion concentration of the potassium bromide into filtrate is 0.06mol/L, and precipitating collects sediment, is dried to get bromine
Change Asia thallium (TlBr) 0.15g.
2, the detection of thallous bromide purity
Use atomic absorption spectrophotometry detect thallous bromide purity for 99.2%.
3, the rate of recovery of thallium calculates:
It is calculated using the method for embodiment 1, the thallium rate of recovery of this example the method is 85.2%.
4, comparative experiments
The 2.5L of acid waste water containing thallium (thallium-containing quantity 52mg/L) for taking above-mentioned Henan smeltery, by Publication No.
4 the method for application for a patent for invention embodiment of CN103833068A obtains the thallous bromide (TlBr) that purity is 99.3%
0.12g, the rate of recovery for being calculated thallium is 66.1%.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as, as long as being obtained using the form of same replacement or equivalent transformation
Technical solution, should all fall within the scope and spirit of the invention.
Claims (10)
1. a kind of method for preparing thallous bromide as raw material using smeltery's acid waste water containing thallium, which is characterized in that including following step
It is rapid:
(1) pretreatment of resin
It is rinsed with water after RCX-5143 anion exchange resin is impregnated with sodium hydroxide solution to neutrality, then is turned with salt acid soak
Type is chlorine type, is then rinsed with water to neutrality, and pretreated resin is obtained；
(2) preparation of thallous bromide
Smeltery's acid waste water containing thallium is taken, insoluble matter is filtered out, it is in orange-yellow that bromine water to waste water is added dropwise under stirring conditions, and is protected
It is colour-fast to hold 10min, keep monovalence thallium fully oxidized and forms trivalent thallium complex anion, pretreated resin is added into waste water,
Stirring is adsorbed, and is filtered, and is collected resin, is used Na2SO3Solution elutes resin, obtains rich Tl+Potassium bromide is added in filtrate
To rich Tl+Bromide ion concentration is 0.05~0.08mol/L in filtrate, and precipitating collects sediment, is dried to get the bromine is arrived
Change sub- thallium.
2. the method according to claim 1 for preparing thallous bromide as raw material using smeltery's acid waste water containing thallium, feature
It is: uses the acid waste water containing thallium of pH < 1 for raw material.
3. the method according to claim 2 for preparing thallous bromide as raw material using smeltery's acid waste water containing thallium, feature
Be: the condition of soaking with sodium hydroxide described in step (1) is to impregnate tree with the 1mol/L sodium hydroxide solution of 4 times of volumes
40~60min of rouge.
4. the method according to claim 3 for preparing thallous bromide as raw material using smeltery's acid waste water containing thallium, feature
Be: described in step (1) with the concrete operations of salt acid soak RCX-5143 resin be with the concentration of 4 times of volumes be 1~
The hydrochloric acid solution of 2mol/L impregnates 40~60min of RCX-5143 resin.
5. the method according to claim 4 for preparing thallous bromide as raw material using smeltery's acid waste water containing thallium, feature
Be: RCX-5143 anion exchange resin mesh granularity described in step (1) is -100 mesh~+150 mesh.
6. the method according to claim 5 for preparing thallous bromide as raw material using smeltery's acid waste water containing thallium, feature
It is: when pretreated resin being added into waste water described in step (2), the solid-to-liquid ratio of resin and waste water is 0.005~
0.01g/ml。
7. the method according to claim 6 for preparing thallous bromide as raw material using smeltery's acid waste water containing thallium, feature
It is: when a length of 40~60min that stirring described in step (2) is adsorbed.
8. the method according to claim 7 for preparing thallous bromide as raw material using smeltery's acid waste water containing thallium, feature
Be: the mass percentage concentration of bromine water described in step (2) is 3%.
9. the method according to claim 8 for preparing thallous bromide as raw material using smeltery's acid waste water containing thallium, feature
It is: Na described in step (2)2SO3The mass percentage concentration of solution is 0.5~1%.
10. the method according to claim 9 for preparing thallous bromide as raw material using smeltery's acid waste water containing thallium, feature
Be: step uses Na described in (2)2SO3When solution elutes resin, resin and Na2SO3The solid-to-liquid ratio of solution is 1:
2g/ml。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109811128A (en) * | 2019-02-14 | 2019-05-28 | 广州大学 | A method of from smelting acid waste water recycling thallium and preparing thallous iodide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109811128A (en) * | 2019-02-14 | 2019-05-28 | 广州大学 | A method of from smelting acid waste water recycling thallium and preparing thallous iodide |
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