CN102505082B - Method and device for extracting barium and barium salt from ore - Google Patents
Method and device for extracting barium and barium salt from ore Download PDFInfo
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- CN102505082B CN102505082B CN2011103437609A CN201110343760A CN102505082B CN 102505082 B CN102505082 B CN 102505082B CN 2011103437609 A CN2011103437609 A CN 2011103437609A CN 201110343760 A CN201110343760 A CN 201110343760A CN 102505082 B CN102505082 B CN 102505082B
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- barium
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- salt
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052788 barium Inorganic materials 0.000 title claims abstract description 75
- 159000000009 barium salts Chemical class 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 89
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 86
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims description 86
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 54
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 42
- 238000001354 calcination Methods 0.000 claims description 38
- 235000010265 sodium sulphite Nutrition 0.000 claims description 32
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 27
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 235000011089 carbon dioxide Nutrition 0.000 claims description 22
- 238000007654 immersion Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000001149 thermolysis Methods 0.000 claims description 15
- 239000003245 coal Substances 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- 230000002829 reductive effect Effects 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- 239000000571 coke Substances 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 abstract description 46
- 239000000126 substance Substances 0.000 abstract description 19
- 238000012545 processing Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 15
- 239000012535 impurity Substances 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229940045511 barium chloride Drugs 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 238000004148 unit process Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001615463 Trichogenes Species 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- -1 this.Like this Chemical compound 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of chemical industry, and particularly to a method and a device for extracting barium and barium salt from ore. The method comprises the steps of: washing the ore; roasting the washed ore, obtaining barium sulfide; processing the barium sulfide to obtain barium salt, wherein the barium salt includes barium sulfate and/or barium sulfide and/or barium carbonate; and processing the barium carbonate to obtain barium. The device comprises a washing device for washing the ore; a roasting device for roasting the washed ore so as to obtain barium sulfide; a first reacting device for processing the barium sulfide so as to obtain barium salt, wherein the barium salt includes barium sulfate and/or barium sulfide and/or barium carbonate; and a second reacting device for processing the barium carbonate so as to obtain barium. The method and the device for extracting barium and barium salt from the ore provided by the invention can make full use of ore resources to obtain barium and barium salt.
Description
Technical field
The present invention relates to chemical field, be specifically related to a kind of method and apparatus that extracts barium and barium salt from ore.
Background technology
Serial products with barium is leading with barium metal, and serial products with barium is byproduct sodium sulphite, calcium phosphate composite fertilizer, yellow soda ash, bariumchloride, barium sulphide, hydrated barta and the barium oxide etc. of barium carbonate, process white and " three wastes " processing.The single-phase shape of the present domestic employing of serial products with barium is produced, namely only produce or handle a kind of in sodium sulphite, calcium phosphate composite fertilizer, yellow soda ash, bariumchloride, barium sulphide, hydrated barta and the barium oxide, single-phase shape is produced the waste ore resources, shortcoming that can not the comprehensive development and utilization resource.
Summary of the invention
The invention provides a kind of method and apparatus from ore extraction barium and barium salt, can take full advantage of ore resources, obtain barium and barium salt simultaneously.
The invention provides a kind of method from ore extraction barium and barium salt, comprising:
Ore is washed;
Described ore after the washing is calcined, obtained barium sulphide;
Described barium sulphide processed obtain barium salt;
Described barium salt processed obtain barium.
In embodiments of the present invention, preferably, described ore is washed comprises:
Described ore is soaked in clear water; Preferably, in described immersion process and after soaking, ore is stirred; Preferred, the time of described immersion is more than 12 hours;
And/or
Described described ore after the washing is calcined and comprised: coal and coke are mixed into the described ore of fuel after to washing calcine.
In embodiments of the present invention, preferably, with after the ore washing, described method further comprises described:
Washings is collected;
Add carbon dioxide, sodium hydroxide solution and the ferric chloride Solution that described calcining produces in the described washings, utilize chemical reaction to extract soluble substance in the described washings.
In embodiments of the present invention, preferably, described described barium sulphide is processed obtains barium salt and comprises:
In barium sulphide, add sulfuric acid or vitriol, utilize chemical reaction to obtain barium sulfate, preferably, in barium sulphide, add sodium sulfate, utilize chemical reaction to obtain barium sulfate;
And/or
Add sodium hydroxide, carbonic acid gas in barium sulphide, utilize chemical reaction to obtain barium carbonate and sodium sulphite, preferably, the carbonic acid gas that produces when adding sodium hydroxide and described calcining in the barium sulphide utilizes chemical reaction to obtain barium carbonate.
In embodiments of the present invention, preferably, the described chemical reaction that obtains the described chemical reaction of barium sulfate and/or obtain barium carbonate further obtains sodium sulphite and hydrogen sulfide,
This method further comprises: collect described hydrogen sulfide, and the described hydrogen sulfide of collecting is compressed or utilizes chemical reaction to reclaim sulphur to the described hydrogen sulfide of collecting;
And/or,
This method further comprises: add sulphur in described sodium sulphite, utilize chemical reaction to obtain Na
2S
x, described x is 2-5, preferably: 2,3,4 or 5.
In embodiments of the present invention, preferably, described described barium salt is processed obtains barium and comprises:
Barium carbonate in the described barium salt is carried out thermolysis obtain barium oxide;
Described barium oxide reduced obtain barium;
Preferably, the described barium oxide solid of heating and aluminium powder obtain described barium in enclosed environment;
More preferably, the described barium that reduction is obtained is purified.
The present invention also provides a kind of device from ore extraction barium and barium salt, it is characterized in that, comprising:
Washing device is used for ore is washed;
Roasting assembly is used for the described ore after the washing is calcined, and obtains barium sulphide;
First reaction unit obtains barium salt for described barium sulphide is processed;
Second reaction unit obtains barium for described barium salt is processed.
In embodiments of the present invention, preferably, described washing device comprises clean water basin, is used for described ore is soaked at clear water; Described washing device preferably includes whipping device, is used at described immersion process with after soaking ore being stirred; Described washing device more preferably comprises timing device, and the time that is used for the described immersion of timing is more than 12 hours;
And/or
Described roasting assembly comprises: calcining furnace is used for being mixed into fuel with coal and coke the described ore after washing is calcined.
In embodiments of the present invention, preferably, described first reaction unit comprises: the barium sulfate conversion unit, be used for adding sulfuric acid or vitriol to barium sulphide, and utilize chemical reaction to obtain barium sulfate;
And/or
Described first reaction unit comprises: the barium carbonate conversion unit, be used for adding sodium hydroxide, carbonic acid gas to barium sulphide, chemical reaction takes place obtain barium carbonate and sodium sulphite, preferably, chemical reaction takes place and obtains barium carbonate in the carbonic acid gas that produces when adding sodium hydroxide and described calcining in the barium sulphide;
And/or
Described second reaction unit comprises: the barium carbonate pyrolysis device, carry out thermolysis for the barium carbonate to described barium salt and obtain barium oxide; The barium reduction apparatus obtains barium for described barium oxide is reduced, and preferably, the described barium oxide solid of heating and aluminium powder obtain described barium in enclosed environment; Described second reaction unit more preferably comprises: the barium equipment for purifying is used for the described barium that reduction obtains is purified.
In embodiments of the present invention, preferably, described washing device further comprises: collecting tank is used for washings is collected; Reaction tank is used for adding carbon dioxide, sodium hydroxide solution and the ferric chloride Solution that described calcining produces to described washings, utilizes chemical reaction to extract soluble substance in the described washings;
And/or,
Described first reaction unit further comprises: the sodium sulphite collecting device, be used for adding sulphur to described sodium sulphite, and utilize chemical reaction to obtain Na
2S
x, described x is 2-5, preferably: 2,3,4 or 5;
And/or,
Described first reaction unit further comprises: the hydrogen sulfide collecting device, and be used for to collect described hydrogen sulfide, and the described hydrogen sulfide of collecting is compressed or utilizes chemical reaction to reclaim sulphur to the described hydrogen sulfide of collecting.
By a kind of method and apparatus from ore extraction barium and barium salt provided by the invention, can take full advantage of ore resources, obtain barium and barium salt simultaneously, and environmental protection.
By ore is washed and calcines, obtain barium sulphide; To described barium sulphide, described barium sulphide is processed obtained barium salt again, the barium carbonate in the described barium salt is processed obtained barium.Thereby on a big production line, can fully handle and utilize ore by different branches, produce barium and barium salt simultaneously.
The soluble substance of washings being collected and being extracted in the described washings when ore is washed is recycled described washings; Recycle by the carbon dioxide that described calcining is produced, saved resource and environmental protection.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, below will do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art, apparently, accompanying drawing in below describing only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other embodiment and accompanying drawing thereof according to these accompanying drawing illustrated embodiments.
Fig. 1 is the synoptic diagram of the present invention from the embodiment of the method for ore extraction barium and barium salt.
Embodiment
Below with reference to accompanying drawing the technical scheme of various embodiments of the present invention is carried out clear, complete description, obviously, described embodiment only is a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are resulting all other embodiment under the prerequisite of not making creative work, all belong to the scope that the present invention protects.
The invention provides a kind of method from ore extraction barium and barium salt, comprising:
Ore is washed;
Described ore after the washing is calcined, obtained barium sulphide;
Described barium sulphide processed obtain barium salt;
Described barium salt processed obtain barium.
The present invention also provides a kind of device from ore extraction barium and barium salt, comprising:
Washing device is used for ore is washed;
Roasting assembly is used for the described ore after the washing is calcined, and obtains barium sulphide;
First reaction unit obtains barium salt for described barium sulphide is processed;
Second reaction unit obtains barium for described barium salt is processed.
At first, ore is positioned in the washing device washs, impurity such as the mud on the ore or branch can be removed, can also dissolve water-soluble material in a part of ore, clean ore.Ore after will washing is then put into roasting assembly and is calcined, thereby calcining can be carried out thermolysis with ore and obtains barium sulphide.The barium sulphide that obtains after the calcining is put into first reaction unit carry out chemical reaction, obtain barium salt, described barium salt comprises multiple, for example barium sulfate, barium carbonate.The barium salt that obtains being put into second reaction unit processes and obtains barium again.
Can adopt different production route production or handle multiple products such as multiple barium salt and barium, reach environmental protection, ore resources comprehensive utilization, resources conservation, the satisfied purpose without application demand of rich and variedization of product category.
In one embodiment, as shown in Figure 1:
Step 101 is: ore is washed.
Step 102 is: the described ore after the washing is calcined obtained barium sulphide.
After this step obtains barium sulphide, can utilize the treating processes of following steps 103 to 104 steps to produce barium salt, for example obtain barium sulfate, and utilize following steps 105 to the treating processes of step 109 to produce barium.
Step 103 is: add sodium sulfate in the barium sulphide and obtain barium sulfate, also can generate sodium sulphite here.
Step 104 is: barium sulfate is washed, packs.
So far, then obtained barium salt.
Step 105 is: collect the gas of calcining in the step 102 and described gas purified and obtain carbonic acid gas.
Step 106 is: add sodium hydroxide in the barium sulphide, step 105 is collected the carbonic acid gas that obtains and obtained barium carbonate and sodium sulphite.
Step 107 is: the barium carbonate that obtains in the step 106 is carried out thermolysis obtain barium oxide.
Step 108 is: barium oxide and aluminium powder are reduced obtain barium.
Step 109 is: the barium that reduction obtains is purified, packed.
So far, then obtained barium.
Step 110 is: collect in the step 106 and obtain hydrogen sulfide unnecessary in the process of sodium sulphite.
Step 111 is: to collecting the sodium sulphite that arrives that the hydrogen sulfide that obtains utilizes the chemical reaction recovery in the step 110.
Step 112 is: add sulphur in the sodium sulphite that obtains in step 106 and the step 111, obtain Na
2S
x
Step 113 is: to Na
2S
x, packing.
Step 110 to the processing of step 113 is to collect the toxic gas hydrogen sulfide that produces in the production process in order further to realize, and hydrogen sulfide is recycled, and has saved resource, has reduced production cost, and environmental protection.
The step of above-mentioned fractionation and order are for convenience of description and the mode that adopts, in practical business is realized, process to 109 of the process of above-mentioned steps 103 to 104, step 105, step 110 are perhaps adjusted arbitrarily according to actual operation demand to there not being fixing execution sequence between three processes of step 113.
Like this, wash according to step 101 pair ore, washing device herein can be clean water basin, is used for described ore in clear water washing and/or immersion.Wherein, washing times can be one or many, Xi Di main purpose is for to clean ore herein, wherein can remove impurity such as mud that ore covers or leaf at the washing initial stage, washing process neutralizes and can utilize whipping device to stir in the middle of twice washing, with help soluble substance in the ore molten with ore separation, enter in the washings., can adopt clear water to the washing of ore herein, the washings behind the washing ore is reclaimed, impurity such as the mud in the washings or leaf are got rid of, can recycle next time when washing ore and use.More preferably, to taking long immersion in the ore washing process, enter in the washings by soaking the soluble substance and the ore separation that promote in the ore.When soaking, can utilize timing device to set soak time, the time of soaking can be for more than 1 hour, in order to reach effect preferably, be preferably more than 12 hours, like this can soluble substance in the ore is as much as possible soluble in water, the cleaning ore can stir ore in described immersion process and after soaking, and accelerates the speed of dissolving.In described whipping process, also can utilize timing to monitor the time of described stirring.Water for after the ore immersion utilizes collecting tank to collect to washings.In reaction tank, in described washings, add carbon dioxide, sodium hydroxide solution and ferric chloride Solution again, utilize chemical reaction to extract soluble substance in the described washings, these soluble substances can further be processed into chemical fertilizer, thereby taken full advantage of various resources, reached resource-effective purpose.
Ore after the washing is carried out drying, and this drying can adopt natural wind, mechanical force or other external force to carry out drying.
Calcine according to the described ore after the step 102 pair washing then and obtain barium sulphide.When calcining, select the fuel that is mixed into of coal and coke to calcine, in the reality, can be that fuel is calcined the described ore after washing with coal or coke separately also, when calcining, adopt calcining furnace to calcine, the roasting assembly that adopts in the present embodiment is preferably calcining furnace, also can adopt pierce smith converter in practice.Calcining furnace need carry out preheating before calcining, refractory brick in the calcining furnace need be burnt during preheating red till, the whole coking coal of preheating, treat refractory brick burn red after, the recrement in the calcining furnace is cleared, add ore again, when calcining, described roasting assembly is rotated, and calcining is more even like this, it is not enough part calcining can not occur, the situation that another part calcining is too much.Converter is that clockwise direction rotates.After calcining is finished, generate barium sulphide.Namely
BaSO
4+2C＝BaS+2CO
2↑
BaSO
4+4C＝BaS+4CO
2↑
Add sodium sulfate in the barium sulphide according to step 103 and obtain barium sulfate, also can generate sodium sulphite here.Add in first reaction unit that barium sulphide is housed sodium sulfate process obtain barium sulfate after, wash according to step 104 pair barium sulfate, the barium sulfate after the washing is packed.Can from ore, obtain one of barium salt like this: barium sulfate.First reaction unit herein is preferably the barium sulfate conversion unit.
Collect the gas of calcining in the step 102 and described gas purified according to step 105 and obtain carbonic acid gas.Utilize the gas after described calcining furnace is calcined to comprise: carbonic acid gas, carbon monoxide, sulfurous gas and coal dust and other impurity, wherein carbonic acid gas is collected, use it for follow-up chemical reaction.Need purify this moment to the gas after the calcining, adopts water spray pouringization method that the gas of collecting is purified, and the impurity major part in the gas is sulfurous gas and coal dust and other impurity, and these impurity are most of for there being the bituminous coal kind to produce.Spray water down deposits together in company with coal smoke impurity, contains a large amount of coal grains in the coal smoke, with the recovery of coal grain with have bituminous coal to mix to do secondary combustion.Carbonic acid gas can be water-soluble, and at normal temperatures, the water-soluble back of carbonic acid gas generates carbonic acid, and carbonic acid is extremely unsettled material, and when being heated or concentration very easily resolves into carbonic acid gas and water when increasing, its reaction is reversible.Sulfurous gas is water soluble also, generates sulfurous acid, and the sulfurous acid instability easily resolves into sulfurous gas and water.Sulfurous gas in the purification of carbon dioxide can adopt and add yellow soda ash or sodium hydroxide or calcium carbonate, obtains purer carbonic acid gas like this.Like this, the gas after the calcining is not discharged in the atmosphere, avoids causing environmental pollution, but also the carbonic acid gas after purifying can be recycled, and has saved resource, has reduced cost.
According to step 106 add sodium hydroxide in the barium sulphide, step 105 is collected the carbonic acid gas that obtains and is obtained barium carbonate and sodium sulphite.Utilize described barium carbonate conversion unit, the carbonic acid gas that produces during with sodium hydroxide, described calcining joins in the barium sulphide, chemical reaction takes place obtain barium carbonate and sodium sulphite.Namely
BaS+Na
2SO
4＝BaSO
4+Na
2S
BaS+CO
2+2NaOH＝BaCO
3+Na
2S+H
2O
Carry out thermolysis according to the barium carbonate that obtains in the step 107 pair step 106 and obtain barium oxide.When utilizing described second reaction unit to carry out that described barium salt processed the step that obtains barium, thermolysis is for to carry out the thermolysis of oxidation class to barium carbonate, being about to barium carbonate puts into the electric smelter of sealing and heats to high temperature, wherein high temperature is more than 1000 ℃, be preferably 1360 ℃, allow barium carbonate carry out thermolysis, make barium oxide separate, described second reaction unit is preferably the barium carbonate pyrolysis device, namely
BaCO
3＝BaO+CO
2↑
Reduce according to step 108 pair barium oxide and aluminium powder and to obtain barium.Use described barium reduction apparatus herein and obtain barium for described barium oxide is reduced.Preferably, the described barium oxide solid of heating and aluminium powder obtain described barium in enclosed environment.Barium oxide and aluminium powder are mixed, and the electric smelter of putting into vacuum heats, and under the condition of high temperature barium is restored.Namely
3BaO+2Al＝Al
2O
3+3Ba
Aluminium just in time is in metal on the position of nonmetal transition in the cycle, so aluminium is a kind of element of both sexes.Its main still character of exhibit metallic but, in chemical reaction, it loses 3 electronics on the high level easily, and becomes the positively charged ion with 3 unit positive charges, so aluminium all shows in its all stable compounds+3 valencys.The reaction of the as easy as rolling off a log and oxygen of aluminium, the protective oxide film of the very fast generation one deck in its surface densification in air is protecting gas such as the not oxidized and hydrogen sulfide of interior metal to corrode, so its quite stable in the air again.Aluminium is quite active metal, under the situation of heating, the easy direct chemical combination of oxygen of merchandiser matter attitude not only, and can also with metal oxide in the oxygen combination, and the generation aluminum oxide, emit a large amount of heat simultaneously, it can also come out those metallic reducings from other metal oxide than its activity difference.Come extracting metals with aluminium as reductive agent.The present invention namely adopts this kind method to refine.
The barium that pair reduction obtains according to step 109 is purified, is packed.The described barium that utilizes described barium equipment for purifying that reduction is obtained is purified and is packed.
So far, then obtained barium.
According to obtaining hydrogen sulfide unnecessary in the process of sodium sulphite in the step 110 collection step 106.In the step 106, utilize described sodium sulphite collection device to collect described sodium sulphite, when obtaining barium carbonate and sodium sulphite, generated poisonous hydrogen sulfide, can cause in the air poisoning if hydrogen sulfide is drained into, so the hydrogen sulfide that generates is collected, in hydrogen sulfide, add sodium hydroxide solution, generate sodium sulphite and water, so just hydrogen sulfide is converted into nontoxic sodium sulphite, the sodium sulphite that obtains is stored.The chemical reaction that takes place is as follows:
H
2S+2NaOH＝2H
2O+Na
2S
At this moment, according to step 111 and step 112 sodium sulphite is added sulphur and react, obtain sodium polysulphide, the chemical reaction of generation is as follows:
Na
2S+(x-1)S＝Na
2S
x
Wherein, X is 2-5, is preferably 2,3,4,5.
Pack according to the step 113 pair sodium polysulphide that obtains.Sodium polysulphide can be used as polymerization terminator, and tanning industry is used as sterilant as the trichogen of raw hide on the agricultural, or the refining of petroleum auxiliary agent.So both reduce the waste degree of ore, reduced pollution again, and increased economic return.
The present invention also provides a kind of device from ore extraction barium and barium salt, it is characterized in that, comprising:
Washing device is used for ore is washed;
Roasting assembly is used for the described ore after the washing is calcined, and obtains barium sulphide;
First reaction unit obtains barium salt for described barium sulphide is processed;
Second reaction unit obtains barium for described barium salt is processed.
At first, ore is positioned in the washing device washs, impurity such as the mud on the ore or branch can be removed, can also dissolve water-soluble material in a part of ore, clean ore.Ore after will washing is then put into roasting assembly and is calcined, thereby calcining can be carried out thermolysis with ore and obtains barium sulphide.The barium sulphide that obtains after the calcining is put into first reaction unit carry out chemical reaction, obtain barium salt, described barium salt comprises multiple, for example barium sulfate, barium carbonate.The barium salt that obtains being put into second reaction unit processes and obtains barium again.
In various embodiments of the present invention, preferably, described washing device comprises clean water basin, is used for described ore is soaked at clear water; Described washing device preferably includes whipping device, is used at described immersion process with after soaking ore being stirred; Described washing device more preferably comprises timing device, and the time that is used for the described immersion of timing is more than 12 hours.
Washing device herein can be clean water basin, is used for described ore in clear water washing and/or immersion.Wherein, washing times can be one or many, Xi Di main purpose is for to clean ore herein, wherein can remove impurity such as mud that ore covers or leaf at the washing initial stage, washing process neutralizes and can utilize whipping device to stir in the middle of twice washing, with help soluble substance in the ore molten with ore separation, enter in the washings., can adopt clear water to the washing of ore herein, the washings behind the washing ore is reclaimed, impurity such as the mud in the washings or leaf are got rid of, can recycle next time when washing ore and use.More preferably, to taking long immersion in the ore washing process, enter in the washings by soaking the soluble substance and the ore separation that promote in the ore.When soaking, can utilize timing device to set soak time, the time of soaking can be for more than 1 hour, in order to reach effect preferably, be preferably more than 12 hours, like this can soluble substance in the ore is as much as possible soluble in water, the cleaning ore can stir ore in described immersion process and after soaking, and accelerates the speed of dissolving.In described whipping process, also can utilize timing to monitor the time of described stirring.
In various embodiments of the present invention, preferably, described roasting assembly comprises: calcining furnace is used for being mixed into fuel with coal and coke the described ore after washing is calcined.Adopting calcining furnace to calcine when calcining, when calcining, select the fuel that is mixed into of coal and coke to calcine, in the reality, can be that fuel is calcined the described ore after washing with coal or coke separately also.
In various embodiments of the present invention, preferably, described first reaction unit comprises: the barium sulfate conversion unit, be used for adding sulfuric acid or vitriol to barium sulphide, and utilize chemical reaction to obtain barium sulfate.The preferential barium sulfate conversion unit of selecting is made barium sulfate when utilizing chemical reaction to obtain barium sulfate.
In various embodiments of the present invention, preferably, described first reaction unit comprises: the barium carbonate conversion unit, be used for adding sodium hydroxide, carbonic acid gas to barium sulphide, chemical reaction takes place obtain barium carbonate and sodium sulphite, preferably, chemical reaction takes place and obtains barium carbonate in the carbonic acid gas that produces when adding sodium hydroxide and described calcining in the barium sulphide.
Utilize described barium carbonate conversion unit, the carbonic acid gas that produces during with sodium hydroxide, described calcining joins in the barium sulphide, chemical reaction takes place obtain barium carbonate and sodium sulphite.Namely
BaS+Na
2SO
4＝BaSO
4+Na
2S
BaS+CO
2+2NaOH＝BaCO
3+Na
2S+H
2O
In various embodiments of the present invention, preferably, described second reaction unit comprises: the barium carbonate pyrolysis device is used for that described barium carbonate is carried out thermolysis and obtains barium oxide; The barium reduction apparatus obtains barium for described barium oxide is reduced, and preferably, the described barium oxide solid of heating and aluminium powder obtain described barium in enclosed environment; Described second reaction unit more preferably comprises: the barium equipment for purifying is used for the described barium that reduction obtains is purified.
When utilizing described second reaction unit to carry out that described barium salt processed the step that obtains barium, thermolysis is for to carry out the thermolysis of oxidation class to barium carbonate, being about to barium carbonate puts into the electric smelter of sealing and heats to high temperature, wherein high temperature is more than 1000 ℃, be preferably 1360 ℃, allow barium carbonate carry out thermolysis, make barium oxide separate, described second reaction unit is preferably the barium carbonate pyrolysis device, namely
BaCO
3＝BaO+CO
2↑
In various embodiments of the present invention, preferably, described washing device further comprises: collecting tank is used for washings is collected; And/or reaction tank is used for adding carbon dioxide, sodium hydroxide solution and the ferric chloride Solution that described calcining produces to described washings, utilizes chemical reaction to extract soluble substance in the described washings.For the water after the ore immersion, utilize collecting tank to collect to washings, in reaction tank, in described washings, add carbon dioxide, sodium hydroxide solution and ferric chloride Solution again, utilize chemical reaction to extract soluble substance in the described washings, these soluble substances can further be processed into chemical fertilizer, thereby taken full advantage of various resources, reached resource-effective purpose.
By a kind of method and apparatus from ore extraction barium and barium salt provided by the invention, can adopt set shape production method to produce barium and barium salt, environmental protection, comprehensive exploitation ore resources.
Need to prove that the carbonic acid gas that the present invention mentions can come from the carbon dioxide of ore calcination generation or the carbon dioxide of introducing from the outside.
Various embodiment provided by the invention can be as required combination mutually in any way, the technical scheme that obtains by this combination, also within the scope of the invention.
Obviously, those skilled in the art can carry out various changes and modification to the present invention and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also comprises these changes and modification interior.
Claims (2)
1. the method from ore extraction barium and barium salt is characterized in that, comprising:
Ore is washed;
Described ore is washed comprises:
Described ore is soaked in clear water, in immersion process and after soaking ore is stirred, the time of immersion is more than 12 hours;
Described ore after the washing is calcined, obtained barium sulphide;
Described described ore after the washing is calcined and comprised: coal and coke are mixed into the described ore of fuel after to washing calcine;
Described barium sulphide processed obtain barium salt;
Described described barium sulphide is processed obtains barium salt and comprises:
In barium sulphide, add sodium hydroxide, carbonic acid gas, utilize chemical reaction to obtain barium carbonate and sodium sulphite;
The described chemical reaction that obtains barium carbonate further obtains sodium sulphite and hydrogen sulfide,
This method further comprises: collect described hydrogen sulfide, and the described hydrogen sulfide of collecting is compressed or utilizes chemical reaction to reclaim sulphur to the described hydrogen sulfide of collecting;
This method further comprises: add sulphur in described sodium sulphite, utilize chemical reaction to obtain Na
2S
x, described x is 2,3,4 or 5;
Described barium salt processed obtain barium;
Described described barium salt is processed obtains barium and comprises:
Barium carbonate in the described barium salt is carried out thermolysis obtain barium oxide;
Described barium oxide reduced obtain barium;
The described barium oxide solid of heating and aluminium powder obtain described barium in enclosed environment;
The described barium that reduction obtains is purified.
2. the device from ore extraction barium and barium salt is characterized in that, comprising:
Washing device is used for ore is washed;
Described washing device comprises clean water basin, is used for described ore is soaked at clear water; Described washing device comprises whipping device, is used at immersion process with after soaking ore being stirred; Described washing device comprises timing device, and the time that is used for the described immersion of timing is more than 12 hours;
Roasting assembly is used for the described ore after the washing is calcined, and obtains barium sulphide;
Described roasting assembly comprises: calcining furnace is used for being mixed into fuel with coal and coke the described ore after washing is calcined;
First reaction unit obtains barium salt for described barium sulphide is processed;
Described first reaction unit comprises: the barium carbonate conversion unit, be used for adding sodium hydroxide, carbonic acid gas to barium sulphide, and chemical reaction takes place obtain barium carbonate and sodium sulphite;
Described first reaction unit further comprises: the sodium sulphite collecting device, be used for adding sulphur to described sodium sulphite, and utilize chemical reaction to obtain Na
2S
x, described x is 2,3,4 or 5;
Described first reaction unit further comprises: the hydrogen sulfide collecting device, and be used for to collect described hydrogen sulfide, and the described hydrogen sulfide of collecting is compressed or utilizes chemical reaction to reclaim sulphur to the described hydrogen sulfide of collecting;
Second reaction unit obtains barium for described barium salt is processed;
Described second reaction unit comprises: the barium carbonate pyrolysis device, carry out thermolysis for the barium carbonate to described barium salt and obtain barium oxide; The barium reduction apparatus obtains barium for described barium oxide is reduced, and the described barium oxide solid of heating and aluminium powder obtain described barium in enclosed environment; Described second reaction unit comprises: the barium equipment for purifying is used for the described barium that reduction obtains is purified.
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| CN106269208B (en) * | 2016-08-23 | 2018-11-23 | 武汉理工大学 | A kind of ore-dressing technique of baric carbonate mine recycling barium carbonate |
| CN107673388A (en) * | 2017-11-03 | 2018-02-09 | 荆门市双创专利技术服务有限公司 | A kind of hydrogen sulfide recycling system barium salt production line |
| CN107673387A (en) * | 2017-11-03 | 2018-02-09 | 荆门市双创专利技术服务有限公司 | A kind of efficiently barium salt production line |
| CN107720799A (en) * | 2017-11-03 | 2018-02-23 | 荆门市双创专利技术服务有限公司 | A kind of barium salt production line with carbonators |
| CN107673386A (en) * | 2017-11-03 | 2018-02-09 | 荆门市双创专利技术服务有限公司 | A kind of barium sulfate leaches groove barium salt production line |
| CN108946675A (en) * | 2018-08-15 | 2018-12-07 | 黑龙江莱睿普思环境科技发展有限公司 | The method that hydrogen sulfide produces NaHS |
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| CN101134596A (en) * | 2006-08-31 | 2008-03-05 | 红星（新晃）精细化学有限责任公司 | Technique for producing fine barium sulfate by barite sulfuric acid process |
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