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.
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.