CN100528754C - Carbon-adding chlorination method for extracting and separating boron and magnesium from boron enriched slag - Google Patents
Carbon-adding chlorination method for extracting and separating boron and magnesium from boron enriched slag Download PDFInfo
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- CN100528754C CN100528754C CNB200710012054XA CN200710012054A CN100528754C CN 100528754 C CN100528754 C CN 100528754C CN B200710012054X A CNB200710012054X A CN B200710012054XA CN 200710012054 A CN200710012054 A CN 200710012054A CN 100528754 C CN100528754 C CN 100528754C
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Abstract
The present invention relates to an extraction and separation technology of the chemistry and chemical engineering, in particular to the extraction and separation technology of boron and magnesium in the chemistry and chemical engineering. The present invention consists of three technical works: An aluminum, a silicon and the boron are primarily separated from a calcium and the magnesium by the low temperature chlorination with carbon. A liquid-phase precipitation method is used to separate the magnesium and the calcium and an ultrafine magnesium oxide is prepared. The classification cooling method is used to separate the chloride of the aluminum, the silicon and the boron. The present invention has the advantages of special processing method, high boron conversion rate, simple production technology, short flow, small equipment investment, little material consumption, no erosion on the equipment in the production process and no discharge of waste liquid, which is easy for industrialization production.
Description
Technical field
The present invention relates to a kind of extraction, separating technology of chemical, particularly relate to extraction, the separating technology of boron and magnesium elements in a kind of chemical class.
Background technology
Paigeite is realized separating of iron and boron after the melt selective reduction in electric furnace or blast furnace, obtain two kinds of materials of pig iron containing boron and boracic slag.Because boron obtains enrichment in slag, so this boracic slag is called rich boron slag.Rich boron slag belongs to secondary boron resource, and the comprehensive utilization process to rich boron slag mainly contains following several at present:
1. rich boron slag melt sodium---pressurized water infuse borax technology
This technology be with paigeite high temperature separating obtained be in the rich boron slag of molten state, directly spray into yellow soda ash high temperature sodium, generate the boric acid sodium salt of different boron sodium ratios.Adopt pressurization water seaoning fast reaction speed to leach the boric acid sodium salt.It is higher that this method has the yield of boron, need not prepare advantages such as carbonic acid gas.Its main products is a borax.This technology main drawback is: the reaction needed pressurization, and extraction time is longer, and reaction process is more loaded down with trivial details.
2. rich boron slag carbon alkaline process system borax technology
Boron in the rich boron slag mainly exists mutually with suanite, generates borax and magnesiumcarbonate during carbon alkaline process system borax behind suanite and yellow soda ash and the carbon dioxide reaction.By control pH value, magnesium generation magnesiumcarbonate or basic carbonate magnesium precipitate are separated with boron in the solution.Pressurization or raising temperature of reaction all can shorten the reaction times.Its main products is a borax.This technology main drawback is: reaction needs to carry out in autoclave, and operation is loaded down with trivial details, and influence factor is more, and the activity of rich boron slag is had certain requirement.
3. rich boron slag sulfuric acid leaches single stage method and produces the boric acid technical study
At a certain temperature, when sulfuric acid leached rich boron slag, boron and sulfuric acid reaction in the rich boron slag that exists with the suanite form generated boric acid and sal epsom, and the difference crystallization control speed of Tc according to the two makes boric acid separate with sal epsom.It is short that this technology has the reaction times, the acidolysis rate advantages of higher.Its main products is a boric acid, but by-product sal epsom also.Its main drawback is: reaction process is loaded down with trivial details, mother liquor complicated component after the acidolysis, and the product that obtains does not reach industrial requirements.
Summary of the invention
The purpose of this invention is to provide and a kind ofly from rich boron slag, extract boron and magnesium and make its effective isolating carburizing chlorination technology; Realized the chemical industry purpose of not only extracting but also separating boron and magnesium elements, the present invention includes: the low temperature carburizing chlorination also makes aluminium, silicon, boron and calcium, magnesium initial gross separation technology; Adopt liquid-phase precipitation method separating magnesium and calcium product and prepare super fine magnesia technology; The gradient cooling method is separated the chloride process of aluminium, silicon, boron.The present invention is applicable to from the mineral of various boracics, magnesium and industrial residue and extracts and separate boron, magnesium elements that fully utilizing wherein, valuable constituent alleviates the environmental pollution and the wasting of resources.
The objective of the invention is to be achieved through the following technical solutions:
Extract and separate the carbon-adding chlorination method of boron and magnesium from rich boron slag, it is made up of three technical operations: i.e. low temperature carburizing chlorination and make aluminium, silicon, boron and calcium, magnesium initial gross separation technology; Adopt liquid-phase precipitation method separating magnesium and calcium product and prepare super fine magnesia technology; The gradient cooling method is separated the chloride process of aluminium, silicon, boron.
The aforesaid carbon-adding chlorination method that from rich boron slag, extracts and separate boron and magnesium, said low temperature carburizing chlorination also makes aluminium, silicon, boron and calcium, magnesium initial gross separation technology, be in rich boron slag, to allocate an amount of carbon into,, make gas-solid phase product be able to initial gross separation at 600～900 ℃ and chlorine reaction; Said carbon is activated carbon, coal, coke.
The aforesaid carbon-adding chlorination method that from rich boron slag, extracts and separate boron and magnesium, said employing liquid-phase precipitation method separating magnesium and calcium product also prepare super fine magnesia technology, be not need pre-separation at solid product calcium chloride and magnesium chloride, directly mix with tensio-active agent, add precipitation agent, the preparation super fine magnesia.Said tensio-active agent is polymeric surface active agents such as polyoxyethylene glycol, polyvinyl alcohol; Precipitation agent is an ammoniacal liquor, urea, and sodium hydroxide, potassium hydroxide, calcium hydroxide is solvable or the slightly soluble bases.
The aforesaid carbon-adding chlorination method that from rich boron slag, extracts and separate boron and magnesium, said gradient cooling method is separated the chloride process of aluminium, silicon, boron, be do not need to be other chemical reagent just the muriate of aluminium, silicon, boron can be able to initial gross separation, reaction residue chlorine reusable edible, the gradient cooling temperature of aluminum chloride is less than 200 ℃, the gradient cooling temperature of silicon tetrachloride is less than 50 ℃, and boron trichloride gradient cooling temperature is less than 8 ℃.
Advantage of the present invention and effect:
1. the present invention extracts from rich boron slag and separates the processing method that boron, magnesium elements unite two into one.Compared with prior art, the present invention has the working method uniqueness, boron transformation efficiency height, and production technique is simple, and flow process is short, low equipment investment, raw material consumption is few, and production process is etching apparatus not, does not produce the discharging of waste liquid, is easy to characteristics such as suitability for industrialized production.
2. the present invention directly makes product boron trichloride and magnesium chloride by the carbon thermal chlorination, the product boron trichloride is compared the economically valuable height with the product boric acid that prior art is produced with borax, characteristics such as purposes is wide, product magnesium chloride do not need removal of impurities can be directly used in the higher super fine magnesia of productive value.
3. this technology is not only applicable to rich boron slag, also can be applicable to boracic, magniferous other ore deposit mineral, as: paigeite.Make the different various boron rocks of boron-containing quantity height really possess extraction value.
4. the present invention not only can extract and separate boron, the magnesium elements in the rich boron slag, but also can make all or part of chlorination of aluminium, element silicon in the rich boron slag, and is separated the real comprehensive utilization of having accomplished resource according to the difference of product physicochemical property;
Embodiment
Technological line of the present invention is: be reductive agent with the activated carbon, chlorine is chlorizating agent, at a certain temperature boron in the rich boron slag and magnesium is separately converted to boron trichloride and magnesium chloride, according to the difference realization boron of physicochemical property and the separating of magnesium of chlorizate.Concrete technical scheme of the present invention is: rich boron ground-slag is broken, granularity need reach 100 orders or thinner, then rich boron slag and activated carbon are mixed by certain carbon slag ratio (1: 2～1: 4), place high temperature reaction stove, control reaction temperature is at 600～900 ℃, chlorine flowrate is 0.15 gram/minute, and the reaction times is 60～120 minutes.After chlorination reaction is finished, the gas-phase product gradient cooling can directly obtain boron trichloride, the water-soluble mixing solutions that obtains calcium chloride and magnesium chloride of solid product is that precipitation agent, polyoxyethylene glycol are that dispersion agent prepares super fine magnesia with direct precipitation method with ammoniacal liquor with mixing solutions.
Embodiment 1
The rich boron slag main chemical (%) of blast furnace: boron oxide (B
2O
3) 10.40; Magnesium oxide (MgO): 39.79; Silicon-dioxide (SiO
2): 28.18; Calcium oxide CaO:12.79; Aluminum oxide (Al
2O
3): 6.88; Other are 1.96 years old.
This is the rich boron slag of the lower blast furnace of boron, Mg content, therefore selects for use the amount of activated carbon lower.
Being behind 75 microns rich boron slag 10 gram and activated carbon 2.5 gram mixings, to place high temperature reaction stove with particle diameter, is the chlorine reaction that restrains of per minute 0.15 2 hours with input speed down at 700 ℃.Gas-phase product aluminum chloride, silicon tetrachloride, boron trichloride and unreacted chlorine are discharged with lower boiling volatile matter or gas form, aluminum chloride is deposited on less than in 200 ℃ the cold zone, pass through fractional condensation, silicon tetrachloride is 50 ℃ of left and right sides condensations, boron trichloride is 8 ℃ of left and right sides condensations, thereby the realization gas-phase product separates.The water-soluble after-filtration of solid product, adding about 0.3 gram polyoxyethylene glycol in filtrate mixes, temperature of reaction is 40 ℃, ammonia magnesium mol ratio is 2.5: 1 o'clock, in reaction system, dropwise add 11% mass percent ammoniacal liquor, and constantly stir, react that co-precipitation goes out magnesium hydroxide and calcium hydroxide after 180 minutes, ageing at room temperature 24 hours, filtration under diminished pressure, washing are to there not being chlorion, obtain magnesium hydrate precipitate, then with magnesium hydroxide 100 ℃ dry 180 minutes down, with dried magnesium hydroxide 600 ℃ down calcining obtained super fine magnesia in 3 hours.
Embodiment 2
Rich boron slag main chemical (%): the B of electric furnace
2O
3: 19.96; MgO:49.35; SiO
2: 24.98; CaO:1.73; Al
2O
3: 2.03; Other are 1.95 years old.
This is the rich boron slag of the higher electric furnace of boron, Mg content, so the activated carbon amount of selecting for use is bigger.
Being behind 75 microns rich boron slag 10 gram and activated carbon 3.5 gram mixings, to place high temperature reaction stove with particle diameter, is the chlorine reaction that restrains of per minute 0.15 2 hours with input speed down at 700 ℃.Gas-phase product aluminum chloride, silicon tetrachloride, boron trichloride and unreacted chlorine are discharged with lower boiling volatile matter or gas form, aluminum chloride is deposited on less than in 200 ℃ the cold zone, pass through fractional condensation, silicon tetrachloride is 50 ℃ of left and right sides condensations, boron trichloride is 8 ℃ of left and right sides condensations, thereby the realization gas-phase product separates.The water-soluble after-filtration of solid product, adding about 0.35 gram polyoxyethylene glycol in filtrate mixes, temperature of reaction is 40 ℃, ammonia magnesium mol ratio is 2.5: 1 o'clock, in reaction system, dropwise add 11% mass percent ammoniacal liquor, and constantly stir, react that co-precipitation goes out magnesium hydroxide (containing a small amount of calcium hydroxide) after 180 minutes.Other steps such as example 1.
Embodiment 3
Paigeite main chemical (%): full iron (TFe): 22.91; B
2O
3: 7.55; MgO:30.91; SiO
2: 18.29; CaO:0.72; Other are 19.62 years old.
This is low-grade paigeite, boron content is lower, and iron level is higher, so the separation of the chlorizate of iron has material impact to the separation of other chlorizates, the amount that reaction will be controlled reductive agent is the lower iron trichloride of boiling point with the iron chlorination, to realize the separation of gas-solid phase product.
With paigeite 780 ℃ of oxidizing roastings, szaibelyite in the paigeite changes suanite, magnetite is transformed into rhombohedral iron ore, antigorite in the mineral removes water of constitution through roasting with decomposition, undergoing phase transition of crystalline structure, be transformed into olivine mineral, roasting causes specific surface area and increases, and satisfies the needs of further chlorination reaction.
Being behind 75 microns paigeite 10 gram and activated carbon 3 gram mixings, to place high temperature reaction stove with particle diameter, is the chlorine reaction that restrains of per minute 0.15 2 hours with input speed down at 750 ℃.Iron trichloride, silicon tetrachloride, boron trichloride and unreacted chlorine are discharged with gas or lower boiling volatile matter form.Iron trichloride is deposited in 200～350 ℃ of temperature ranges, and by fractional condensation, silicon tetrachloride is 50 ℃ of left and right sides condensations, and boron trichloride is 8 ℃ of left and right sides condensations, thereby the realization gas-phase product separates.The water-soluble after-filtration of solid product, adding about 0.25 gram polyoxyethylene glycol in filtrate mixes, temperature of reaction is 40 ℃, ammonia magnesium mol ratio is 2.5: 1 o'clock, in reaction system, dropwise add 11% mass percent ammoniacal liquor, and constantly stir, react that co-precipitation goes out magnesium hydroxide (containing a small amount of calcium hydroxide) after 180 minutes.Other steps such as example 1.
Claims (3)
1. from rich boron slag, extract and separate the carbon-adding chlorination method of boron and magnesium, it is characterized in that it is made up of three technical operations: i.e. low temperature carburizing chlorination and make aluminium, silicon, boron and calcium, magnesium initial gross separation technology, this technology is to allocate an amount of carbon in rich boron slag, said carbon is gac, coal, coke, at 600～900 ℃ and chlorine reaction, make gas-solid phase product be able to initial gross separation; Adopt liquid-phase precipitation method separating magnesium and calcium product and prepare super fine magnesia technology, this technology is not need pre-separation at solid product calcium chloride and magnesium chloride, directly mixes with tensio-active agent, adds precipitation agent, the preparation super fine magnesia; The gradient cooling method is separated the chloride process of aluminium, silicon, boron, this technology does not need other chemical reagent just the muriate of aluminium, silicon, boron can be able to initial gross separation, wherein, the gradient cooling temperature of aluminum chloride is less than 200 ℃, the gradient cooling temperature of silicon tetrachloride is less than 50 ℃, and boron trichloride gradient cooling temperature is less than 8 ℃.
2. the carbon-adding chlorination method that from rich boron slag, extracts and separate boron and magnesium according to claim 1, it is characterized in that said employing liquid-phase precipitation method separating magnesium and calcium product and prepare in the super fine magnesia technology that said tensio-active agent is polyoxyethylene glycol, high-molecular polyvinyl alcohol tensio-active agent; Precipitation agent is an ammoniacal liquor, urea, and sodium hydroxide, potassium hydroxide, calcium hydroxide is solvable or the slightly soluble bases.
3. the carbon-adding chlorination method that extracts and separate boron and magnesium from rich boron slag according to claim 1 is characterized in that in the chloride process of said gradient cooling method separation aluminium, silicon, boron the recycle of reaction residue chlorine.
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|---|---|---|---|
| CNB200710012054XA CN100528754C (en) | 2007-07-12 | 2007-07-12 | Carbon-adding chlorination method for extracting and separating boron and magnesium from boron enriched slag |
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| CNB200710012054XA CN100528754C (en) | 2007-07-12 | 2007-07-12 | Carbon-adding chlorination method for extracting and separating boron and magnesium from boron enriched slag |
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| CN100528754C true CN100528754C (en) | 2009-08-19 |
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| CN105253905B (en) * | 2015-11-18 | 2017-02-01 | 金川集团股份有限公司 | Method for extracting aluminum from aluminum waste |
| CN108893572A (en) * | 2018-06-15 | 2018-11-27 | 河北工程大学 | A kind of method of valuable constituent element comprehensive reutilization in paigeite |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4183904A (en) * | 1977-10-03 | 1980-01-15 | Monsanto Company | Recovery of boron from waste streams |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4183904A (en) * | 1977-10-03 | 1980-01-15 | Monsanto Company | Recovery of boron from waste streams |
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