CN106276984B - A kind of preparation method of potassium nitrate - Google Patents
A kind of preparation method of potassium nitrate Download PDFInfo
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- CN106276984B CN106276984B CN201610584010.3A CN201610584010A CN106276984B CN 106276984 B CN106276984 B CN 106276984B CN 201610584010 A CN201610584010 A CN 201610584010A CN 106276984 B CN106276984 B CN 106276984B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D9/00—Nitrates of sodium, potassium or alkali metals in general
- C01D9/02—Preparation by working-up natural salt mixtures
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Abstract
The invention discloses a kind of preparation method of potassium nitrate, including step：A, nitrate is heated to being no more than 300 DEG C, is melted, obtain the first fusant；B, potassium-enriched rock is crushed and be placed in first fusant, continue to be heated to being no more than 600 DEG C, and keep the temperature 12h~36h, obtain the second fusant；Wherein, the potassium-enriched rock refers to K2O timing K2The mass percent of O is not less than 8% silicate mineral；C, second fusant is cooled to after 100 DEG C~120 DEG C and is passed through water thereto, obtain mixed system, the mixed system is kept the temperature 6h~48h at 50 DEG C~90 DEG C, separation of solid and liquid, obtains the first filter residue and the first filtrate；D, first concentrating filter liquor, cooling, separate out potassium nitrate.The preparation method of potassium nitrate according to the present invention, it can obtain potassium nitrate aqueous solution using potassium-enriched rock as raw material, by leaching twice, and technique is simple, energy consumption is low and environmentally protective.
Description
Technical field
The invention belongs to inorganic salts preparing technical field, specifically, is related to a kind of preparation method of potassium nitrate.
Background technology
China is a large agricultural country, and potash fertilizer is as a kind of important strategic means of agricultural production, concerning the food supply safety of country.
At present, China crops potash fertilizer market annual requirement is about 4,600,000 tons (with K2O is counted), plus industrial potassium and rational inventory, always
Sylvite year expense be about 6,490,000 tons.The year two thousand twenty is expected, China's only crops potash fertilizer market demand just can reach 1000
Ten thousand tons.At present, potash fertilizer production capacity in China's is limited, and year output is only 3,200,000 tons or so (with K2O is counted), it can not meet the country
The demand in market, 30% or so of annual potash fertilizer demand needs import；Meanwhile China's soluble potassium salt resource critical shortage,
Potassium resource totality reserves are with K2O is calculated as 1.36 hundred million tons, only accounts for the 1.64% of global reserves.
China's potassium-enriched rock is (i.e. with K2O timing, potassium content are not less than 8% silicates mineral) resource very abundant,
Its reserves is much larger than soluble potassium salt resource, has the characteristics that species is more, has a very wide distribution, in volcanic rock, sedimentary rock, metamorphic rock
In have presence, potassium bearing rock is widely distributed, have development potash fertilizer advantage.Such as southern Guizhou province potassium bearing rock ore deposit
Point just has more or less a hundred, and the reserves for having more than ten ore deposit points reach more than ten million ton, and only the reserves of Tongren mine belt are just more than 5,000,000,000 tons.With
The progressively expansion of potash fertilizer production capacity, after 40 years, China's soluble potassium ore deposit will face the serious problems of resource exhaustion.According to associated specialist
, it is expected that the only insoluble potassium rock resource in the Guizhou Wanshan Mountain, can at least exploit 500 years.Therefore, potash fertilizer is produced using potassium-enriched rock resource
It is imperative.
Potassium nitrate is a kind of free from chloride nitrogen, potassium binary compound fertilizer, is had been widely used in agriculture field tool, in the world nitric acid
The yield of potassium is largely used to agricultural.Potassium nitrate is applied to tobacco, has fertilizer efficiency high, easily absorbs, and promotes Winter wheat, increase
The advantages that tobacco production, for improving cigarette quality important role.Remove agricultural aspect purposes, potassium nitrate food,
The industry fields such as ceramics, medicine and military affairs are also widely used.
At present, the technique that potassium nitrate is prepared using potassium-enriched rock is both needed to, by Multi-step conversion, decompose potassium-enriched rock first, obtain
Answered to the rich potassium solution such as potassium hydroxide or potassium hexafluorosilicate or potassium carbonate, then through nitric acid neutralization or caustic digestion or calcium nitrate
The processes such as decomposition, just can obtain potassium nitrate solution.Not only technique is cumbersome for method of the prior art, and wherein uses in soda acid
And/or other metathesis reactions, there are cost of material it is high the problem of, while generate more industrial residues, substantially increase
Process costs.
The content of the invention
To solve the above-mentioned problems of the prior art, the present invention provides a kind of preparation method of potassium nitrate, it is with richness
Potassium rock is raw material, can obtain potassium nitrate aqueous solution by leaching twice, technique is simple, energy consumption is low and environmentally protective.
In order to reach foregoing invention purpose, present invention employs following technical solution：
A kind of preparation method of potassium nitrate, including step：A, nitrate is heated to being no more than 300 DEG C, is melted, obtained
Obtain the first fusant；B, potassium-enriched rock is crushed and be placed in first fusant, continue to be heated to no more than 600 DEG C, and
12h~36h is kept the temperature, obtains the second fusant；Wherein, the potassium-enriched rock refers to convert the potassium-containing compound in potassium-enriched rock
For K2After the form of O, the K2The mass percent of O is not less than 8% silicate mineral；C, second fusant is cooled down
Water is passed through after to 100 DEG C~120 DEG C thereto, mixed system is obtained, the mixed system is kept the temperature 6h at 50 DEG C~90 DEG C
~48h, separation of solid and liquid, obtains the first filter residue and the first filtrate；D, first concentrating filter liquor, cooling, separate out potassium nitrate.
Further, the step A is further included：Congruent melting auxiliary salt is mixed with the nitrate；Wherein, the nitrate
It is not less than 1 with the mass ratio of the congruent melting auxiliary salt:1.
Further, the co-melting auxiliary salt includes metal cation and acid radical anion；Wherein, the metal cation
In sodium ion, potassium ion, lithium ion, magnesium ion, calcium ion, manganese ion, iron ion, zinc ion, aluminium ion, lead ion
Any one, any one of the acid radical anion in sulfate radical, carbonate, chlorion, bromide ion.
Further, the nitrate is selected from sodium nitrate, potassium nitrate, lithium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, nitric acid
Barium, lanthanum nitrate, cerous nitrate, manganese nitrate, nitric acid niobium, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, cadmium nitrate, nitric acid
At least one of aluminium, plumbi nitras, bismuth nitrate, nitric acid tin, gallium nitrate, nitric acid molybdenum.
Further, in the step B, the potassium-enriched rock is crushed to the mesh of 50 mesh~400.
Further, the mass ratio of the potassium-enriched rock and first fusant is 1:2~2:1.
Further, the mass ratio of the water and second fusant is 1:2~2:1.
Further, in the step D, first concentrating filter liquor, be cooled to -20 DEG C~25 DEG C, described in precipitation
Potassium nitrate.
Further, after the potassium nitrate separates out, first filtrate is separated, obtains the second filtrate, second filtrate
Separated through evaporation, obtain the 3rd filter residue, the 3rd filter residue is incorporated in the nitrate of the step A.
Further, the step C is further included：First filter residue is washed and obtains cleaning solution, the washing
Liquid is incorporated in first filtrate.
Further, the potassium-enriched rock be potassium feldspar, leucite, glauconite, illite, in the shale of sand containing potassium at least
It is a kind of.
The present invention obtains the first fusant using nitrate and congruent melting auxiliary salt melt blending first, you can the rich potassium rock of leaching
Potassium in stone, then passes through water logging and separation of solid and liquid, you can obtains potassium nitrate solution, is finally by operations such as concentration, coolings
Potassium nitrate can be obtained, preparation method is simple, melting process heating-up temperature be no more than 600 DEG C, compared with prior art in high temperature melting
Reactant salt, considerably reduces process energy consumption, so as to reduce manufacturing cost；At the same time, compared with prior art in preparation
Method, preparation method of the invention also avoid the operation such as cumbersome neutralization, acidleach, decomposition, and potassium-enriched rock is not decomposed,
Environmental contaminants are not present in raw material and accessory substance.
Embodiment
Hereinafter, it will be described in the embodiment of the present invention.However, it is possible to implement the present invention in many different forms,
And the present invention should not be construed as limited to the specific embodiment illustrated here.Conversely, there is provided these embodiments be in order to
The principle of the present invention and its practical application are explained, so that others skilled in the art are it will be appreciated that the various realities of the present invention
Apply example and be suitable for the various modifications of specific intended application.
It will be appreciated that although can be used term " first ", " second " etc. to describe various materials herein, but these
Material should not be limited by these terms.These terms are only used to distinguish a material with another material.
The invention discloses a kind of method that potassium nitrate is prepared using potassium-enriched rock；The potassium-enriched rock refers to wherein potassium
Content is (with K2The mass percentage of O) be not less than 8% silicate mineral, that is to say, that by the potassium-enriched rock with each
The potassium-containing compound of kind form preservation is converted into K2After the form of O, K2The mass percent of O is not less than 8% silicate mineral,
Such as potassium feldspar, leucite, glauconite, illite, the mineral that the shale of sand containing potassium main component is silicate.
A kind of preparation method of potassium nitrate includes the following steps：
In step 1, nitrate is heated to be no more than 300 DEG C, is melted, obtains the first fusant.
Preferably, congruent melting auxiliary salt can be mixed with the nitrate, be again heated to no more than 300 DEG C；Wherein, the nitre
Hydrochlorate and the mass ratio of the congruent melting auxiliary salt are not less than 1:1.
Specifically, the nitrate is selected from sodium nitrate, potassium nitrate, lithium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, nitric acid
Barium, lanthanum nitrate, cerous nitrate, manganese nitrate, nitric acid niobium, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, cadmium nitrate, nitric acid
At least one of aluminium, plumbi nitras, bismuth nitrate, nitric acid tin, gallium nitrate, nitric acid molybdenum；Preferably, nitrate is selected from sodium nitrate, nitre
At least one of sour potassium, lithium nitrate, magnesium nitrate, calcium nitrate, manganese nitrate, ferric nitrate, zinc nitrate, aluminum nitrate, plumbi nitras.It is described
Congruent melting auxiliary salt is in sodium, potassium, lithium, magnesium, calcium, manganese, iron, zinc, aluminium, the sulfate of lead, carbonate, chloride, bromide
Any one；That is, congruent melting auxiliary includes metal cation and acid radical anion, and its have with it is above-mentioned preferably
The identical metal cation of nitrate, and its acid radical anion is selected from sulfate radical, carbonate, chlorion, bromide ion.
What deserves to be explained is congruent melting auxiliary salt should not decompose during subsequent melt is blended, meanwhile, also not
Obtain and the reaction such as precipitation occurs between above-mentioned nitrate.
In step 2, potassium-enriched rock is crushed and is placed in the first fusant, continue to be heated to no more than 600 DEG C, and
12h~36h is kept the temperature, obtains the second fusant.
Specifically, the mass ratio of potassium-enriched rock and the first fusant is 1:2~2:1.
Preferably, the potassium-enriched rock is crushed to the mesh of 50 mesh~400, to obtain preferably leaching effect.
In step 3, the second fusant is cooled to after 100 DEG C~120 DEG C and is passed through water thereto, obtain mixed system,
And the mixed system is kept the temperature 6h~48h at 50 DEG C~90 DEG C, separation of solid and liquid, obtains the first filter residue and the first filtrate.
Specifically, the mass ratio of water and the second fusant is 1:2~2:1.
Preferably, waste, first filter residue can be washed, then will be obtained using water as detergent to reduce
The cleaning solution obtained is incorporated in the first filtrate.
In step 4, through evaporating, concentrating and be cooled to -20 DEG C~25 DEG C, potassium nitrate separates out the first filtrate, solid-liquid point
From rear, gained solid phase is potassium nitrate.
Specifically, after potassium nitrate separates out, such as centrifugation, flotation, filtering any means can be used to realize solid-liquid point
From to obtain the potassium nitrate of solid phase；At the same time, the second filtrate is have also obtained, the second filtrate separates through evaporation, obtains the 3rd filter
Slag.What deserves to be explained is being obtained when the first fusant is only melted by nitrate, the 3rd filter residue is mainly the nitrate at this time,
It will can be recycled in its direct return to step one；When the first fusant is obtained by nitrate and congruent melting auxiliary salt mixed melting,
The 3rd filter residue is mainly the nitrate and congruent melting auxiliary salt at this time, the two can be re-started according to the ratio in step 1 and matched somebody with somebody
Put and recycle；That is, the 3rd filter residue is incorporated in the nitrate of step 1 and is recycled.
Hereinafter, the preparation method of potassium nitrate according to the present invention will be described in detail with reference to specific embodiment,
For convenience of being contrasted to each embodiment, analysis in table form contrasts each embodiment.Embodiment 1-5 is in different experiments parameter
Under comparing result it is as shown in table 1.
Contrasts of the 1-5 under different experiments parameter according to an embodiment of the invention of table 1
Note：In table 1, " --- " represents not containing
What deserves to be explained is in example 2, congruent melting auxiliary salt is epsom salt, those skilled in the art can pass through
Simple conversion, calculate the content of wherein magnesium sulfate is 50g or so, thus calculate nitrate and the mass ratio of congruent melting auxiliary salt are
1:1, and since the crystallization water in epsom salt can escape in melting process, the quality of thus obtained first fusant is
100g or so, that is, ensure that the mass ratio of the first fusant and potassium-enriched rock is 2 in the present embodiment:1；Similarly, implementing
In example 4, one of nitrate is six water manganese nitrates, calculate wherein manganese nitrate for 35g or so, and due to the crystallization in six water manganese nitrates
Water can escape in melting process, and the quality of thus obtained first fusant is 100g or so, that is, be ensure that in the present embodiment
In the mass ratio of the first fusant and potassium-enriched rock be 2:1.
The average yield of the potassium nitrate of the preparation method of the potassium nitrate of above-described embodiment 1-5 is counted, such as the institute of table 2
Show.
The average yield of potassium nitrate in the preparation method of 2 embodiment 1-5 of table
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Potassium nitrate average yield | ＞ 70% | ＞ 65% | ＞ 50% | ＞ 60% | ＞ 60% |
The preparation method of potassium nitrate according to an embodiment of the invention is existed using low-temperature molten salt system (i.e. the first fusant)
The potassium ion in potassium-enriched rock is leached under conditions of no more than 600 DEG C, the low-temperature molten salt system is for this kind of silicic acid of potassium-enriched rock
Salt form rock has good wellability, it can come into full contact with potassium-enriched rock powder granule surface, and high in the first fusant
The ion of concentration has high exchange activity, and higher potassium can be obtained in the case where not destroying the skeleton structure of potassium-enriched rock
Ion leaching rate；Relatively low preparation temperature can effectively reduce the energy consumption put forward during potassium, reduce manufacturing cost.At the same time,
The preparation method of the present invention can directly obtain potassium nitrate aqueous solution by leaching twice at different temperatures, compared to existing skill
Preparation method in art, technique is simple, without conversion reactions such as cumbersome neutralization, acidleach or double decompositions.In addition, used in the present invention
Raw material is nitrate and potassium-enriched rock, and products therefrom is silicates caused by potassium nitrate and displacement；Rich potassium in reaction process
Rock not recurring structure decomposition reaction, the strong acid and highly basic of environmental pollution are not easily caused in raw material and accessory substance, and technique is green
Colour circle is protected.
Although the present invention has shown and described with reference to specific embodiment, it should be appreciated by those skilled in the art that：
In the case where not departing from the spirit and scope of the present invention limited by claim and its equivalent, can carry out herein form and
Various change in details.
Claims (7)
1. a kind of preparation method of potassium nitrate, it is characterised in that including step：
A, congruent melting auxiliary salt and nitrate are mixed and heated to no more than 300 DEG C, are melted, obtain the first fusant；Wherein,
The nitrate and the mass ratio of the congruent melting auxiliary salt are not less than 1:1；The congruent melting auxiliary salt include metal cation and
Acid radical anion；Wherein, the metal cation be selected from sodium ion, potassium ion, lithium ion, magnesium ion, calcium ion, manganese ion,
Any one in iron ion, zinc ion, aluminium ion, lead ion, the acid radical anion be selected from sulfate radical, carbonate, chlorine from
Son, any one in bromide ion；The nitrate is selected from sodium nitrate, potassium nitrate, lithium nitrate, magnesium nitrate, calcium nitrate, nitric acid
Strontium, barium nitrate, lanthanum nitrate, cerous nitrate, manganese nitrate, nitric acid niobium, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, nitric acid
At least one of cadmium, aluminum nitrate, plumbi nitras, bismuth nitrate, nitric acid tin, gallium nitrate, nitric acid molybdenum；
B, potassium-enriched rock is crushed and is placed in first fusant, continue to be heated to be no more than 600 DEG C, and keep the temperature 12h~
36h, obtains the second fusant；Wherein, the potassium-enriched rock refers to the potassium-containing compound in potassium-enriched rock being converted into K2After O,
The K2The mass percent of O is not less than 8% silicate mineral；The potassium-enriched rock for potassium feldspar, leucite, glauconite,
At least one of illite, the shale of sand containing potassium；
C, second fusant is cooled to after 100 DEG C~120 DEG C and is passed through water thereto, obtain mixed system, made described mixed
Zoarium ties up to insulation 6h~48h at 50 DEG C~90 DEG C, and separation of solid and liquid, obtains the first filter residue and the first filtrate；
D, first concentrating filter liquor, cooling, separate out potassium nitrate.
2. preparation method according to claim 1, it is characterised in that in the step B, the potassium-enriched rock is crushed to
The mesh of 50 mesh~400.
3. preparation method according to claim 1, it is characterised in that the matter of the potassium-enriched rock and first fusant
The ratio between amount is 1:2~2:1.
4. preparation method according to claim 2, it is characterised in that the mass ratio of the water and second fusant
For 1:2~2:1.
5. preparation method according to claim 1, it is characterised in that in the step D, first filtrate is through dense
Contract, be cooled to -20 DEG C~25 DEG C, separate out the potassium nitrate.
6. preparation method according to claim 1 or 5, it is characterised in that after the potassium nitrate separates out, separation described first
Filtrate, obtains the second filtrate, and second filtrate separates through evaporation, obtains the 3rd filter residue, and the 3rd filter residue is incorporated to the step
In the nitrate of rapid A.
7. preparation method according to claim 1, it is characterised in that the step C is further included：To first filter residue into
Row washs and obtains cleaning solution, and the cleaning solution is incorporated in first filtrate.
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