CN105523573B - A kind of epsom salt and preparation method thereof - Google Patents
A kind of epsom salt and preparation method thereof Download PDFInfo
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- CN105523573B CN105523573B CN201610040065.8A CN201610040065A CN105523573B CN 105523573 B CN105523573 B CN 105523573B CN 201610040065 A CN201610040065 A CN 201610040065A CN 105523573 B CN105523573 B CN 105523573B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
Abstract
The invention discloses a kind of epsom salt and preparation method thereof.The preparation method of epsom salt disclosed by the invention includes S1100 calcium carbides sludge filter, heating stepses, S1200 magnesium hydroxide synthesis steps, S1300 solid-liquid suspension separating steps, S1500 magnesium sulfate synthesis steps, S1600 heating, concentration, filtration step, S1800 is separated, drying steps：The magnesium sulfate crystalline solid is isolated with centrifuge, the magnesium sulfate crystalline solid that centrifugation is gone out is dried to obtain epsom salt in 50~55 DEG C of downstreams.According to the epsom salt preparation method that the present invention is provided, effective environmental protection can be realized, protecting ecology balance reduces the production cost of enterprise, while the large-scale production of epsom salt can also be realized.
Description
Technical field
The present invention relates to a kind of compound of chemical field and preparation method thereof, more particularly to a kind of epsom salt and its system
Preparation Method.
Background technology
Epsom salt (molecular formula MgSO4·7H2) also known as magnesium sulphate, sal amarum, epsomite, Epsom salts, O it is white or colourless
Needle-like or batter post shape crystalline solid, odorless, cool and slight bitter, molecular weight：246.47, proportion 1.68 is soluble in water, be slightly soluble in ethanol and
Glycerine, in being dissolved in the crystallization water of itself at 67.5 DEG C.Thermally decomposed, 70,80 DEG C is to lose the tetramolecular crystallization water.About 200 DEG C
Lose all of crystallization water into anhydride.Easy-weathering is powdery in air (drying), the crystallization water is gradually sloughed during heating and is changed into
Anhydrous magnesium sulfate, this product is free of any poisonous impurities.Epsom salt is easier because being not easily dissolved than anhydrous magnesium sulfate
Weigh, be easy to the quantitative control for carrying out in the industry.It is commercially used for process hides, explosive, fertilizer, papermaking, porcelain, printing and dyeing material, lead
The industry such as acid accumulator.As the mineral matters such as magnesium sulfate and other potassium, calcium, amino-acid salt, silicate, bath salt is can serve as；Agriculture
As fertilizer magnesium sulfate it is for improveing the soil of magnesium deficiency in industry (magnesium is a fundamental for chlorophyll molecule).In feed side
On face, feed grade magnesium sulfate as magnesium in feed manufacturing replenishers.Pharmaceutically can be used as purgatives, analgestic, antidote etc..
Traditional epsom salt production technology has sulfuric acid process, vapor phase method, carbonizatin method, bittern recrystallization method.Wherein：
1st, sulfuric acid process is obtained with magnesia, magnesium hydroxide, magnesium carbonate, magnesia etc. for raw material adds sulfuric acid decomposition or neutralization.
Relevant chemical equation：
MgO+H2SO4=H2O+MgSO4
Mg(OH)2+H2SO4=2H2O+MgSO4
MgCO3+H2SO4=CO2↑+H2O+MgSO4
2nd, after vapor phase method is with magnesium hydroxide slurry sulfur dioxide absorption, in the presence of a catalyst with air by magnesium bisulfite
Solution oxide and obtain.Relevant chemical equation：
Mg(OH)2+2SO2=MgH2(SO3)2
MgH2(SO3)2+Mg(OH)2=2MgSO3+2H2O
2MgSO3+O2=2MgSO4
3rd, carbonizatin method carbon dioxide carbonization magnesia and gypsum water slurry and make.Relevant chemical equation：
MgO+CO2+CaSO4=MgSO4+CaCO3
4th, bittern recrystallization method will extract potassium chloride or produce bittern heating concentration, cooling containing magnesium sulfate after bromine
Magnesium sulfate crude product is crystallized out, recrystallizes to produce after dissolving crude product.
In above-mentioned various production technologies, only use sulfuric acid and magnesia preparing magnesium sulfate and use magnesium hydroxide water slurry
There is preferable economic benefit using vapor phase method preparing magnesium sulfate after sulfur dioxide in removing fire coal, and widely used.Although
It is although relatively inexpensive with sulfuric acid and magnesia preparing magnesium sulfate, but soaked by sulfuric acid after the magnesia extracted in magnesia can be produced
The acidified soil discarded object of bubble, causes new pollution sources.
Because the purposes of magnesium sulfate is not only very wide but also consumption is also larger, with two in magnesium hydroxide water slurry removing fire coal
Vapor phase method preparing magnesium sulfate is used after sulfur oxide, although with preferable economic benefit, but it is total by sulfur dioxide in removing fire coal
The resource constraint of amount, the magnesium sulfate total amount of production is also relatively limited.
Accordingly, it is desirable to provide one kind being capable of environmental protection, and the larger epsom salt of yield and preparation method thereof.
The content of the invention
Therefore, the present invention propose a kind of at least one of new epsom salt that can be solved the above problems and its
Preparation method.
According to an aspect of the invention, there is provided a kind of preparation method of epsom salt, comprises the following steps：
S1100 calcium carbides sludge filter, heating stepses：Carbide slag is configured to carbide slag slurries, the mistake that water content is 70-75%
Filter, will heat after the carbide slag slurries injection reactor after filtering；
Carbide slag is that calcium carbide hydrolysis obtains the waste residue with calcium hydroxide as main component after acetylene gas.Acetylene (C2H2) be
One of important source material of basic organic synthesis industry, with calcium carbide (CaC2) it is raw material, the technique letter of (wet method) production acetylene that adds water
It is single ripe, account for larger specific gravity in China at present.1t calcium carbides add water can generate kg acetylene gas more than 300, while generating 10t solid contents about
12% industrial wastes, is commonly called as carbide slag slurries.Lime cement made of stones, production quick lime can be replaced to be used as calcium carbide using carbide slag
Raw material, production chemical products, production construction material and for environmental improvement etc..
Calcium carbide is starched or the main methods of carbide slag are press filtrations first to 40%~60% (butt), then using flue
Gas is baked to 3%~5% (butt), for producing cement, or direct replacement lime for producing soda ash, the method need
A large amount of coals or natural gas resource are consumed, and requires there is large-scale cement or soda ash enterprise near factory.Contain hydrogen in carbide slag
Calcium oxide, is one of the raw material for preparing epsom salt, and the present invention produces the carbide slag slurries discarded after acetylene gas with calcium carbide hydrolysis
It is primary raw material, is that carbide slag slurries treatment have found new outlet, also provides abundant raw material to prepare magnesium hydroxide.It is excellent
Filtered with the stainless (steel) wire of 80 mesh in selection of land, this step, remove carbide slag slurries in containing tiny ferro-silicon slag, lime stone and
Other impurity, to improve purity and efficiency that the present invention prepares magnesium sulfate.
S1200 magnesium hydroxide synthesis steps：The bittern of magnesium chloride containing is injected into the reactor, stirring, suspension is obtained；
Bittern of the present invention, including the bittern containing magnesium chloride and sodium chloride after potassium chloride, sodium chloride is extracted, can be used for
Production anhydrous magnesium chloride, magnesia, cement etc., but chloride bittern salt pan is most positioned at Gobi desert barren beach, neighboring markets magnesium chloride
Demand is limited, it is impossible to digest bittern by-product of magnesium chloride；Magnesium sulfate demand is much larger than magnesium chloride with price.The present invention is extracting
Bittern containing magnesium chloride and sodium chloride after potassium chloride, sodium chloride is primary raw material, is a kind of new technology that magnesium chloride adds deeply, no
It is only capable of reducing the production cost of epsom salt and magnesium chloride, additionally it is possible to environmental protection, improves the utilization rate of resource.
Preferably, the composition of the bittern of the magnesium chloride containing includes：MgCl2Content is 180g~300g/L, and KCl contents are
1.0g~1.3g/L, NaCl content are 3g~4g/L.Due to just from the old halogen and the old halogen tedded by solarization salt pond of factory building discharge
Middle content of magnesium chloride is different, it is preferable that the calculating benchmark that the present invention chooses is 200g/L.
The suspension includes magnesium hydroxide solid and calcium chloride filtrate.
S1300 solid-liquid suspension separating steps：The suspension is separated, magnesium hydroxide solid and calcium chloride filter is obtained
Liquid；
S1500 magnesium sulfate synthesis steps：Magnesium hydroxide solid described in press filtration, in the magnesium hydroxide filter cake obtained after press filtration
Waste Sulfuric Acid is added, until pH value is 5, reaction solution is obtained；
In this step, the reaction solution includes magnesium sulfate.
Heretofore described Waste Sulfuric Acid, including the Waste Sulfuric Acid for being used to dry produced by moist chlorine in chlor-alkali production can not be direct
Outer row, it is necessary to do environmental protection treatment, current domestic common processing method is that, for producing gypsum, the price of gypsum is relatively low, consumption
It is few；More environmentally friendly processing method also has alkylation sulfuric acid through methods such as Pintsch process production sulfuric acid, and this technique can be processed effectively
Waste Sulfuric Acid, environment protecting preferably, but invests larger, and production cost is higher than sulfuric acid price.This technique with chlor-alkali production be used for do
Waste Sulfuric Acid produced by eliminating dampness chlorine is primary raw material, is a kind of economic and environment-friendly solution of Waste Sulfuric Acid.Can not only drop simultaneously
Low epsom salt and chlor-alkali production cost, additionally it is possible to environmental protection, improve the utilization rate of resource.
S1600 heating, concentration, filtration step：Filtrate will be obtained after reaction solution heating, concentration, filtering, by institute
State filtrate and adjust pH value to 4 with Waste Sulfuric Acid, add magnesium sulfate crystal seed, crystallized after being cooled to 30 DEG C, obtain magnesium sulfate crystalline solid and
Mother liquor；
The filtrate includes magnesium sulfate.
The magnesium sulfate crystal seed is included to the solid magnesium sulfate added in the filtrate under saturation state.Add magnesium sulfate crystal seed
Have the beneficial effect that：It is the crystallization rate quickening in order that magnesium sulfate to be firstly added crystal seed, so as to improve crystalline rate；Secondly add
Entering crystal seed can reduce the generation of nucleus, make the crystal of precipitation in its superficial growth, reduce crystalline solid quantity so as to reach, increase
The grain diameter of magnesium sulfate.
The mother liquor includes magnesium sulfate.
By the test of many times of inventor, when the PH of reaction solution is 4, transformation efficiency is optimal.
S1800 is separated, drying steps：The magnesium sulfate crystalline solid, the sulfuric acid that centrifugation is gone out are isolated with centrifuge
Magnesium crystalline solid is dried to obtain epsom salt in 50~55 DEG C of downstreams.
Alternatively, an implementation method of the invention, after the S1300 solid-liquid suspensions separating step, S1500
Before magnesium sulfate synthesis step, S1400 cleanings, collection step are further included：The magnesium hydroxide solid is cleaned, collects described
Calcium chloride filtrate.In this step, the magnesium hydroxide solid crude product collected is washed with industry water, further remove and attach
Magnesium hydroxide surface can be dissolved in the inorganic salt of water (such as：Calcium chloride, sodium chloride etc.), to improve the pure of reaction speed and product
Degree.Calcium chloride filtrate is used to produce commodity calcium chloride after collecting, and to reduce the production cost of enterprise, improves the utilization rate of resource.
Alternatively, an implementation method of the invention, after S1600 steps, further includes S1700 disposing mother liquors
Step：The mother liquor that S1600 steps are obtained is collected, and returns it to S1500 magnesium sulfate synthesis steps, for preparing magnesium hydroxide
Filter cake, so can further improve the utilization rate of raw material, reduce production cost, preserve the ecological environment.
Alternatively, an implementation method of the invention, in S1100 steps, by the carbide slag slurries with 80 purposes not
Rust steel mesh is filtered,
The heating-up temperature of the carbide slag slurries after filtering is 80 DEG C.
The heating-up temperature of the carbide slag slurries after filtering is 80 DEG C, to accelerate calcium hydroxide and chlorine in S1200 steps
Change reactive magnesium, improve reaction efficiency.
Alternatively, an implementation method of the invention, in S1200 steps, rubs by content of magnesium chloride in the bittern
Your number is that the amount of liquid of 1.05-1.1 times of calcium hydroxide content molal quantity in the carbide slag slurries is added in the reactor.This
It is that, because calcium hydroxide is slightly soluble in water, if equimolar material is reacted, the complete calcium hydroxide of unreacted is mainly with solid
Form is present, and the magnesium hydroxide of generation is also exist in solid form, and the complete calcium hydroxide of unreacted then cannot be from the hydrogen of generation
Separated in magnesia, and magnesium chloride is water miscible inorganic salts, it is easy to be separated with magnesium hydroxide solid.Institute
With, in order that calcium hydroxide reacts completely, therefore makes magnesium chloride somewhat excessive, so as to after the completion of reaction, there is no hydrogen in system
Calcium oxide is present, it is to avoid brings calcium ion into below operation and produces sulfuric acid calcium impurities.
Alternatively, an implementation method of the invention, in S1200 steps, mixing speed is 20-30r/min.
Verified through test of many times, when mixing speed is 20-30r/min, reaction efficiency is optimal.
Alternatively, an implementation method of the invention, in S1600 steps, the reaction solution is concentrated into molten
Liquid concentration is 30-40 ° of B é, and filtration temperature is 80-85 DEG C.
Baume degrees (° B é) is a kind of method for representing solution concentration.Baume hydrometer immersion is surveyed in solution, is obtained
The number of degrees are Baume degrees.Gravity Baume is in respect of two kinds：One kind is weight table, for measuring the liquid than water weight；Another kind is light table, uses
In the measurement liquid lighter than water.Baume degrees numerical value is larger, convenient reading, so Baume degrees is commonly used in production represents the dense of solution
Degree.
Alternatively, an implementation method of the invention, reactor described in S1100 steps, S1200 steps includes warding off
Porcelain kettle.Enamel still is enamel reaction still, enamel distillation still, the abbreviation of enamel storage still, is reacted also known as enamel tank or enamel
Kettle, enamel still be will contain high silicon dioxide glass, lining steel vessel inner surface, through high temperature sintering securely adherence in
Turn into composite product on metal surface, so, it has the stability of glass and the two-fold advantage of metal strength.Enamel sets
It is standby that there is the premium properties such as acidproof, alkaline-resisting, impact resistance and temperature variation resistant, it is a kind of excellent corrosion resistant apparatus, widely apply
In industry such as chemical industry, oil, medicine, agricultural chemicals, food..Present invention enamel still prepares epsom salt, can effectively improve system
The service life of standby equipment, so as to reduce the production cost of enterprise.
According to another aspect of the present invention, there is provided a kind of epsom salt.
According to the epsom salt preparation method that the present invention is provided, effective environmental protection can be realized, maintaining ecological balance,
The production cost of enterprise is reduced, while the large-scale production of epsom salt can also be realized.The preparation method life that the present invention is provided
Product can produce the epsom salt of high-purity.
Brief description of the drawings
By reading the detailed description of hereafter preferred embodiment, various other advantages and benefit is common for this area
Technical staff will be clear understanding.Accompanying drawing is only used for showing the purpose of preferred embodiment, and is not considered as to the present invention
Limitation.And in whole accompanying drawing, identical part is denoted by the same reference numerals.Wherein in the accompanying drawings, reference numeral
Alphabetic flag afterwards indicates multiple identical parts, when these parts are referred to, will omit its last alphabetic flag.Attached
In figure：
Fig. 1 shows the preparation method of the epsom salt of a preferred embodiment of the invention.
Fig. 2 shows the preparation method of the epsom salt of a preferred embodiment of the invention.And
Fig. 3 shows the technological process of the preparation method of the epsom salt of a preferred embodiment of the invention
Figure.
Specific embodiment
The invention provides many applicable creative concepts, the creative concept can be reflected in a large number of on specific
Hereinafter.Specific embodiment described in following embodiments of the present invention is only as specific embodiment of the invention
Exemplary illustration, and be not meant to limit the scope of the invention.
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Fig. 1 shows the preparation method of the epsom salt of an implementation method of the invention.It is first according to this method
It is introduced into S1100 calcium carbides sludge filter, heating stepses：Carbide slag is configured to carbide slag slurries, the mistake that water content is 70-75%
Filter, will heat after the carbide slag slurries injection reactor after filtering；Enter S1200 magnesium hydroxide synthesis steps afterwards：By chloride containing
The bittern of magnesium injects the reactor, stirring, obtains suspension；Subsequently into S1300 solid-liquid suspension separating steps：Will be described
Suspension is separated, and obtains magnesium hydroxide solid and calcium chloride filtrate；Enter back into S1500 magnesium sulfate synthesis steps：Hydrogen described in press filtration
Magnesia solid, Waste Sulfuric Acid is added in the magnesium hydroxide filter cake obtained after press filtration, until pH value is 5, obtains reaction solution；
Subsequently enter S1600 heating, concentration, filtration step：Filtrate will be obtained after reaction solution heating, concentration, filtering, by institute
State filtrate and adjust pH value to 4 with Waste Sulfuric Acid, add magnesium sulfate crystal seed, crystallized after being cooled to 30 DEG C, obtain magnesium sulfate crystalline solid and
Mother liquor；Finally enter S1800 separation, drying steps：The crystalline solid is isolated with centrifuge, the magnesium sulfate that centrifugation is gone out
Crystalline solid is dried to obtain epsom salt in 50~55 DEG C of downstreams, and the so far preparation of epsom salt is completed.
Preferably as a preferred embodiment of the present invention, after the S1300 solid-liquid suspensions separating step,
Before S1500 magnesium sulfate synthesis steps, S1400 cleanings, collection step are further included：The magnesium hydroxide solid is cleaned, is received
Collect the calcium chloride filtrate.
Preferably as it is of the invention another preferred embodiment, after S1600 steps, further include S1700
Disposing mother liquor step：The mother liquor that S1600 steps are obtained is collected, and returns it to S1500 magnesium sulfate synthesis steps, for preparing
Magnesium hydroxide filter cake.
According to the epsom salt preparation method that the present invention is provided, effective environmental protection can be realized, maintaining ecological balance,
The production cost of enterprise is reduced, while the large-scale production of epsom salt can also be realized.
The preparation method of epsom salt of the present invention is related to parameter more, and processing step is more complicated, therefore specific implementation
Example only as the exemplary illustration of specific implementation of the present invention, without composition limiting the scope of the invention.Below will
The preparation process of the epsom salt provided using the present invention is described further as embodiment.
In addition, in the present invention, step S1100, step S1200, step S1300, step S1500, step S1600, step
During rapid S1800 is to prepare the essential step of epsom salt, and step S1400 and step S1700 add this preparation method,
The epsom salt for preparing the aspect such as is increased in the utilization of resource, environmental protection and yield and obtain carrying to a greater extent
It is high.Therefore it is to design to obtain on the basis of S1400 and S1700 steps are included in the embodiment for designing in the present embodiment
's.
Embodiment 1
Fig. 2 has gone out the preparation method of the epsom salt of an implementation method of the invention.According to this method, first
Into step S1100, carbide slag is configured to the carbide slag slurries, the stainless (steel) wire filtering with 80 mesh that water content is 70%, incited somebody to action
Heated after carbide slag slurries injection enamel still after filter, heating-up temperature is 80 DEG C.Enter step S1200 afterwards, by the bittern
Content of magnesium chloride molal quantity be 1.05 times of calcium hydroxide content molal quantity in the carbide slag slurries amount of liquid add described in ward off
In porcelain kettle, stirred with the speed of 20r/min, obtain suspension.Subsequently into step S1300, the suspension is separated, obtained
Magnesium hydroxide solid and calcium chloride filtrate.Step S1400 is subsequently entered, the magnesium hydroxide solid is cleaned, the chlorination is collected
Calcium filtrate.Step S1500 is entered back into, magnesium hydroxide solid described in press filtration is added in the magnesium hydroxide filter cake obtained after press filtration
Waste Sulfuric Acid, until pH value is 5, obtains reaction solution.Step S1600 is subsequently entered, by reaction solution heating, is reduced to
After 30 ° of B é, filtered at a temperature of 80 DEG C, the filtrate is adjusted into pH value to 4 with Waste Sulfuric Acid, add magnesium sulfate crystal seed, cooling
Crystallized after to 30 DEG C, obtain crystalline solid and mother liquor.Proceed immediately to step S1700：The mother liquor that collection step S1600 is obtained, and
S1500 magnesium sulfate synthesis steps are returned it to, for preparing magnesium hydroxide filter cake.Step S1800 is finally entered, centrifuge is used
The crystalline solid is isolated, the crystalline solid that centrifugation is gone out is dried to obtain epsom salt in 50 DEG C of downstreams.
Embodiment 2
Fig. 2 has gone out the preparation method of the epsom salt of an implementation method of the invention.According to this method, first
Into step S1100, carbide slag is configured to the carbide slag slurries, the stainless (steel) wire filtering with 80 mesh that water content is 75%, incited somebody to action
Heated after carbide slag slurries injection enamel still after filter, heating-up temperature is 80 DEG C.Enter step S1200 afterwards, by the bittern
Content of magnesium chloride molal quantity is that the amount of liquid of 1.1 times of calcium hydroxide content molal quantity in the carbide slag slurries adds the enamel
In kettle, stirred with the speed of 30r/min, obtain suspension.Subsequently into step S1300, the suspension is separated, obtain hydrogen
Magnesia solid and calcium chloride filtrate.Step S1400 is subsequently entered, the magnesium hydroxide solid is cleaned, the calcium chloride is collected
Filtrate.Step S1500 is entered back into, magnesium hydroxide solid described in press filtration is added useless in the magnesium hydroxide filter cake obtained after press filtration
Sulfuric acid, until pH value is 5, obtains reaction solution.Step S1600 is subsequently entered, by reaction solution heating, is reduced to
After 40 ° of B é, filtered at a temperature of 85 DEG C, the filtrate is adjusted into pH value to 4 with Waste Sulfuric Acid, add magnesium sulfate crystal seed, cooling
Crystallized after to 30 DEG C, obtain crystalline solid and mother liquor.Proceed immediately to step S1700：The mother liquor that collection step S1600 is obtained, and
S1500 magnesium sulfate synthesis steps are returned it to, for preparing magnesium hydroxide filter cake.Step S1800 is finally entered, centrifuge is used
The crystalline solid is isolated, the crystalline solid that centrifugation is gone out is dried to obtain epsom salt in 55 DEG C of downstreams.
Embodiment 3
Fig. 2 has gone out the preparation method of the epsom salt of an implementation method of the invention.According to this method, first
Into step S1100, carbide slag is configured to water content and is 72 carbide slag slurries, is filtered with the stainless (steel) wire of 80 mesh, after filtering
Carbide slag slurries injection enamel still after heat, heating-up temperature be 80 DEG C.Enter step S1200 afterwards, by chlorination in the bittern
Content of magnesium molal quantity be 1.05-1.1 times of calcium hydroxide content molal quantity in the carbide slag slurries amount of liquid add described in ward off
In porcelain kettle, stirred with the speed of 22min, obtain suspension.Subsequently into step S1300, the suspension is separated, obtain hydrogen
Magnesia solid and calcium chloride filtrate.Step S1400 is subsequently entered, the magnesium hydroxide solid is cleaned, the calcium chloride is collected
Filtrate.Step S1500 is entered back into, magnesium hydroxide solid described in press filtration is added useless in the magnesium hydroxide filter cake obtained after press filtration
Sulfuric acid, until pH value is 5, obtains reaction solution.Step S1600 is subsequently entered, by reaction solution heating, is reduced to
After 35 ° of B é, filtered at a temperature of 83 DEG C, the filtrate is adjusted into pH value to 4 with Waste Sulfuric Acid, add magnesium sulfate crystal seed, cooling
Crystallized after to 30 DEG C, obtain crystalline solid and mother liquor.Proceed immediately to step S1700：The mother liquor that collection step S1600 is obtained, and
S1500 magnesium sulfate synthesis steps are returned it to, for preparing magnesium hydroxide filter cake.Step S1800 is finally entered, centrifuge is used
The crystalline solid is isolated, the crystalline solid that centrifugation is gone out is dried to obtain epsom salt in 51 DEG C of downstreams.
Embodiment 4
Fig. 2 has gone out the preparation method of the epsom salt of an implementation method of the invention.According to this method, first
Into step S1100, carbide slag is configured to the carbide slag slurries, the stainless (steel) wire filtering with 80 mesh that water content is 74%, incited somebody to action
Heated after carbide slag slurries injection enamel still after filter, heating-up temperature is 80 DEG C.Enter step S1200 afterwards, by the bittern
Content of magnesium chloride molal quantity be 1.03 times of calcium hydroxide content molal quantity in the carbide slag slurries amount of liquid add described in ward off
In porcelain kettle, stirred with the speed of 25r/min, obtain suspension.Subsequently into step S1300, the suspension is separated, obtained
Magnesium hydroxide solid and calcium chloride filtrate.Step S1400 is subsequently entered, the magnesium hydroxide solid is cleaned, the chlorination is collected
Calcium filtrate.Step S1500 is entered back into, magnesium hydroxide solid described in press filtration is added in the magnesium hydroxide filter cake obtained after press filtration
Waste Sulfuric Acid, until pH value is 5, obtains reaction solution.Step S1600 is subsequently entered, by reaction solution heating, is reduced to
After 33 ° of B é, filtered at a temperature of 85 DEG C, the filtrate is adjusted into pH value to 4 with Waste Sulfuric Acid, add magnesium sulfate crystal seed, cooling
Crystallized after to 30 DEG C, obtain crystalline solid and mother liquor.Proceed immediately to step S1700：The mother liquor that collection step S1600 is obtained, and
S1500 magnesium sulfate synthesis steps are returned it to, for preparing magnesium hydroxide filter cake.Step S1800 is finally entered, centrifuge is used
The crystalline solid is isolated, the crystalline solid that centrifugation is gone out is dried to obtain epsom salt in 55 DEG C of downstreams.
According to embodiment 1 to 4 in effective environmental protection, protecting ecology balance reduces the premise of the production cost of enterprise
Under prepared epsom salt, realize the large-scale production of the epsom salt of higher degree.Specifically, due to hardship used
It is low compared with iron content in magnesia in halogen, so iron (Fe) content in product is also compared with 0.005 requirement in HG/T2680-95 standards
Low, its content is below 0.002%.
Because reaction product Adlerika has carried out filter filtering, and the such as oxidation brought into carbide slag slurries
Calcium, silica, alundum (Al2O3) equal size have filter mistake also far below content in magnesia during the production of centre
Filter step.So the water insoluble matter content in product is also below 0.10% in national standard HG/T2680-95, site-test analysis
Within 0.05%.
For 1 ton of magnesium sulfate often being produced in magnesia production magnesium sulfate technique and need to consume 0.51 ton of dilute sulfuric acid, this
The dilute sulfuric acid that technique is consumed is 0.498 ton, therefore is converted to if magnesium sulfate earning rate than the magnesium sulfate in magnesia technique
Earning rate improves 2.4%.
The preparation method that the present invention is provided is further explained below：
The raw material that this technique is utilized mainly has calcium carbide to hydrolyze the carbide slag slurries produced and discarded after acetylene gas, in chlor-alkali production
For drying the Waste Sulfuric Acid produced by moist chlorine, the bittern containing magnesium chloride and a small amount of sodium chloride after potassium chloride, sodium chloride is extracted
Deng.These raw materials belong to chemical industry waste, directly outer row are not allowed, it is necessary to recycle, or carry out corresponding environmental protection treatment, but
Treatment or cost recovery are higher, and economic worth is relatively low.
Calcium carbide is starched or the main methods of carbide slag are baked to 3%~5% (butt) using flue gas, is being used for
Production cement, or be used to produce soda ash instead of lime, the method needs to consume a large amount of coals or natural gas resource, and requires factory
Nearby there are large-scale cement or soda ash enterprise.The carbide slag slurries that this technique is discarded after producing acetylene gas with calcium carbide hydrolysis are as main former
Material, can have found new outlet for carbide slag slurries treatment.
The bittern containing magnesium chloride and sodium chloride after potassium chloride, sodium chloride is extracted, can be used to produce anhydrous magnesium chloride, oxidation
Magnesium, cement etc., but chloride bittern salt pan is most positioned at Gobi desert barren beach, and the demand of neighboring markets magnesium chloride is limited, it is impossible to digest
Bittern by-product of magnesium chloride；Magnesium sulfate demand is much larger than magnesium chloride with price.This technique after extracting potassium chloride, sodium chloride containing
The bittern of magnesium chloride and sodium chloride is primary raw material, is a kind of new technology that magnesium chloride adds deeply.
It is used to dry the Waste Sulfuric Acid produced by moist chlorine in chlor-alkali production directly outer to arrange, it is necessary to do environmental protection treatment, mesh
Preceding domestic common processing method is that, for producing gypsum, the price of gypsum is relatively low, and consumption is few；More environmentally friendly processing method is also
There is alkylation sulfuric acid through methods such as Pintsch process production sulfuric acid, this technique can effectively process Waste Sulfuric Acid, environment protecting preferably, but is thrown
Money is larger, and production cost is higher than sulfuric acid price.This technique is to be used for the Waste Sulfuric Acid for drying produced by moist chlorine in chlor-alkali production
Primary raw material, is a kind of economic and environment-friendly solution of Waste Sulfuric Acid.
This technique is contained after carbide slag slurries, extraction potassium chloride, the sodium chloride discarded after acetylene gas are produced using calcium carbide hydrolysis
Have in bittern, the chlor-alkali production of magnesium chloride and sodium chloride for drying the Waste Sulfuric Acid produced by moist chlorine to produce seven water sulfuric acid
Magnesium.Specific steps are as shown in Figure 3：
1. the filtering of carbide slag slurries is water content is configured to by the carbide slag that water content after plate compression is 50%
70% carbide slag slurries, are filtered with the stainless (steel) wire of 80 mesh, and tiny ferro-silicon slag, lime stone are contained in removing carbide slag slurries
With other impurity.
2. the quantity the carbide slag slurries after filtering on request is squeezed into enamel still, and the reality for analyzing calcium hydroxide contains
Amount, and it is warming up to 80 DEG C.
3. press that content of magnesium chloride molal quantity in bittern is calcium hydroxide content molal quantity in carbide slag slurries 1.05-1.1 times
Amount of liquid also add in enamel still, keep reaction temperature still be 80 DEG C, and rotating speed for 20-30r/min agitation under carry out
The reaction of generation magnesium hydroxide and calcium chloride, visual response termination when in question response system substantially without calcium hydroxide slurry.This step
Chemical equation be：
Ca(HO)2+ 2MgCL=Mg (HO)2+2CaCL
4. the suspension after this reaction termination is carried out into separation of solid and liquid with plate and frame filter press, the magnesium hydroxide solid collected
Crude product is washed with industry water, is further removed and is attached the inorganic salt that can be dissolved in water on magnesium hydroxide surface (such as：Chlorination
Calcium, sodium chloride etc.).Calcium chloride filtrate is used to produce commodity calcium chloride after collecting.
5. the magnesium hydroxide solid after washing is carried out into press filtration again, the magnesium hydroxide filter cake and mother liquor after press filtration are put into band
Have in the enamel still of stirring, addition content is about 80% Waste Sulfuric Acid successively, it is 5 to control pH value.The chemical reaction equation of this step
Formula is：
Mg(HO)2+H2SO4+5H2O=MgSO4·7H2O
After reaction terminates, reaction solution heating is concentrated in vacuo, is concentrated into solution concentration for 30~40 ° of B é, concentrate
Filtered at 80 DEG C, filtrate adjusts pH value to 4 with Waste Sulfuric Acid, added a certain amount of magnesium sulfate crystal seed, tied after being cooled to 30 DEG C
It is brilliant.
Crystalline solid is isolated with centrifuge, mother liquor returns to magnesium hydroxide filter cake preparation steps.
The crystallization that centrifugation is gone out is dried to obtain epsom salt in 50~55 DEG C of downstreams.
The innovative point of the preparation method that the present invention is provided is also resided in：Due to the purposes not only very wide but also consumption of magnesium sulfate
It is larger, use vapor phase method preparing magnesium sulfate after sulfur dioxide with magnesium hydroxide water slurry removing fire coal, although with preferable
Economic benefit, but by the resource constraint of total sulfur dioxide in removing fire coal, the magnesium sulfate total amount of production is also relatively limited.With
Sulfuric acid and magnesia preparing magnesium sulfate are although relatively inexpensive, but are soaked by sulfuric acid after producing the magnesia extracted in magnesia
Acidified soil discarded object, cause new pollution sources.
As recycling economy is continued to develop, circular economy industrial lattice chain is also being gradually formed and perfect, and this is given in industry
" the eating dry bleeding ", " turning waste into wealth " of resource is provided into basic basis as far as possible in chain, is also to different branch in industrial chain
" three wastes " comprehensive reutilization that chain is each produced is created superior not only in technical feasibility in economic benefit
Condition.Because the raw material selected by the technology is the very big waste residue and waste liquid of yield, effective recovery of Waste Sulfuric Acid
It is larger using difficulty, and above-mentioned discarded object simultaneously can be present in potash production industrial chain in, therefore, using the technique skill
Art, can not only reduce the generation of a certain amount of discarded object, the completely problem of neutralizing treatment Waste Sulfuric Acid, moreover it is possible to using discarded pollution
Thing come produce the very big basic chemical industry of widely used, usage amount, medicine and fertilizer material, realize the place that can both save discarded object
Put expense, moreover it is possible to increase the new benefit produced produced by product, this is that other epsom salt production technologies are incomparable.
One will be made to various data below to contrast：
First, mass balance and raw and auxiliary material are contrasted
1st, mass balance of the present utility model
Account selection of datum 1t epsom salts (MgSO4·7H2O) product is adjusted, and raw material chooses solid calcium hydroxide
Content be 40%~60% waste carbide slag (wherein butt containing calcium hydroxide be 96.30%), sulfuric acid content be 75%~
80% Waste Sulfuric Acid and content of magnesium chloride is about 200g/l bitterns as accounting foundation.Institute is calculated thus according to reaction equation
Need magnesium hydroxide and sulfuric acid consumption as follows：
Mg(OH)2+H2SO4+5H2O→MgSO4·7H2O
58 98 90 246
X Y Z 1
According to can be calculated：
X=58/246=0.236t Y=98/246=0.398t Z=90/246=0.366t
It is Waste Sulfuric Acid because what is used in this technique, wherein sulfuric acid content is 75~80%, it is required if being calculated by 80%
Spent acid amount is：
Consumption spent acid amount：0.398/0.8=0.498t
Magnesium chloride is calculated according to reaction equation as follows with the consumption of calcium hydroxide：
MgCL2+Ca(OH)2→Mg(OH)2+CaCL2
95 74 58 111
X2 Y2 0.236 Z
According to can be calculated：
X2=95 × 0.236/58=0.387t Y2=74 × 0.236/58=0.30t
Z=111 × 0.236/58=0.45t
The content of magnesium chloride is 200g/L in the bittern used by this time, thus can calculate 1 ton of epsom salt institute of production
The bittern amount is needed to be：
VBittern=0.387/200 × 1000=1.94m3
Because of carbide slag butt (OH) containing Ca for being used2It is 96.30%, thus can calculates 1 ton of epsom salt institute of production
The carbide slag butt amount is needed to be：
MCarbide slag butt=0.30/0.963=0.312t
By calcium hydroxide content 40%~60% in carbide slag, calculated by 50%, then can draw the consumed calcium carbide quantity of slag
For：
MCarbide slag=0.312/0.5=0.624t
According to chemical industry standard HG/T 2680-95, industrial epsom salt should meet table 1 and require：
The industrial epsom salt (m/m) of table 1
2nd, raw and auxiliary material contrast
Accounted with this process stream according to chemical industry standard HG/T 2680-95, the water sulphur of 1 ton of industry of this technique productions seven
The amount of sour magnesium consumption discarded object is as shown in table 2：
2, table, 1 ton of technique productions industry epsom salt consumes the amount of discarded object
| Title | Consumption |
| Carbide slag | 0.624t |
| Waste Sulfuric Acid (80%) | 0.498t |
| Bittern |
By taking sulfuric acid process as an example：
According to chemical industry standard HG/T 2680-95, the industrial epsom salt consumption of raw material of 1 ton of Production By Sulfuric Acid Process
Amount is as shown in table 3：
The industrial epsom salt of 1 ton of 3 Production By Sulfuric Acid Process of table consumes the amount of discarded object
| Title | Consumption |
| Magnesia | 0.23t |
| Dilute sulfuric acid (80%) | 0.51t |
Contrast conclusion：Production By Sulfuric Acid Process need to be by diluting concentrated sulfuric acid, while bring a large amount of impurity in magnesia into (containing in magnesite
Have point：The impurity such as calcium oxide, silica, di-iron trioxide, alundum (Al2O3)), it is to avoid produce some solid waste.
This technique is using spent acid, useless bittern production, it is not necessary to dilute sulphuric acid, reduces sulfuric acid consumption.
2nd, energy ezpenditure contrast
By taking sulfuric acid process as an example：
By taking Liaoning Mei Kuang companies Haicheng City magnesium ore deposit production magnesite as an example, its group will constitute and be：MgO：46.56%, CaO：
0.74%；Magnesium carbonate need to be converted into magnesia (magnesia) by material magnesite high-temperature calcination (800~1000 DEG C or so), forged
Burning needs to consume substantial amounts of heat.
, it is necessary to 0.23 ton of magnesia, the heat waste rate of magnesite is 51%, then need water chestnut in terms of producing 1 ton of epsom salt
Magnesium ore deposit is：
MMagnesite=0.23/0.51=0.45 tons
It is known：Calcium carbonate specific heat capacity c：(J/(g·℃))：0.836~0.8951 (0~100 DEG C), the hot Δ of Decomposition of Calcium Carbonate
H:(because the place of production of magnesite is different, composition difference is larger, therefore does not find accurate specific heat capacity and decomposition heat number for -178.5kJ/mol
According to because sodium carbonate is close with magnesium carbonate property, therefore temporarily with the calculating of sodium carbonate data), heating-up temperature t：850 DEG C, calcination time h：3
Hour, heat waste is about 5% per hour, then can calculate：
Q1 life warmThe ≈ 332300kJ of=cm Δ t ≈ 0.8951 × 450 × 825
Q2 losses=Q1 life warm*h*0.05≈332300×0.05×3≈49845kJ
Q3 calcining heatThe ≈ 934983kJ of=m/M* Δ H ≈ 0.4656 × 0.45 × 178.5 × 1000000/40
QBlock is heated=Q1 life warm+Q2 losses+Q3 calcining heat≈332300kJ+49845kJ+934983kJ≈1317128kJ
This new technology production process is low-temperature operation, it is not necessary to additional energy, therefore compares with Production By Sulfuric Acid Process magnesium sulfate,
Energy 1317128kJ can about be saved.
It is worth noting that, the various equipment mentioned by the present invention not only include what prior art was provided, also including future
What technology was provided.Not specifically mentioned technological parameter is prior art in the present invention.
It should be noted that above-described embodiment the present invention will be described rather than limiting the invention, and this
Art personnel can design alternative embodiment without departing from the scope of the appended claims.In claim
In, any reference symbol being located between bracket should not be configured to limitations on claims.Word "comprising" is not excluded for depositing
In element or step not listed in the claims.Word "a" or "an" before element do not exclude the presence of it is multiple this
The element of sample.The use of word first, second, and third does not indicate that any order.These words can be construed to title.
Claims (5)
1. a kind of preparation method of epsom salt, comprises the following steps：
S1100 calcium carbides sludge filter, heating stepses：Carbide slag is configured to the carbide slag slurries, filtering that water content is 70-75%,
Heated after carbide slag slurries injection reactor after by filtering；
S1200 magnesium hydroxide synthesis steps：The bittern of magnesium chloride containing is injected into the reactor, stirring, suspension is obtained,
By the 1.05-1.1 that content of magnesium chloride molal quantity in the bittern is calcium hydroxide content molal quantity in the carbide slag slurries
Amount of liquid again is added in the reactor,
The bittern includes extracting the bittern containing magnesium chloride and sodium chloride after potassium chloride, sodium chloride；
S1300 solid-liquid suspension separating steps：The suspension is separated, magnesium hydroxide solid and calcium chloride filtrate is obtained；
S1400 cleanings, collection step：The magnesium hydroxide solid is cleaned, the calcium chloride filtrate is collected；
S1500 magnesium sulfate synthesis steps：Magnesium hydroxide solid described in press filtration, adds in the magnesium hydroxide filter cake obtained after press filtration
Waste Sulfuric Acid, until pH value is 5, obtains reaction solution；
S1600 heating, concentration, filtration step：Filtrate will be obtained after reaction solution heating, concentration, filtering, by the filter
Liquid adjusts pH value to 4 with Waste Sulfuric Acid, adds magnesium sulfate crystal seed, is crystallized after being cooled to 30 DEG C, obtains magnesium sulfate crystalline solid and mother liquor,
Wherein, the Waste Sulfuric Acid is used to dry the Waste Sulfuric Acid produced by moist chlorine in being selected from chlor-alkali production；
S1700 disposing mother liquor steps：The mother liquor that S1600 steps are obtained is collected, and returns it to S1500 magnesium sulfate synthesis step
Suddenly, for preparing the reaction solution；
S1800 is separated, drying steps：The magnesium sulfate crystalline solid is isolated with centrifuge, the sulfuric acid that centrifugation is gone out
Magnesium crystalline solid is dried to obtain epsom salt in 50~55 DEG C of downstreams.
2. the carbide slag slurries in S1100 steps, are used 80 by the preparation method of epsom salt according to claim 1
Purpose stainless (steel) wire is filtered,
The heating-up temperature of the carbide slag slurries after filtering is 80 DEG C.
3. the preparation method of epsom salt according to claim 1, in S1200 steps, mixing speed is 20-30r/
min。
4. the preparation method of epsom salt according to claim 1, dense by the reaction solution in S1600 steps
Solution concentration is reduced to for 30~40 ° of B é,
Filtration temperature is 80-85 DEG C.
5. the preparation method of the epsom salt according to any one in claim 1-4, S1100 steps, S1200 steps
Described in reactor include enamel still.
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