CN101736404B - Co-production method of calcium sulfate whisker and phosphoric acid - Google Patents
Co-production method of calcium sulfate whisker and phosphoric acid Download PDFInfo
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- CN101736404B CN101736404B CN2010100281596A CN201010028159A CN101736404B CN 101736404 B CN101736404 B CN 101736404B CN 2010100281596 A CN2010100281596 A CN 2010100281596A CN 201010028159 A CN201010028159 A CN 201010028159A CN 101736404 B CN101736404 B CN 101736404B
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Abstract
The invention relates to a co-production method of calcium sulfate whisker and phosphoric acid. The method comprises the following technical steps of: (1) acid-hydrolyzing phosphate rock powder by hydrochloric acid with the mass concentration of 15 to 26% or nitric acid with the mass concentration of 20 to 90%, filtering the acid-hydrolyzed slurry into the acid hydrolysis solution containing Ca2<+>; (2) using the acid hydrolysis solution containing Ca2<+> and the sulfuric acid with the mass concentration of 20 to 90% as the raw materials, wherein the use level of the sulfuric acid is 100% of the needed theoretical amount of the sulfuric acid when the Ca2<+> in the acid hydrolysis solution and the sulfuric acid react completely, adding the sulfuric acid to the acid hydrolysis solution containing Ca<2+> under the stirring condition, reacting the sulfuric acid with the acid hydrolysis solution containing Ca2<+> at the normal pressure and at 50 to 90 DEG, filtering and separating the calcium sulfate whisker after the reaction is finished, and then washing and drying the calcium sulfate whisker; and (3) carrying out the counter-current extraction on the filtrate obtained in the step (2), wherein the extracted water phase is the phosphoric acid, and acid-hydrolyzing the phosphate rock powder by using the hydrochloric acid obtained by the counter-extraction of the soft water to the extracted organic phase which is separated in the counter-current extraction.
Description
Technical field
The invention belongs to the manufacturing technology field of calcium sulfate crystal whiskers and phosphoric acid by wet process, relate to a kind of method of producing calcium sulfate crystal whiskers and phosphoric acid simultaneously.
Background technology
Calcium sulfate crystal whiskers is a kind of novel material that has development potentiality, has intensity height, good toughness, premium properties such as high temperature resistant and corrosion-resistant.According to the length and the diameter of calcium sulfate crystal whiskers, can be divided into three types of short whisker, middle long whisker and long whiskers.Short diameter of whiskers is generally 0.1～4 μ m, and length is 5～300 μ m, is mainly used in industries such as rubber, plastics, coating, sticker; Middle long whisker length is mainly used in papermaking and paper product industries between 0.3～3.0mm; Long whisker length is mainly used in the demanding industry of staple length, like insulation, health care, weaving etc. greater than 3.0mm.
At present, the main working method of calcium sulfate crystal whiskers is a hydrothermal method, but there is following problem in hydrothermal method: under high temperature or high pressure, produce, energy consumption is big, and is high to equipment requirements; Raw material impurity content is many, needs purification and impurity removal, complex process, and production cost is high; The calcium sulfate crystal whiskers that makes can not satisfy the industry that length-to-diameter ratio is had relatively high expectations.
The patent No. is that the Chinese patent of ZL 200410024348.0 discloses a kind of method of in phosphoric acid, making crystal whisker of gypsum; Said method is with excessive concentration 30～40% phosphorolytic cleavage phosphorus ores; Obtain the phosphoric acid leaching liquid, the phosphoric acid leaching liquid is joined in the sulphuric acid soln of concentration 30～35% produce crystal whisker of gypsum again.Not enough below this method exists: 1, at CaO-P
2O
5-H
2In the O system; The concentration of CaO≤5% (see " phosphatic production and application ", chief editor Chen Jiafu, Tan Guang smokes; Press of Chengdu Univ. of Science & Technology; And phosphoric acid is excessive and the phosphoric acid leaching liquid joined gradually in 30～35% the sulphuric acid soln during decomposing phosphate rock, also can reduce Ca in the suspension-s 116 pages of Fig. 8-4.),
2+Concentration, and Ca
2+Content is low excessively, is unfavorable for the whisker growth, thereby influences the pattern of calcium sulfate crystal whiskers, is difficult to obtain the bigger whisker of length-to-diameter ratio (whisker length of the said method preparation of this patent belongs to short whisker at 30～200 μ m, and range of application is restricted); 2, phosphoric acid concentration is big, though can increase phosphorus ore resolution ratio, also can increase HPO
4 2-Replace SO in the lattice
4 2-Tendency, simultaneously the viscosity of solution can corresponding increase, causes crystallization condition to worsen, and adds to the difficulties for follow-up filter operation; 3, will reach higher phosphorus ore resolution ratio, the round-robin phosphoric acid amount is very big, needs pump to carry, and increases power consumption, also can require bigger reactor drum, increases facility investment, thereby has also strengthened production cost.
The patent No. is the preparation method that the Chinese patent of ZL 200710065806.9 discloses a kind of calcium sulfate crystal whiskers and phosphoric acid; This method comprises phosphorus ore decomposition, slurry filtration separation, calcium sulfate crystal whiskers preparation and separation, washing, drying course, in the phosphorus ore decomposition course, adds P
2O
5The phosphoric acid of concentration 18～35% and composite additive first (the composite additive first is made up of humic acid and zeyssatite) add composite additive second (composite additive second is made up of sodium laurylsulfonate and the vitriol or the phosphoric acid salt that contain magnesium, aluminium) in the calcium sulfate crystal whiskers crystallisation process.Though add the rate of decomposition that the composite additive first can improve phosphorus ore,, still be CaO-P because phosphorus ore decomposes though add the crystal formation that composite additive second can be regulated calcium sulfate crystal whiskers
2O
5-H
2The O system; The problem that ZL 200410024348.0 patents exist can not fundamentally solve; Composite additive second is many-sided to the influence of crystal of calcium sulfate, and the reaction solution composition is different, and the additive capacity of required adding is also different; General optimum quantum of utilization need be definite through experiment, and contain Mg in the phosphoric acid leaching liquid
2+, Al
3+, Fe
2+Deng impurity, the existence of these impurity is also influential to the usage quantity of additive, so the bad control of the usage quantity of additive wants to obtain ideal whisker shape and size through additive and has any problem.The shape and size of ZL 200710065806.9 and unexposed prepared calcium sulfate crystal whiskers can't be checked the Application of Additives effect.In addition, adding additive also can increase cost and make complex process.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, the co-production method of a kind of calcium sulfate crystal whiskers and phosphoric acid is provided, this kind method can not only improve Ca in the acid hydrolysis solution
2+Concentration, obtain dissimilar calcium sulfate crystal whiskers and phosphoric acid, and technology is simple, environmental protection and energy saving.
Technical scheme of the present invention: obtain containing Ca with hydrochloric acid or nitric acid decomposing phosphate rock
2+Acid hydrolysis solution is again to containing Ca
2+The gas washing in SA production phosphoric acid co-producing sulfuric acid calcium pyroborate that adds mass concentration 20～90% in the acid hydrolysis solution.
The present invention meets following chemical principle
Ca
10(PO
4)
6F
2+20HCl→10CaCl
2+6H
3PO
4+2HF↑
Ca
10(PO
4)
6F
2+20HNO
3→10Ca(NO
3)
2+6H
3PO
4+2HF↑
The co-production method of calcium sulfate crystal whiskers according to the invention and phosphoric acid, process step is following:
(1) acidolysis of ground phosphate rock
With ground phosphate rock with the hydrochloric acid of mass concentration 15～26% or the nitric acid solution of mass concentration 30～54%; The consumption of said hydrochloric acid or nitric acid is: when CaO in the ground phosphate rock and hydrochloric acid or nitric acid complete reaction 100～130% of required hydrochloric acid or nitric acid theoretical amount, the slip after the ground phosphate rock acidolysis obtains through filtration and contains Ca
2+Acid hydrolysis solution;
(2) Preparation methods of gypsum whiskers
Obtained with step (1) and to be contained Ca
2+Acid hydrolysis solution and mass concentration 20～90% sulfuric acid be raw material, the vitriolic consumption is: the Ca in the acid hydrolysis solution
2+During with the sulfuric acid complete reaction 100% of required sulfuric acid theoretical amount, under agitation said sulfuric acid is joined and contain Ca
2+Acid hydrolysis solution in; React in normal pressure, 50～90 ℃, hydrochloric acid vapour that volatilizes in the reaction process or nitric acid vapor are back to (said water coolant is tap water or process water, and its temperature is room temperature or is lower than room temperature) in the reaction slurry with water quench; Reaction times was at least 1.5 hours; After reaction finishes, isolate calcium sulfate crystal whiskers, then obtaining calcium sulfate crystal whiskers is washed with dry through filtering;
(3) preparation of phosphoric acid
Carry out counter-current extraction with filtering institute's obtain filtrate in the step (2), the surplus water that comes together is phosphoric acid, the volume ratio of said filtrating and extraction agent=1: 1～5: 1,20～60 ℃ of extraction temperature, 5～60 minutes residence time of extraction.
Isolated extracted organic phase was carried out countercurrent reextraction with soft water and can be obtained hydrochloric acid or nitric acid when said filtrating was carried out counter-current extraction; Obtaining hydrochloric acid or nitric acid are used for the technical process that the acidolysis of ground phosphate rock can form an environmental protection, improve resource utilization; During back extraction; Extracted organic phase and soft volume ratio=0.5: 1～5: 1,20～60 ℃ of back extraction temperature, 5～60 minutes residence time of washing.
Aforesaid method, said ground phosphate rock can adopt the mid low grade phosphate rock powder of particle diameter≤1165 μ m.
In the aforesaid method, preferred following technological operation and processing parameter:
When 1, ground phosphate rock being carried out acidolysis with the hydrochloric acid of mass concentration 15～26%; At first said hydrochloric acid is joined in the reaction vessel; Under agitation in hydrochloric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, room temperature, and the time was at least 0.5 hour; Ground phosphate rock during with the nitric acid solution of mass concentration 30～54%, is at first joined said nitric acid in the reaction vessel, under agitation in nitric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, 30～50 ℃, and the time was at least 0.5 hour.
2, the washing of said calcium sulfate crystal whiskers is washed with zero(ppm) water, industrial spirit successively, and washing times is at least 2 times.
When 3, the middle filtration of step (2) institute obtain filtrate being carried out counter-current extraction, extraction agent is made up of trioctylamine and n-Octanol, the volume ratio of trioctylamine and n-Octanol=2: 1～5: 1.
Room temperature in the method for the invention is meant indoor natural temperature.
The present invention has following beneficial effect:
1, since the method for the invention with ground phosphate rock with the hydrochloric acid of mass concentration 15～26% or the nitric acid solution of mass concentration 30～54%, thereby improved Ca in the acid hydrolysis solution
2+Content, for whisker growth provides advantageous conditions.
2, adopt the method for the invention, can obtain the calcium sulfate crystal whiskers of dissimilar (or specifications), help enlarging the range of application of calcium sulfate crystal whiskers.
3, because hydrochloric acidolysis ground phosphate rock carries out under normal pressure, room temperature, nitric acid solution ground phosphate rock carries out under normal pressure, 30～50 ℃, helps save energy.
4, the method for the invention can realize non-pollutant discharge, and improves resource utilization, is a kind of environmental protection, saving type technology.
5, the method for the invention both can obtain phosphoric acid, can obtain the calcium sulfate crystal whiskers of dissimilar (or specifications) again, had tangible economic benefit and social benefit.
Description of drawings
Fig. 1 is the process flow sheet of the co-production method of calcium sulfate crystal whiskers according to the invention and phosphoric acid;
Fig. 2 is the shape appearance figure of calcium sulfate crystal whiskers under electron microscope of embodiment 1 preparation;
Fig. 3 is the shape appearance figure of calcium sulfate crystal whiskers under electron microscope of embodiment 4 preparations;
Fig. 4 is the shape appearance figure of calcium sulfate crystal whiskers under electron microscope of embodiment 7 preparations.
Embodiment
Through embodiment the co-production method of calcium sulfate crystal whiskers according to the invention and phosphoric acid is described further below.Below among each embodiment, the used reaction vessel of calcium sulfate crystal whiskers preparation process is the band whipping appts and is provided with the container of two mouths at least, the grade of raw material Rock Phosphate (72Min BPL) is seen table 1, the particle diameter of ground phosphate rock≤1165 μ m.
Table 1: the grade of Rock Phosphate (72Min BPL)
| P 2O 5 | CaO | Fe 2O 3 | MgO | Al 2O 3 | Cl | Acid non-soluble substance |
| 23.5～24％ | 46～47％ | 0.9～1.3％ | 0.3～0.7％ | 0.3～0.6％ | 0.6～2％ | 14～16％ |
Annotate: in the table 1, said percentage ratio is mass percent
Embodiment 1
The process step of present embodiment is following:
(1) acidolysis of ground phosphate rock
With hydrochloric acid (the analytical pure hydrochloric acid preparation) acidolysis of ground phosphate rock with mass concentration 15%, the content of CaO is by 46% in the ground phosphate rock, and the hydrochloric acid consumption is: when CaO in the ground phosphate rock and hydrochloric acid complete reaction 130% of required hydrochloric acid theoretical amount; At first said hydrochloric acid is joined in the reaction vessel; Under agitation in hydrochloric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, room temperature (26 ℃), and the time is 2 hours; Reaction after finishing is left standstill reaction slurry to layering, obtains through suction filtration then to contain Ca
2+Acid hydrolysis solution, get acid hydrolysis solution and detect, record Ca in the acid hydrolysis solution
2+Content be 5.70% (mass percent).
(2) Preparation methods of gypsum whiskers
Obtained with step (1) and to be contained Ca
2+Acid hydrolysis solution and the sulfuric acid of mass concentration 20% be raw material, the vitriolic consumption is: the Ca in the acid hydrolysis solution
2+During with the sulfuric acid complete reaction 100% of required sulfuric acid theoretical amount; The Ca that contains with step (1) preparation
2+Acid hydrolysis solution add reaction vessel; A mouth that under agitation passes through said reaction vessel then adds sulfuric acid; Another mouth through said reaction vessel connects prolong, the tap water that the logical temperature of prolong outer tube is a room temperature (26 ℃) with the hydrochloric acid vapour cooling for reflux that volatilizes in the reaction process in reaction slurry, stirring velocity 250r/min; 50 ℃ of temperature of reaction, 1.5 hours reaction times; Reaction finishes after filter to isolate calcium sulfate crystal whiskers; And with isolated calcium sulfate crystal whiskers successively with distilled water wash 2 times, industrial spirit washing 2 times; Remove surface-moisture 80 ℃ of dryings 60 minutes then, the whisker of the acquisition fine acicular that is white in color, long 20～40 μ m; Diameter 2～5 μ m, its pattern under electron microscope is seen Fig. 2.
(3) preparation of phosphoric acid
Carry out the extraction of 5 stage countercurrents with filtering institute's obtain filtrate in the step (2); Extraction agent is made up of trioctylamine and n-Octanol; The volume ratio of trioctylamine and n-Octanol=2: 1, the volume ratio of said filtrating and extraction agent=1: 1,20 ℃ of extraction temperature; 5 minutes residence time of extraction, the surplus water that comes together is phosphoric acid aftertreatments such as (can concentrate as required or) removal of impurities; The isolated extracted organic phase of counter-current extraction is carried out 5 stage countercurrent back extractions with soft water, extracted organic phase and soft volume ratio=and 0.5: 1,20 ℃ of back extraction temperature, 5 minutes residence time of washing, hydrochloric acid that back extraction obtains is used for the acidolysis of ground phosphate rock.
Embodiment 2
The process step of present embodiment is following:
(1) acidolysis of ground phosphate rock
With hydrochloric acid (the analytical pure hydrochloric acid preparation) acidolysis of ground phosphate rock with mass concentration 21%, the content of CaO is by 46% in the ground phosphate rock, and the hydrochloric acid consumption is: when CaO in the ground phosphate rock and hydrochloric acid complete reaction 110% of required hydrochloric acid theoretical amount; At first said hydrochloric acid is joined in the reaction vessel; Under agitation in hydrochloric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, room temperature (28 ℃), and the time is 1 hour; Reaction after finishing is left standstill reaction slurry to layering, obtains through suction filtration then to contain Ca
2+Acid hydrolysis solution, get acid hydrolysis solution and detect, record Ca in the acid hydrolysis solution
2+Content be 7.83% (mass percent).
(2) Preparation methods of gypsum whiskers
Obtained with step (1) and to be contained Ca
2+Acid hydrolysis solution and the sulfuric acid of mass concentration 50% be raw material, the vitriolic consumption is: the Ca in the acid hydrolysis solution
2+During with the sulfuric acid complete reaction 100% of required sulfuric acid theoretical amount; The Ca that contains with step (1) preparation
2+Acid hydrolysis solution add reaction vessel; A mouth that under agitation passes through said reaction vessel then adds sulfuric acid; Another mouth through said reaction vessel connects prolong, the tap water that the logical temperature of prolong outer tube is a room temperature (28 ℃) with the hydrochloric acid vapour cooling for reflux that volatilizes in the reaction process in reaction slurry, stirring velocity 300r/min; 60 ℃ of temperature of reaction, 2 hours reaction times; Reaction finishes after filter to isolate calcium sulfate crystal whiskers; And with isolated calcium sulfate crystal whiskers successively with distilled water wash 3 times, industrial spirit washing 3 times; Removed surface-moisture in 60 minutes 80 ℃ of dryings then; The whisker that the obtains fine acicular that is white in color is observed calcium sulfate crystal whiskers: grow 150～300 μ m, diameter 5～10 μ m under electron microscope.
(3) preparation of phosphoric acid
Carry out the extraction of 3 stage countercurrents with filtering institute's obtain filtrate in the step (2); Extraction agent is made up of trioctylamine and n-Octanol; The volume ratio of trioctylamine and n-Octanol=3: 1, the volume ratio of said filtrating and extraction agent=3: 1,40 ℃ of extraction temperature; 20 minutes residence time of extraction, the surplus water that comes together is phosphoric acid aftertreatments such as (can concentrate as required or) removal of impurities; The isolated extracted organic phase of counter-current extraction is carried out 3 stage countercurrent back extractions with soft water, extracted organic phase and soft volume ratio=and 3: 1,30 ℃ of back extraction temperature, 20 minutes residence time of washing, hydrochloric acid that back extraction obtains is used for the acidolysis of ground phosphate rock.
Embodiment 3
The process step of present embodiment is following:
(1) acidolysis of ground phosphate rock
With hydrochloric acid (the analytical pure hydrochloric acid preparation) acidolysis of ground phosphate rock with mass concentration 26%, the content of CaO is by 46% in the ground phosphate rock, and the hydrochloric acid consumption is: when CaO in the ground phosphate rock and hydrochloric acid complete reaction 100% of required hydrochloric acid theoretical amount; At first said hydrochloric acid is joined in the reaction vessel; Under agitation in hydrochloric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, room temperature (26 ℃), and the time is 0.5 hour; Reaction after finishing is left standstill reaction slurry to layering, obtains through suction filtration then to contain Ca
2+Acid hydrolysis solution, get acid hydrolysis solution and detect, record Ca in the acid hydrolysis solution
2+Content be 8.98% (mass percent).
(2) Preparation methods of gypsum whiskers
Obtained with step (1) and to be contained Ca
2+Acid hydrolysis solution and the sulfuric acid of mass concentration 90% be raw material, the vitriolic consumption is: the Ca in the acid hydrolysis solution
2+During with the sulfuric acid complete reaction 100% of required sulfuric acid theoretical amount; The Ca that contains with step (1) preparation
2+Acid hydrolysis solution add reaction vessel; A mouth that under agitation passes through said reaction vessel then adds sulfuric acid; Another mouth through said reaction vessel connects prolong, the tap water that the logical temperature of prolong outer tube is a room temperature (26 ℃) with the hydrochloric acid vapour cooling for reflux that volatilizes in the reaction process in reaction slurry, stirring velocity 300r/min; 90 ℃ of temperature of reaction, 2 hours reaction times; Reaction finishes after filter to isolate calcium sulfate crystal whiskers; And with isolated calcium sulfate crystal whiskers successively with distilled water wash 4 times, industrial spirit washing 4 times; Removed surface-moisture in 60 minutes 80 ℃ of dryings then; The whisker that the obtains fine acicular that is white in color is observed calcium sulfate crystal whiskers: grow 40～100 μ m, diameter 2～5 μ m under electron microscope.
(3) preparation of phosphoric acid
Carry out the extraction of 2 stage countercurrents with filtering institute's obtain filtrate in the step (2); Extraction agent is made up of trioctylamine and n-Octanol; The volume ratio of trioctylamine and n-Octanol=5: 1, the volume ratio of said filtrating and extraction agent=5: 1,60 ℃ of extraction temperature; 60 minutes residence time of extraction, the surplus water that comes together is phosphoric acid aftertreatments such as (can concentrate as required or) removal of impurities; The isolated extracted organic phase of counter-current extraction is carried out 2 stage countercurrent back extractions with soft water, extracted organic phase and soft volume ratio=and 5: 1,60 ℃ of back extraction temperature, 60 minutes residence time of washing, hydrochloric acid that back extraction obtains is used for the acidolysis of ground phosphate rock.
Embodiment 4
The process step of present embodiment is following:
(1) acidolysis of ground phosphate rock
With hydrochloric acid (the analytical pure hydrochloric acid preparation) acidolysis of ground phosphate rock with mass concentration 26%, the content of CaO is by 46% in the ground phosphate rock, and the hydrochloric acid consumption is: when CaO in the ground phosphate rock and hydrochloric acid complete reaction 100% of required hydrochloric acid theoretical amount; At first said hydrochloric acid is joined in the reaction vessel; Under agitation in hydrochloric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, room temperature (26 ℃), and the time is 3 hours; Reaction after finishing is left standstill reaction slurry to layering, obtains through suction filtration then to contain Ca
2+Acid hydrolysis solution, get acid hydrolysis solution and detect, record Ca in the acid hydrolysis solution
2+Content be 9.23% (mass percent).
(2) Preparation methods of gypsum whiskers
Obtained with step (1) and to be contained Ca
2+Acid hydrolysis solution and the sulfuric acid of mass concentration 90% be raw material, the vitriolic consumption is: the Ca in the acid hydrolysis solution
2+During with the sulfuric acid complete reaction 100% of required sulfuric acid theoretical amount; The Ca that contains with step (1) preparation
2+Acid hydrolysis solution add reaction vessel; A mouth that under agitation passes through said reaction vessel then adds sulfuric acid; Another mouth through said reaction vessel connects prolong, the tap water that the logical temperature of prolong outer tube is a room temperature (26 ℃) with the hydrochloric acid vapour cooling for reflux that volatilizes in the reaction process in reaction slurry, stirring velocity 250r/min; 60 ℃ of temperature of reaction, 2.5 hours reaction times; Reaction finishes after filter to isolate calcium sulfate crystal whiskers; And with isolated calcium sulfate crystal whiskers successively with distilled water wash 3 times, industrial spirit washing 3 times; Remove surface-moisture 80 ℃ of dryings 60 minutes then, the whisker of the acquisition fine acicular that is white in color, long 600～1000 μ m; Diameter 10～20 μ m, its pattern under electron microscope is seen Fig. 3.
(3) preparation of phosphoric acid
Carry out the extraction of 3 stage countercurrents with filtering institute's obtain filtrate in the step (2); Extraction agent is made up of trioctylamine and n-Octanol; The volume ratio of trioctylamine and n-Octanol=3: 1, the volume ratio of said filtrating and extraction agent=3: 1,30 ℃ of extraction temperature; 30 minutes residence time of extraction, the surplus water that comes together is phosphoric acid aftertreatments such as (can concentrate as required or) removal of impurities; The isolated extracted organic phase of counter-current extraction is carried out 3 stage countercurrent back extractions with soft water, extracted organic phase and soft volume ratio=and 2: 1,30 ℃ of back extraction temperature, 30 minutes residence time of washing, hydrochloric acid that back extraction obtains is used for the acidolysis of ground phosphate rock.
Embodiment 5
The process step of present embodiment is following:
(1) acidolysis of ground phosphate rock
With nitric acid (the analytical pure nitric acid preparation) acidolysis of ground phosphate rock with mass concentration 30%, the content of CaO is by 46% in the ground phosphate rock, and nitric acid dosage is: when CaO in the ground phosphate rock and nitric acid complete reaction 130% of required nitric acid theoretical amount; At first said nitric acid is joined in the reaction vessel, under agitation in nitric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, 50 ℃, and the time is 1 hour, and reaction after finishing is left standstill reaction slurry to layering, obtains through suction filtration then to contain Ca
2+Acid hydrolysis solution, get acid hydrolysis solution and detect, record Ca in the acid hydrolysis solution
2+Content be 6.42% (mass percent).
(2) Preparation methods of gypsum whiskers
Obtained with step (1) and to be contained Ca
2+Acid hydrolysis solution and the sulfuric acid of mass concentration 20% be raw material, the vitriolic consumption is: the Ca in the acid hydrolysis solution
2+During with the sulfuric acid complete reaction 100% of required sulfuric acid theoretical amount; The Ca that contains with step (1) preparation
2+Acid hydrolysis solution add reaction vessel; A mouth that under agitation passes through said reaction vessel then adds sulfuric acid; Another mouth through said reaction vessel connects prolong, the tap water that the logical temperature of prolong outer tube is a room temperature (26 ℃) with the nitric acid vapor cooling for reflux that volatilizes in the reaction process in reaction slurry, stirring velocity 250r/min; 50 ℃ of temperature of reaction, 2.5 hours reaction times; Reaction finishes after filter to isolate calcium sulfate crystal whiskers; And with isolated calcium sulfate crystal whiskers successively with distilled water wash 2 times, industrial spirit washing 2 times; Removed surface-moisture in 60 minutes 80 ℃ of dryings then; The whisker that the obtains fine acicular that is white in color is observed calcium sulfate crystal whiskers: grow 30～50 μ m, diameter 5～10 μ m under electron microscope.
(3) preparation of phosphoric acid
Carry out the extraction of 5 stage countercurrents with filtering institute's obtain filtrate in the step (2); Extraction agent is made up of trioctylamine and n-Octanol; The volume ratio of trioctylamine and n-Octanol=2: 1, the volume ratio of said filtrating and extraction agent=1: 1,20 ℃ of extraction temperature; 5 minutes residence time of extraction, the surplus water that comes together is phosphoric acid aftertreatments such as (can concentrate as required or) removal of impurities; The isolated extracted organic phase of counter-current extraction is carried out 5 stage countercurrent back extractions with soft water, extracted organic phase and soft volume ratio=and 0.5: 1,20 ℃ of back extraction temperature, 5 minutes residence time of washing, nitric acid that back extraction obtains is used for the acidolysis of ground phosphate rock.
Embodiment 6
The process step of present embodiment is following:
(1) acidolysis of ground phosphate rock
With nitric acid (the analytical pure nitric acid preparation) acidolysis of ground phosphate rock with mass concentration 40%, the content of CaO is by 46% in the ground phosphate rock, and nitric acid dosage is: when CaO in the ground phosphate rock and nitric acid complete reaction 110% of required nitric acid theoretical amount; At first said nitric acid is joined in the reaction vessel, under agitation in nitric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, 40 ℃, and the time is 0.5 hour, and reaction after finishing is left standstill reaction slurry to layering, obtains through suction filtration then to contain Ca
2+Acid hydrolysis solution, get acid hydrolysis solution and detect, record Ca in the acid hydrolysis solution
2+Content be 9.87% (mass percent).
(2) Preparation methods of gypsum whiskers
Obtained with step (1) and to be contained Ca
2+Acid hydrolysis solution and the sulfuric acid of mass concentration 50% be raw material, the vitriolic consumption is: the Ca in the acid hydrolysis solution
2+During with the sulfuric acid complete reaction 100% of required sulfuric acid theoretical amount; The Ca that contains with step (1) preparation
2+Acid hydrolysis solution add reaction vessel; A mouth that under agitation passes through said reaction vessel then adds sulfuric acid; Another mouth through said reaction vessel connects prolong, the tap water that the logical temperature of prolong outer tube is a room temperature (26 ℃) with the nitric acid vapor cooling for reflux that volatilizes in the reaction process in reaction slurry, stirring velocity 250r/min; 90 ℃ of temperature of reaction, 2.5 hours reaction times; Reaction finishes after filter to isolate calcium sulfate crystal whiskers; And with isolated calcium sulfate crystal whiskers successively with distilled water wash 3 times, industrial spirit washing 3 times; Removed surface-moisture in 60 minutes 80 ℃ of dryings then; The whisker that the obtains fine acicular that is white in color is observed calcium sulfate crystal whiskers: grow 50～120 μ m, diameter 2～5 μ m under electron microscope.
(3) preparation of phosphoric acid
Carry out the extraction of 3 stage countercurrents with filtering institute's obtain filtrate in the step (2); Extraction agent is made up of trioctylamine and n-Octanol; The volume ratio of trioctylamine and n-Octanol=3: 1, the volume ratio of said filtrating and extraction agent=3: 1,40 ℃ of extraction temperature; 20 minutes residence time of extraction, the surplus water that comes together is phosphoric acid aftertreatments such as (can concentrate as required or) removal of impurities; The isolated extracted organic phase of counter-current extraction is carried out 3 stage countercurrent back extractions with soft water, extracted organic phase and soft volume ratio=and 3: 1,30 ℃ of back extraction temperature, 20 minutes residence time of washing, nitric acid that back extraction obtains is used for the acidolysis of ground phosphate rock.
Embodiment 7
The process step of present embodiment is following:
(1) acidolysis of ground phosphate rock
With nitric acid (the analytical pure nitric acid preparation) acidolysis of ground phosphate rock with mass concentration 54%, the content of CaO is by 46% in the ground phosphate rock, and nitric acid dosage is: when CaO in the ground phosphate rock and nitric acid complete reaction 100% of required nitric acid theoretical amount; At first said nitric acid is joined in the reaction vessel, under agitation in nitric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, 50 ℃, and the time is 0.5 hour, and reaction after finishing is left standstill reaction slurry to layering, obtains through suction filtration then to contain Ca
2+Acid hydrolysis solution, get acid hydrolysis solution and detect, record Ca in the acid hydrolysis solution
2+Content be 13.65% (mass percent).
(2) Preparation methods of gypsum whiskers
Obtained with step (1) and to be contained Ca
2+Acid hydrolysis solution and the sulfuric acid of mass concentration 90% be raw material, the vitriolic consumption is: the Ca in the acid hydrolysis solution
2+During with the sulfuric acid complete reaction 100% of required sulfuric acid theoretical amount; The Ca that contains with step (1) preparation
2+Acid hydrolysis solution add reaction vessel; A mouth that under agitation passes through said reaction vessel then adds sulfuric acid; Another mouth through said reaction vessel connects prolong, the tap water that the logical temperature of prolong outer tube is a room temperature (26 ℃) with the nitric acid vapor cooling for reflux that volatilizes in the reaction process in reaction slurry, stirring velocity 250r/min; 60 ℃ of temperature of reaction, 2.5 hours reaction times; Reaction finishes after filter to isolate calcium sulfate crystal whiskers; And with isolated calcium sulfate crystal whiskers successively with distilled water wash 4 times, industrial spirit washing 4 times; Remove surface-moisture 80 ℃ of dryings 60 minutes then, the whisker of the acquisition fine acicular that is white in color is observed calcium sulfate crystal whiskers: grow 600～800 μ m under electron microscope; Diameter 10～20 μ m, its pattern under electron microscope is seen Fig. 4.
(3) preparation of phosphoric acid
Carry out the extraction of 2 stage countercurrents with filtering institute's obtain filtrate in the step (2); Extraction agent is made up of trioctylamine and n-Octanol; The volume ratio of trioctylamine and n-Octanol=5: 1, the volume ratio of said filtrating and extraction agent=5: 1,60 ℃ of extraction temperature; 60 minutes residence time of extraction, the surplus water that comes together is phosphoric acid aftertreatments such as (can concentrate as required or) removal of impurities; The isolated extracted organic phase of counter-current extraction is carried out 2 stage countercurrent back extractions with soft water, extracted organic phase and soft volume ratio=and 5: 1,60 ℃ of back extraction temperature, 60 minutes residence time of washing, nitric acid that back extraction obtains is used for the acidolysis of ground phosphate rock.
Claims (8)
1. the co-production method of calcium sulfate crystal whiskers and phosphoric acid is characterized in that process step is following:
(1) acidolysis of ground phosphate rock
With ground phosphate rock with the hydrochloric acid of mass concentration 15～26% or the nitric acid solution of mass concentration 30～54%; The consumption of said hydrochloric acid or nitric acid is: when CaO in the ground phosphate rock and hydrochloric acid or nitric acid complete reaction 100～130% of required hydrochloric acid or nitric acid theoretical amount, the slip after the ground phosphate rock acidolysis obtains through filtration and contains Ca
2+Acid hydrolysis solution;
(2) Preparation methods of gypsum whiskers
Obtained with step (1) and to be contained Ca
2+Acid hydrolysis solution and the sulfuric acid of mass concentration 20～90% be raw material, said vitriolic consumption is: the Ca in the acid hydrolysis solution
2+During with the sulfuric acid complete reaction 100% of required sulfuric acid theoretical amount, under agitation said sulfuric acid is joined and contain Ca
2+Acid hydrolysis solution in; React in normal pressure, 50～90 ℃; Hydrochloric acid vapour that volatilizes in the reaction process or nitric acid vapor are back in the reaction slurry with water quench, and the reaction times was at least 1.5 hours, after reaction finishes; Isolate calcium sulfate crystal whiskers through filtering, then obtaining calcium sulfate crystal whiskers is washed with dry;
(3) preparation of phosphoric acid
Carry out counter-current extraction with filtering institute's obtain filtrate in the step (2), the surplus water that comes together is phosphoric acid, the volume ratio of said filtrating and extraction agent=1: 1～5: 1,20～60 ℃ of extraction temperature, 5～60 minutes residence time of extraction;
Isolated extracted organic phase was carried out the hydrochloric acid of countercurrent reextraction acquisition or the acidolysis that nitric acid is used for ground phosphate rock with soft water when said filtrating was carried out counter-current extraction; During back extraction; Extracted organic phase and soft volume ratio=0.5: 1～5: 1,20～60 ℃ of back extraction temperature, 5～60 minutes residence time of washing.
2. the co-production method of calcium sulfate crystal whiskers according to claim 1 and phosphoric acid is characterized in that said ground phosphate rock is the mid low grade phosphate rock powder of particle diameter≤1165 μ m.
3. the co-production method of calcium sulfate crystal whiskers according to claim 1 and 2 and phosphoric acid; When it is characterized in that ground phosphate rock carried out acidolysis with the hydrochloric acid of mass concentration 15～26%; At first said hydrochloric acid is joined in the reaction vessel; Under agitation in hydrochloric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, room temperature, and the time was at least 0.5 hour;
Ground phosphate rock during with the nitric acid solution of mass concentration 30～54%, is at first joined said nitric acid in the reaction vessel, under agitation in nitric acid, add ground phosphate rock then, acidolysis reaction under agitation carries out in normal pressure, 30～50 ℃, and the time was at least 0.5 hour.
4. the co-production method of calcium sulfate crystal whiskers according to claim 1 and 2 and phosphoric acid is characterized in that the washing of said calcium sulfate crystal whiskers is washed with zero(ppm) water, industrial spirit successively, and washing times is at least 2 times.
5. the co-production method of calcium sulfate crystal whiskers according to claim 3 and phosphoric acid is characterized in that the washing of said calcium sulfate crystal whiskers is washed with zero(ppm) water, industrial spirit successively, and washing times is at least 2 times.
6. the co-production method of calcium sulfate crystal whiskers according to claim 1 and 2 and phosphoric acid; It is characterized in that when filtering institute's obtain filtrate in the step (2) and carry out counter-current extraction; Extraction agent is made up of trioctylamine and n-Octanol, the volume ratio of trioctylamine and n-Octanol=2: 1～5: 1.
7. the co-production method of calcium sulfate crystal whiskers according to claim 3 and phosphoric acid is characterized in that when filtering institute's obtain filtrate in the step (2) and carry out counter-current extraction, extraction agent is made up of trioctylamine and n-Octanol, the volume ratio of trioctylamine and n-Octanol=2: 1～5: 1.
8. the co-production method of calcium sulfate crystal whiskers according to claim 5 and phosphoric acid is characterized in that when filtering institute's obtain filtrate in the step (2) and carry out counter-current extraction, extraction agent is made up of trioctylamine and n-Octanol, the volume ratio of trioctylamine and n-Octanol=2: 1～5: 1.
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| CN102352528B (en) * | 2011-09-30 | 2013-09-11 | 瓮福（集团）有限责任公司 | Method for extracting phosphorite co-production gypsum whisker by utilizing nitric acid |
| CN102534801A (en) * | 2012-02-23 | 2012-07-04 | 云南民族大学 | Method for improving quality of calcium sulfate whiskers |
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| CN104630877B (en) * | 2015-01-28 | 2017-05-03 | 江苏理工学院 | Method for preparing calcium sulfate dihydrate whisker from tin-smelting waste slag |
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| CN114804061B (en) * | 2021-01-19 | 2024-01-26 | 中国科学院过程工程研究所 | Device system and method for preparing wet-process phosphoric acid by synchronously extracting and separating impurities through acidolysis of phosphorite |
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