CN102826574A - Method for extracting potassium from sea water by using continuous ion exchange method - Google Patents
Method for extracting potassium from sea water by using continuous ion exchange method Download PDFInfo
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Abstract
The invention discloses a method for extracting potassium from sea water by using a continuous ion exchange method and relates to a method for treating the sea water by using an ion exchange method. The method comprises the following steps that a simulation moving table is arranged by using 36 continuous ion exchange devices consisting of ion exchange columns which are provided with jackets and filled with sodium type clinoptilolite; the simulation moving table is divided into an adsorption zone, an elution zone and a regeneration zone; the adsorption process is operated in the adsorption zone by layers and three layers are carried out in parallel; the concentration of potassium in the sea water as a raw material is 0.61-1.52g/L; the concentration of potassium in the drained sea water after adsorption is 0.01-0.15g/L; the elution process is operated in the elution zone by columns and three layers are carried out in series to obtain a potassium-rich solution and the concentration of K<+> in the potassium-rich solution is 36.00-44.12g/L; and the regeneration process is operated in the regeneration zone by columns and three layers are carried out in series to obtain ammonium-containing salt water. The adsorption, elution and regeneration processes are simultaneously and continuously operated, and thus the operation period is shortened, the efficiency is increased, the cost is reduced and economic benefits are improved.
Description
Technical field
Technical scheme of the present invention relates to ion exchange method handles seawater, specifically from seawater, puies forward the method for potassium with the continuous ionic exchange process.
Background technology
Potassium is one of fertilizer element.Potassium content is only second to nitrogen in the plant materials, is requisite element in the plant growth and development process.In addition, potassium is in the industrial industries such as chemical industry, oil and medicine that are widely used in.At present, the potassium product mainly is to be processed and got by land solid kalium mine or salt lake brine both at home and abroad.Because the shortage of China land potassium ore resources, main dependence on import, therefore, the R&D work of new technology that the exploitation total reserves reaches 550,000,000,000,000 tons seawater potassium resource is very necessary.
The prior art of potassium from sea water method comprises the kinds of processes method of chemical precipitation method, solvent extration, membrane separation process and four kinds of technological lines of ion exchange method.In the Extracting Potash from Seawater by Ion Exchange Method technology that with the natural zeolite is ionite; CN101850991B discloses a kind of " using preparing potassium chloride from seawater "; This method seawater is that raw material adsorbs; Mixture with ammonium chloride and sodium-chlor is the solution that eluent obtains rich potassium, obtains Repone K through the pervaporation sepn process.CN1792797 has disclosed a kind of " extracting the method for vitriolate of tartar with seawater "; This method is to be raw material with seawater and ammonium sulfate; At first adopt ammoniumsulphate soln that the wash-out operation that the adsorptive in the ion exchange column of filling sodium type clinoptilolite carries out wash-out is prepared rich potassium liquid, be employed in then and feed ammonia in the rich potassium liquid and analyse operation with the ammonia of separating out vitriolate of tartar and produce vitriolate of tartar.The more than existing related rich potassium step of patented technology all adopts bed technology, periodical operation, and the operational cycle is long, and the rich potassium liquid of gained composition is unstable, and the recovery is lower than 50% in the seawater.
Summary of the invention
Technical problem to be solved by this invention is: the method for from seawater, carrying potassium with the continuous ionic exchange process is provided; It is the process method of the rich potassium of a kind of simulation moving-bed continuous ionic exchange process seawater; Through the material import and export position of the single fixed-bed ion exchanger of conversion, realize the continuous reverse relative movement of seawater and eluent, be that raw material adsorbs with the seawater; The rich saspachite of ammonium chloride solution wash-out is prepared stable components and K
+Content at the rich potassium liquid of 36～44g/L, overcome the periodical operation of the rich potassium process using of existing patented technology, the operational cycle is long, the rich potassium liquid of gained composition instability, and the recovery is lower than 50% shortcoming in the seawater.
The present invention solves this technical problem the technical scheme that is adopted: from seawater, putting forward the method for potassium with the continuous ionic exchange process, is the process method of the rich potassium of a kind of simulation moving-bed continuous ionic exchange process seawater, and step is following:
The first step, simulation moving-bed setting
Simulation moving-bed setting is the continuous ionic switch of forming with the ion exchange column of the sodium type of the inserting clinoptilolite of 36 jacketed; The sodium type clinoptilolite that every ion exchange column is inserted is 1000g; Highly be 1.0m, every ion exchange column suitable for reading passes through a valve and is connected with a four-way, and this four-way connects three valves again; The end opening of every ion exchange column also is connected with a four-way through a valve, and this four-way connects three valves again; Following three layers was I-III layer during these 36 ion exchange columns were divided into, and totally 12 row are the 1-12 row; Pipeline connecting mode between every layer of 12 ion exchange column is: the end opening of first ion exchange column is connected the suitable for reading of the second ion exchange column of this layer through four-way with valve; Connect successively, the end opening of the 12 ion exchange column is connected the suitable for reading of first ion exchange column of this layer through four-way with valve; Pipeline connecting mode between three ion exchange columns of every row is: the end opening that is connected the ion exchange column of the 1st II layer that is listed as through four-way with valve suitable for reading of the ion exchange column of the III layer of the 1st row; The end opening of ion exchange column that is connected the I layer of the 1st row through four-way with valve suitable for reading of the ion exchange column of II layer; The end opening that is connected the ion exchange column of the 2nd III layer that is listed as through four-way with valve suitable for reading of the ion exchange column of the I layer of the 1st row; And the like connection, the end opening that is connected the ion exchange column of the 1st III layer that is listed as through four-way with valve suitable for reading of the ion exchange column of the I layer of the 12nd row; Above-mentioned whole continuous ionic switch is divided into adsorption zone, elution zone and breeding blanket; Wherein, every layer constitutes an absorbing unit by the series connection of 3～6 ion exchange columns in the adsorption zone, makes the height of mass transfer of each absorbing unit be controlled to be 3～6m; Comprise three absorbing units altogether, form 3～6 row; Elution zone by placed in-line 2～4 row totally 6～12 absorption saturated ion exchange columns constitute, the elution process height of mass transfer is 6～12m; Accomplish the ion exchange column of wash-out operation and form the breeding blanket, the breeding blanket by placed in-line 2～4 row the ion exchange column behind totally 6～12 wash-outs constitute, the regenerative process height of mass transfer is 6～12m;
Second step, adsorption process
Adsorption process is carried out at the described adsorption zone of the first step; The adsorption process hierarchical operations; Three layers of parallel connection are carried out, under 0～30 ℃, with raw material seawater respectively from the sub-exchange column of three leafing of an absorbing unit of the described continuous ionic switch of the ion exchange column feeding the first step suitable for reading; Sodium ion on potassium ion in the seawater and the sodium type clinoptilolite exchanges, and the absorption flow velocity of raw material seawater is that the void tower flow velocity is 5～50m/h; The density range of raw material seawater is 2 ° of Be '～12 ° Be ' (degree Beaume); The seawater that discharge the absorption back is flowed out by the ion exchange column end opening; Treat to withdraw from first ion exchange column after the sodium ion on the clinoptilolite and potassium ion generation permutoid reaction are fully in first ion exchange column of each layer of this absorbing unit; And then the ion exchange column to be adsorbed of connecting is as next absorbing unit; It is suitable for reading that the raw material seawater import is changed first ion exchange column that is passed into this next one absorbing unit, and the seawer outlet that discharge the absorption back also changes new placed in-line ion exchange column into, successively operation;
The 3rd step, elution process
Elution process is carried out in the described elution zone of the first step, the operation of elution process apportion, and three layers of series connection are carried out; Under 25 ℃～100 ℃ temperature; Use concentration be the ammonium chloride solution of 198～310g/L as eluent, with fresh water the seawater in the sodium type clinoptilolite post in the ion exchange column is ejected earlier, more above-mentioned eluent is fed the saturated ion exchange column of the 1st row absorption of the absorbing unit of accomplishing adsorption process in second step; Elution flow rate is that the void tower flow velocity is 5～10m/h; Discharge behind the wash-out and obtain rich potassium liquid, withdraw from the saturated ion exchange column of the 2nd row absorption of connecting again after the saturated ion exchange column wash-out of the 1st row absorption of treating this elution zone finishes; Push ahead with the fixed height of mass transfer, successively operation;
The 4th step, regenerative process
Elution process is carried out in the described breeding blanket of the first step, the operation of regenerative process apportion, and three layers of series connection are carried out; Under 50～100 ℃ of temperature; Feed the ion exchange column behind the second step wash-out with the regenerator saturated brine, regeneration velocity is that the void tower flow velocity is 5～10m/h, and discharging and obtaining regenerated liquid is ammonium salt-containing water; Clinoptilolite regeneration in the ion exchange column at this moment transfers the sodium type again to and can recycle repeatedly; The IX column regeneration of treating the 1st row of this breeding blanket finishes and withdraws from, the ion exchange column of series connection next column, operation successively; The regenerated liquid ammonium salt-containing water that obtains in the regenerative process adds sodium hydroxide and carries out ammonia still process processing recovery ammonia, and the recovered brine after the ammonia still process also supplies to recycle;
In operate continuously, the second step adsorption process, the 3rd step elution process and the 4th step regenerative process are carried out simultaneously.
Above-mentionedly from seawater, put forward the method for potassium with the continuous ionic exchange process, the size of said every ion exchange column is φ 36 * 1000mm.
Above-mentionedly from seawater, put forward the method for potassium with the continuous ionic exchange process, containing potassium concn in the said raw material seawater is 0.61g/L～1.52g/L, and containing potassium concn in the seawater that discharge the absorption back is 0.01g/L～0.15g/L.
Above-mentionedly from seawater, put forward the method for potassium with the continuous ionic exchange process, discharge behind the wash-out in the said elution process and obtain rich potassium liquid, it contains K
+Be 36.00g/L～44.12g/L.
Above-mentionedly from seawater, put forward the method for potassium with the continuous ionic exchange process, it is ammonium salt-containing water that the discharge in the said regenerative process obtains regenerated liquid, and it contains NH
4 +Be 5.09g/L～6.27g/L.
Above-mentionedly from seawater, put forward the method for potassium with the continuous ionic exchange process, all through being purchased acquisition, related operating procedure is well-known to those having ordinary skill in the art for involved equipment, raw material and reagent.
The invention has the beneficial effects as follows: compare with CN1792797 with prior art CN101850991B; The present invention puies forward the method for potassium from seawater with the continuous ionic exchange process outstanding substantive distinguishing features is to change operate continuously into by the fixed bed periodical operation; The sub-exchange column parallel connection of adsorption process three leafing is carried out, and adsorption time shortens to 1/3 of fixed bed, and the extraction yield of potassium rises to 2～3 times of prior art in the seawater; Reach more than 90%, and can control according to demand.
Compare with CN1792797 with prior art CN101850991B; The marked improvement of the inventive method is: the fixed bed operation cycle mainly is adsorption time control; The inventive method adopts the continuous ionic exchange process to carry out, and has shortened the operational cycle, has improved efficient; Further reduce cost, improved economic benefit; The inventive method has improved potassium extraction yield in the seawater again; Obtain rich potassium liquid stable components; And have raw material and be easy to get, the advantage that cost is low is because the potassium reserves of seawater are inexhaustible; Thereby can not be restricted with the raw materials used source of the inventive method, opened up new approach for realizing the agricultural potash fertilizer self-sufficiency of China.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Fig. 1 connects used component and mode of connection synoptic diagram each other for the ion exchange column in the inventive method.
Fig. 2 is the pipeline connection synoptic diagram between 36 ion exchange columns of following three layers and 12 row in being divided into of the continuous ionic switch in the inventive method.
Fig. 3 be the inventive method in operate continuously, the synoptic diagram that adsorption process, elution process and regenerative process are carried out simultaneously.
Among the figure, 1. ion exchange column, 2. four-way, 3. valve is 4. suitable for reading, 5. end opening.
Embodiment
Embodiment illustrated in fig. 1 showing; Every ion exchange column 1 in the inventive method carries out pipeline through four-way 2 with valve 3 each other and is connected; Suitable for reading 4 of every ion exchange column 1 passes through a valve 3 and is connected with a four-way 2; This four-way 2 connects three valves 3 again, and the end opening 5 of every ion exchange column 1 also is connected with a four-way 2 through a valve 3, and this four-way 2 connects three valves 3 again.
Embodiment illustrated in fig. 2 showing, following three layers was I～III layer during 36 ion exchange columns 1 in the inventive method were divided into, and totally 12 row promptly 1～12 are listed as; Pipeline connecting mode between every layer of 12 ion exchange column 1 is: the end opening 5 of first ion exchange column 1 is connected suitable for reading 4 of the second ion exchange column of this layer 1 through four-way 2 with valve 3; Connect successively, the end opening 5 of the 12 ion exchange column 1 is connected suitable for reading 4 of first ion exchange column 1 of this layer through four-way 2 with valve 3; Pipeline connecting mode between three ion exchange columns 1 of every row is: suitable for reading 4 of the ion exchange column 1 of the III layer of the 1st row is connected the end opening 5 of the ion exchange column 1 of the 1st II layer that is listed as through four-way 2 with valve 3; Suitable for reading 4 of the ion exchange column 1 of II layer is connected the end opening 5 of the ion exchange column 1 of the 1st I layer that is listed as through four-way 2 with valve 3; Suitable for reading 4 of the ion exchange column 1 of the I layer of the 1st row is connected the end opening 5 of ion exchange column 1 of the III layer of secondary series through four-way 2 with valve 3; And the like connection, suitable for reading 4 of the ion exchange column 1 of the I layer of the 12nd row is connected the end opening 5 of the ion exchange column 1 of the 1st III layer that is listed as through four-way 2 with valve 3.Mean the suitable for reading 4 of the ion exchange column 1 that connects I layer the 12nd row " connect (1)-I-12 suitable for reading " that is indicated among this figure, by that analogy.
Demonstration embodiment illustrated in fig. 3; 36 ion exchange columns 1 in the inventive method are pressed 1#～36# numbering; Following three layers is I～III layer in being divided into; Wherein, The I layer has 1#, 4#, 7#, 10#, 13#, 16#, 19#, 22#, 25#, 28#, 31# and 34# ion exchange column 1, the II layer to have 2#, 5#, 8#, 11#, 14#, 17#, 20#, 23#, 26#, 29#, 32# and 35# ion exchange column 1, the III layer that 3#, 6#, 9#, 12#, 15#, 18#, 21#, 24#, 27#, 30#, 33# and 36# ion exchange column 1 are arranged; Be arranged in i.e. 1～12 row of 12 row again, wherein, the 1st shows 1#, 2# and 3# ion exchange column 1, is arranged in order, and shows 34#, 35# and 36# ion exchange column 1 to the 12nd.When last 3 row; When promptly the 10th row 28#, 29# and 30# ion exchange column 1 and the 11st row 31#, 32# and 33# ion exchange column 1 and the 12nd row 34#, 35# and 36# ion exchange column 1 are adsorption zone; Raw material seawater gets into from suitable for reading 4 of the 10th row 28#, 29# and 30# ion exchange column 1 respectively simultaneously, and the seawater that discharge the absorption back is discharged by the end opening 5 of the 12nd row 34#, 35# and 36# ion exchange column 1 respectively simultaneously.At this moment; The ion exchange column 1 of the 5th～8 row is an elution zone; Eluent gets into from the end opening 5 of the 15# ion exchange column 1 of the 3rd layer of the 5th row; Through placed in-line 14#, 13#, 18#, 17#, 16#, 21#, 20#, 19#, 24#, 23# and 22# ion exchange column 1, flow out rich potassium liquid by suitable for reading 4 of 22# ion exchange column 1.Same this moment; The ion exchange column 1 of the 1st～4 row is the breeding blanket; Regenerator gets into from the end opening 5 of the 3# ion exchange column 1 of the 3rd layer of the 1st row; Through placed in-line 2#, 1#, 6#, 5#, 4#, 9#, 8#, 7#, 12#, 11# and 10# ion exchange column 1, flow out regenerated liquid by suitable for reading 4 of 10# ion exchange column 1.25#, 26# and three pillars of 27# are in the state that adsorbs the wait wash-out that finishes at this moment.
Below used continuous ionic switch among all embodiment; It is the continuous ionic switch that uses the size of the sodium type of the inserting clinoptilolite of 36 jacketed to form as the ion exchange column of φ 36 * 1000mm 1; The sodium type clinoptilolite that every ion exchange column 1 is inserted is 1000g; Highly be 1.0m, be provided with by above-mentioned embodiment illustrated in figures 1 and 2 and accomplish the used whole continuous ionic switch of the following example.
The first step, simulation moving-bed setting
Accomplish simulation moving-bed setting as stated; Whole continuous ionic switch is divided into adsorption zone, elution zone and breeding blanket; Wherein, constitute an absorbing unit by 1 series connection of 6 ion exchange columns in the adsorption zone, make the height of mass transfer of each absorbing unit be controlled to be 6m; Comprise three absorbing units altogether, form 3 row; Elution zone by placed in-line 3 row totally 9 absorption saturated ion exchange columns 1 constitute, the elution process height of mass transfer is 9m; Accomplish the ion exchange column 1 composition breeding blanket of wash-out operation, the breeding blanket by placed in-line 3 row the ion exchange column 1 behind totally 9 wash-outs constitute, the regenerative process height of mass transfer is 9m;
Second step, adsorption process
Adsorption process is carried out at the described adsorption zone of the first step; The adsorption process hierarchical operations; Three layers of parallel connection are carried out, and under 10 ℃, just 13L is that the raw material seawater of 14.18Kg feeds the ion exchange column 1 of absorbing unit of the described continuous ionic switch of the first steps from the ion exchange column of the sub-exchange column 1 of three leafing suitable for reading 4 respectively; Sodium ion on potassium ion in the seawater and the sodium type clinoptilolite exchanges, and the absorption flow velocity of raw material seawater is that the void tower flow velocity is 20m/h; The density of raw material seawater is 12 ° of Be ' (degree Beaume); The seawater that discharge the absorption back is flowed out by ion exchange column end opening 5; Treat that sodium ion and potassium ion generation permutoid reaction on the sodium type clinoptilolite in first ion exchange column 1 of each layer of this absorbing unit withdraw from first ion exchange column 1 after fully, and then the ion exchange column to be adsorbed 1 of connecting changes the raw material seawater import first ion exchange column suitable for reading 4 that is passed into this next one absorbing unit as next absorbing unit; The seawer outlet that discharge the absorption back also changes the ion exchange column end opening 5 of new placed in-line ion exchange column 1 into; Operation successively, containing potassium concn in the raw material seawater is 1.52g/L, containing potassium concn in the seawater that discharge the absorption back is 0.15g/L; Potassium ion in the seawater is switched in the sodium type clinoptilolite, and adsorption rate is 90.13%.
The 3rd step, elution process
Elution process is carried out in the described elution zone of the first step, the operation of elution process apportion, and three layers of series connection are carried out; Under 80 ℃ of temperature, use concentration as the ammonium chloride solution of 198g/L as eluent, with fresh water the seawater in the clinoptilolite post in the ion exchange column 1 is ejected earlier; Above-mentioned eluent is fed the saturated ion exchange column 1 of the 1st row absorption of the absorbing unit of accomplishing adsorption process in second step, elution flow rate is that the void tower flow velocity is 8m/h again, when discharging behind the wash-out when obtaining rich potassium liquid 1.5L and being 1.74Kg; After finishing, withdraws from saturated ion exchange column 1 wash-out of the 1st row absorption of this elution zone; This elution zone the 2nd of connecting again is listed as the saturated ion exchange column 1 of absorption, pushes ahead with the fixed height of mass transfer, successively operation; Obtain rich potassium liquid, contain K
+Be 42.00g/L.
The 4th step, regenerative process
Elution process is carried out in the described breeding blanket of the first step; The operation of regenerative process apportion, three layers of series connection are carried out, under 50 ℃ of temperature; With 5L is that 6.00Kg regenerator saturated brine feeds the ion exchange column 1 behind the second step wash-out; Regeneration velocity is that the void tower flow velocity is 5m/h, and discharging and obtaining regenerated liquid is ammonium salt-containing water 5L, and it contains NH
4 +Be 5.81g/L; Clinoptilolite regeneration in the ion exchange column 1 at this moment transfers the sodium type again to and can recycle repeatedly; Ion exchange column 1 regeneration of treating the 1st row of this breeding blanket finishes and withdraws from the ion exchange column 1 of the next column of this breeding blanket of connecting, operation successively; The regenerated liquid ammonium salt-containing water that obtains in the regenerative process adds sodium hydroxide and carries out ammonia still process processing recovery ammonia, and the recovered brine after the ammonia still process also supplies to recycle;
In operate continuously, the second step adsorption process, the 3rd step elution process and the 4th step regenerative process are carried out simultaneously.Material composition in each operating process is seen table 1.
Material composition in table 1 embodiment 1 each operating process
The first step, simulation moving-bed setting
Accomplish simulation moving-bed setting as stated; Above-mentioned whole continuous ionic switch is divided into adsorption zone, elution zone and breeding blanket; Wherein, every layer constitutes an absorbing unit by 3 ion exchange columns 1 series connection in the adsorption zone, makes the height of mass transfer of each absorbing unit be controlled to be 3m; Comprise three absorbing units altogether, form 3 row; Elution zone by placed in-line 2 row totally 6 absorption saturated ion exchange columns 1 constitute, the elution process height of mass transfer is 6m; Accomplish the ion exchange column 1 composition breeding blanket of wash-out operation, the breeding blanket by placed in-line 4 row the ion exchange column 1 behind totally 12 wash-outs constitute, the regenerative process height of mass transfer is 12m;
Second step, adsorption process
Adsorption process is carried out at the described adsorption zone of the first step; The adsorption process hierarchical operations; Three layers of parallel connection are carried out, and under 30 ℃, just 37L is that the raw material seawater of 37.18Kg feeds the ion exchange column 1 of absorbing unit of the described continuous ionic switch of the first steps from the ion exchange column of the sub-exchange column 1 of three leafing suitable for reading 4 respectively; Sodium ion on potassium ion in the seawater and the sodium type clinoptilolite exchanges, and the absorption flow velocity of raw material seawater is that the void tower flow velocity is 50m/h; The density of raw material seawater is 2 ° of Be ' (degree Beaume); The seawater that discharge the absorption back is flowed out by ion exchange column end opening 5; Treat that sodium ion and potassium ion generation permutoid reaction on the sodium type clinoptilolite in first ion exchange column 1 of each layer of this absorbing unit withdraw from first ion exchange column 1 after fully, and then the ion exchange column to be adsorbed 1 of connecting changes the raw material seawater import first ion exchange column suitable for reading 4 that is passed into this next one absorbing unit as next absorbing unit; The seawer outlet that discharge the absorption back also changes the ion exchange column end opening 5 of new placed in-line ion exchange column 1 into; Operation successively, containing potassium concn in the raw material seawater is 0.61g/L, containing potassium concn in the seawater that discharge the absorption back is 0.01g/L; Potassium ion in the seawater is switched in the sodium type clinoptilolite, and adsorption rate is 98.36%.
The 3rd step, elution process
Elution process is carried out in the described elution zone of the first step, the operation of elution process apportion, and three layers of series connection are carried out; Under 100 ℃ of temperature, use concentration as the ammonium chloride solution of 310g/L as eluent, with fresh water the seawater in the clinoptilolite post in the ion exchange column 1 is ejected earlier; Above-mentioned eluent is fed the saturated ion exchange column 1 of the 1st row absorption of the absorbing unit of accomplishing adsorption process in second step, elution flow rate is that the void tower flow velocity is 10m/h again, when discharging behind the wash-out when obtaining rich potassium liquid 1.4L and being 1.62Kg; After finishing, withdraws from saturated ion exchange column 1 wash-out of the 1st row absorption of this elution zone; This elution zone the 2nd of connecting again is listed as the saturated ion exchange column 1 of absorption, pushes ahead with the fixed height of mass transfer, successively operation; Obtain rich potassium liquid, contain K
+Be 44.12g/L.
The 4th step, regenerative process
Elution process is carried out in the described breeding blanket of the first step; Three layers of series connection of regenerative process are carried out; Under 100 ℃ of temperature, be that 4.80Kg regenerator saturated brine feeds the ion exchange column 1 behind the second step wash-out with 4L, regeneration velocity is that the void tower flow velocity is 10m/h; It is ammonium salt-containing water 3L that discharge obtains regenerated liquid, and it contains NH
4 +Be 5.09g/L; Clinoptilolite regeneration in the ion exchange column 1 at this moment transfers the sodium type again to and can recycle repeatedly; Ion exchange column 1 regeneration of treating the 1st row of this breeding blanket finishes and withdraws from the ion exchange column 1 of the next column of this breeding blanket of connecting, operation successively; The regenerated liquid ammonium salt-containing water that obtains in the regenerative process adds sodium hydroxide and carries out ammonia still process processing recovery ammonia, and the recovered brine after the ammonia still process also supplies to recycle;
In operate continuously, the second step adsorption process, the 3rd step elution process and the 4th step regenerative process are carried out simultaneously.Material composition in each operating process is seen table 2.
Material composition in table 2 embodiment 2 each operating process
The first step, simulation moving-bed setting
Accomplish simulation moving-bed setting as stated; Above-mentioned whole continuous ionic switch is divided into adsorption zone, elution zone and breeding blanket; Wherein, every layer constitutes an absorbing unit by 5 ion exchange columns 1 series connection in the adsorption zone, makes the height of mass transfer of each absorbing unit be controlled to be 5m; Comprise three absorbing units altogether, form 5 row; Elution zone by placed in-line 4 row totally 12 absorption saturated ion exchange columns 1 constitute, the elution process height of mass transfer is 12m; Accomplish the ion exchange column 1 composition breeding blanket of wash-out operation, the breeding blanket by placed in-line 2 row the ion exchange column 1 behind totally 6 wash-outs constitute, the regenerative process height of mass transfer is 6m;
Second step, adsorption process
Adsorption process is carried out at the described adsorption zone of the first step; The adsorption process hierarchical operations; Three layers of parallel connection are carried out, and under 0 ℃, just 17L is that the raw material seawater of 17.87Kg feeds the ion exchange column 1 of absorbing unit of the described continuous ionic switch of the first steps from the ion exchange column of the sub-exchange column 1 of three leafing suitable for reading 4 respectively; Sodium ion on potassium ion in the seawater and the sodium type clinoptilolite exchanges, and the absorption flow velocity of raw material seawater is that the void tower flow velocity is 5m/h; The density of raw material seawater is 7 ° of Be ' (degree Beaume); The seawater that discharge the absorption back is flowed out by ion exchange column end opening 5; Treat that sodium ion and potassium ion generation permutoid reaction on the sodium type clinoptilolite in first ion exchange column 1 of each layer of this absorbing unit withdraw from first ion exchange column 1 after fully, and then the ion exchange column to be adsorbed 1 of connecting changes the raw material seawater import first ion exchange column suitable for reading 4 that is passed into this next one absorbing unit as next absorbing unit; The seawer outlet that discharge the absorption back also changes the ion exchange column end opening 5 of new placed in-line ion exchange column 1 into; Operation successively, containing potassium concn in the raw material seawater is 1.35g/L, containing potassium concn in the seawater that discharge the absorption back is 0.07g/L; Potassium ion in the seawater is switched in the sodium type clinoptilolite, and adsorption rate is 94.81%.
The 3rd step, elution process
Elution process is carried out in the described elution zone of the first step, the operation of elution process apportion, and three layers of series connection are carried out; Under 25 ℃ of temperature, use concentration as the ammonium chloride solution of 250g/L as eluent, with fresh water the seawater in the sodium type clinoptilolite post in the ion exchange column is ejected earlier; Above-mentioned eluent is fed the saturated ion exchange column of the 1st row absorption of the absorbing unit of accomplishing adsorption process in second step, elution flow rate is that the void tower flow velocity is 5m/h again, when discharging behind the wash-out when obtaining rich potassium liquid 1.7L and being 1.97Kg; After finishing, withdraws from the saturated ion exchange column wash-out of the 1st row absorption of this elution zone; This elution zone the 2nd of connecting again is listed as the saturated ion exchange column of absorption, pushes ahead with the fixed height of mass transfer, successively operation; Obtain rich potassium liquid, contain K
+Be 36.00g/L.
The 4th step, regenerative process
Elution process is carried out in the described breeding blanket of the first step; Three layers of series connection of regenerative process are carried out; Under 80 ℃ of temperature, be that 3.60Kg regenerator saturated brine feeds the ion exchange column behind the second step wash-out with 3L, regeneration velocity is that the void tower flow velocity is 8m/h; It is ammonium salt-containing water 4.5L that discharge obtains regenerated liquid, and it contains NH
4 +Be 6.27g/L; Clinoptilolite regeneration in the ion exchange column at this moment transfers the sodium type again to and can recycle repeatedly; Ion exchange column 1 regeneration of treating the 1st row of this breeding blanket finishes and withdraws from the ion exchange column 1 of the next column of this breeding blanket of connecting, operation successively; The regenerated liquid ammonium salt-containing water that obtains in the regenerative process adds sodium hydroxide and carries out ammonia still process processing recovery ammonia, and the recovered brine after the ammonia still process also supplies to recycle;
In operate continuously, the second step adsorption process, the 3rd step elution process and the 4th step regenerative process are carried out simultaneously.Material composition in each operating process is seen table 3.
Material composition in table 3 embodiment 3 each operating process
Equipment, raw material and reagent involved in the foregoing description are all through being purchased acquisition, and related operating procedure is well-known to those having ordinary skill in the art.
Claims (5)
1. from seawater, put forward the method for potassium with the continuous ionic exchange process, it is characterized in that: be the process method of the rich potassium of a kind of simulation moving-bed continuous ionic exchange process seawater, step is following:
The first step, simulation moving-bed setting
Simulation moving-bed setting is the continuous ionic switch of forming with the ion exchange column of the sodium type of the inserting clinoptilolite of 36 jacketed; The sodium type clinoptilolite that every ion exchange column is inserted is 1000g; Highly be 1.0m, every ion exchange column suitable for reading passes through a valve and is connected with a four-way, and this four-way connects three valves again; The end opening of every ion exchange column also is connected with a four-way through a valve, and this four-way connects three valves again; Following three layers was I-III layer during these 36 ion exchange columns were divided into, and totally 12 row are the 1-12 row; Pipeline connecting mode between every layer of 12 ion exchange column is: the end opening of first ion exchange column is connected the suitable for reading of the second ion exchange column of this layer through four-way with valve; Connect successively, the end opening of the 12 ion exchange column is connected the suitable for reading of first ion exchange column of this layer through four-way with valve; Pipeline connecting mode between three ion exchange columns of every row is: the end opening that is connected the ion exchange column of the 1st II layer that is listed as through four-way with valve suitable for reading of the ion exchange column of the III layer of the 1st row; The end opening of ion exchange column that is connected the I layer of the 1st row through four-way with valve suitable for reading of the ion exchange column of II layer; The end opening that is connected the ion exchange column of the 2nd III layer that is listed as through four-way with valve suitable for reading of the ion exchange column of the I layer of the 1st row; And the like connection, the end opening that is connected the ion exchange column of the 1st III layer that is listed as through four-way with valve suitable for reading of the ion exchange column of the I layer of the 12nd row; Above-mentioned whole continuous ionic switch is divided into adsorption zone, elution zone and breeding blanket; Wherein, every layer constitutes an absorbing unit by the series connection of 3～6 ion exchange columns in the adsorption zone, makes the height of mass transfer of each absorbing unit be controlled to be 3～6m; Comprise three absorbing units altogether, form 3～6 row; Elution zone by placed in-line 2～4 row totally 6～12 absorption saturated ion exchange columns constitute, the elution process height of mass transfer is 6～12m; Accomplish the ion exchange column of wash-out operation and form the breeding blanket, the breeding blanket by placed in-line 2～4 row the ion exchange column behind totally 6～12 wash-outs constitute, the regenerative process height of mass transfer is 6～12m;
Second step, adsorption process
Adsorption process is carried out at the described adsorption zone of the first step; The adsorption process hierarchical operations; Three layers of parallel connection are carried out, under 0～30 ℃, with raw material seawater respectively from the sub-exchange column of three leafing of an absorbing unit of the described continuous ionic switch of the ion exchange column feeding the first step suitable for reading; Sodium ion on potassium ion in the seawater and the sodium type clinoptilolite exchanges, and the absorption flow velocity of raw material seawater is that the void tower flow velocity is 5～50m/h; The density range of raw material seawater is 2 ° of Be '～12 ° Be ' (degree Beaume); The seawater that discharge the absorption back is flowed out by the ion exchange column end opening; Treat to withdraw from first ion exchange column after the sodium ion on the clinoptilolite and potassium ion generation permutoid reaction are fully in first ion exchange column of each layer of this absorbing unit; And then the ion exchange column to be adsorbed of connecting is as next absorbing unit; It is suitable for reading that the raw material seawater import is changed first ion exchange column that is passed into this next one absorbing unit, and the seawer outlet that discharge the absorption back also changes new placed in-line ion exchange column into, successively operation;
The 3rd step, elution process
Elution process is carried out in the described elution zone of the first step, the operation of elution process apportion, and three layers of series connection are carried out; Under 25 ℃～100 ℃ temperature; Use concentration be the ammonium chloride solution of 198～310g/L as eluent, with fresh water the seawater in the sodium type clinoptilolite post in the ion exchange column is ejected earlier, more above-mentioned eluent is fed the saturated ion exchange column of the 1st row absorption of the absorbing unit of accomplishing adsorption process in second step; Elution flow rate is that the void tower flow velocity is 5～10m/h; Discharge behind the wash-out and obtain rich potassium liquid, withdraw from the saturated ion exchange column of the 2nd row absorption of connecting again after the saturated ion exchange column wash-out of the 1st row absorption of treating this elution zone finishes; Push ahead with the fixed height of mass transfer, successively operation;
The 4th step, regenerative process
Elution process is carried out in the described breeding blanket of the first step, the operation of regenerative process apportion, and three layers of series connection are carried out; Under 50～100 ℃ of temperature; Feed the ion exchange column behind the second step wash-out with the regenerator saturated brine, regeneration velocity is that the void tower flow velocity is 5～10m/h, and discharging and obtaining regenerated liquid is ammonium salt-containing water; Clinoptilolite regeneration in the ion exchange column at this moment transfers the sodium type again to and can recycle repeatedly; The IX column regeneration of treating the 1st row of this breeding blanket finishes and withdraws from, the ion exchange column of series connection next column, operation successively; The regenerated liquid ammonium salt-containing water that obtains in the regenerative process adds sodium hydroxide and carries out ammonia still process processing recovery ammonia, and the recovered brine after the ammonia still process also supplies to recycle.
In operate continuously, the second step adsorption process, the 3rd step elution process and the 4th step regenerative process are carried out simultaneously.
2. from seawater, put forward the method for potassium according to claim 1 is said with the continuous ionic exchange process, it is characterized in that: the size of said every ion exchange column is φ 36 * 1000mm.
3. from seawater, put forward the method for potassium according to claim 1 is said with the continuous ionic exchange process, it is characterized in that: containing potassium concn in the said raw material seawater is 0.61g/L～1.52g/L, and containing potassium concn in the seawater that discharge the absorption back is 0.01g/L～0.15g/L.
4. from seawater, put forward the method for potassium according to claim 1 is said with the continuous ionic exchange process, it is characterized in that: discharge behind the wash-out in the said elution process and obtain rich potassium liquid, it contains K
+Be 36.00g/L～44.12g/L.
5. from seawater, put forward the method for potassium according to claim 1 is said with the continuous ionic exchange process, it is characterized in that: it is ammonium salt-containing water that the discharge in the said regenerative process obtains regenerated liquid, and it contains NH
4 +Be 5.09g/L～6.27g/L.
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