CN102826574B - 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 by ion exchange method processes seawater, specifically by continuous ionic exchange process, from seawater, puies forward the method for potassium.
Background technology
Potassium is one of fertilizer element.Potassium In Plants content is only second to nitrogen, is requisite element in 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, potassium product is mainly to be processed and obtained by land solid kalium mine or salt lake brine both at home and abroad.Due to the shortage of China land potassium ore resources, main dependence on import, therefore, the R&D work of new technology that exploitation total reserves reaches the seawater potassium resource of 550,000,000,000,000 tons 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.Take in the Extracting Potash from Seawater by Ion Exchange Method technique that natural zeolite is ion-exchanger, CN101850991B discloses a kind of " by the processing method of seawater preparing potassium chloride ", the method seawater is that raw material adsorbs, take the mixture of ammonium chloride and sodium-chlor as eluent obtains the solution of rich potassium, through pervaporation sepn process, obtain Repone K.CN1792797 has disclosed a kind of " with seawater, extracting the method for potassium sulfate ", the method is that to take seawater and ammonium sulfate be raw material, first the wash-out operation that adopts ammoniumsulphate soln to carry out wash-out to the adsorptive in the ion exchange column of filling sodium type clinoptilolite is prepared rich potassium liquid, then adopts in rich potassium liquid, to pass into ammonia and analyse operation preparing potassium sulfate to separate out the ammonia of potassium sulfate.The related rich potassium step of existing patented technology all adopts bed technology above, periodical operation, the operational cycle is long, the rich potassium liquid of gained composition is unstable, and in seawater the rate of recovery lower than 50%.
Summary of the invention
Technical problem to be solved by this invention is: the method for carrying potassium by continuous ionic exchange process from seawater is provided, it is the processing method of the rich potassium of a kind of simulation moving-bed continuous ionic exchange process seawater, by converting the material import and export position of single fixed-bed ion exchanger, realize the continuous reverse relative movement of seawater and eluent, the seawater of take adsorbs as raw material, the rich saspachite of ammonium chloride solution wash-out, prepares 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, gained richness potassium liquid composition is unstable, and in seawater the rate of recovery lower than 50% shortcoming.
The present invention solves this technical problem adopted technical scheme: by continuous ionic exchange process, from seawater, putting forward the method for potassium, is the processing method of the rich potassium of a kind of simulation moving-bed continuous ionic exchange process seawater, and step is as follows:
The first step, simulation moving-bed setting
Simulation moving-bed setting is the continuous ion exchange unit with the ion exchange column composition of the sodium type of the inserting clinoptilolite of 36 jacketeds, the sodium type clinoptilolite that every ion exchange column is inserted is 1000g, be highly 1.0m, every ion exchange column suitable for reading passes through a valve and is connected with a four-way, this four-way connects again three valves, the end opening of every ion exchange column is also connected with a four-way by a valve, and this four-way connects again three valves, it is I-III layer that these 36 ion exchange columns are divided into three layers of upper, middle and lowers, and totally 12 row are 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 with valve by four-way, 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 with valve by four-way, 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 being listed as by four-way with valve suitable for reading of the ion exchange column of the III layer of the 1st row, the end opening that is connected the ion exchange column of the 1st I layer being listed as by 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 being listed as by four-way with valve suitable for reading of the ion exchange column of the I layer of the 1st row, the like connection, the end opening that is connected the ion exchange column of the 1st III layer being listed as by four-way with valve suitable for reading of the ion exchange column of the I layer of the 12nd row, above-mentioned whole continuous ion exchange unit is divided into adsorption zone, elution zone and breeding blanket, wherein, in adsorption zone every layer by 3～6 ion exchange column absorbing units in series, it is 3～6m that the height of mass transfer of each absorbing unit is controlled, comprise altogether three absorbing units, form 3～6 row, elution zone by connect 2～4 row totally 6～12 absorption saturated ion exchange columns form, elution process height of mass transfer is 6～12m, the ion exchange column that completes wash-out operation forms breeding blanket, breeding blanket by 2～4 row of connecting the ion exchange column after totally 6～12 wash-outs form, regenerative process height of mass transfer is 6～12m,
Second step, adsorption process
Adsorption process is carried out in the adsorption zone described in the first step, adsorption process hierarchical operations, three layers of parallel connection are carried out, at 0～30 ℃, by raw material seawater respectively from three layers of ion exchange column of an ion exchange column absorbing unit that passes into the continuous ion exchange unit described in the first step suitable for reading, sodium ion on potassium ion in seawater and sodium type clinoptilolite exchanges, and the absorption flow velocity of raw material seawater is that 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 of discharging after absorption is flowed out by ion exchange column end opening, until the sodium ion on clinoptilolite in first ion exchange column of every one deck of this absorbing unit and potassium ion generation permutoid reaction, withdraw from first ion exchange column after completely, and then the ion exchange column upon adsorption of connecting is as next absorbing unit, raw material seawater import is changed to be passed into first ion exchange column of this next one absorbing unit suitable for reading, the seawer outlet of discharging after absorption also changes the ion exchange column end opening of new series connection into, operation successively,
The 3rd step, elution process
Elution process is carried out in the elution zone described in the first step, the operation of elution process apportion, three layers of series connection are carried out, at 25 ℃～100 ℃ temperature, the ammonium chloride solution that is 198～310g/L by concentration is as eluent, first with fresh water, the seawater in the sodium type clinoptilolite post in ion exchange column is ejected, again above-mentioned eluent is passed into the saturated ion exchange column of the 1st row absorption of the absorbing unit that completes adsorption process in second step, elution flow rate is that void tower flow velocity is 5～10m/h, after wash-out, discharge and obtain rich potassium liquid, treat to withdraw from after the 1st of this elution zone is listed as the saturated ion exchange column wash-out of absorption, the 2nd row of connecting again adsorb saturated ion exchange column, with the height of mass transfer of fixing, push ahead, operation successively,
The 4th step, regenerative process
Elution process is carried out in the breeding blanket described in the first step, the operation of regenerative process apportion, three layers of series connection are carried out, at 50～100 ℃ of temperature, with regenerator saturated brine, pass into the ion exchange column after the 3rd step wash-out, regeneration velocity is that void tower flow velocity is 5～10m/h, it is ammonium salt-containing water that discharge obtains regenerated liquid, the now regeneration of the clinoptilolite in ion exchange column transfers again sodium type to and can use by iterative cycles, treat complete the withdrawing from of ion-exchange column regeneration of the 1st row of this breeding blanket, the ion exchange column of series connection next column, operation successively, the regenerated liquid ammonium salt-containing water obtaining in regenerative process adds sodium hydroxide to carry out ammonia still process processing recovery ammonia, recovered brine after ammonia still process is also for recycling,
In operate continuously, second step adsorption process, the 3rd step elution process and the 4th step regenerative process are carried out simultaneously.
The above-mentioned method of carrying potassium by continuous ionic exchange process from seawater, the size of described every ion exchange column is φ 36 * 1000mm.
The above-mentioned method of carrying potassium by continuous ionic exchange process from seawater, is 0.61g/L～1.52g/L containing potassium concn in described raw material seawater, in the seawater of discharging after absorption, containing potassium concn, is 0.01g/L～0.15g/L.
The above-mentioned method of carrying potassium by continuous ionic exchange process from seawater, discharges and obtains rich potassium liquid after the wash-out in described elution process, and it is containing K
+for 36.00g/L～44.12g/L.
The above-mentioned method of carrying potassium by continuous ionic exchange process from seawater, it is ammonium salt-containing water that the discharge in described regenerative process obtains regenerated liquid, it is containing NH
4 +for 5.09g/L～6.27g/L.
The above-mentioned method of carrying potassium by continuous ionic exchange process from seawater, involved equipment, raw material and reagent are all by commercially available, and related operating procedure is well-known to those having ordinary skill in the art.
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 outstanding substantive distinguishing features by continuous ionic exchange process is to change operate continuously into by fixed-bed intermittent operation, three layers of ion exchange column parallel connection of adsorption process are carried out, adsorption time shortens to 1/3 of fixed bed, in seawater, the extraction yield of potassium rises to 2～3 times of prior art, 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 is mainly that adsorption time is controlled, the inventive method adopts continuous ionic exchange process to carry out, shortened the operational cycle, improved efficiency, further reduce cost, improved economic benefit; The inventive method has improved again potassium extraction yield in seawater, obtain rich potassium liquid stable components, and having raw material is easy to get, the advantage that cost is low, because the potassium reserves of seawater are inexhaustible, thereby can not be restricted with the raw materials used source of the inventive method, for realizing China's Agricultural Potassium self-sufficiency, opened up new approach.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is that the ion exchange column in the inventive method connects component used and mode of connection schematic diagram each other.
Fig. 2 is the pipeline connection diagram between three layers of upper, middle and lowers and 36 ion exchange columns of 12 row that is divided into of continuous ion exchange unit in the inventive method.
Fig. 3 be the inventive method in operate continuously, the schematic diagram that adsorption process, elution process and regenerative process are carried out simultaneously.
In figure, 1. ion exchange column, 2. four-way, 3. valve, 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 connection by four-way 2 and valve 3 each other, suitable for reading 4 of every ion exchange column 1 is connected with a four-way 2 by a valve 3, this four-way 2 connects again three valves 3, the end opening 5 of every ion exchange column 1 is also connected with a four-way 2 by a valve 3, and this four-way 2 connects again three valves 3.
Embodiment illustrated in fig. 2 showing, it is I～III layer that 36 ion exchange columns 1 in the inventive method are divided into three layers of upper, middle and lowers, and totally 12 row 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 by 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 by 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 passes through four-way 2 is connected the ion exchange column 1 of the 1st II layer being listed as end opening 5 with valve 3, suitable for reading 4 of the ion exchange column 1 of II layer passes through four-way 2 is connected the ion exchange column 1 of the 1st I layer being listed as end opening 5 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 by four-way 2 with valve 3, the like connection, suitable for reading 4 of the ion exchange column 1 of the I layer of the 12nd row passes through four-way 2 is connected the ion exchange column 1 of the 1st III layer being listed as end opening 5 with valve 3.Mean ion exchange column 1 suitable for reading 4 that connects I layer the 12nd row " connect (1)-I-12 suitable for reading " indicating in this figure, by that analogy.
Demonstration embodiment illustrated in fig. 3,36 ion exchange columns 1 in the inventive method are pressed to 1#～36# numbering, being divided into three layers of upper, middle and lowers is I～III layer, wherein, I layer has 1#, 4#, 7#, 10#, 13#, 16#, 19#, 22#, 25#, 28#, 31# and 34# ion exchange column 1, II layer has 2#, 5#, 8#, 11#, 14#, 17#, 20#, 23#, 26#, 29#, 32# and 35# ion exchange column 1, the III layer to have 3#, 6#, 9#, 12#, 15#, 18#, 21#, 24#, 27#, 30#, 33# and 36# ion exchange column 1; Be arranged in again i.e. 1～12 row of 12 row, 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 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 enters from suitable for reading 4 of the 10th row 28#, 29# and 30# ion exchange column 1 respectively simultaneously, and the seawater of discharging after absorption is discharged by the end opening 5 of the 12nd row 34#, 35# and 36# ion exchange column 1 respectively simultaneously.Now, the ion exchange column 1 of 5th～8 row is elution zone, eluent enters from the end opening 5 of the 15# ion exchange column 1 of the 3rd layer of the 5th row, through 14#, 13#, 18#, 17#, 16#, 21#, 20#, 19#, 24#, 23# and the 22# ion exchange column 1 of series connection, by suitable for reading 4 of 22# ion exchange column 1, flow out rich potassium liquid.Equally now, the ion exchange column 1 of 1st～4 row is breeding blanket, regenerator enters from the end opening 5 of the 3# ion exchange column 1 of the 3rd layer of the 1st row, through 2#, 1#, 6#, 5#, 4#, 9#, 8#, 7#, 12#, 11# and the 10# ion exchange column 1 of series connection, by suitable for reading 4 of 10# ion exchange column 1, flow out regenerated liquid.Now tri-pillars of 25#, 26# and 27# are in adsorbing the state of complete wait wash-out.
Below continuous ion exchange unit used in all embodiment, that size with the sodium type of the inserting clinoptilolite of 36 jacketeds is the continuous ion exchange unit that the ion exchange column 1 of φ 36 * 1000mm forms, the sodium type clinoptilolite that every ion exchange column 1 is inserted is 1000g, be highly 1.0m, by above-mentioned Fig. 1 and setting embodiment illustrated in fig. 2, complete the following example whole continuous ion exchange unit used.
The first step, simulation moving-bed setting
Complete as mentioned above simulation moving-bed setting, whole continuous ion exchange unit is divided into adsorption zone, elution zone and breeding blanket, wherein, in adsorption zone by 6 ion exchange column 1 absorbing units in series, the height of mass transfer of each absorbing unit is controlled as 6m, comprise altogether three absorbing units, form 3 row; Elution zone by connect 3 row totally 9 absorption saturated ion exchange columns 1 form, elution process height of mass transfer is 9m; The ion exchange column 1 that completes wash-out operation forms breeding blanket, breeding blanket by 3 row of connecting the ion exchange column 1 after totally 9 wash-outs form, regenerative process height of mass transfer is 9m;
Second step, adsorption process
Adsorption process is carried out in the adsorption zone described in the first step, adsorption process hierarchical operations, three layers of parallel connection are carried out, at 10 ℃, just 13L is that the raw material seawater of 14.18Kg is respectively from the ion exchange column 1 of the absorbing unit of the continuous ion exchange unit described in the ion exchange column suitable for reading 4 of three layers of ion exchange column 1 passes into the first step, sodium ion on potassium ion in seawater and sodium type clinoptilolite exchanges, and the absorption flow velocity of raw material seawater is that void tower flow velocity is 20m/h, the density of raw material seawater is 12 ° of Be ' (degree Beaume), the seawater of discharging after absorption is flowed out by ion exchange column end opening 5, until the sodium ion on the sodium type clinoptilolite in first ion exchange column 1 of every one deck of this absorbing unit and potassium ion generation permutoid reaction, withdraw from first ion exchange column 1 after completely, and then the ion exchange column upon adsorption 1 of connecting is as next absorbing unit, raw material seawater import is changed to first ion exchange column suitable for reading 4 that is passed into this next one absorbing unit, the seawer outlet of discharging after absorption also changes the ion exchange column end opening 5 of the ion exchange column 1 of new series connection into, operation successively, in raw material seawater, containing potassium concn, be 1.52g/L, in the seawater of discharging after absorption, containing potassium concn, be 0.15g/L, potassium ion in seawater is switched in sodium type clinoptilolite, adsorption rate is 90.13%.
The 3rd step, elution process
Elution process is carried out in the elution zone described in the first step, the operation of elution process apportion, three layers of series connection are carried out, at 80 ℃ of temperature, the ammonium chloride solution that is 198g/L by concentration is as eluent, first with fresh water, the seawater in the clinoptilolite post in ion exchange column 1 is ejected, again above-mentioned eluent is passed into the saturated ion exchange column 1 of the 1st row absorption of the absorbing unit that completes adsorption process in second step, elution flow rate is that void tower flow velocity is 8m/h, after wash-out, discharge when obtaining rich potassium liquid 1.5L and being 1.74Kg, after adsorbing saturated ion exchange column 1 wash-out, withdraw from the 1st row of this elution zone, this elution zone the 2nd row of connecting again adsorb saturated ion exchange column 1, with the height of mass transfer of fixing, push ahead, operation successively, obtain rich potassium liquid, containing K
+for 42.00g/L.
The 4th step, regenerative process
Elution process is carried out in the breeding blanket described in the first step, the operation of regenerative process apportion, three layers of series connection are carried out, under temperature 50 C, with 5L, be that 6.00Kg regenerator saturated brine passes into the ion exchange column 1 after the 3rd step wash-out, regeneration velocity is that void tower flow velocity is 5m/h, and discharging and obtaining regenerated liquid is ammonium salt-containing water 5L, and it is containing NH
4 +for 5.81g/L, the now regeneration of the clinoptilolite in ion exchange column 1 transfers again sodium type to and can use by iterative cycles, treat complete the withdrawing from of ion exchange column 1 regeneration of the 1st row of this breeding blanket, the connect ion exchange column 1 of next column of this breeding blanket, operation successively, the regenerated liquid ammonium salt-containing water obtaining in regenerative process adds sodium hydroxide to carry out ammonia still process processing recovery ammonia, and the recovered brine after ammonia still process is also for recycling;
In operate continuously, 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 in Table 1.
Material composition in table 1 embodiment 1 each operating process
The first step, simulation moving-bed setting
Complete as mentioned above simulation moving-bed setting, above-mentioned whole continuous ion exchange unit is divided into adsorption zone, elution zone and breeding blanket, wherein, in adsorption zone every layer by 3 ion exchange column 1 absorbing units in series, the height of mass transfer of each absorbing unit is controlled as 3m, comprise altogether three absorbing units, form 3 row; Elution zone by connect 2 row totally 6 absorption saturated ion exchange columns 1 form, elution process height of mass transfer is 6m; The ion exchange column 1 that completes wash-out operation forms breeding blanket, breeding blanket by 4 row of connecting the ion exchange column 1 after totally 12 wash-outs form, regenerative process height of mass transfer is 12m;
Second step, adsorption process
Adsorption process is carried out in the adsorption zone described in the first step, adsorption process hierarchical operations, three layers of parallel connection are carried out, at 30 ℃, just 37L is that the raw material seawater of 37.18Kg is respectively from the ion exchange column 1 of the absorbing unit of the continuous ion exchange unit described in the ion exchange column suitable for reading 4 of three layers of ion exchange column 1 passes into the first step, sodium ion on potassium ion in seawater and sodium type clinoptilolite exchanges, and the absorption flow velocity of raw material seawater is that void tower flow velocity is 50m/h, the density of raw material seawater is 2 ° of Be ' (degree Beaume), the seawater of discharging after absorption is flowed out by ion exchange column end opening 5, until the sodium ion on the sodium type clinoptilolite in first ion exchange column 1 of every one deck of this absorbing unit and potassium ion generation permutoid reaction, withdraw from first ion exchange column 1 after completely, and then the ion exchange column upon adsorption 1 of connecting is as next absorbing unit, raw material seawater import is changed to first ion exchange column suitable for reading 4 that is passed into this next one absorbing unit, the seawer outlet of discharging after absorption also changes the ion exchange column end opening 5 of the ion exchange column 1 of new series connection into, operation successively, in raw material seawater, containing potassium concn, be 0.61g/L, in the seawater of discharging after absorption, containing potassium concn, be 0.01g/L, potassium ion in seawater is switched in sodium type clinoptilolite, adsorption rate is 98.36%.
The 3rd step, elution process
Elution process is carried out in the elution zone described in the first step, the operation of elution process apportion, three layers of series connection are carried out, at 100 ℃ of temperature, the ammonium chloride solution that is 310g/L by concentration is as eluent, first with fresh water, the seawater in the clinoptilolite post in ion exchange column 1 is ejected, again above-mentioned eluent is passed into the saturated ion exchange column 1 of the 1st row absorption of the absorbing unit that completes adsorption process in second step, elution flow rate is that void tower flow velocity is 10m/h, after wash-out, discharge when obtaining rich potassium liquid 1.4L and being 1.62Kg, after adsorbing saturated ion exchange column 1 wash-out, withdraw from the 1st row of this elution zone, this elution zone the 2nd row of connecting again adsorb saturated ion exchange column 1, with the height of mass transfer of fixing, push ahead, operation successively, obtain rich potassium liquid, containing K
+for 44.12g/L.
The 4th step, regenerative process
Elution process is carried out in the breeding blanket described in the first step, three layers of series connection of regenerative process are carried out, at 100 ℃ of temperature, with 4L, be that 4.80Kg regenerator saturated brine passes into the ion exchange column 1 after the 3rd step wash-out, regeneration velocity is that void tower flow velocity is 10m/h, it is ammonium salt-containing water 3L that discharge obtains regenerated liquid, and it is containing NH
4 +for 5.09g/L, the now regeneration of the clinoptilolite in ion exchange column 1 transfers again sodium type to and can use by iterative cycles, treat complete the withdrawing from of ion exchange column 1 regeneration of the 1st row of this breeding blanket, the connect ion exchange column 1 of next column of this breeding blanket, operation successively, the regenerated liquid ammonium salt-containing water obtaining in regenerative process adds sodium hydroxide to carry out ammonia still process processing recovery ammonia, and the recovered brine after ammonia still process is also for recycling;
In operate continuously, 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 in Table 2.
Material composition in table 2 embodiment 2 each operating process
The first step, simulation moving-bed setting
Complete as mentioned above simulation moving-bed setting, above-mentioned whole continuous ion exchange unit is divided into adsorption zone, elution zone and breeding blanket, wherein, in adsorption zone every layer by 5 ion exchange column 1 absorbing units in series, the height of mass transfer of each absorbing unit is controlled as 5m, comprise altogether three absorbing units, form 5 row; Elution zone by connect 4 row totally 12 absorption saturated ion exchange columns 1 form, elution process height of mass transfer is 12m; The ion exchange column 1 that completes wash-out operation forms breeding blanket, breeding blanket by 2 row of connecting the ion exchange column 1 after totally 6 wash-outs form, regenerative process height of mass transfer is 6m;
Second step, adsorption process
Adsorption process is carried out in the adsorption zone described in the first step, adsorption process hierarchical operations, three layers of parallel connection are carried out, at 0 ℃, just 17L is that the raw material seawater of 17.87Kg is respectively from the ion exchange column 1 of the absorbing unit of the continuous ion exchange unit described in the ion exchange column suitable for reading 4 of three layers of ion exchange column 1 passes into the first step, sodium ion on potassium ion in seawater and sodium type clinoptilolite exchanges, and the absorption flow velocity of raw material seawater is that void tower flow velocity is 5m/h, the density of raw material seawater is 7 ° of Be ' (degree Beaume), the seawater of discharging after absorption is flowed out by ion exchange column end opening 5, until the sodium ion on the sodium type clinoptilolite in first ion exchange column 1 of every one deck of this absorbing unit and potassium ion generation permutoid reaction, withdraw from first ion exchange column 1 after completely, and then the ion exchange column upon adsorption 1 of connecting is as next absorbing unit, raw material seawater import is changed to first ion exchange column suitable for reading 4 that is passed into this next one absorbing unit, the seawer outlet of discharging after absorption also changes the ion exchange column end opening 5 of the ion exchange column 1 of new series connection into, operation successively, in raw material seawater, containing potassium concn, be 1.35g/L, in the seawater of discharging after absorption, containing potassium concn, be 0.07g/L, potassium ion in seawater is switched in sodium type clinoptilolite, adsorption rate is 94.81%.
The 3rd step, elution process
Elution process is carried out in the elution zone described in the first step, the operation of elution process apportion, three layers of series connection are carried out, at 25 ℃ of temperature, the ammonium chloride solution that is 250g/L by concentration is as eluent, first with fresh water, the seawater in the sodium type clinoptilolite post in ion exchange column is ejected, again above-mentioned eluent is passed into the saturated ion exchange column of the 1st row absorption of the absorbing unit that completes adsorption process in second step, elution flow rate is that void tower flow velocity is 5m/h, after wash-out, discharge when obtaining rich potassium liquid 1.7L and being 1.97Kg, after adsorbing saturated ion exchange column wash-out, withdraw from the 1st row of this elution zone, this elution zone the 2nd row of connecting again adsorb saturated ion exchange column, with the height of mass transfer of fixing, push ahead, operation successively, obtain rich potassium liquid, containing K
+for 36.00g/L.
The 4th step, regenerative process
Elution process is carried out in the breeding blanket described in the first step, three layers of series connection of regenerative process are carried out, at 80 ℃ of temperature, with 3L, be that 3.60Kg regenerator saturated brine passes into the ion exchange column after the 3rd step wash-out, regeneration velocity is that void tower flow velocity is 8m/h, it is ammonium salt-containing water 4.5L that discharge obtains regenerated liquid, and it is containing NH
4 +for 6.27g/L, the now regeneration of the clinoptilolite in ion exchange column transfers again sodium type to and can use by iterative cycles, treat complete the withdrawing from of ion exchange column 1 regeneration of the 1st row of this breeding blanket, the connect ion exchange column 1 of next column of this breeding blanket, operation successively, the regenerated liquid ammonium salt-containing water obtaining in regenerative process adds sodium hydroxide to carry out ammonia still process processing recovery ammonia, and the recovered brine after ammonia still process is also for recycling;
In operate continuously, 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 in Table 3.
Material composition in table 3 embodiment 3 each operating process
Equipment, raw material and reagent involved in above-described embodiment are all by commercially available, and related operating procedure is well-known to those having ordinary skill in the art.
Claims (5)
1. by continuous ionic exchange process, from seawater, put forward the method for potassium, it is characterized in that: be the processing method of the rich potassium of a kind of simulation moving-bed continuous ionic exchange process seawater, step is as follows:
The first step, simulation moving-bed setting
Simulation moving-bed setting is the continuous ion exchange unit with the ion exchange column composition of the sodium type of the inserting clinoptilolite of 36 jacketeds, the sodium type clinoptilolite that every ion exchange column is inserted is 1000g, be highly 1.0m, every ion exchange column suitable for reading passes through a valve and is connected with a four-way, this four-way connects again three valves, the end opening of every ion exchange column is also connected with a four-way by a valve, and this four-way connects again three valves, it is I-III layer that these 36 ion exchange columns are divided into three layers of upper, middle and lowers, and totally 12 row are 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 with valve by four-way, 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 with valve by four-way, 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 being listed as by four-way with valve suitable for reading of the ion exchange column of the III layer of the 1st row, the end opening that is connected the ion exchange column of the 1st I layer being listed as by 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 being listed as by four-way with valve suitable for reading of the ion exchange column of the I layer of the 1st row, the like connection, the end opening that is connected the ion exchange column of the 1st III layer being listed as by four-way with valve suitable for reading of the ion exchange column of the I layer of the 12nd row, above-mentioned whole continuous ion exchange unit is divided into adsorption zone, elution zone and breeding blanket, wherein, in adsorption zone every layer by 3～6 ion exchange column absorbing units in series, it is 3～6m that the height of mass transfer of each absorbing unit is controlled, comprise altogether three absorbing units, form 3～6 row, elution zone by connect 2～4 row totally 6～12 absorption saturated ion exchange columns form, elution process height of mass transfer is 6～12m, the ion exchange column that completes wash-out operation forms breeding blanket, breeding blanket by 2～4 row of connecting the ion exchange column after totally 6～12 wash-outs form, regenerative process height of mass transfer is 6～12m,
Second step, adsorption process
Adsorption process is carried out in the adsorption zone described in the first step, adsorption process hierarchical operations, three layers of parallel connection are carried out, at 0～30 ℃, by raw material seawater respectively from three layers of ion exchange column of an ion exchange column absorbing unit that passes into the continuous ion exchange unit described in the first step suitable for reading, sodium ion on potassium ion in seawater and sodium type clinoptilolite exchanges, and the absorption flow velocity of raw material seawater is that 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 of discharging after absorption is flowed out by ion exchange column end opening, until the sodium ion on clinoptilolite in first ion exchange column of every one deck of this absorbing unit and potassium ion generation permutoid reaction, withdraw from first ion exchange column after completely, and then the ion exchange column upon adsorption of connecting is as next absorbing unit, raw material seawater import is changed to be passed into first ion exchange column of this next one absorbing unit suitable for reading, the seawer outlet of discharging after absorption also changes the ion exchange column end opening of new series connection into, operation successively,
The 3rd step, elution process
Elution process is carried out in the elution zone described in the first step, the operation of elution process apportion, three layers of series connection are carried out, at 25 ℃～100 ℃ temperature, the ammonium chloride solution that is 198～310g/L by concentration is as eluent, first with fresh water, the seawater in the sodium type clinoptilolite post in ion exchange column is ejected, again above-mentioned eluent is passed into the saturated ion exchange column of the 1st row absorption of the absorbing unit that completes adsorption process in second step, elution flow rate is that void tower flow velocity is 5～10m/h, after wash-out, discharge and obtain rich potassium liquid, treat to withdraw from after the 1st of this elution zone is listed as the saturated ion exchange column wash-out of absorption, the 2nd row of connecting again adsorb saturated ion exchange column, with the height of mass transfer of fixing, push ahead, operation successively,
The 4th step, regenerative process
Elution process is carried out in the breeding blanket described in the first step, the operation of regenerative process apportion, three layers of series connection are carried out, at 50～100 ℃ of temperature, with regenerator saturated brine, pass into the ion exchange column after the 3rd step wash-out, regeneration velocity is that void tower flow velocity is 5～10m/h, it is ammonium salt-containing water that discharge obtains regenerated liquid, the now regeneration of the clinoptilolite in ion exchange column transfers again sodium type to and can use by iterative cycles, treat complete the withdrawing from of ion-exchange column regeneration of the 1st row of this breeding blanket, the ion exchange column of series connection next column, operation successively, the regenerated liquid ammonium salt-containing water obtaining in regenerative process adds sodium hydroxide to carry out ammonia still process processing recovery ammonia, recovered brine after ammonia still process is also for recycling,
In operate continuously, second step adsorption process, the 3rd step elution process and the 4th step regenerative process are carried out simultaneously.
2. according to the said method of carrying potassium by continuous ionic exchange process from seawater of claim 1, it is characterized in that: the size of described every ion exchange column is φ 36 * 1000mm.
3. according to the said method of carrying potassium by continuous ionic exchange process from seawater of claim 1, it is characterized in that: in described raw material seawater, containing potassium concn, being 0.61g/L～1.52g/L, is 0.01g/L～0.15g/L containing potassium concn in the seawater of discharging after absorption.
4. according to the said method of carrying potassium by continuous ionic exchange process from seawater of claim 1, it is characterized in that: after the wash-out in described elution process, discharge and obtain rich potassium liquid, it is containing K
+for 36.00g/L～44.12g/L.
5. according to the said method of carrying potassium by continuous ionic exchange process from seawater of claim 1, it is characterized in that: it is ammonium salt-containing water that the discharge in described regenerative process obtains regenerated liquid, it is containing NH
4 +for 5.09g/L～6.27g/L.
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| CN103482656A (en) * | 2013-09-23 | 2014-01-01 | 河北工业大学 | Method for beneficiation of potassium from salt lake brine |
| CN107673372B (en) * | 2017-11-15 | 2023-09-08 | 河北工业大学 | Large-scale potassium-rich method and device based on coupling technology |
| CN108996521B (en) * | 2018-08-07 | 2021-03-26 | 泉州师范学院 | Process for producing high-purity refined salt by using selective electrodialysis concentrated brine |
| CN112723381A (en) * | 2019-10-14 | 2021-04-30 | 山东潍坊润丰化工股份有限公司 | Recycling method of ammonium chloride and sodium chloride mixed salt |
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