CN102814058A - Method for implementing nickel-magnesium separation, enrichment and purification by using heavy metal adsorbing material - Google Patents
Method for implementing nickel-magnesium separation, enrichment and purification by using heavy metal adsorbing material Download PDFInfo
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- CN102814058A CN102814058A CN2012103447446A CN201210344744A CN102814058A CN 102814058 A CN102814058 A CN 102814058A CN 2012103447446 A CN2012103447446 A CN 2012103447446A CN 201210344744 A CN201210344744 A CN 201210344744A CN 102814058 A CN102814058 A CN 102814058A
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- sorbing material
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000000926 separation method Methods 0.000 title claims abstract description 33
- 238000000746 purification Methods 0.000 title claims abstract description 23
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 168
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 164
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 81
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 75
- 239000007788 liquid Substances 0.000 claims abstract description 52
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 65
- 235000021110 pickles Nutrition 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 238000010521 absorption reaction Methods 0.000 claims description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 239000003153 chemical reaction reagent Substances 0.000 claims description 34
- 239000000741 silica gel Substances 0.000 claims description 32
- 229910002027 silica gel Inorganic materials 0.000 claims description 32
- 238000001291 vacuum drying Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000004070 electrodeposition Methods 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 230000008030 elimination Effects 0.000 claims description 8
- 238000003379 elimination reaction Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 159000000003 magnesium salts Chemical class 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000000693 micelle Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 abstract description 7
- 239000011777 magnesium Substances 0.000 abstract description 7
- 238000002386 leaching Methods 0.000 abstract 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- 239000000395 magnesium oxide Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention provides a method for implementing nickel-magnesium separation, enrichment and purification by using a heavy metal adsorbing material, which comprises the following steps: S1. filling a heavy metal adsorbing material into an adsorption column of continuous adsorption exchange equipment; S2. regulating the pH value of a solution to be treated containing nickel ions and magnesium ions to 1.0-5.5, thereby obtaining an acid leaching solution; S3. injecting the acid leaching solution into the continuous adsorption exchange equipment after the operation of S1; and S4. carrying out separation, enrichment and purification on the acid leaching solution by using the continuous adsorption exchange equipment. The experiment proves that the accurate control on the temperature and flow rate of the treatment solution can implement separation of nickel and magnesium; and therefore, the method provided by the invention can be used for separating and recovering slight or trace amounts of nickel and magnesium in the liquid.
Description
Technical field
The invention belongs to the heavy metal separation technology field, be specifically related to a kind of method that realizes the separation of nickel magnesium, enrichment, purification through the heavy metal sorbing material.
Background technology
Along with the develop rapidly of World Economics and the continuous increase of the size of population, become the important bottleneck of world development a little less than relative inadequacy of resources and the environmental carrying capacity.Build resource-conserving and friendly environment society, advance the conservation culture construction, become the theme that various countries, the world today pay close attention to.
At present; For the various industrial wastewaters that contain heavy metal ion, sanitary sewage and nuclear industry waste water; Generally adopt methods such as chemical precipitation method, oxidation-reduction method or ion-exchange that it is handled, thereby reduce content of beary metal in the water resource, reduce the harm of heavy metal pollution.
But there is the low and defect of high cost of removal efficient of heavy metal ions in wastewater in the processing method of all kinds of heavy metal wastewater therebies that adopt at present.
Summary of the invention
To the defective that prior art exists, the present invention provides a kind of method through the separation of heavy metal sorbing material realization nickel magnesium, enrichment, purification, has the advantage strong to the selective absorption of nickel ion.
The technical scheme that the present invention adopts is following:
The present invention provides a kind of method through the separation of heavy metal sorbing material realization nickel magnesium, enrichment, purification, may further comprise the steps:
S1 fills the heavy metal sorbing material in the adsorption column of continuous adsorption switching equipment;
S2, the pH that adjustment contains the pending liquid of nickel ion and magnesium ion is 1.0-5.5, obtains pickle liquor;
S3 injects the said continuous adsorption switching equipment after S1 operates with said pickle liquor;
S4, said continuous adsorption switching equipment carry out separation and concentration to said pickle liquor and purify under 25-40 ℃, specifically comprise: with pH is the inlet that the said pickle liquor of 1.0-5.5 pumps into said continuous adsorption switching equipment; Nickel ion in the said pickle liquor of said adsorption column adsorption and enrichment; Collect the magnesium ion solution that contains then from said adsorption column liquid outlet outflow;
S5 is that the sulfuric acid of 5-30% washes said adsorption column with mass fraction; Said heavy metal sorbing material in the said adsorption column carries out the desorb operation, after the desorb operation, obtains containing the nickel ion stripping liquid and by the said heavy metal sorbing material of desorb;
S6, the said nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation through direct electrodeposition equipment, obtains nickel metallic plate or nickel metal powder; Simultaneously, recover absorption property after the said heavy metal sorbing material process flushing by desorb in the adsorption column is handled;
After concentrating, magnesium ion solution processed magnesium salts said the containing that S4 obtains.
Preferably, said heavy metal sorbing material is prepared through following method:
Preliminary treatment: under ultrasonic field, raw material silica gel is scattered in the hydrochloric acid solution of 7-10mol/L, reflux 20-30 hour, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution was 4-6: 1; Filter then, the elimination acid solution, Cake Wash obtains activated silica gel to neutral after the 110-140 ℃ of vacuum drying;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent, stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent, obtains first solution, and wherein, the mass ratio of silylating reagent and xylene solution is 5-8: 1; In activated silica gel, add dry DMF, stirring makes and mixes, and obtains second solution, and wherein, the mass ratio of activated silica gel and DMF is 5-10: 1; Silylating reagent and activated silica gel mass ratio are 2-4: 1;
First flow of solution is added in second solution of reflux state, stream add finish after, continued back flow reaction 10-20 hour; Filtering reacting liquid after reducing to 20-30 ℃, filter cake are used methyl alcohol and toluene wash successively, and vacuum drying obtains said heavy metal sorbing material then.
Preferably, the power of said ultrasonic field is 150-250 watt;
Said vacuum drying in the silica gel bonded reaction specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, think that the speed cooling of 5-8 ℃/min is refrigerated to-50--45 ℃, keep-time of 50--45 ℃ is 4-5 hour;
Second stage is warming up to-10--5 ℃ with the speed of 3-6 ℃/min, keep-time of 10--5 ℃ is 5-7 hour;
Phase III puts fast and is 160 ℃-170 ℃ vacuum drying chamber to temperature, promptly obtains said heavy metal sorbing material 13-17 hour drying time.
Preferably, said silylating reagent is 3-ethylenediamine base propyl trimethoxy silicane or 3-Diethylenetriamine base propyl trimethoxy silicane.
Preferably, the aperture of said heavy metal sorbing material is 5.25-7.38nm, and the pore volume of said heavy metal sorbing material is 1.0-1.4 cubic centimetre/gram.
Preferably, said raw silicon micelle degree is a 300-400 order silica gel.
Preferably, S4 specifically comprises following three phases:
Phase I: the pickle liquor that with pH is 1.0-5.5 pumps into the inlet of said continuous adsorption switching equipment with the speed of 2-4ml/min, and is by said adsorption column absorbed Ni ion and magnesium ion simultaneously, saturated to nickel ion absorption up to said adsorption column;
Second stage: the inlet that pickle liquor is pumped into said continuous adsorption switching equipment with the speed of 7-9ml/min; The continuous absorbed Ni ion of said adsorption column; And the nickel ion of new absorption replaces the magnesium ion of former absorption, and the magnesium ion that adsorbs up to adsorption column is replaced by nickel ion fully;
After second stage is handled, collect the magnesium ion solution that contains from said adsorption column liquid outlet outflow.
Preferably, S4 specifically comprises following three phases:
Phase I: the pickle liquor that with pH is 3.5-4.0 pumps into the inlet of said continuous adsorption switching equipment with the speed of 3ml/min, and is by said adsorption column absorbed Ni ion and magnesium ion simultaneously, saturated to nickel ion absorption up to said adsorption column;
Second stage: the inlet that pickle liquor is pumped into said continuous adsorption switching equipment with the speed of 8ml/min; The continuous absorbed Ni ion of said adsorption column; And the nickel ion of new absorption replaces the magnesium ion of former absorption, and the magnesium ion that adsorbs up to adsorption column is replaced by nickel ion fully;
After second stage is handled, collect the magnesium ion solution that contains from said adsorption column liquid outlet outflow.
Below the present invention is further introduced:
Novelty of the present invention prepare a heavy metal species sorbing material, through experiment showed, this heavy metal sorbing material nickel ion is had stronger adsorptivity; Adsorb magnesium ion hardly, to these characteristics, for realizing separating to nickel ion and magnesium ion; The inventor has carried out test of many times to the technology of using adsorption column to cross post, and unexpected the discovery is through to the temperature of crossing post and the accurate control of flow velocity; Can realize separating of nickel ion and magnesium ion preferably, and, in the preparation process of heavy metal sorbing material; As well known to those skilled in the art, silica gel is the porous mass that is formed by the intermolecular dehydration of poly silica gel, and the water in the silica gel structure formula comprises constitution water and adsorbed water; Wherein, constitution water links to each other with silicon atom with OH-form, is covered in the silica gel surface.The inventor is carrying out in the activation process silica gel, introduces ultrasonic technology, and has taked the violent condition with the concentrated hydrochloric acid reflux.Carry out having taked special temperature controlled processes in the dry process at heavy metal sorbing material to the hygrometric state that finally obtains, the heavy metal sorbing material of preparing thus through experiment showed, can extraordinary realization separating nickel ion and magnesium ion.Therefore, provided by the inventionly realize the method for the separation of nickel magnesium, enrichment, purification, can be applied to separating and recovery of trace in the liquid or Determination of Trace Nickel and magnesium through the heavy metal sorbing material.
The specific embodiment
Below realize that through the heavy metal sorbing material method of the separation of nickel magnesium, enrichment, purification describes in detail to provided by the invention:
Heavy metal sorbing material preparation method embodiment 1
Preliminary treatment: under 150 watts of ultrasonic fields, raw material silica gel is scattered in the hydrochloric acid solution of 10mol/L, reflux 20-30 hour, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution was 4: 1; Filter then, the elimination acid solution, Cake Wash obtains activated silica gel to neutral after 140 ℃ of vacuum drying;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-ethylenediamine base propyl trimethoxy silicane; Stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent; Obtain first solution; Wherein, the mass ratio of silylating reagent and xylene solution is 5: 1; In activated silica gel, add dry DMF, stirring makes and mixes, and obtains second solution, and wherein, the mass ratio of activated silica gel and DMF is 10: 1; Silylating reagent and activated silica gel mass ratio are 3.5: 1;
First flow of solution is added in second solution of reflux state, stream add finish after, continued back flow reaction 12 hours; Filtering reacting liquid after reducing to 24 ℃, filter cake are used methyl alcohol and toluene wash successively, and vacuum drying obtains said heavy metal sorbing material then.In this step, vacuum drying specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, and think that the speed cooling of 5 ℃/min will be refrigerated to-50 ℃, the time of keeping-50 ℃ is 4 hours;
Second stage is warming up to-7 ℃ with the speed of 5 ℃/min, and the time of keeping-7 ℃ is 5.5 hours;
Phase III puts fast and is 160 ℃ ℃ vacuum drying chamber to temperature, promptly obtains said heavy metal sorbing material 13 hours drying times.
Making the aperture is that 6.85nm, pore volume are the heavy metal sorbing material of 1.3 cubic centimetres/gram.
Heavy metal sorbing material preparation method embodiment 2
Preliminary treatment: under 250 watts of ultrasonic fields, raw material silica gel is scattered in the hydrochloric acid solution of 7mol/L, reflux 20-30 hour, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution was 6: 1; Filter then, the elimination acid solution, Cake Wash obtains activated silica gel to neutral after 110 ℃ of vacuum drying;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-Diethylenetriamine base propyl trimethoxy silicane; Stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent; Obtain first solution; Wherein, the mass ratio of silylating reagent and xylene solution is 8: 1; In activated silica gel, add dry DMF, stirring makes and mixes, and obtains second solution, and wherein, the mass ratio of activated silica gel and DMF is 10: 1; Silylating reagent and activated silica gel mass ratio are 4: 1;
First flow of solution is added in second solution of reflux state, stream add finish after, continued back flow reaction 18 hours; Filtering reacting liquid after reducing to 27 ℃, filter cake are used methyl alcohol and toluene wash successively, and vacuum drying obtains said heavy metal sorbing material then.In this step, vacuum drying specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, and think that the speed cooling of 8 ℃/min will be refrigerated to-45 ℃, the time of keeping-45 ℃ is 5 hours;
Second stage is warming up to-9 ℃ with the speed of 5 ℃/min, and the time of keeping-9 ℃ is 5.5 hours;
Phase III puts fast and is 170 ℃ vacuum drying chamber to temperature, promptly obtains said heavy metal sorbing material 13 hours drying times.
Making the aperture is that 6.32nm, pore volume are the heavy metal sorbing material of 1.1 cubic centimetres/gram.
Heavy metal sorbing material preparation method embodiment 3
Preliminary treatment: under 200 watts of ultrasonic fields, raw material silica gel is scattered in the hydrochloric acid solution of 8mol/L, reflux 20-30 hour, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution was 5: 1; Filter then, the elimination acid solution, Cake Wash obtains activated silica gel to neutral after 120 ℃ of vacuum drying;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-ethylenediamine base propyl trimethoxy silicane; Stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent; Obtain first solution; Wherein, the mass ratio of silylating reagent and xylene solution is 6: 1; In activated silica gel, add dry DMF, stirring makes and mixes, and obtains second solution, and wherein, the mass ratio of activated silica gel and DMF is 6: 1; Silylating reagent and activated silica gel mass ratio are 3.2: 1;
First flow of solution is added in second solution of reflux state, stream add finish after, continued back flow reaction 18 hours; Filtering reacting liquid after reducing to 25 ℃, filter cake are used methyl alcohol and toluene wash successively, and vacuum drying obtains said heavy metal sorbing material then.In this step, vacuum drying specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, and think that the speed cooling of 7 ℃/min will be refrigerated to-47 ℃, the time of keeping-47 ℃ is 4.5 hours;
Second stage is warming up to-6 ℃ with the speed of 5 ℃/min, and the time of keeping-6 ℃ is 6 hours;
Phase III puts fast and is 162 ℃ vacuum drying chamber to temperature, promptly obtains said heavy metal sorbing material 14 hours drying times.
Making the aperture is that 7.12nm, pore volume are the heavy metal sorbing material of 1.3 cubic centimetres/gram.
Heavy metal sorbing material preparation method embodiment 4
Preliminary treatment: under 220 watts of ultrasonic fields, raw material silica gel is scattered in the hydrochloric acid solution of 9mol/L, reflux 20-30 hour, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution was 5: 1; Filter then, the elimination acid solution, Cake Wash obtains activated silica gel to neutral after 120 ℃ of vacuum drying;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-Diethylenetriamine base propyl trimethoxy silicane; Stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent; Obtain first solution; Wherein, the mass ratio of silylating reagent and xylene solution is 7: 1; In activated silica gel, add dry DMF, stirring makes and mixes, and obtains second solution, and wherein, the mass ratio of activated silica gel and DMF is 6: 1; Silylating reagent and activated silica gel mass ratio are 3.7: 1;
First flow of solution is added in second solution of reflux state, stream add finish after, continued back flow reaction 15 hours; Filtering reacting liquid after reducing to 22 ℃, filter cake are used methyl alcohol and toluene wash successively, and vacuum drying obtains said heavy metal sorbing material then.In this step, vacuum drying specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, and think that the speed cooling of 7 ℃/min will be refrigerated to-46 ℃, the time of keeping-46 ℃ is 4.2 hours;
Second stage is warming up to-8 ℃ with the speed of 4 ℃/min, and the time of keeping-8 ℃ is 6 hours;
Phase III puts fast and is 165 ℃ vacuum drying chamber to temperature, promptly obtains said heavy metal sorbing material 15 hours drying times.
Making the aperture is that 6.32nm, pore volume are the heavy metal sorbing material of 1.2 cubic centimetres/gram.
Heavy metal sorbing material preparation method embodiment 5
Preliminary treatment: under 220 watts of ultrasonic fields, raw material silica gel is scattered in the hydrochloric acid solution of 9mol/L, reflux 20-30 hour, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution was 5.5: 1; Filter then, the elimination acid solution, Cake Wash obtains activated silica gel to neutral after 130 ℃ of vacuum drying;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-Diethylenetriamine base propyl trimethoxy silicane; Stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent; Obtain first solution; Wherein, the mass ratio of silylating reagent and xylene solution is 7: 1; In activated silica gel, add dry DMF, stirring makes and mixes, and obtains second solution, and wherein, the mass ratio of activated silica gel and DMF is 8: 1; Silylating reagent and activated silica gel mass ratio are 3.8: 1;
First flow of solution is added in second solution of reflux state, stream add finish after, continued back flow reaction 20 hours; Filtering reacting liquid after reducing to 20 ℃, filter cake are used methyl alcohol and toluene wash successively, and vacuum drying obtains said heavy metal sorbing material then.In this step, vacuum drying specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, and think that the speed cooling of 7.5 ℃/min will be refrigerated to-48 ℃, the time of keeping-48 ℃ is 4.8 hours;
Second stage is warming up to-10 ℃ with the speed of 6 ℃/min, and the time of keeping-10 ℃ is 7 hours;
Phase III puts fast and is 166 ℃ vacuum drying chamber to temperature, promptly obtains said heavy metal sorbing material 136 hours drying times.
Making the aperture is that 7.38nm, pore volume are the heavy metal sorbing material of 1.4 cubic centimetres/gram.
Heavy metal sorbing material preparation method embodiment 6
Preliminary treatment: under 160 watts of ultrasonic fields, raw material silica gel is scattered in the hydrochloric acid solution of 8mol/L, reflux 20-30 hour, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution was 4.3: 1; Filter then, the elimination acid solution, Cake Wash obtains activated silica gel to neutral after 130 ℃ of vacuum drying;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-Diethylenetriamine base propyl trimethoxy silicane; Stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent; Obtain first solution; Wherein, the mass ratio of silylating reagent and xylene solution is 5.5: 1; In activated silica gel, add dry DMF, stirring makes and mixes, and obtains second solution, and wherein, the mass ratio of activated silica gel and DMF is 7: 1; Silylating reagent and activated silica gel mass ratio are 3.2: 1;
First flow of solution is added in second solution of reflux state, stream add finish after, continued back flow reaction 10 hours; Filtering reacting liquid after reducing to 30 ℃, filter cake are used methyl alcohol and toluene wash successively, and vacuum drying obtains said heavy metal sorbing material then.In this step, vacuum drying specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, and think that the speed cooling of 7.8 ℃/min will be refrigerated to-48 ℃, the time of keeping-48 ℃ is 4.3 hours;
Second stage is warming up to-5 ℃ with the speed of 3 ℃/min, and the time of keeping-5 ℃ is 5 hours;
Phase III puts fast and is 168 ℃ vacuum drying chamber to temperature, promptly obtains said heavy metal sorbing material 15 hours drying times.
Making the aperture is that 5.25nm, pore volume are the heavy metal sorbing material of 1.0 cubic centimetres/gram.
The separation of nickel magnesium, enrichment, method of purification experimental example 1
The heavy metal sorbing material that this experimental example adopts heavy metal sorbing material preparation method embodiment 1 to prepare.
S1 fills the heavy metal sorbing material in the adsorption column of continuous adsorption switching equipment;
S2, the pH that adjustment contains the pending liquid of nickel ion and magnesium ion is 3.5, obtains pickle liquor;
S3 injects the said continuous adsorption switching equipment after S1 operates with said pickle liquor;
S4, said continuous adsorption switching equipment carry out separation and concentration to said pickle liquor and purify under 25 ℃, specifically comprise: with pH is the inlet that 3.5 said pickle liquor pumps into said continuous adsorption switching equipment; Nickel ion in the said pickle liquor of said adsorption column adsorption and enrichment; Collect the magnesium ion solution that contains then from said adsorption column liquid outlet outflow;
Wherein, specifically comprise following three phases:
Phase I: being 3.5 pickle liquor with pH pumps into the inlet of said continuous adsorption switching equipment with the speed of 2ml/min, by said adsorption column absorbed Ni ion and magnesium ion simultaneously, saturated to nickel ion absorption up to said adsorption column;
Second stage: the inlet that pickle liquor is pumped into said continuous adsorption switching equipment with the speed of 8.5ml/min; The continuous absorbed Ni ion of said adsorption column; And the nickel ion of new absorption replaces the magnesium ion of former absorption, and the magnesium ion that adsorbs up to adsorption column is replaced by nickel ion fully;
After second stage is handled, collect the magnesium ion solution that contains from said adsorption column liquid outlet outflow.
S5 is that 29% sulfuric acid washes said adsorption column with mass fraction; Said heavy metal sorbing material in the said adsorption column carries out the desorb operation, after the desorb operation, obtains containing the nickel ion stripping liquid and by the said heavy metal sorbing material of desorb;
S6, the said nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation through direct electrodeposition equipment, obtains nickel metallic plate or nickel metal powder; Simultaneously, recover absorption property after the said heavy metal sorbing material process flushing by desorb in the adsorption column is handled;
After concentrating, magnesium ion solution processed magnesium salts said the containing that S4 obtains.
The nickel mass fraction is 99.999% in the nickel powder for preparing, and magnesia amount mark is 0.001%.
The separation of nickel magnesium, enrichment, method of purification experimental example 2
The heavy metal sorbing material that this experimental example adopts heavy metal sorbing material preparation method embodiment 1 to prepare.
S1 fills the heavy metal sorbing material in the adsorption column of continuous adsorption switching equipment;
S2, the pH that adjustment contains the pending liquid of nickel ion and magnesium ion is 4.0, obtains pickle liquor;
S3 injects the said continuous adsorption switching equipment after S1 operates with said pickle liquor;
S4, said continuous adsorption switching equipment carry out separation and concentration to said pickle liquor and purify under 40 ℃, specifically comprise: with pH is the inlet that 4.0 said pickle liquor pumps into said continuous adsorption switching equipment; Nickel ion in the said pickle liquor of said adsorption column adsorption and enrichment; Collect the magnesium ion solution that contains then from said adsorption column liquid outlet outflow;
Wherein, specifically comprise following three phases:
Phase I: being 4.0 pickle liquor with pH pumps into the inlet of said continuous adsorption switching equipment with the speed of 4ml/min, by said adsorption column absorbed Ni ion and magnesium ion simultaneously, saturated to nickel ion absorption up to said adsorption column;
Second stage: the inlet that pickle liquor is pumped into said continuous adsorption switching equipment with the speed of 8.2ml/min; The continuous absorbed Ni ion of said adsorption column; And the nickel ion of new absorption replaces the magnesium ion of former absorption, and the magnesium ion that adsorbs up to adsorption column is replaced by nickel ion fully;
After second stage is handled, collect the magnesium ion solution that contains from said adsorption column liquid outlet outflow.
S5 is that 25% sulfuric acid washes said adsorption column with mass fraction; Said heavy metal sorbing material in the said adsorption column carries out the desorb operation, after the desorb operation, obtains containing the nickel ion stripping liquid and by the said heavy metal sorbing material of desorb;
S6, the said nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation through direct electrodeposition equipment, obtains nickel metallic plate or nickel metal powder; Simultaneously, recover absorption property after the said heavy metal sorbing material process flushing by desorb in the adsorption column is handled;
After concentrating, magnesium ion solution processed magnesium salts said the containing that S4 obtains.
The nickel mass fraction is 99.997% in the nickel powder for preparing, and magnesia amount mark is 0.003%.
The separation of nickel magnesium, enrichment, method of purification experimental example 3
The heavy metal sorbing material that this experimental example adopts heavy metal sorbing material preparation method embodiment 1 to prepare.
S1 fills the heavy metal sorbing material in the adsorption column of continuous adsorption switching equipment;
S2, the pH that adjustment contains the pending liquid of nickel ion and magnesium ion is 5.5, obtains pickle liquor;
S3 injects the said continuous adsorption switching equipment after S1 operates with said pickle liquor;
S4, said continuous adsorption switching equipment carry out separation and concentration to said pickle liquor and purify under 35 ℃, specifically comprise: with pH is the inlet that 5.5 said pickle liquor pumps into said continuous adsorption switching equipment; Nickel ion in the said pickle liquor of said adsorption column adsorption and enrichment; Collect the magnesium ion solution that contains then from said adsorption column liquid outlet outflow;
Wherein, specifically comprise following three phases:
Phase I: being 5.5 pickle liquor with pH pumps into the inlet of said continuous adsorption switching equipment with the speed of 3ml/min, by said adsorption column absorbed Ni ion and magnesium ion simultaneously, saturated to nickel ion absorption up to said adsorption column;
Second stage: the inlet that pickle liquor is pumped into said continuous adsorption switching equipment with the speed of 7.5ml/min; The continuous absorbed Ni ion of said adsorption column; And the nickel ion of new absorption replaces the magnesium ion of former absorption, and the magnesium ion that adsorbs up to adsorption column is replaced by nickel ion fully;
After second stage is handled, collect the magnesium ion solution that contains from said adsorption column liquid outlet outflow.
S5 is that 30% sulfuric acid washes said adsorption column with mass fraction; Said heavy metal sorbing material in the said adsorption column carries out the desorb operation, after the desorb operation, obtains containing the nickel ion stripping liquid and by the said heavy metal sorbing material of desorb;
S6, the said nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation through direct electrodeposition equipment, obtains nickel metallic plate or nickel metal powder; Simultaneously, recover absorption property after the said heavy metal sorbing material process flushing by desorb in the adsorption column is handled;
After concentrating, magnesium ion solution processed magnesium salts said the containing that S4 obtains.
The nickel mass fraction is 99.998% in the nickel powder for preparing, and magnesia amount mark is 0.002%.
The separation of nickel magnesium, enrichment, method of purification experimental example 4
The heavy metal sorbing material that this experimental example adopts heavy metal sorbing material preparation method embodiment 1 to prepare.
S1 fills the heavy metal sorbing material in the adsorption column of continuous adsorption switching equipment;
S2, the pH that adjustment contains the pending liquid of nickel ion and magnesium ion is 1.0, obtains pickle liquor;
S3 injects the said continuous adsorption switching equipment after S1 operates with said pickle liquor;
S4, said continuous adsorption switching equipment carry out separation and concentration to said pickle liquor and purify under 29 ℃, specifically comprise: with pH is the inlet that 1.0 said pickle liquor pumps into said continuous adsorption switching equipment; Nickel ion in the said pickle liquor of said adsorption column adsorption and enrichment; Collect the magnesium ion solution that contains then from said adsorption column liquid outlet outflow;
Wherein, specifically comprise following three phases:
Phase I: being 1.0 pickle liquor with pH pumps into the inlet of said continuous adsorption switching equipment with the speed of 3.5ml/min, by said adsorption column absorbed Ni ion and magnesium ion simultaneously, saturated to nickel ion absorption up to said adsorption column;
Second stage: the inlet that pickle liquor is pumped into said continuous adsorption switching equipment with the speed of 8ml/min; The continuous absorbed Ni ion of said adsorption column; And the nickel ion of new absorption replaces the magnesium ion of former absorption, and the magnesium ion that adsorbs up to adsorption column is replaced by nickel ion fully;
After second stage is handled, collect the magnesium ion solution that contains from said adsorption column liquid outlet outflow.
S5 is that 24% sulfuric acid washes said adsorption column with mass fraction; Said heavy metal sorbing material in the said adsorption column carries out the desorb operation, after the desorb operation, obtains containing the nickel ion stripping liquid and by the said heavy metal sorbing material of desorb;
S6, the said nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation through direct electrodeposition equipment, obtains nickel metallic plate or nickel metal powder; Simultaneously, recover absorption property after the said heavy metal sorbing material process flushing by desorb in the adsorption column is handled;
After concentrating, magnesium ion solution processed magnesium salts said the containing that S4 obtains.
The nickel mass fraction is 99.998% in the nickel powder for preparing, and magnesia amount mark is 0.002%.
The separation of nickel magnesium, enrichment, method of purification experimental example 5
The heavy metal sorbing material that this experimental example adopts heavy metal sorbing material preparation method embodiment 1 to prepare.
S1 fills the heavy metal sorbing material in the adsorption column of continuous adsorption switching equipment;
S2, the pH that adjustment contains the pending liquid of nickel ion and magnesium ion is 2.7, obtains pickle liquor;
S3 injects the said continuous adsorption switching equipment after S1 operates with said pickle liquor;
S4, said continuous adsorption switching equipment carry out separation and concentration to said pickle liquor and purify under 38 ℃, specifically comprise: with pH is the inlet that 2.7 said pickle liquor pumps into said continuous adsorption switching equipment; Nickel ion in the said pickle liquor of said adsorption column adsorption and enrichment; Collect the magnesium ion solution that contains then from said adsorption column liquid outlet outflow;
Wherein, specifically comprise following three phases:
Phase I: being 2.7 pickle liquor with pH pumps into the inlet of said continuous adsorption switching equipment with the speed of 2.5ml/min, by said adsorption column absorbed Ni ion and magnesium ion simultaneously, saturated to nickel ion absorption up to said adsorption column;
Second stage: the inlet that pickle liquor is pumped into said continuous adsorption switching equipment with the speed of 9ml/min; The continuous absorbed Ni ion of said adsorption column; And the nickel ion of new absorption replaces the magnesium ion of former absorption, and the magnesium ion that adsorbs up to adsorption column is replaced by nickel ion fully;
After second stage is handled, collect the magnesium ion solution that contains from said adsorption column liquid outlet outflow.
S5 is that 12% sulfuric acid washes said adsorption column with mass fraction; Said heavy metal sorbing material in the said adsorption column carries out the desorb operation, after the desorb operation, obtains containing the nickel ion stripping liquid and by the said heavy metal sorbing material of desorb;
S6, the said nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation through direct electrodeposition equipment, obtains nickel metallic plate or nickel metal powder; Simultaneously, recover absorption property after the said heavy metal sorbing material process flushing by desorb in the adsorption column is handled;
After concentrating, magnesium ion solution processed magnesium salts said the containing that S4 obtains.
The nickel mass fraction is 99.998% in the nickel powder for preparing, and magnesia amount mark is 0.002%.
The separation of nickel magnesium, enrichment, method of purification experimental example 6
The heavy metal sorbing material that this experimental example adopts heavy metal sorbing material preparation method embodiment 1 to prepare.
S1 fills the heavy metal sorbing material in the adsorption column of continuous adsorption switching equipment;
S2, the pH that adjustment contains the pending liquid of nickel ion and magnesium ion is 3.8, obtains pickle liquor;
S3 injects the said continuous adsorption switching equipment after S1 operates with said pickle liquor;
S4, said continuous adsorption switching equipment carry out separation and concentration to said pickle liquor and purify under 32 ℃, specifically comprise: with pH is the inlet that 3.8 said pickle liquor pumps into said continuous adsorption switching equipment; Nickel ion in the said pickle liquor of said adsorption column adsorption and enrichment; Collect the magnesium ion solution that contains then from said adsorption column liquid outlet outflow;
Wherein, specifically comprise following three phases:
Phase I: being 3.8 pickle liquor with pH pumps into the inlet of said continuous adsorption switching equipment with the speed of 2.9ml/min, by said adsorption column absorbed Ni ion and magnesium ion simultaneously, saturated to nickel ion absorption up to said adsorption column;
Second stage: the inlet that pickle liquor is pumped into said continuous adsorption switching equipment with the speed of 7ml/min; The continuous absorbed Ni ion of said adsorption column; And the nickel ion of new absorption replaces the magnesium ion of former absorption, and the magnesium ion that adsorbs up to adsorption column is replaced by nickel ion fully;
After second stage is handled, collect the magnesium ion solution that contains from said adsorption column liquid outlet outflow.
S5 is that 6% sulfuric acid washes said adsorption column with mass fraction; Said heavy metal sorbing material in the said adsorption column carries out the desorb operation, after the desorb operation, obtains containing the nickel ion stripping liquid and by the said heavy metal sorbing material of desorb;
S6, the said nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation through direct electrodeposition equipment, obtains nickel metallic plate or nickel metal powder; Simultaneously, recover absorption property after the said heavy metal sorbing material process flushing by desorb in the adsorption column is handled;
After concentrating, magnesium ion solution processed magnesium salts said the containing that S4 obtains.
The nickel mass fraction is 99.998% in the nickel powder for preparing, and magnesia amount mark is 0.002%.
Test Example 1
This Test Example is used to test the absorption property of heavy metal sorbing material to nickel and magnesium, specifically comprises: pH is to the influence to adsorbance of the influence of adsorbance and temperature.
Experimental technique: compound concentration is the nickel ion solution of 0.02mol/L, utilizes acidometer to regulate the pH of nickel ion solution; The solution 50ml that mixes up pH is placed in the wide-mouth bottle that 1g heavy metal sorbing material is housed, wide-mouth bottle is placed in 25 degrees centigrade the water bath with thermostatic control 36 hours, take out and filter, measure nickel concentration in the filtrating.
Calculate adsorbance according to formula ();
Q＝(C
0-C)*V/m
Wherein, Q is adsorbance (mmol/g); C
0For adsorbing preceding nickel ion concentration (mol/L); C is absorption back nickel ion concentration (mol/L); V is the volume (ml) of solution; The attach most importance to quality (g) of metal-adsorbing material of m.
Experimental technique to magnesium ion is identical with above-mentioned experimental technique to nickel ion.
(1) pH is to the influence experiment of adsorbance
Change the pH of above-mentioned experimental technique, carry out adsorption experiment to nickel ion with to magnesium ion respectively, experimental result is seen table 1.
Table 1
| Nickel adsorbance (mmol/g) | Magnesium adsorbance (mmol/g) | |
| pH＝1 | 0.16 | 0.00 |
| pH＝2 | 0.23 | 0.00 |
| pH＝3 | 0.48 | 0.00 |
| pH＝3.5 | 0.83 | 0.00 |
| pH＝4 | 0.95 | 0.00 |
| pH＝4.5 | 0.65 | 0.00 |
| pH＝5 | 0.35 | 0.00 |
| pH＝5.5 | 0.29 | 0.00 |
Can find out that from table 1 the heavy metal sorbing material that the present invention prepares has certain adsorption capacity to nickel, and magnesium is had no adsorption activity.So,, after separating technology is optimized, can realize the effect that nickel ion is separated with magnesium ion through the heavy metal sorbing material that adopts the present invention to prepare.
In addition, for the adsorption experiment to nickel ion, along with the increase of pH, the heavy metal sorbing material increases rapidly the adsorbance of nickel ion, and when pH reached 4.0, adsorbance reached maximum; Along with the increase of pH, adsorbance slowly reduces then.So, can confirm that in carrying out nickel ion and magnesium ion separating process, best pH is 4.0.
(2) temperature is to the influence experiment of adsorbance
Under the experiment condition of best pH 4.0, change the bath temperature of above-mentioned experimental technique, carry out adsorption experiment to nickel ion with to magnesium ion respectively, experimental result is seen table 2.
Table 2
| Nickel adsorbance (mmol/g) | Magnesium adsorbance (mmol/g) | |
| 10 | 0.20 | 0.00 |
| 15 | 0.42 | 0.00 |
| 20 | 0.63 | 0.00 |
| 28 | 0.95 | 0.00 |
| 30 | 0.96 | 0.00 |
| 35 | 0.96 | 0.00 |
| 40 | 0.97 | 0.00 |
| 45 | 0.63 | 0.00 |
| 50 | 0.42 | 0.00 |
Can find out that from table 2 along with the increase of temperature, the heavy metal sorbing material increases rapidly the adsorbance of nickel ion, when temperature reached 28 ℃, adsorbance was bigger; Continuation along with temperature increases then, and the adsorbance increasing degree is slow.So, can confirm that in carrying out nickel ion and magnesium ion separating process, optimum temperature is 28 ℃.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be looked protection scope of the present invention.
Claims (8)
1. the method through the separation of heavy metal sorbing material realization nickel magnesium, enrichment, purification is characterized in that, may further comprise the steps:
S1 fills the heavy metal sorbing material in the adsorption column of continuous adsorption switching equipment;
S2, the pH that adjustment contains the pending liquid of nickel ion and magnesium ion is 1.0-5.5, obtains pickle liquor;
S3 injects the said continuous adsorption switching equipment after S1 operates with said pickle liquor;
S4, said continuous adsorption switching equipment carry out separation and concentration to said pickle liquor and purify under 25-40 ℃, specifically comprise: with pH is the inlet that the said pickle liquor of 1.0-5.5 pumps into said continuous adsorption switching equipment; Nickel ion in the said pickle liquor of said adsorption column adsorption and enrichment; Collect the magnesium ion solution that contains then from said adsorption column liquid outlet outflow;
S5 is that the sulfuric acid of 5-30% washes said adsorption column with mass fraction; Said heavy metal sorbing material in the said adsorption column carries out the desorb operation, after the desorb operation, obtains containing the nickel ion stripping liquid and by the said heavy metal sorbing material of desorb;
S6, the said nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation through direct electrodeposition equipment, obtains nickel metallic plate or nickel metal powder; Simultaneously, recover absorption property after the said heavy metal sorbing material process flushing by desorb in the adsorption column is handled;
After concentrating, magnesium ion solution processed magnesium salts said the containing that S4 obtains.
2. the method through the separation of heavy metal sorbing material realization nickel magnesium, enrichment, purification according to claim 1 is characterized in that said heavy metal sorbing material is prepared through following method:
Preliminary treatment: under ultrasonic field, raw material silica gel is scattered in the hydrochloric acid solution of 7-10mol/L, reflux 20-30 hour, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution was 4-6: 1; Filter then, the elimination acid solution, Cake Wash obtains activated silica gel to neutral after the 110-140 ℃ of vacuum drying;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent, stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent, obtains first solution, and wherein, the mass ratio of silylating reagent and xylene solution is 5-8: 1; In activated silica gel, add dry DMF, stirring makes and mixes, and obtains second solution, and wherein, the mass ratio of activated silica gel and DMF is 5-10: 1; Silylating reagent and activated silica gel mass ratio are 2-4: 1;
First flow of solution is added in second solution of reflux state, stream add finish after, continued back flow reaction 10-20 hour; Filtering reacting liquid after reducing to 20-30 ℃, filter cake are used methyl alcohol and toluene wash successively, and vacuum drying obtains said heavy metal sorbing material then.
3. the method through the separation of heavy metal sorbing material realization nickel magnesium, enrichment, purification according to claim 2 is characterized in that the power of said ultrasonic field is 150-250 watt;
Said vacuum drying in the silica gel bonded reaction specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, think that the speed cooling of 5-8 ℃/min is refrigerated to-50--45 ℃, keep-time of 50--45 ℃ is 4-5 hour;
Second stage is warming up to-10--5 ℃ with the speed of 3-6 ℃/min, keep-time of 10--5 ℃ is 5-7 hour;
Phase III puts fast and is 160 ℃-170 ℃ vacuum drying chamber to temperature, promptly obtains said heavy metal sorbing material 13-17 hour drying time.
4. the method through the separation of heavy metal sorbing material realization nickel magnesium, enrichment, purification according to claim 2 is characterized in that said silylating reagent is 3-ethylenediamine base propyl trimethoxy silicane or 3-Diethylenetriamine base propyl trimethoxy silicane.
5. the method that realizes the separation of nickel magnesium, enrichment, purification through the heavy metal sorbing material according to claim 2; It is characterized in that; The aperture of said heavy metal sorbing material is 5.25-7.38nm, and the pore volume of said heavy metal sorbing material is 1.0-1.4 cubic centimetre/gram.
6. the method through the separation of heavy metal sorbing material realization nickel magnesium, enrichment, purification according to claim 2 is characterized in that said raw silicon micelle degree is a 300-400 order silica gel.
7. the method through the separation of heavy metal sorbing material realization nickel magnesium, enrichment, purification according to claim 1 is characterized in that S4 specifically comprises following three phases:
Phase I: the pickle liquor that with pH is 1.0-5.5 pumps into the inlet of said continuous adsorption switching equipment with the speed of 2-4ml/min, and is by said adsorption column absorbed Ni ion and magnesium ion simultaneously, saturated to nickel ion absorption up to said adsorption column;
Second stage: the inlet that pickle liquor is pumped into said continuous adsorption switching equipment with the speed of 7-9ml/min; The continuous absorbed Ni ion of said adsorption column; And the nickel ion of new absorption replaces the magnesium ion of former absorption, and the magnesium ion that adsorbs up to adsorption column is replaced by nickel ion fully;
After second stage is handled, collect the magnesium ion solution that contains from said adsorption column liquid outlet outflow.
8. the method through the separation of heavy metal sorbing material realization nickel magnesium, enrichment, purification according to claim 7 is characterized in that S4 specifically comprises following three phases:
Phase I: the pickle liquor that with pH is 3.5-4.0 pumps into the inlet of said continuous adsorption switching equipment with the speed of 3ml/min, and is by said adsorption column absorbed Ni ion and magnesium ion simultaneously, saturated to nickel ion absorption up to said adsorption column;
Second stage: the inlet that pickle liquor is pumped into said continuous adsorption switching equipment with the speed of 8ml/min; The continuous absorbed Ni ion of said adsorption column; And the nickel ion of new absorption replaces the magnesium ion of former absorption, and the magnesium ion that adsorbs up to adsorption column is replaced by nickel ion fully;
After second stage is handled, collect the magnesium ion solution that contains from said adsorption column liquid outlet outflow.
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| CN109593961A (en) * | 2018-12-19 | 2019-04-09 | 广西银亿新材料有限公司 | The method that resin adsorption method recycles metal and output magnesium salts in red soil nickel ore leaching liquid |
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