CN115254000A - Synthetic method and application of magnetic coal gasification slag-based magnesium adsorbent - Google Patents
Synthetic method and application of magnetic coal gasification slag-based magnesium adsorbent Download PDFInfo
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- CN115254000A CN115254000A CN202210944379.6A CN202210944379A CN115254000A CN 115254000 A CN115254000 A CN 115254000A CN 202210944379 A CN202210944379 A CN 202210944379A CN 115254000 A CN115254000 A CN 115254000A
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- magnesium
- adsorbent
- magnetic
- coal gasification
- slag
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 65
- 239000011777 magnesium Substances 0.000 title claims abstract description 65
- 239000003463 adsorbent Substances 0.000 title claims abstract description 40
- 239000002893 slag Substances 0.000 title claims abstract description 39
- 239000003245 coal Substances 0.000 title claims abstract description 36
- 238000002309 gasification Methods 0.000 title claims abstract description 34
- 238000010189 synthetic method Methods 0.000 title claims description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- 239000012267 brine Substances 0.000 claims abstract description 17
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 17
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000012265 solid product Substances 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940072056 alginate Drugs 0.000 claims abstract description 13
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 13
- 229920000615 alginic acid Polymers 0.000 claims abstract description 13
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 230000005284 excitation Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 230000010355 oscillation Effects 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract 6
- 239000007788 liquid Substances 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 14
- 150000001413 amino acids Chemical class 0.000 claims description 12
- -1 magnesium hexafluorophosphate Chemical compound 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002791 soaking Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract 2
- 238000012986 modification Methods 0.000 abstract 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- XRZQDFZZNCAKIZ-UHFFFAOYSA-N B([O-])([O-])[O-].[Mg+2].C(C(=O)F)(=O)F.B([O-])([O-])[O-].[Mg+2].[Mg+2] Chemical compound B([O-])([O-])[O-].[Mg+2].C(C(=O)F)(=O)F.B([O-])([O-])[O-].[Mg+2].[Mg+2] XRZQDFZZNCAKIZ-UHFFFAOYSA-N 0.000 description 1
- CMEMUESADVTUQN-UHFFFAOYSA-N B([O-])([O-])[O-].[Mg+2].C(C(=O)OF)(=O)OF.B([O-])([O-])[O-].[Mg+2].[Mg+2] Chemical compound B([O-])([O-])[O-].[Mg+2].C(C(=O)OF)(=O)OF.B([O-])([O-])[O-].[Mg+2].[Mg+2] CMEMUESADVTUQN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- DMFBPGIDUUNBRU-UHFFFAOYSA-N magnesium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Mg+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F DMFBPGIDUUNBRU-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- 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
Abstract
The invention discloses a method for synthesizing a magnetic coal gasification slag-based magnesium adsorbent. Mixing the coal gasification coarse slag and an electrolyte solution, putting the mixture into a plasma ball mill, and carrying out ball milling for 3-5h at an excitation voltage of 3-10kV and a rotating speed of 400-800 r/min. The product is transferred and heated to 200-500 ℃ and reacts for 1-3h under the steam atmosphere. Soaking the product in magnesium alginate and amino acidsIn the iron solution, centrifuging after ultrasonic oscillation for 1-3h. Transferring the solid product into a tubular reaction furnace, heating to 300-600 ℃, and reacting for 1-5h under the steam atmosphere. Soaking the product in dilute acid solution, reacting for 0.5-2 hr, centrifuging, and drying to obtain product with specific surface area of 300-500m 2 The adsorbent has a pore diameter of 2-70nm and a magnesium adsorption capacity of 30-60mg/g. The method takes the coal gasification coarse slag as a raw material, and obtains the magnetic multilevel pore magnesium adsorbent by the reinforced load of the plasma ball mill, the micro-etching modification of electrolyte and the magnesium dipping modification, and the magnetic multilevel pore magnesium adsorbent can be used for extracting and separating magnesium in salt lake brine, and reduces the magnesium-lithium ratio, and has the advantages of simple preparation process, high magnesium ion selectivity, large adsorption capacity and the like.
Description
Technical Field
The invention belongs to the technical field of adsorbent preparation, and particularly relates to a synthetic method of a magnetic coal gasification slag-based magnesium adsorbent.
Background
Magnesium, lithium and compounds thereof have important strategic positions in national economy and national defense construction. In the middle of the 80 th century in the last century, lithium salts were produced mainly from lithium ores in countries of the world. The method has long history and mature process, but has high energy consumption, can pollute the environment to a certain extent, and increasingly lacks the lithium ore resources, thereby increasingly showing the limitation. On the other hand, the lithium storage capacity of the salt lake brine is rich, the cost is lower than that of the exploitation of lithium ores, and the lithium extraction from the salt lake gradually becomes a development trend along with the exploration and development of lithium resources in the huge salt lake brine in south America. China is a large lithium resource country, and reserves are in the forefront of the world. Wherein, the lithium resource reserves of the salt lake of Qinghai and Tibet account for more than 85 percent of the total reserves. Generally, the ratio of magnesium to lithium in the brine of the salt lake determines the feasibility of producing lithium salt by using brine resources and the production cost and economic benefit of lithium salt products. However, the Qinghai salt lake brine has high magnesium-lithium ratio which is dozens to hundreds or even thousands, the magnesium-lithium ratio in the east Gillel salt lake old brine with relatively small magnesium-lithium ratio also reaches 20: 1, and the problems of high difficulty in lithium extraction, high production cost and the like are caused by the excessively high magnesium-lithium ratio.
The prior method for separating magnesium and lithium from salt lake brine comprises a precipitation method, a calcination leaching method, an extraction method, a membrane separation method, an adsorption method and the like. The precipitation method is simple in process and low in cost, and is suitable for extracting lithium from the salt lake brine with low magnesium-lithium ratio. However, when the magnesium and lithium are relatively large, the method causes excessive alkali consumption and serious lithium salt loss. The adsorption method has the advantages of simple process, high recovery rate, environmental friendliness and the like, and the magnesium-lithium ratio can be reduced by selectively adsorbing magnesium. However, the research and development on magnesium adsorbents are relatively few. Therefore, the development of the adsorbent with high magnesium ion selectivity and large adsorption capacity has great significance for reducing the magnesium-lithium ratio and comprehensively utilizing magnesium-lithium resources.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a synthetic method of a magnetic coal gasification slag-based magnesium adsorbent;
the method comprises the following steps:
step (1), mixing the coal gasification coarse slag and an electrolyte solution containing magnesium ions according to a solid-to-liquid ratio of 1:5-10 (g/ml) of the raw materials are mixed and then placed in a plasma ball mill, and the mixture is ball milled for 3-5 hours under the excitation voltage of 3-10kV and the rotating speed of 400-800 r/min;
transferring the product after ball milling treatment to a tubular reaction furnace, heating to 200-500 ℃, and reacting for 1-3h in a water vapor atmosphere;
and (3) enabling a reaction product obtained in the tubular furnace in the step (2) to react according to a solid-to-liquid ratio of 1:10-20 (g/ml) of the solid product is immersed in a magnesium alginate and ferric amino acid solution, and the solid product is obtained by centrifugal separation after ultrasonic oscillation for 1-3h.
And (4) transferring the solid product to a tubular reaction furnace, heating to 300-600 ℃, and reacting for 1-5h in a water vapor atmosphere.
And (5) mixing the reaction product obtained in the step (4) according to a solid-liquid ratio of 1:5 to 10 g/ml of the magnetic coal gasification slag-based magnesium adsorbent is soaked in 0.5 to 2mol/L of dilute acid solution, centrifugally separated after reacting for 0.5 to 2 hours, and dried to obtain the magnetic coal gasification slag-based magnesium adsorbent.
Preferably, in the step (1), the electrolyte is one or more of magnesium hexafluorophosphate, magnesium perchlorate, magnesium tetrafluoroborate, magnesium hexafluoroarsenate, magnesium bistrifluoromethanesulfonylimide, perfluoroalkyl sulfonyl methyl magnesium and magnesium difluoro oxalate borate; the molar concentration of the electrolyte is 0.2-2mol/L.
Preferably, in step (3), the solution is prepared in the following manner: the molar concentration of magnesium alginate is 3-5mol/L, the molar concentration of ferric amino acid is 2-6mol/L, and the volume ratio of the mixture of the magnesium alginate and the ferric amino acid is 1:0.2-0.6.
Preferably, in the step (5), the diluted acid is one or more of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the magnetic coal gasification slag-based magnesium adsorbent obtained in the step (5)Has a specific surface area of 300-500m 2 The pore diameter is 2-70nm, and the magnesium adsorption capacity is 30-60mg/g.
The invention also provides the magnetic coal gasification slag-based magnesium adsorbent prepared by the synthesis method of the magnetic coal gasification slag-based magnesium adsorbent.
The invention also provides a method for extracting lithium from salt lake brine by using the magnetic coal gasification slag-based magnesium adsorbent, which comprises the following steps:
s1, extracting magnesium in salt lake brine by using the magnetic coal gasification slag-based magnesium adsorbent to reduce the magnesium-lithium ratio;
s2, extracting lithium from the salt lake brine with the magnesium-lithium ratio reduced.
The method takes the coal gasification coarse slag as a raw material, the coal gasification coarse slag is subjected to reinforced loading of magnesium through a plasma ball mill and an electrolyte solution, and then the coal gasification coarse slag is activated in a steam atmosphere of a tubular reaction furnace, wherein the electrolyte is decomposed to carry out micro-etching on the coal gasification coarse slag, so that the specific surface area of the coal gasification coarse slag is increased, and the pore structure is improved. The selectivity of magnesium ions is improved by acid elution after the magnesium alginate is impregnated. The purpose of magnetic separation is achieved by loading ferric amino acid and performing heat treatment to make the magnetic iron magnetic. Therefore, the invention overcomes the defects of small adsorption capacity, low selectivity and difficult separation of the traditional magnesium adsorbent, has the advantages of simple preparation process, high magnesium ion selectivity, large adsorption capacity, easy separation and the like, and is easy for large-scale production and application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
Example 1:
1. a synthetic method of a magnetic coal gasification slag-based magnesium adsorbent is characterized by comprising the following steps:
(1) And mixing the coal gasification coarse slag with 0.2mol/L magnesium hexafluorophosphate solution according to the solid-to-liquid ratio of 1:5 mixing, placing in a plasma ball mill, and carrying out ball milling for 3 hours at an excitation voltage of 3kV and a rotation speed of 400 r/min;
(2) Transferring the product after ball milling treatment to a tubular reaction furnace, heating to 200 ℃, and reacting for 1h in a water vapor atmosphere;
(3) And mixing the reaction product in the tubular furnace according to the solid-liquid ratio of 1:10, soaking in 3mol/L magnesium alginate and 2mol/L ferric amino acid solution, wherein the volume ratio of the two is 1: and (3) 0.2, carrying out ultrasonic oscillation for 1h, and then carrying out centrifugal separation to obtain a solid product.
(4) And transferring the solid product into a tubular reaction furnace, heating to 300 ℃, and reacting for 1h in a water vapor atmosphere.
(5) And reacting products in a solid-liquid ratio of 1:5 is soaked in 0.5mol/L hydrochloric acid solution, centrifugal separation is carried out after 0.5h of reaction, and the specific surface area is 300m after drying 2 The adsorbent has a pore diameter of 2-30nm and a magnesium adsorption capacity of 30 mg/g.
Example 2:
(1) And mixing the coal gasification coarse slag and 2mol/L magnesium perchlorate solution according to the solid-liquid ratio of 1:10, mixing, placing in a plasma ball mill, and carrying out ball milling for 5 hours at an excitation voltage of 10kV and a rotation speed of 800 r/min;
(2) Transferring the product after ball milling treatment to a tubular reaction furnace, heating to 500 ℃, and reacting for 3 hours in a water vapor atmosphere;
(3) And mixing the reaction product in the tubular furnace according to the solid-liquid ratio of 1:20, soaking in 5mol/L magnesium alginate and 6mol/L ferric amino acid solution, wherein the volume ratio of the two is 1:0.6, carrying out ultrasonic oscillation for 3 hours, and then carrying out centrifugal separation to obtain a solid product.
(4) And transferring the solid product into a tubular reaction furnace, heating to 600 ℃, and reacting for 5 hours in a water vapor atmosphere.
(5) And (3) mixing the products after the reaction according to a solid-liquid ratio of 1:10 is immersed in 2mol/L sulfuric acid solution, centrifugal separation is carried out after 2h reaction, and the specific surface area is 500m after drying 2 The adsorbent has a pore diameter of 5-70nm and a magnesium adsorption capacity of 60mg/g.
Example 3:
(1) And mixing the coal gasification coarse slag with 0.5mol/L magnesium tetrafluoroborate solution according to the solid-to-liquid ratio of 1:6 mixing, placing in a plasma ball mill, and ball-milling for 4 hours at an excitation voltage of 5kV and a rotation speed of 600 r/min;
(2) Transferring the product after ball milling treatment to a tubular reaction furnace, heating to 300 ℃, and reacting for 1.5h in a water vapor atmosphere;
(3) And (3) mixing the reaction product in the tubular furnace according to the solid-liquid ratio of 1:15, soaking in 3.5mol/L magnesium alginate and 4mol/L ferric amino acid solution, wherein the volume ratio of the two is 1: and (3) carrying out ultrasonic oscillation for 1.5h, and then carrying out centrifugal separation to obtain a solid product.
(4) And transferring the solid product to a tubular reaction furnace, heating to 400 ℃, and reacting for 3 hours in a water vapor atmosphere.
(5) And (3) mixing the products after the reaction according to a solid-liquid ratio of 1:6 is immersed in 1.5mol/L nitric acid solution, centrifugal separation is carried out after 1 hour of reaction, and the specific surface area is 350m after drying 2 The adsorbent has a pore diameter of 10-50nm and a magnesium adsorption capacity of 45 mg/g.
Example 4:
(1) And mixing the coal gasification coarse slag with 0.8mol/L bis (trifluoromethanesulfonimide) magnesium solution according to a solid-to-liquid ratio of 1:7.5 mixing, placing in a plasma ball mill, and ball milling for 3h at an excitation voltage of 7.5kV and a rotation speed of 650 r/min;
(2) Transferring the product after ball milling treatment to a tubular reaction furnace, heating to 350 ℃, and reacting for 3 hours in a water vapor atmosphere;
(3) And mixing the reaction product in the tubular furnace according to the solid-liquid ratio of 1:13, soaking in 3mol/L magnesium alginate and 5.5mol/L ferric amino acid solution, wherein the volume ratio of the two is 1: and (3) carrying out ultrasonic oscillation for 2.5 hours, and then carrying out centrifugal separation to obtain a solid product.
(4) And transferring the solid product to a tubular reaction furnace, heating to 400 ℃, and reacting for 3 hours in a water vapor atmosphere.
(5) And (3) mixing the products after the reaction according to a solid-liquid ratio of 1:7 is immersed in 0.5mol/L dilute hydrochloric acid and sulfuric acid solution (volume ratio 1 2 The/g, the aperture is 5-60nm, and the magnesium adsorption capacity is 55 mg/g.
Example 5:
(1) Mixing the coal gasification coarse slag with 0.4mol/L perfluoroalkyl sulfonyl methyl magnesium and 1mol/L difluoro oxalic acid magnesium borate solution (volume ratio 1:6, mixing, placing in a plasma ball mill, and carrying out ball milling for 5 hours at an excitation voltage of 4kV and a rotation speed of 700 r/min;
(2) Transferring the product after ball milling treatment to a tubular reaction furnace, heating to 400 ℃, and reacting for 2 hours in a water vapor atmosphere;
(3) And mixing the reaction product in the tubular furnace according to the solid-liquid ratio of 1:10, soaking the mixture in 4mol/L magnesium alginate and 2mol/L ferric amino acid solution, wherein the volume ratio of the two is 1:0.45, carrying out ultrasonic oscillation for 2 hours, and then carrying out centrifugal separation to obtain a solid product.
(4) And transferring the solid product into a tubular reaction furnace, heating to 550 ℃, and reacting for 4.5h under a water vapor atmosphere.
(5) And (3) mixing the products after the reaction according to a solid-liquid ratio of 1:8, soaking in 0.8mol/L dilute hydrochloric acid and nitric acid solution (volume ratio is 1 2 The adsorbent has a pore diameter of 8-60nm and a magnesium adsorption capacity of 48 mg/g.
Specific surface area and pore size distribution were tested in a nitrogen atmosphere using a Micromeritics ASAP 2020 analyzer.
Testing of magnesium ion adsorption capacity: and (3) mixing the adsorbent according to a solid-liquid ratio of 1:20 adding the mixture into simulated brine, adsorbing the mixture for a certain time in a constant-temperature water bath, centrifuging the mixture to obtain supernatant, and detecting the concentration of magnesium ions in the brine by using an inductively coupled plasma emission spectrometer. Adsorption capacity Qt as Qt = (rho) 0 -ρ 1 ) V/m is calculated, wherein Qt is the adsorption capacity at the t moment, mg/g; ρ is a unit of a gradient 0 The mass concentration of initial magnesium ions of the solution is mg/L; ρ is a unit of a gradient 1 The mass concentration of the magnesium ions after adsorption is mg/L, m is the mass of the adsorbent, g; v is the volume of the adsorption solution, L. Compared with the prior art, the invention has the advantages of simple preparation process, high magnesium ion selectivity, large adsorption capacity and the like.
The adsorption performance of kaolinite, coal and montmorillonite on magnesium ions is researched by the research on the adsorption characteristics of calcium and magnesium ions in coal slurry water [ J ]. Chinese coal, 2011,37 (11): 71-74 ], and the saturated adsorption capacity distribution of the three adsorbents is 5mg/g, 1mg/g and 0.5mg/g. The adsorption characteristics of the modified sawdust on calcium and magnesium ions are researched by He Yu Yan [ He Yu Yan & gt ] energy and environment, 2009 (02): 17-18+47 ], so that the saturated adsorption capacity of the magnesium ions is investigated, and the saturated adsorption capacity is 24.13mg/g under a static condition. Li Jian [ Li Jian. Kaolin preparation white carbon black and experimental research on calcium and magnesium ion adsorption by applying the white carbon black [ D ] inner Mongolia university, 2015 ] use synthesized white carbon black as an adsorbent, the removal capacity of the white carbon black on magnesium ions in an aqueous solution under different conditions is investigated, and the saturated adsorption capacity is 11.58mg/g.
The above description is only a part of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (7)
1. A synthetic method of a magnetic coal gasification slag-based magnesium adsorbent is characterized by comprising the following steps:
step (1), mixing the coal gasification coarse slag and an electrolyte solution containing magnesium ions according to a solid-to-liquid ratio of 1:5-10 g/ml, placing the mixture into a plasma ball mill, and carrying out ball milling for 3-5h at the excitation voltage of 3-10kV and the rotating speed of 400-800 r/min;
transferring the product after ball milling treatment to a tubular reaction furnace, heating to 200-500 ℃, and reacting for 1-3h in a water vapor atmosphere;
and (3) enabling a reaction product obtained in the tubular furnace in the step (2) to react according to a solid-to-liquid ratio of 1:10-20 (g/ml) of the solution is soaked in a magnesium alginate and ferric amino acid solution, and a solid product is obtained by centrifugal separation after ultrasonic oscillation for 1-3 hours;
transferring the solid product to a tubular reaction furnace, heating to 300-600 ℃, and reacting for 1-5h in a water vapor atmosphere;
and (5) mixing the reaction product obtained in the step (4) according to a solid-liquid ratio of 1:5-10 (g/ml) of the magnetic gas slag-based magnesium adsorbent is immersed in 0.5-2mol/L of dilute acid solution, centrifugal separation is carried out after 0.5-2h of reaction, and drying is carried out to obtain the magnetic gas slag-based magnesium adsorbent.
2. The method for synthesizing the magnetic gasified slag-based magnesium adsorbent according to claim 1, wherein in the step (1), the electrolyte is one or more of magnesium hexafluorophosphate, magnesium perchlorate, magnesium tetrafluoroborate, magnesium hexafluoroarsenate, magnesium bistrifluoromethanesulfonylimide, perfluoroalkyl sulfonylmethyl magnesium, and magnesium difluorooxalato borate; the molar concentration of the electrolyte is 0.2-2mol/L.
3. The method for synthesizing the magnetic gasified slag-based magnesium adsorbent according to claim 1, wherein in the step (3), the solution is prepared in the following way: the molar concentration of the magnesium alginate is 3-5mol/L, the molar concentration of the ferric amino acid is 2-6mol/L, and the mixing volume ratio of the magnesium alginate to the ferric amino acid is 1:0.2-0.6.
4. The method for synthesizing the magnetic coal gasification slag-based magnesium adsorbent according to claim 1, wherein in the step (5), the dilute acid is one or more of hydrochloric acid, sulfuric acid and nitric acid.
5. The method for synthesizing the magnetic coal gasification slag-based magnesium adsorbent according to claim 1, wherein the specific surface area of the magnetic coal gasification slag-based magnesium adsorbent obtained in the step (5) is 300-500m 2 The pore diameter is 2-70nm, and the magnesium adsorption capacity is 30-60mg/g.
6. The magnetic coal gasification slag-based magnesium adsorbent is prepared by using the method for synthesizing the magnetic coal gasification slag-based magnesium adsorbent as claimed in any one of claims 1 to 6.
7. The method for extracting lithium from salt lake brine by using the magnetic gasified slag-based magnesium adsorbent as claimed in claim 6, wherein the method comprises the following steps:
s1, extracting magnesium in salt lake brine by using the magnetic coal gasification slag-based magnesium adsorbent to reduce the magnesium-lithium ratio;
s2, extracting lithium from the salt lake brine with the magnesium-lithium ratio reduced.
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