CN115254000B - Synthesis method and application of magnetic coal gas slag-based magnesium adsorbent - Google Patents
Synthesis method and application of magnetic coal gas slag-based magnesium adsorbent Download PDFInfo
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- CN115254000B CN115254000B CN202210944379.6A CN202210944379A CN115254000B CN 115254000 B CN115254000 B CN 115254000B CN 202210944379 A CN202210944379 A CN 202210944379A CN 115254000 B CN115254000 B CN 115254000B
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 58
- 239000011777 magnesium Substances 0.000 title claims abstract description 58
- 239000002893 slag Substances 0.000 title claims abstract description 33
- 239000003463 adsorbent Substances 0.000 title claims abstract description 32
- 239000003034 coal gas Substances 0.000 title claims abstract description 9
- 238000001308 synthesis method Methods 0.000 title claims description 5
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 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
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000012265 solid product Substances 0.000 claims abstract description 15
- 239000003245 coal Substances 0.000 claims abstract description 14
- 238000002309 gasification Methods 0.000 claims abstract description 12
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 12
- 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 11
- 229940072056 alginate Drugs 0.000 claims abstract description 11
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 11
- 229920000615 alginic acid Polymers 0.000 claims abstract description 11
- 150000001413 amino acids Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 230000005284 excitation Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- -1 magnesium hexafluorophosphate Chemical compound 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 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
- 230000010355 oscillation Effects 0.000 claims description 7
- 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
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 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 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract 2
- 238000012986 modification Methods 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 5
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 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 2
- 230000007547 defect Effects 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
- 238000002386 leaching Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 230000004913 activation Effects 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
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002950 deficient 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
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 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
- 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
- 150000003839 salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J2220/00—Aspects relating to sorbent materials
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- 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
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- 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
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Abstract
The invention discloses a method for synthesizing a magnetic coal gas slag-based magnesium adsorbent. Mixing the coal gasification coarse slag with electrolyte solution, placing the mixture in a plasma ball mill, and ball milling for 3-5 hours under the excitation voltage of 3-10kV and the rotating speed of 400-800 r/min. The product is transferred and heated to 200-500 ℃ and reacted for 1-3h under the atmosphere of water vapor. Immersing the product in magnesium alginate and amino acid iron solution, ultrasonic oscillating for 1-3h, and centrifuging. Transferring the solid product into a tubular reaction furnace, heating to 300-600 ℃, and reacting for 1-5h under the water vapor atmosphere. Immersing the product in diluted acid solution, reacting for 0.5-2 hr, centrifuging, and drying to obtain specific surface area 300-500m 2 And/g, pore diameter of 2-70nm, and magnesium adsorption capacity of 30-60mg/g. The invention uses coal gasification coarse slag as raw material, and adopts the plasma ball mill to reinforce the load, the electrolyte microetching modification and the magnesium dipping modification to obtain the magnetic multistage pore magnesium adsorbent, which can be used for extracting and separating magnesium in salt lake brine, 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 method for synthesizing a magnetic coal gas slag-based magnesium adsorbent.
Background
Magnesium, lithium and their compounds have important strategic positions in national economy and defense construction. In the middle of the 80 s of the last century, the world countries mainly use lithium ores as raw materials to produce lithium salts. The method has longer history and mature process, but has higher energy consumption, can pollute the environment to a certain extent, and has increasingly deficient lithium ore resources, and increasingly shows the limitation. On the other hand, the lithium reserves in the salt lake brine are rich, the cost is lower than that of the exploitation of lithium ores, and along with the exploration and development of huge salt lake brine lithium resources in south america, the lithium extraction in the salt lake gradually becomes a development trend. China is a large country of lithium resources, and reserves are in the first place of the world. Wherein, the lithium resource reserves of the salt lakes of Qinghai and Tibet account for more than 85 percent of the total reserves. Generally, the ratio of magnesium to lithium in salt lake brine determines the feasibility of producing lithium salt by utilizing brine resources and the production cost and economic benefit of lithium salt products. However, the Qinghai salt lake brine has higher magnesium-lithium ratio, from tens to hundreds, even thousands, and the east Ji Naier salt lake brine with relatively smaller magnesium-lithium ratio also reaches 20:1, and the too high magnesium-lithium ratio causes the problems of great lithium extraction difficulty, high production cost and the like.
The current methods for separating magnesium and lithium in salt lake brine include precipitation, calcination leaching, extraction, membrane separation, adsorption and the like. The precipitation method is simple in process and low in cost, and is suitable for extracting lithium from salt lake brine with low magnesium-lithium ratio. However, the method can cause excessive alkali consumption and serious lithium salt loss when magnesium and lithium are relatively large. 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, there are few studies and developments on magnesium adsorbents. Therefore, developing an adsorbent with high magnesium ion selectivity and large adsorption capacity has important 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 method for synthesizing a magnetic coal gasification slag-based magnesium adsorbent;
the method comprises the following steps:
step (1), mixing the coal gasification coarse slag with electrolyte solution containing magnesium ions according to a solid-to-liquid ratio of 1:5-10 (g/ml) of the materials are mixed and then placed in a plasma ball mill, and ball milling is carried out for 3-5 hours under the excitation voltage of 3-10kV and the rotating speed of 400-800 r/min;
transferring the ball-milled product to a tubular reaction furnace, heating to 200-500 ℃, and reacting for 1-3h in a steam atmosphere;
step (3), the reaction product obtained in the tubular furnace in the step (2) is prepared according to a solid-to-liquid ratio of 1:10-20 (g/ml) of the mixture is immersed in magnesium alginate and amino acid iron solution, and the solid product is obtained after ultrasonic oscillation for 1-3h and centrifugal separation.
And (4) transferring the solid product into a tubular reaction furnace, heating to 300-600 ℃, and reacting for 1-5h in a water vapor atmosphere.
Step (5), the reaction product obtained in the step (4) is prepared according to a solid-to-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, reacted for 0.5-2h, centrifugally separated and dried to obtain the magnetic gas 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 bistrifluoromethane sulfonyl imide, perfluoroalkyl sulfonyl methyl magnesium and difluoro oxalic acid magnesium borate; the molar concentration of the electrolyte is 0.2-2mol/L.
Preferably, in step (3), the solution is formulated as follows: the molar concentration of the magnesium alginate is 3-5mol/L, the molar concentration of the amino acid iron is 2-6mol/L, and the mixing volume ratio of the two is 1:0.2-0.6.
Preferably, in the step (5), the dilute acid is one or a combination of more of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the specific surface area of the magnetic gas slag-based magnesium adsorbent obtained in the step (5) is 300-500m 2 And/g, the pore diameter is 2-70nm, and the magnesium adsorption capacity is 30-60mg/g.
The invention also provides a method for synthesizing the magnetic gas slag-based magnesium adsorbent, and the prepared magnetic gas slag-based magnesium adsorbent.
The invention also provides a method for extracting lithium from salt lake brine by using the magnetic coal gas slag-based magnesium adsorbent, which comprises the following steps:
s1, extracting magnesium in salt lake brine by using the magnetic coal gas slag-based magnesium adsorbent so as to reduce the magnesium-lithium ratio;
s2, extracting lithium from the salt lake brine with the magnesium-lithium ratio reduced.
The method takes coal gasification coarse slag as a raw material, carries out intensified magnesium loading through a plasma ball mill and an electrolyte solution, and then carries out activation under the steam atmosphere of a tubular reaction furnace, wherein electrolyte decomposition carries out microetching on the coal gasification coarse slag, improves the specific surface area and improves the pore channel structure. The magnesium ion selectivity is improved by acid leaching after dipping the magnesium alginate. Through loading amino acid iron and heat treatment, the magnetic separation is realized. 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 mass production and application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
Example 1:
1. the synthesis method of the magnetic coal gas slag-based magnesium adsorbent is characterized by comprising the following steps of:
(1) Mixing the coal gasification coarse slag with 0.2mol/L magnesium hexafluorophosphate solution according to a solid-to-liquid ratio of 1:5, placing the mixture in a plasma ball mill, and ball milling for 3 hours under the excitation voltage of 3kV and the rotating speed of 400 r/min;
(2) Transferring the ball-milled product to a tubular reaction furnace, heating to 200 ℃, and reacting for 1h in a steam atmosphere;
(3) The reaction products in the tube furnace are mixed according to a solid-liquid ratio of 1:10 is immersed in 3mol/L magnesium alginate and 2mol/L amino acid iron solution, and the volume ratio of the two is 1: and 0.2, carrying out ultrasonic oscillation for 1h, and then carrying out centrifugal separation to obtain a solid product.
(4) The solid product was transferred to a tube reactor and heated to 300℃and reacted for 1h under a water vapor atmosphere.
(5) And (3) mixing the reaction product according to a solid-liquid ratio of 1:5 is immersed in 0.5mol/L hydrochloric acid solution, reacted for 0.5h, centrifugally separated and dried to obtain the specific surface area of 300m 2 Per gram, pore diameter 2-30nm, magnesium adsorption capacity 30mg/g adsorbent。
Example 2:
(1) Mixing the coal gasification coarse slag with 2mol/L magnesium perchlorate solution according to a solid-liquid ratio of 1:10, placing the mixture in a plasma ball mill, and ball milling for 5 hours under the excitation voltage of 10kV and the rotating speed of 800 r/min;
(2) Transferring the ball-milled product to a tubular reaction furnace, heating to 500 ℃, and reacting for 3 hours in a steam atmosphere;
(3) The reaction products in the tube furnace are mixed according to a solid-liquid ratio of 1:20 are immersed in 5mol/L magnesium alginate and 6mol/L amino acid iron solution, and the volume ratio of the two is 1: and 0.6, carrying out ultrasonic oscillation for 3 hours, and then carrying out centrifugal separation to obtain a solid product.
(4) The solid product was transferred to a tube reactor and heated to 600 c and reacted for 5 hours under a water vapor atmosphere.
(5) And (3) mixing the reaction product according to a solid-liquid ratio of 1:10 is immersed in 2mol/L sulfuric acid solution, reacted for 2 hours, centrifugally separated and dried to obtain the specific surface area of 500m 2 And/g, pore size of 5-70nm, and magnesium adsorption capacity of 60mg/g.
Example 3:
(1) Mixing the coal gasification coarse slag with 0.5mol/L magnesium tetrafluoroborate solution according to a solid-to-liquid ratio of 1:6, placing the mixture in a plasma ball mill, and ball milling for 4 hours under the excitation voltage of 5kV and the rotating speed of 600 r/min;
(2) Transferring the ball-milled product to a tubular reaction furnace, heating to 300 ℃, and reacting for 1.5h in a steam atmosphere;
(3) The reaction products in the tube furnace are mixed according to a solid-liquid ratio of 1:15 is immersed in 3.5mol/L magnesium alginate and 4mol/L amino acid iron solution, and the volume ratio of the two is 1: and 0.3, carrying out ultrasonic oscillation for 1.5 hours, and then carrying out centrifugal separation to obtain a solid product.
(4) The solid product was transferred to a tube reactor and heated to 400℃and reacted for 3 hours under a water vapor atmosphere.
(5) And (3) mixing the reaction product according to a solid-liquid ratio of 1:6 immersing in 1.5mol/L nitric acid solution, reacting for 1h, centrifuging, and drying to obtain the specific surface area 350m 2 And/g, pore diameter of 10-50nm, and magnesium adsorption capacity of 45 mg/g.
Example 4:
(1) Mixing the coal gasification coarse slag with 0.8mol/L bis (trifluoromethanesulfonyl) imide magnesium solution according to a solid-liquid ratio of 1:7.5, mixing and then placing the mixture into a plasma ball mill, and ball milling for 3 hours at the excitation voltage of 7.5kV and the rotating speed of 650 r/min;
(2) Transferring the ball-milled product to a tubular reaction furnace, heating to 350 ℃, and reacting for 3 hours in a steam atmosphere;
(3) The reaction products in the tube furnace are mixed according to a solid-liquid ratio of 1:13 is immersed in 3mol/L magnesium alginate and 5.5mol/L amino acid iron solution, and the volume ratio of the two is 1: and 0.4, carrying out ultrasonic oscillation for 2.5 hours, and then carrying out centrifugal separation to obtain a solid product.
(4) The solid product was transferred to a tube reactor and heated to 400℃and reacted for 3 hours under a water vapor atmosphere.
(5) And (3) mixing the reaction product according to a solid-liquid ratio of 1:7 immersing in 0.5mol/L dilute hydrochloric acid and sulfuric acid solution (volume ratio of 1:1), reacting for 1h, centrifuging, and drying to obtain the product with specific surface area of 500m 2 And/g, pore size of 5-60nm, and magnesium adsorption capacity of 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 1:1) according to solid-liquid ratio 1:6, placing the mixture in a plasma ball mill, and ball milling for 5 hours under the excitation voltage of 4kV and the rotating speed of 700 r/min;
(2) Transferring the ball-milled product to a tubular reaction furnace, heating to 400 ℃, and reacting for 2 hours in a steam atmosphere;
(3) The reaction products in the tube furnace are mixed according to a solid-liquid ratio of 1:10 is immersed in a solution of 4mol/L magnesium alginate and 2mol/L amino acid iron, and the volume ratio of the two is 1: and (5) carrying out ultrasonic oscillation for 2 hours and then carrying out centrifugal separation to obtain a solid product.
(4) The solid product was transferred to a tube reactor and heated to 550 c and reacted under a water vapor atmosphere for 4.5 hours.
(5) And (3) mixing the reaction product according to a solid-liquid ratio of 1:8 is immersed in 0.8mol/L dilute hydrochloric acid and nitric acid solution (volume ratio is 1:2), reacted for 1.5h, centrifugally separated, dried to obtain the specific surface area of 400m 2 And/g, pore diameter of 8-60nm, and magnesium adsorption capacity of 48 mg/g.
The specific surface area and pore size distribution were tested using a Micromeritics ASAP 2020 analyzer under nitrogen atmosphere.
Test of magnesium ion adsorption capacity: the adsorbent is prepared according to a solid-to-liquid ratio of 1:20 is added into simulated brine, after being adsorbed for a certain time in a constant-temperature water bath, supernatant is taken through centrifugation, and the concentration of magnesium ions in the brine is detected by adopting an inductively coupled plasma emission spectrometer. Adsorption capacity Qt is equal to qt= (ρ) 0 -ρ 1 ) V/m is calculated, wherein Qt is the adsorption capacity at time t, and mg/g; ρ 0 mg/L is the mass concentration of the initial magnesium ions of the solution; ρ 1 mg/L, m is the mass of the adsorbent and g is the mass concentration of magnesium ions after adsorption; v is the volume of the adsorption liquid and L. Compared with the following prior art, the method has the advantages of simple preparation process, high magnesium ion selectivity, large adsorption capacity and the like.
Zhu Guojun et al [ Zhu Guojun, gui Xiahui, xu Zhongjin, cui Zongxia ] study of adsorption characteristics of calcium and magnesium ions in slime water [ J ]. Chinese coal, 2011,37 (11): 71-74 ] study of adsorption performance of kaolinite, coal, montmorillonite on magnesium ions, and saturated adsorption amounts of the three adsorbents were distributed at 5mg/g, 1mg/g and 0.5mg/g. He Yuyan [ He Yuyan ] study of adsorption characteristics of modified sawdust on calcium and magnesium ions [ J ] energy and environment, 2009 (02): 17-18+47 ] saw dust was modified to examine saturated adsorption capacity of magnesium ions, and the saturated adsorption amount was 24.13mg/g under static conditions. Li Jian (Li Jian) kaolin is used for preparing white carbon black and experimental research (D) on adsorption of calcium and magnesium ions, and the white carbon black synthesized is taken as an adsorbent, so that the removal capability of the white carbon black to magnesium ions in aqueous solution under different conditions is examined, and the saturated adsorption capacity is 11.58mg/g.
While the invention has been described with respect to certain preferred embodiments, it will be apparent to those skilled in the art that various changes and substitutions can be made herein without departing from the scope of the invention as defined by the appended claims.
Claims (6)
1. The synthesis method of the magnetic coal gas slag-based magnesium adsorbent is characterized by comprising the following steps of:
step (1), mixing the coal gasification coarse slag with electrolyte solution containing magnesium ions according to a solid-to-liquid ratio of 1:5-10 (g/ml) of the materials are mixed and then placed in a plasma ball mill, and ball milling is carried out for 3-5 hours under the excitation voltage of 3-10kV and the rotating speed of 400-800 r/min; the electrolyte is one or a combination of more of magnesium hexafluorophosphate, magnesium perchlorate, magnesium tetrafluoroborate, magnesium hexafluoroarsenate, magnesium bistrifluoromethane sulfonyl imide, perfluoroalkyl sulfonyl methyl magnesium and magnesium difluoro oxalate borate; the molar concentration of the electrolyte is 0.2-2mol/L;
transferring the ball-milled product to a tubular reaction furnace, heating to 200-500 ℃, and reacting for 1-3h in a steam atmosphere;
step (3), the reaction product obtained in the tubular furnace in the step (2) is prepared according to a solid-to-liquid ratio of 1:10-20 (g/ml) of the mixture is immersed in magnesium alginate and amino acid iron solution, and the solid product is obtained after ultrasonic oscillation for 1-3h and centrifugal separation;
transferring the solid product into a tubular reaction furnace, heating to 300-600 ℃, and reacting for 1-5h in a water vapor atmosphere;
step (5), the reaction product obtained in the step (4) is prepared according to a solid-to-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, reacted for 0.5-2h, centrifugally separated and dried to obtain the magnetic gas slag-based magnesium adsorbent.
2. The method of synthesizing a magnetic gas slag-based magnesium adsorbent according to claim 1, wherein in step (3), the solution is prepared in the following manner: the molar concentration of the magnesium alginate is 3-5mol/L, the molar concentration of the amino acid iron is 2-6mol/L, and the mixing volume ratio of the two is 1:0.2-0.6.
3. The method of claim 1, wherein in step (5), the dilute acid is one or more of hydrochloric acid, sulfuric acid, and nitric acid.
4. The method for synthesizing a magnetic gas slag-based magnesium adsorbent according to claim 1, which is characterized in thatCharacterized in that the specific surface area of the magnetic gas slag-based magnesium adsorbent obtained in the step (5) is 300-500m 2 And/g, the pore diameter is 2-70nm, and the magnesium adsorption capacity is 30-60mg/g.
5. A magnetic gas slag-based magnesium adsorbent prepared by the synthesis method of any one of claims 1 to 4.
6. The method for extracting lithium from salt lake brine by using the magnetic gas slag-based magnesium adsorbent according to claim 5, which is characterized by comprising the following steps:
s1, extracting magnesium in salt lake brine by using the magnetic coal gas slag-based magnesium adsorbent so as to reduce the magnesium-lithium ratio;
s2, extracting lithium from the salt lake brine with the magnesium-lithium ratio reduced.
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