CN115350694B - Method for preparing formed acid gas adsorbent by utilizing iron-containing waste residues and formed acid gas adsorbent prepared by method - Google Patents
Method for preparing formed acid gas adsorbent by utilizing iron-containing waste residues and formed acid gas adsorbent prepared by method Download PDFInfo
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- CN115350694B CN115350694B CN202210644802.0A CN202210644802A CN115350694B CN 115350694 B CN115350694 B CN 115350694B CN 202210644802 A CN202210644802 A CN 202210644802A CN 115350694 B CN115350694 B CN 115350694B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 103
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002699 waste material Substances 0.000 title claims abstract description 82
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 45
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 44
- 239000011230 binding agent Substances 0.000 claims description 35
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- 239000010703 silicon Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000002956 ash Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000010883 coal ash Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 43
- 239000007789 gas Substances 0.000 abstract description 34
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 16
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 5
- 239000002440 industrial waste Substances 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- 230000035515 penetration Effects 0.000 description 13
- 239000011787 zinc oxide Substances 0.000 description 12
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/28014—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 form
-
- 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
- B01J20/28054—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 surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- 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
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparing a formed acid gas adsorbent by utilizing iron-containing waste residues and the formed acid gas adsorbent prepared by the method. The invention prepares the adsorbent powder by utilizing industrial wastes such as iron-containing waste residues and the like, and then obtains the formed adsorbent with uniform component mixing, stable effect and smoother surface through secondary forming. The prepared formed adsorbent has high strength, low density and large pore number, and the inside adsorbent can be fully contacted with acid gases such as hydrogen sulfide, hydrogen chloride and the like, so that the adsorption capacity and the utilization rate of the adsorbent are improved, and the formed adsorbent has excellent adsorption capacity. The invention has the advantages of low cost and easy obtainment of raw materials, simple molding process, low requirement on equipment and suitability for popularization and use.
Description
Technical Field
The invention relates to an adsorbent and a preparation and forming method thereof, in particular to an acid gas adsorbent containing silicon, aluminum and iron waste residues and a preparation and forming method thereof.
Background
Hydrogen sulfide and hydrogen chloride are common acid harmful gases, and can pollute the environment and damage human health. At present, wet absorption is a common acid gas treatment method, has good effect, is easy to corrode equipment, and also faces the problem of wastewater treatment. The dry method for removing the acid gas has simple process, no corrosion to equipment and high adsorption selectivity, and is widely studied by students.
Dry powdered adsorbents are difficult to industrialize due to the disadvantages of high pressure drop, poor mass and heat transfer performance, large diffusion resistance, low contact efficiency and the like. To solve these problems, the powder is generally supported on a carrier or molded by adding a binder to form a supported adsorbent or molded monolithic adsorbent. Compared with the load type adsorbent, the formed adsorbent has the advantages of uniform quality and high strength, and has no problem of occupying adsorption space by the carrier, thereby increasing the utilization rate of the product.
The formed desulfurization adsorbents commonly used in the market at present are mainly two metal oxide adsorbents, namely iron oxide and zinc oxide. The source of the ferric oxide raw material is wide, the cost is low, and the method is a good choice for low-precision desulfurization in the market. But the adsorption capacity and adsorption efficiency are low, and the method is not suitable for desulfurization application with higher precision. Zinc oxide is a hydrogen sulfide adsorbent with better effect and higher precision in the current commercial desulfurizing agent, and is widely applied to removing hydrogen sulfide in raw materials such as natural gas, coal field gas, refinery gas and the like. However, the application cost is high, the bulk density of the zinc oxide is too high, the internal zinc oxide cannot fully react with the hydrogen sulfide gas, and the utilization rate of the zinc oxide is reduced. In recent years, expert scholars have started to research adsorption materials such as activated carbon, zeolite, metal organic frameworks, etc., but it has been difficult to research commercial desulfurizing agents that replace iron oxide and zinc oxide.
At present, the low-concentration hydrogen chloride adsorption mainly adopts metal oxide adsorption, but mainly has the problems of low adsorption selectivity and incapability of deeply removing hydrogen chloride. There is also a problem that scholars adsorb hydrogen chloride gas through molecular sieves, but the adsorption amount is too low. How to simultaneously improve the adsorption quantity and the adsorption effect and achieve the deep removal of hydrogen sulfide with low cost still needs to be studied.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art, provide a method for preparing a formed acid gas adsorbent by utilizing iron-containing waste residues and the formed acid gas adsorbent prepared by the method, and provide a method for preparing and forming the acid gas adsorbent by using silicon-containing, aluminum-containing and iron-containing waste residues, wherein the iron-containing waste residues are used as raw materials, and the formed acid gas adsorbent with high adsorption capacity and adsorption efficiency is prepared by a simple forming process at low cost.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for preparing a formed acid gas adsorbent by utilizing iron-containing waste residues comprises the following steps:
(1) Pretreating aluminum-containing waste residues and silicon-containing waste residues in a liquid phase according to a certain proportion, filtering and drying to obtain a mixture A;
the aluminum content of the aluminum-containing waste residue is 30-50 wt%, and the silicon content of the silicon-containing waste residue is 30-50 wt%; the molar mass ratio of aluminum in the aluminum-containing waste residue to silicon in the silicon-containing waste residue is 1:1-1:4; the pretreatment conditions of the aluminum-containing waste residues and the silicon-containing waste residues are that water is added according to the solid-to-liquid ratio of 1:3-1:5, and the mixture is stirred and filtered and repeated for 2-3 times; the drying temperature is not lower than 105 ℃, and the drying time is 1-2 h;
(2) Mixing the mixture A with an alkali source according to a certain proportion, and calcining to obtain a mixture B;
the mass ratio of the mixture A to the alkali source is 2:1-1:2; the calcination temperature is 300-500 ℃ and the calcination time is 2-4 h;
(3) Taking iron-containing waste residues, drying, grinding and sieving to 50 meshes;
the iron content of the iron-containing waste residue is 40-60 wt%; the drying temperature is not lower than 105 ℃, and the drying time is 2-4 hours;
(4) Grinding the mixture B to 50 meshes, and mixing the mixture B with the iron-containing waste residue treated in the step (3) according to a certain proportion to obtain a mixture C;
the mass ratio of the mixture B to the iron-containing waste residue treated in the step (3) is 2:1-1:2;
(5) Mixing the mixture C and water according to a certain proportion, stirring, standing, re-stirring, drying, grinding and sieving to 50 meshes to obtain adsorbent raw powder;
the mixture C and water are mixed according to the solid-to-liquid ratio of 1:5-1:10; the stirring temperature is 50-70 ℃, and the stirring time is at least 2h; the standing time is 6-12 h; the re-stirring temperature is 90-150 ℃, and the re-stirring time is 6-12 h; the drying temperature is not lower than 105 ℃, and the drying time is 1-2 h;
(6) Mixing an organic binder and an inorganic binder according to a certain proportion, regulating the pH value to 6-8 by using ammonia water with the concentration not lower than 0.01mol/L, and stirring for a period of time to obtain the required mixed binder;
the mass ratio of the organic binder to the inorganic binder is 2:1 to 1:2; the stirring time is 0.5-1 h;
(7) Taking a proper amount of raw powder of the adsorbent, adding a proper amount of mixed binder, fully mixing for a period of time by using a mixer, and drying to obtain a mixture of the adsorbent and the binder;
the mass ratio of the raw powder of the adsorbent to the mixed binder is 4: 3-3: 4, a step of; the mixing time is 20-50 min;
(8) Placing the mixture into a hydraulic forming machine, and extruding through a cylindrical die with a bar shape according to a certain horizontal inclination angle to obtain a primary wet forming body; then the wet formed body is placed in a hydraulic forming machine again for extrusion to obtain a secondary wet formed body;
the horizontal dip angle of the hydraulic forming machine during extrusion is 30-90 degrees; the diameter phi of the cylindrical bar-shaped die is=3-4 mm;
(9) And (3) drying the secondary wet formed body at the temperature of not lower than 105 ℃ for 1-2 h to obtain the formed acid gas adsorbent.
Preferably, in the step (1), the aluminum-containing waste residue is at least one of aluminum ash, aluminum slag, high-alumina fly ash and aluminum sulfate waste residue; the silicon-containing waste residue is at least one of high silicon coal ash, steel slag, coal slag and incineration ash.
Preferably, in the step (1), the molar mass ratio of aluminum in the aluminum-containing waste residue to silicon in the silicon-containing waste residue is 1:3 to 1:4; the pretreatment conditions of the aluminum-containing waste residues and the silicon-containing waste residues are that water is added according to the solid-to-liquid ratio of 1:4-1:5, and the mixture is stirred and filtered and repeated for 2-3 times; the drying temperature is 105 ℃, and the drying time is 2 hours.
Preferably, in the step (2), the alkali source is at least one of sodium hydroxide, aluminum hydroxide, calcium hydroxide, and sodium carbonate.
Preferably, in the step (2), the mass ratio of the mixture A to the alkali source is 1:1-1:2; the calcination temperature is 400-500 ℃ and the calcination time is 3-4 h.
Preferably, in the step (3), the iron-containing waste residue is ferrous sulfate waste residue.
Preferably, in the step (3), the drying temperature is 105 ℃ and the drying time is 3-4 hours.
Preferably, in the step (4), the mass ratio of the mixture B to the iron-containing waste residue treated in the step (3) is 2:1-1:1.
Preferably, in the step (5), the mixture C and water are mixed in a solid-to-liquid ratio of 1:5 to 1:8; the stirring temperature is 50-60 ℃, and the stirring time is 2 hours; the standing time is 7-10 h; the re-stirring temperature is 90-110 ℃, and the re-stirring time is 8-12 h; the drying temperature is 105 ℃, and the drying time is 2 hours.
Preferably, in the step (6), the organic binder is at least one of carboxymethyl cellulose sodium sol, sesbania powder hydrosol, epoxy resin and glycerin, and the inorganic binder is at least one of silica sol, alumina sol, zirconium sol and pseudo-boehmite gel.
Preferably, in the step (6), the mass ratio of the organic binder to the inorganic binder is 1:1 to 1:2; the stirring time is 0.5h.
Preferably, in the step (7), the drying temperature is not lower than 105 ℃ and the drying time is 1-2 h.
Preferably, in the step (7), the mass ratio of the raw powder of the adsorbent to the mixed binder is 4: 3-1: 1.
preferably, in the step (8), the horizontal inclination angle of the hydraulic forming machine when extruding is 60-90 degrees; the diameter phi of the cylindrical bar mold=3 mm.
Preferably, in the step (9), the secondarily wet molded body is dried at 105 ℃ for 2 hours.
The molded acid gas adsorbent is prepared by the method for preparing the molded acid gas adsorbent by using the iron-containing waste residues, and the specific surface area of the molded acid gas adsorbent is not less than 88.33m 2 Per gram, pore volume of not less than 0.21cm 3 /g。
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. the invention prepares the adsorbent by taking the iron-containing waste residue as the raw material, has low cost, and achieves the aim of preparing waste from waste;
2. the prepared adsorbent has high strength, low density and large pore number, and the inside adsorbent can be fully contacted with acid gases such as hydrogen sulfide, hydrogen chloride and the like, so that the adsorption capacity, adsorption efficiency and the utilization rate of the adsorbent are improved;
3. according to the invention, through secondary extrusion molding, the molded adsorbent and the binder are mixed more uniformly, the effect is more stable, and the surface is smoother;
4. the invention has the advantages of low cost and easy obtainment of raw materials, simple molding process, low requirement on equipment and suitability for popularization and use.
Drawings
FIG. 1 is a physical view of the shaped acid gas adsorbent prepared by the method of example 1 of the present invention.
FIG. 2 is a graph showing the comparison of the hydrogen sulfide adsorption effect of the molded adsorbent of examples 1 to 2 according to comparative example 2 of the present invention and that of zinc oxide adsorbent.
Fig. 3 is a graph showing the temperature programmed desorption of CO before and after adsorption in examples 1 to 2 of the present invention.
Detailed Description
For the purpose of making the technical solution and advantages of the present invention more apparent, the following detailed description of the implementation process and the advantageous effects of the present invention by means of specific embodiments is provided to help the reader better understand the essence and characteristics of the present invention, and is not intended to limit the scope of the implementation of the present invention.
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
example 1
In this example, a method for preparing a shaped acid gas adsorbent from iron-containing waste residues comprises the steps of:
(1) The aluminum content of the aluminum-containing waste residue is 45 wt%, and the silicon content of the silicon-containing waste residue is 48 wt%; fully mixing aluminum-containing waste residues and silicon-containing waste residues in a liquid phase according to a molar mass ratio of 1:3 and a solid-liquid ratio of 1:4, repeatedly filtering for 2-3 times, and drying at 105 ℃ for 2 hours to obtain a mixture A;
(2) Mixing the mixture A and an alkali source according to a ratio of 1:1, and calcining at 400 ℃ for 3 hours to obtain a mixture B;
(3) Taking iron-containing waste residue with the iron content of 52wt.% and drying at 105 ℃ for 2 hours, grinding and sieving to 50 meshes;
(4) Grinding the mixture B to 50 meshes, and mixing the mixture B with the iron-containing waste residue treated in the step (3) according to the proportion of 1:1 to obtain a mixture C;
(5) Mixing the mixture C and water according to the solid-to-liquid ratio of 1:8, stirring for 2 hours at 50 ℃, standing for 8 hours, stirring for 10 hours again, drying for 2 hours at 105 ℃, grinding, and sieving to 50 meshes to obtain the adsorbent raw powder;
(6) Mixing an organic binder and an inorganic binder according to a ratio of 1:1, regulating the pH to 8 by using 0.01mol/L ammonia water, and stirring for 0.5h to obtain a required mixed binder;
(7) Adding the raw powder of the adsorbent and the mixed binder according to the mass ratio of 1:1; fully mixing for 30min by using a mixing machine to obtain a mixture of the adsorbent and the binder;
(8) Placing the mixture into a hydraulic forming machine, and extruding through a cylindrical die with phi=4mm according to a horizontal inclination angle of 60 degrees to obtain a primary wet forming body; then the wet formed body is placed in a hydraulic forming machine again for extrusion to obtain a secondary wet formed body;
(9) And (3) drying the secondary wet formed body at the temperature of not lower than 105 ℃ for 2 hours to obtain the formed acid gas adsorbent.
The shaped acid gas adsorbent prepared in this example is shown in FIG. 1.
Example 2
This embodiment is substantially the same as embodiment 1, except that:
in this example, a method for preparing a shaped acid gas adsorbent from iron-containing waste residues comprises the steps of:
(1) The aluminum content of the aluminum-containing waste residue is 45 wt%, and the silicon content of the silicon-containing waste residue is 41 wt%; fully mixing aluminum-containing waste residues and silicon-containing waste residues in a liquid phase according to a molar mass ratio of 1:4 and a solid-liquid ratio of 1:5, repeatedly filtering for 2-3 times, and drying at 105 ℃ for 2 hours to obtain a mixture A;
(2) Mixing the mixture A and an alkali source according to the proportion of 2:3, and calcining for 4 hours at the temperature of 500 ℃ to obtain a mixture B;
(3) Taking iron-containing waste residue with the iron content of 52wt.% and drying at 105 ℃ for 2 hours, grinding and sieving to 50 meshes;
(4) Grinding the mixture B to 50 meshes, and mixing the mixture B with the iron-containing waste residue treated in the step (3) according to the proportion of 3:2 to obtain a mixture C;
(5) Mixing the mixture C and water according to the solid-to-liquid ratio of 1:6, stirring for 2 hours at the temperature of 50 ℃, standing for 7 hours, stirring for 8 hours again, drying for 2 hours at the temperature of 105 ℃, grinding, and sieving to 50 meshes to obtain the adsorbent raw powder;
(6) Mixing an organic binder and an inorganic binder according to the proportion of 2:3, regulating the pH value to 8 by using 0.01mol/L ammonia water, and stirring for 0.5h to obtain the required mixed binder;
(7) Adding the raw powder of the adsorbent and the mixed binder according to the mass ratio of 4:3; fully mixing for 30min by using a mixing machine to obtain a mixture of the adsorbent and the binder;
(8) Placing the mixture into a hydraulic forming machine, and extruding through a cylindrical die with phi=3mm according to a horizontal inclination angle of 60 degrees to obtain a primary wet forming body; then the wet formed body is placed in a hydraulic forming machine again for extrusion to obtain a secondary wet formed body;
(9) And (3) drying the secondary wet formed body at the temperature of not lower than 105 ℃ for 2 hours to obtain the formed acid gas adsorbent.
Comparative example 1:
TABLE 1 specific surface area and pore volume test results before and after Molding of examples 1-2
| Project | Example 1 before shaping | Example 1 after shaping | Example 2 before shaping | Example 2 after shaping |
| Specific surface area (m) 2 /g) | 98.61 | 88.87 | 96.92 | 88.33 |
| Pore volume (cm) 3 /g) | 0.22 | 0.21 | 0.22 | 0.22 |
As is clear from Table 1, the adsorbent prepared by the method has little change in specific surface area before and after molding. The compressive strength of the embodiment 2 is improved by 16% compared with the embodiment 1 by testing the compressive properties of the embodiment 1 and 2, the requirement on strength during transportation can be completely met, and the specific surface area and the pore volume are basically kept unchanged.
Performance test
The adsorption effect of the molded adsorbent prepared in examples 1 to 2 was compared with that of the molded zinc oxide desulfurizing agent. Defining the position of the outlet end with the concentration of 0.01ppm as a penetration point, and calculating the penetration time; the breakthrough capacity of the adsorbent was calculated according to the following formula:
wherein S is cap Represents the total adsorption capacity, Q, of the adsorbent H2S Represents the mass flow rate of hydrogen sulfide, m represents the mass of adsorbent used, t represents the time elapsed until saturation of adsorption is reached, C in And C out Representing the hydrogen sulfide concentration at the inlet and outlet, respectively.
250g of the molded adsorbent of example 1, the molded adsorbent of example 2 and the zinc oxide adsorbent were placed in polytetrafluoroethylene-inertly treated S304 stainless steel tubes of a catalytic evaluation apparatus having an inner diameter of 100mm, respectively, and the bottoms of the adsorbents were packed with cordierite having an outer diameter of 98 mm. The entire system was purged with nitrogen and stabilized for 30min. Then, hydrogen sulfide was introduced into the tube at an inlet gas concentration of 6000ppm, and the breakthrough time and the adsorption capacity before breakthrough were calculated.
FIG. 2 is a graph showing the hydrogen sulfide adsorption breakthrough curves of the molded adsorbents prepared in examples 1 and 2 and the molded zinc oxide adsorbent. The adsorption experiments were conducted under the above conditions, and examples 1 and 2 exhibited excellent adsorption performance at a mass space velocity of 1.5L/min. Wherein the penetration time of the formed zinc oxide adsorbent is 80min, and the adsorption capacity before penetration is 24 mg/g; the penetration time of the molded adsorbent of example 2 can reach 290min, and the adsorption capacity before penetration is 87mg/g, which is 3-4 times that of the zinc oxide adsorbent.
Comparative example 2:
the adsorption effect of hydrogen chloride of the molded adsorbent prepared in examples 1 to 2 was compared with that of molded Y-type molecular sieve and alumina pellets, and the breakthrough point was defined at the position where the concentration of hydrogen sulfide at the outlet end changed by more than 0.2ppm per minute, and the breakthrough time was calculated.
250g of the molded adsorbent of example 1, the molded adsorbent of example 2, the molded Y-type molecular sieve and alumina were each placed in a polytetrafluoroethylene inert-treated S304 stainless steel tube of a catalytic evaluation apparatus having an inner diameter of 100mm, and a cordierite mat having an outer diameter of 98mm was placed on the bottom of the adsorbent. The entire system was purged with nitrogen and stabilized for 30min. Then, the waste gas of the iron and steel industry containing 500-1000 ppm (dynamic change) hydrogen chloride is introduced into the pipe at the mass airspeed of 1.5L/min, and the adsorption efficiency and the penetration time before penetration are calculated.
TABLE 2 comparison of Hydrogen chloride adsorption data for the shaped adsorbents of examples 1-2 and shaped Y-shaped molecular sieves and alumina pellets
| Example 1 | Example 2 | Shaped Y-type molecular sieve | Alumina pellets | |
| Adsorption efficiency before penetration | 99.8％ | 99.8％ | 99.0％ | 95.7％ |
| Adsorption penetration time | 52min | 57min | 7min | 36min |
Table 2 is a comparison of the results of the adsorption experiments, and it can be seen that the adsorption efficiency before penetration is higher and the penetration time is longer in examples 1 and 2; the adsorption efficiency of the Y-type molecular sieve and the alumina pellets cannot achieve the effect of removing hydrogen chloride with high precision, and the adsorption penetration time is far shorter than that of the embodiment 1 and the embodiment 2.
Comparative example 3:
fig. 3 is a graph showing desorption of CO at a temperature programmed level before and after adsorption by the adsorbents of examples 1 and 2. As can be seen from the figure, before adsorption, there are a large number of weakly basic sites at 150-400 ℃ and a large number of strongly basic sites at 600-700 ℃. After adsorption, these basic sites disappear, indicating that the basic sites present in the adsorbent are key factors in creating the chemisorption effect. From the variation in the number of basic sites in examples 1-2, it can be seen that: with the increase of alkaline sites, the selectivity of the adsorbent to acid gases such as hydrogen sulfide, hydrogen chloride and the like is improved, so that the combination and full reaction of the adsorbent and the gases are facilitated, and the adsorption capacity is improved.
The invention relates to a preparation and forming method of an adsorbent, in particular to a preparation and forming method of an acid gas adsorbent containing silicon, aluminum and iron waste residues. According to the embodiment of the invention, the adsorbent powder is prepared from industrial wastes such as iron-containing waste residues, and the formed adsorbent with uniform component mixing, stable effect and relatively flat surface is obtained through secondary forming. The formed adsorbent prepared by the embodiment has high strength, low density and large pore number, and the inside adsorbent can be fully contacted with acid gases such as hydrogen sulfide, hydrogen chloride and the like, so that the adsorption capacity and the utilization rate of the adsorbent are improved, and the formed adsorbent has excellent adsorption capacity. The raw materials of the embodiment of the invention are cheap and easy to obtain, the molding process is simple, the requirements on equipment are not high, and the method is suitable for popularization and use
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the embodiments described above, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principles of the technical solution of the present invention can be made according to the purpose of the present invention, and all the changes, modifications, substitutions, combinations or simplifications should be equivalent to the substitution, so long as the purpose of the present invention is met, and all the changes are within the scope of the present invention without departing from the technical principles and the inventive concept of the present invention.
Claims (10)
1. A method for preparing a formed acid gas adsorbent by utilizing iron-containing waste residues is characterized by comprising the following steps:
(1) Pretreating aluminum-containing waste residues and silicon-containing waste residues in a liquid phase according to a certain proportion, filtering and drying to obtain a mixture A;
the aluminum content of the aluminum-containing waste residue is 30-50 wt%, and the silicon content of the silicon-containing waste residue is 30-50 wt%; the molar mass ratio of aluminum in the aluminum-containing waste residue to silicon in the silicon-containing waste residue is 1:1-1:4; the pretreatment conditions of the aluminum-containing waste residues and the silicon-containing waste residues are that water is added according to the solid-to-liquid ratio of 1:3-1:5, and the mixture is stirred and filtered and repeated for 2-3 times; the drying temperature is not lower than 105 ℃, and the drying time is 1-2 h;
(2) Mixing the mixture A with an alkali source according to a certain proportion, and calcining to obtain a mixture B;
the mass ratio of the mixture A to the alkali source is 2:1-1:2; the calcination temperature is 300-500 ℃ and the calcination time is 2-4 h;
(3) Taking iron-containing waste residues, drying, grinding and sieving to 50 meshes;
the iron content of the iron-containing waste residue is 40-60 wt%; the drying temperature is not lower than 105 ℃, and the drying time is 2-4 hours;
(4) Grinding the mixture B to 50 meshes, and mixing the mixture B with the iron-containing waste residue treated in the step (3) according to a certain proportion to obtain a mixture C;
the mass ratio of the mixture B to the iron-containing waste residue treated in the step (3) is 2:1-1:2;
(5) Mixing the mixture C and water according to a certain proportion, stirring, standing, re-stirring, drying, grinding and sieving to 50 meshes to obtain adsorbent raw powder;
the mixture C and water are mixed according to the solid-to-liquid ratio of 1:5-1:10; the stirring temperature is 50-70 ℃, and the stirring time is at least 2h; the standing time is 6-12 h; the re-stirring temperature is 90-150 ℃, and the re-stirring time is 6-12 h; the drying temperature is not lower than 105 ℃, and the drying time is 1-2 h;
(6) Mixing an organic binder and an inorganic binder according to a certain proportion, regulating the pH value to 6-8 by using ammonia water with the concentration not lower than 0.01mol/L, and stirring for a period of time to obtain the required mixed binder;
the mass ratio of the organic binder to the inorganic binder is 2:1 to 1:2; the stirring time is 0.5-1 h;
(7) Taking a proper amount of raw powder of the adsorbent, adding a proper amount of mixed binder, fully mixing for a period of time by using a mixer, and drying to obtain a mixture of the adsorbent and the binder;
the mass ratio of the raw powder of the adsorbent to the mixed binder is 4: 3-3: 4, a step of; the mixing time is 20-50 min;
(8) Placing the mixture into a hydraulic forming machine, and extruding through a cylindrical die with a bar shape according to a certain horizontal inclination angle to obtain a primary wet forming body; then the wet formed body is placed in a hydraulic forming machine again for extrusion to obtain a secondary wet formed body;
the horizontal dip angle of the hydraulic forming machine during extrusion is 30-90 degrees; the diameter phi of the cylindrical bar-shaped die is=3-4 mm;
(9) And (3) drying the secondary wet formed body at the temperature of not lower than 105 ℃ for 1-2 h to obtain the formed acid gas adsorbent.
2. The method for preparing a shaped acid gas adsorbent from iron-containing waste residues according to claim 1, wherein: in the step (1), the aluminum-containing waste residue is at least one of aluminum ash, aluminum slag, high-alumina fly ash and aluminum sulfate waste residue; the silicon-containing waste residue is at least one of high silicon coal ash, steel slag, coal slag and incineration ash.
3. The method for preparing a shaped acid gas adsorbent from iron-containing waste residues according to claim 1, wherein: in the step (1), the molar mass ratio of aluminum in the aluminum-containing waste residue to silicon in the silicon-containing waste residue is 1:3-1:4; the pretreatment conditions of the aluminum-containing waste residues and the silicon-containing waste residues are that water is added according to the solid-to-liquid ratio of 1:4-1:5, and the mixture is stirred and filtered and repeated for 2-3 times; the drying temperature is 105 ℃, and the drying time is 2 hours.
4. The method for preparing a shaped acid gas adsorbent from iron-containing waste residues according to claim 1, wherein: in the step (2), the alkali source is at least one of sodium hydroxide, aluminum hydroxide, calcium hydroxide and sodium carbonate.
5. The method for preparing a shaped acid gas adsorbent from iron-containing waste residues according to claim 1, wherein: in the step (2), the mass ratio of the mixture A to the alkali source is 1:1-1:2; the calcination temperature is 400-500 ℃ and the calcination time is 3-4 h.
6. The method for preparing a shaped acid gas adsorbent from iron-containing waste residues according to claim 1, wherein: in the step (3), the iron-containing waste residue is ferrous sulfate waste residue.
7. The method for preparing a shaped acid gas adsorbent from iron-containing waste residues according to claim 1, wherein: in the step (3), the drying temperature is 105 ℃, and the drying time is 3-4 hours.
8. The method for preparing a shaped acid gas adsorbent from iron-containing waste residues according to claim 1, wherein: in the step (6), the organic binder is at least one of sodium carboxymethyl cellulose sol, sesbania powder hydrosol, epoxy resin and glycerin, and the inorganic binder is at least one of silica sol, alumina sol, zirconium sol and pseudo-boehmite gel.
9. The method for preparing a shaped acid gas adsorbent from iron-containing waste residues according to claim 1, wherein: in the step (7), the drying temperature is not lower than 105 ℃, and the drying time is 1-2 h.
10. A shaped acid gas adsorbent, characterized by: prepared by the method for preparing the shaped acid gas adsorbent by using the iron-containing waste residues according to claim 1, wherein the specific surface area of the shaped acid gas adsorbent is not less than 88.33m 2 Per gram, pore volume of not less than 0.21cm 3 /g。
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