CN113797888A - Iron-loaded cement-based composite particle adsorption material and preparation method thereof - Google Patents
Iron-loaded cement-based composite particle adsorption material and preparation method thereof Download PDFInfo
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- CN113797888A CN113797888A CN202111163480.XA CN202111163480A CN113797888A CN 113797888 A CN113797888 A CN 113797888A CN 202111163480 A CN202111163480 A CN 202111163480A CN 113797888 A CN113797888 A CN 113797888A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000004568 cement Substances 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 73
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 70
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 48
- 239000011246 composite particle Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 46
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 32
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 19
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 17
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 16
- 239000010457 zeolite Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000007873 sieving Methods 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 abstract description 31
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 27
- 235000021317 phosphate Nutrition 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 description 21
- 239000010452 phosphate Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229910017251 AsO4 Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000755 effect on ion Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- XDKQHWPIRIUHHJ-UHFFFAOYSA-L iron(2+);sulfate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O XDKQHWPIRIUHHJ-UHFFFAOYSA-L 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- CDBAKLRDFBGJOX-UHFFFAOYSA-K sodium arsenate Chemical compound [Na+].[Na+].[Na+].[O-][As]([O-])([O-])=O CDBAKLRDFBGJOX-UHFFFAOYSA-K 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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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
- 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
- B01J20/165—Natural alumino-silicates, e.g. zeolites
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- 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
- B01J20/14—Diatomaceous earth
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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
- B01J20/28—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
- B01J20/28016—Particle form
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention provides a loaded iron cement-based composite particle adsorption material and a preparation method thereof, wherein the loaded iron cement-based composite particle adsorption material comprises the following steps: (1) mixing sulphoaluminate cement, zeolite powder and diatomite uniformly to obtain solid powder; (2) adding a ferric sulfate solution or a ferrous sulfate solution into the solid powder, and keeping stirring in the adding process; (3) after reacting for 10-20 minutes, when the slurry is a blocky solid, crushing and grinding the blocky solid, and continuously putting the blocky solid into an oven to heat the blocky solid until particles are formed; (4) drying the obtained particles in an oven, and sieving to obtain the loaded iron cement-based composite particle adsorption material. The adsorbing material can better adsorb heavy metals and phosphates in water, has simple preparation process and low price, and can be widely applied to a sewage treatment system.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to an iron-loaded cement-based composite particle adsorption material and a preparation method thereof.
Background
In recent 30 years, the water pollution in China is more and more serious due to the development of industry and agriculture. The methods commonly used for removing heavy metals and phosphates in water at present include adsorption method, chemical precipitation method, biological method, ion exchange and the like. Among them, the adsorption method is widely used with the advantages of low energy consumption, recyclability, simple process, reliable operation, etc.
At present, the common adsorbents for removing heavy metals and phosphate in water comprise activated carbon, biomass materials, heavy metal loaded adsorbents and the like. Wherein the adsorption capacity of the activated carbon is limited; the biomass material has low phosphorus adsorption, and the average adsorption capacity is 3 mg/g; the loaded heavy metal adsorbent mainly loaded with lanthanide adsorbents has high phosphorus removal efficiency which can reach 66.23mg/g, but has high cost and is difficult to popularize and apply. Therefore, the preparation of the loaded metal adsorbent which has low cost and good adsorption performance and can be widely applied has important significance. In recent years, reports of preparing an adsorbent by combining a cement-based material are provided, for example, patent CN105536702A discloses a graphene cement-based material for adsorbing heavy metals and a preparation method thereof, the patent is characterized in that functionalized graphene is mixed and stirred with cement, sand and water to obtain a blank, the blank is molded and formed, and a graphene cement-based material finished product is finally obtained through maintenance; the patent CN102249630A discloses a cement-based material capable of adsorbing heavy metal ions, which is characterized in that ferro-aluminate cement, fly ash, zeolite, coarse aggregate and fine aggregate are added with water according to different proportions and are uniformly stirred, common concrete or a secondary material distribution process is used for forming, and the cement-based material is finally obtained through steam curing; publication No. CN102766465A discloses a mineralization stabilizer for treating heavy metal ion polluted soil and a using method thereof, and the patent is characterized in that a sulfur-based compound, a calcium-based compound, a phosphorus-based compound and a silicon-based compound are sieved by a 200-mesh sieve and are uniformly mixed according to different proportions, and the ion mineralization stabilizer is obtained.
These adsorbents lack certain drawbacks, which in turn manifest as: (1) the synthetic adsorbent has long period and high cost. The maintenance and the molding of the graphene cement base require nearly one month, and the time is long. (2) The needed balancing time of the blocky adsorbent is long, and the adsorption capacity needs to be improved. The cement-based material has obvious effect on adsorbing heavy metals, but is only limited to low content of heavy metal ions. (3) The powder adsorbent is difficult to separate and is easy to cause secondary pollution. The powdered stabilizer is difficult to separate from soil, has the problem of desorption, and is easy to cause secondary pollution to the environment. Aiming at the defects, the invention provides an iron-loaded cement-based composite particle adsorption material for removing heavy metals and phosphates in water. 42.5-grade sulphoaluminate cement, zeolite powder and diatomite are mixed, and ferric sulfate or ferrous sulfate solution is used for increasing adsorption sites, so that the time consumption is short, the solid-liquid separation is easy, and the heavy metals and the phosphate in water can be effectively removed.
Disclosure of Invention
In view of the above, the invention provides an iron-loaded cement-based composite particle adsorption material and a preparation method thereof, and the iron-loaded cement-based composite particle adsorption material which is simple in preparation process, low in price, strong in practicability and capable of being recycled is obtained and can be used for removing phosphorus and other heavy metal elements in eutrophic water.
The technical scheme of the invention is realized as follows: a preparation method of a loaded iron cement-based composite particle adsorption material,
the method comprises the following steps:
(1) mixing sulphoaluminate cement, zeolite powder and diatomite uniformly to obtain solid powder;
(2) adding a ferric sulfate solution or a ferrous sulfate solution into the solid powder, and keeping stirring in the adding process;
(3) after reacting for 10-20 minutes, when the slurry is a blocky solid, crushing and grinding the blocky solid, and putting the blocky solid into an oven to be heated until particles are formed;
(4) drying the obtained particles in an oven, and sieving to obtain the loaded iron cement-based composite particle adsorption material.
Further, in the step (2), the mass molar ratio kg/mol of the sulphoaluminate cement to ferric sulfate in the ferric sulfate solution or ferrous sulfate in the ferrous sulfate solution is 2: 2-5, preferably 2: 2.5.
further, in the step (2), the concentration of the ferric sulfate solution or the ferrous sulfate solution is 2-5mol/L, preferably 2.5 mol/L; the mass volume ratio g/ml of the sulphoaluminate cement to the ferric sulfate solution or the ferrous sulfate solution is 1: 0.5-0.8, preferably 1: 0.5.
further, in the step (1), the grade of the sulphoaluminate cement is 42.5; the mass ratio of the sulphoaluminate cement to the zeolite powder to the diatomite is 4: 1.8-2.2: 0.9-1.1, preferably 4: 2: 1.
further, in the step (2), the stirring operation: slowly stirring for 1-2min, then rapidly stirring for 1-2min, preferably slowly stirring for 1.5min, and then rapidly stirring for 1.5 min.
Further, in the step (2), the rotation speed of the slow stirring is 20-25 rpm; the speed of the rapid stirring is 50-60 rpm.
Further, in the step (3), the heating temperature is 45-60 ℃, and the heating time is 10-13 hours. The heating temperature is preferably 45 ℃ and the heating time is 12 hours.
The invention discloses an iron-loaded cement-based composite particle adsorption material which is prepared by any one of the preparation methods.
Compared with the prior art, the invention has the beneficial effects that:
(1) the iron-loaded cement-based composite particle adsorbing material prepared by the invention can better adsorb heavy metal and phosphate in water, can be used for removing phosphorus and other heavy metal elements in eutrophic water body, and can be widely applied to a sewage treatment system.
(2) The iron-loaded cement-based composite particle adsorbing material prepared by the invention has the advantages of simple preparation process, low price, regeneration and utilization, and large-area popularization and application.
Drawings
Fig. 1 is a graph of X-ray diffraction (a, XRD) and energy dispersive X-ray spectroscopy (B, EDX) of a supported iron cement-based composite particle adsorbent material.
Fig. 2 is a graph showing the results of a kinetic experiment of the iron-loaded cement-based composite particle adsorption material. Initial phosphorus and Cd2+The concentration is 50mg/L, and experiments compare the addition of ferric iron and ferrous iron phosphate to the synthesis method of the two materials in the example 1 and the example 2And heavy metal Cd2+Difference in adsorption capacity.
FIG. 3 is a graph showing the results of different amounts of ferric iron added on the phosphate removal efficiency in water.
FIG. 4 shows the particle size of the iron-loaded cement-based composite particle adsorption material for phosphate radical and heavy metal Cd in water2+Influence of adsorption results.
FIG. 5 shows a coexisting ion pair PO4 3-As a result of adsorption, the initial phosphorus concentration was 50mg/L and the coexisting ion concentration was 0.01 mol/L. The materials were synthesized by the method of example 1, and the adsorption capacities of different ions to phosphate in water were compared at a pH of 7.
FIG. 6 is a graph showing the adsorption capacity of iron-loaded cement-based composite particle adsorption material to phosphate and heavy metals, which is synthesized by the method of example 1, and Cd is performed under the condition of pH72+、Pb2+、PO4 3-、AsO4 3-Adsorption isotherm experiment of (1).
Detailed Description
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention can be obtained commercially without specific description.
The reagents used in the present invention are shown in table 1:
| reagent | Purity of | Producing area |
| Sulphoaluminate cement | AR | Guangxi Yunyan special cement building materials Co.,Ltd. |
| Zeolite powder | AR | Ningbo Ding Innovative materials Co Ltd |
| Diatomite | AR | Shijiazhuang Tianxu environmental protection science and technology Limited |
| Iron sulfate nonahydrate | AR | GUANGDONG GUANGSHI REAGENTS TECHNOLOGY Co.,Ltd. |
| Ferrous sulfate heptahydrate | AR | GUANGDONG GUANGSHI REAGENTS TECHNOLOGY Co.,Ltd. |
| Potassium dihydrogen phosphate | AR | XILONG SCIENTIFIC Co.,Ltd. |
| Cadmium nitrate | AR | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
| Arsenate sodium salt | AR | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
| Lead nitrate | AR | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
Example 1 preparation of loaded iron Cement-based composite particulate adsorbent Material
200g of sulphoaluminate cement with the grade of 42.5, 100g of zeolite powder and 50g of diatomite are uniformly mixed in a mechanical stirrer to obtain solid powder, and 100mL (Fe) of ferric sulfate solution is slowly added in the stirring process2(SO4)3·9H2O, 2.5mol/L), the stirring process is firstly carried out for 1.5min at 20-25rpm, and then is carried out for 1.5min at 50-60rpm, namely the ferric sulfate solution is added within 3 min. And adding a ferric sulfate solution, reacting for 10-20 minutes, when the slurry is a blocky solid, smashing and grinding the blocky solid, putting the blocky solid into an oven, heating at the temperature of 45 ℃ for 12 hours to obtain particles, and sieving to obtain the loaded iron cement-based composite particle adsorbing material.
Example 2 preparation of iron-loaded Cement-based composite particulate adsorption Material
200g of sulphoaluminate cement with the grade of 42.5, 100g of zeolite powder and 50g of diatomite are evenly mixed in a mechanical stirrer to obtain solid powder, and 100mL of ferrous sulfate solution (FeSO) is slowly added in the stirring process4·7H2O, 2.5mol/L), the stirring process is firstly carried out for 1.5min at 20-25rpm, and then is carried out for 1.5min at 50-60rpm, namely the ferric sulfate solution is added within 3 min. And adding a ferric sulfate solution, reacting for 10-20 minutes, when the slurry is a blocky solid, smashing and grinding the blocky solid, putting the blocky solid into an oven, heating at the temperature of 45 ℃ for 12 hours to obtain particles, and sieving to obtain the loaded iron cement-based composite particle adsorbing material.
Example 3 preparation of iron-loaded Cement-based composite particulate adsorbent Material
150g of sulphoaluminate cement with the grade of 42.5, 150g of zeolite powder and 50g of diatomite are evenly mixed in a mechanical stirrer to obtain solid powder, and ferrous sulfate is slowly added to dissolve the solid powder in the stirring processLiquid 100mL (FeSO)4·7H2O, 1.25mol/L), the stirring process is firstly carried out for 1.5min at 20-25rpm, and then is carried out for 1.5min at 50-60rpm, namely the ferric sulfate solution is added within 3 min. And adding a ferric sulfate solution, reacting for 10-20 minutes, when the slurry is a blocky solid, smashing and grinding the blocky solid, putting the blocky solid into an oven, heating at the temperature of 45 ℃ for 12 hours to obtain particles, and sieving to obtain the loaded iron cement-based composite particle adsorbing material.
Example 4 preparation of iron-loaded Cement-based composite particulate adsorbent Material
200g of sulphoaluminate cement with the grade of 42.5, 100g of zeolite powder and 50g of diatomite are uniformly mixed in a mechanical stirrer to obtain solid powder, and 100mL (Fe) of ferric sulfate solution is slowly added in the stirring process2(SO4)3·9H2O, 0.15mol/L), the stirring process is firstly carried out for 1.5min at 20-25rpm, and then is carried out for 1.5min at 50-60rpm, namely the ferric sulfate solution is added within 3 min. And adding a ferric sulfate solution, reacting for 10-20 minutes, when the slurry is a blocky solid, smashing and grinding the blocky solid, putting the blocky solid into an oven, heating at the temperature of 45 ℃ for 12 hours to obtain particles, and sieving to obtain the loaded iron cement-based composite particle adsorbing material.
Test example-test of adsorption Effect of iron-loaded Cement-based composite particle adsorbing Material
1.1, a certain mass of the iron-loaded cement-based composite particle adsorbing material prepared in the above examples 1-4 is put into a 50mL centrifuge tube, and 50mL of water samples containing heavy metals and phosphates with different concentrations are added. After adjusting to the specified pH, the reaction mixture was placed on a rotary incubator at 40rpm for 12 hours. The final adsorption results are shown in FIGS. 2-6 and Table 2.
(1) As shown in fig. 1 to 6, fig. 1 is an X-ray diffraction (a, XRD) and energy dispersion X-ray spectrum (B, EDX) chart of the iron-loaded cement-based composite particle adsorbing material prepared in example 1.
FIG. 2 shows the results of dynamic experiments of loaded iron-cement-based composite particle adsorption materials, initial phosphorus and Cd2+The concentration is 50mg/L, and the experiment compares two materials of example 1 and example 2In the material synthesis method, ferric iron, ferrous iron phosphate and heavy metal Cd are added2+Difference in adsorption capacity. Analysis data results show that the adsorption effect of phosphate radicals is not obviously affected by the addition of ferric iron and ferrous iron, but the time required for reaching the equilibrium in the example 1 of adding ferric iron is short; for cation Cd2+The adsorption of (2) with the addition of divalent iron is slightly inferior to that of (1), but the adsorption equilibrium time required for the two synthetic methods is basically the same.
FIG. 3 shows the effect of different amounts of trivalent iron on the removal efficiency of phosphate from water, the initial phosphorus concentration is 50mg/L, and the ferric iron content in the material synthesis is adjusted based on example 1 to synthesize the adsorbing material with the same particle size. The analysis data result shows that the addition of ferric iron obviously improves the absorption effect of phosphate radical, the removal efficiency of phosphorus is continuously increased along with the increase of the content of ferric iron in the material synthesis, and the absorption rate can be improved by nearly 30 percent.
FIG. 4 shows the particle size of the iron-loaded cement-based composite particle adsorption material for phosphate radical and heavy metal Cd in water2+Effect of adsorption results, initial phosphate and Cd2+The concentration was 50mg/L, and the method of example 1 was used to synthesize adsorbents having different particle sizes. Analysis data results show that the particle size of the adsorbing material has an obvious effect on ion removal, wherein the influence on the adsorption performance of phosphate radicals in water is obvious, and the larger the particle size of the material is, the smaller the adsorption amount of ions is.
FIG. 5 shows a coexisting ion pair PO4 3-As a result of the influence of adsorption, the initial phosphorus concentration was 50mg/L, and the coexisting ion concentration was 0.01 mol/L. Experiment the material was synthesized by the method of example 1, and the adsorption capacity of different ions to phosphate in water was compared at pH 7. The analysis data result shows that the inhibition effect of adding different anions on the adsorption of phosphate radicals is small, and the influence of the anions on the adsorption quantity is from small to large: cl-＜NO3 -＜SO4 3-＜HCO3 -。
FIG. 6 shows the results of the adsorption capacity of the iron-loaded cement-based composite particle adsorption material on phosphate and heavy metals, and the experimental implementationEXAMPLE 1 Synthesis of materials, Cd Synthesis was carried out at pH72+、Pb2+、PO4 3-、AsO4 3-Adsorption isotherm experiment of (1). The analysis data result shows that the adsorbent synthesized by the invention can achieve satisfactory adsorption effect in several pollutants. Wherein Cd2+The adsorption effect is best and can reach 46.4 mg/g. The adsorption capacity of phosphate is 33.4mg/g, and the adsorption capacity of arsenate is 32.6 mg/g.
(2) The iron-loaded cement-based composite particle adsorbing material prepared in examples 1 to 4 is used for PO4 3-And heavy metal Cd2+The results of the adsorption capacity (pH 7) are shown in Table 2.
TABLE 2 for PO4 3-And heavy metal Cd2+Adsorption capacity (under the condition of pH 7)
| Adsorption capacity (mg/g) | Example 1 | Example 2 | Example 3 | Example 4 |
| PO4 3- | 33.6 | 34.3 | 27.5 | 16.3 |
| Cd2+ | 126.1 | 120.5 | 92.7 | 75.5 |
As can be seen from the experimental results, examples 1 to 2 are for PO4 3-And heavy metal Cd2+The adsorption capacity of the adsorbent can achieve a satisfactory effect. In example 3, the amount of sulphoaluminate cement added of 42.5 was reduced to 150g, the zeolite powder was increased to 150g, and the amount of ferrous sulphate added was reduced to 50% of that of example 2, showing PO4 3-And heavy metal Cd2+The adsorption capacity of the adsorbent is reduced. Example 4 it can be seen that PO was added only by reducing the amount of iron sulfate to 6.0% of example 1, with the other conditions being maintained, in addition to example 14 3-The adsorption capacity of (2) was reduced by 51.5% compared with that of example 1, and Cd was2+The adsorption capacity of (a) was reduced by 40.1% as compared with example 1.
Example 5 preparation of loaded iron Cement-based composite particulate adsorbent Material
200g of sulphoaluminate cement with the grade of 42.5, 100g of zeolite powder and 50g of diatomite are uniformly mixed in a mechanical stirrer to obtain solid powder, and 105mL (Fe) of ferric sulfate solution is slowly added in the stirring process2(SO4)3·9H2O, 4.5mol/L), the stirring process is firstly carried out for 1.5min at 20-25rpm, and then is carried out for 1.5min at 50-60rpm, namely the ferric sulfate solution is added within 3 min. And adding a ferric sulfate solution, reacting for 10-20 minutes, when the slurry is a blocky solid, smashing and grinding the blocky solid, putting the blocky solid into an oven, heating at the temperature of 45 ℃ for 12 hours to obtain particles, and sieving to obtain the loaded iron cement-based composite particle adsorbing material.
Example 6 preparation of loaded iron Cement-based composite particulate adsorbent Material
200g of sulphoaluminate cement with the grade of 42.5, 100g of zeolite powder and 50g of diatomite are evenly mixed in a mechanical stirrer to obtain solid powder, and the solid powder is slowly added in the stirring process140mL of ferric sulfate solution (Fe)2(SO4)3·9H2O, 2.0mol/L), the stirring process is firstly carried out for 1.5min at 20-25rpm, and then is carried out for 1.5min at 50-60rpm, namely the ferric sulfate solution is added within 3 min. And adding a ferric sulfate solution, reacting for 10-20 minutes, when the slurry is a blocky solid, smashing and grinding the blocky solid, putting the blocky solid into an oven, heating at the temperature of 45 ℃ for 12 hours to obtain particles, and sieving to obtain the loaded iron cement-based composite particle adsorbing material.
Example 7-preparation of iron-loaded Cement-based composite particulate adsorbent Material
200g of sulphoaluminate cement with the grade of 42.5, 100g of zeolite powder and 50g of diatomite are uniformly mixed in a mechanical stirrer to obtain solid powder, and 100mL (Fe) of ferric sulfate solution is slowly added in the stirring process2(SO4)3·9H2O, 2.5mol/L), the stirring process is firstly carried out for 1.5min at 20-25rpm, and then is carried out for 1.5min at 50-60rpm, namely the ferric sulfate solution is added within 3 min. And adding a ferric sulfate solution, reacting for 10-20 minutes, when the slurry is a blocky solid, smashing and grinding the blocky solid, putting the blocky solid into an oven, heating at the temperature of 60 ℃ for 10 hours to obtain particles, and sieving to obtain the loaded iron cement-based composite particle adsorbing material.
Table 3 examples 5-7 for PO4 3-And heavy metal Cd2+Adsorption capacity (under the condition of pH 7)
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a loaded iron cement-based composite particle adsorption material is characterized in that,
the method comprises the following steps:
(1) mixing sulphoaluminate cement, zeolite powder and diatomite uniformly to obtain solid powder;
(2) adding a ferric sulfate solution or a ferrous sulfate solution into the solid powder, and keeping stirring in the adding process;
(3) after reacting for 10-20 minutes, when the obtained slurry is blocky solid, crushing and grinding the blocky solid, and putting the blocky solid into an oven to heat to obtain particles;
(4) and sieving the obtained particles to obtain the loaded iron cement-based composite particle adsorbing material.
2. The preparation method of the loaded iron-cement-based composite particle adsorption material according to claim 1, wherein in the step (2), the mass molar ratio kg/mol of the sulphoaluminate cement to the ferrous sulfate of the ferric sulfate solution or the ferrous sulfate solution is 2: 2-5.
3. The preparation method of the loaded iron-cement-based composite particle adsorption material according to claim 1, wherein in the step (2), the concentration of the ferric sulfate solution or the ferrous sulfate solution is 2-5mol/L, and the mass-to-volume ratio g/ml of the sulphoaluminate cement to the ferric sulfate solution or the ferrous sulfate solution is 1: 0.5-0.8.
4. The preparation method of the loaded iron-cement-based composite particle adsorption material according to claim 3, wherein in the step (2), the concentration of the ferric sulfate solution or the ferrous sulfate solution is 2.5mol/L, and the mass-to-volume ratio g/ml of the sulphoaluminate cement to the ferric sulfate solution or the ferrous sulfate solution is 1: 0.5.
5. the preparation method of the iron-loaded cement-based composite particle adsorption material according to claim 1, wherein in the step (1), the grade of the sulphoaluminate cement is 42.5; the mass ratio of the sulphoaluminate cement to the zeolite powder to the diatomite is 4: 1.8-2.2: 0.9-1.1.
6. The preparation method of the iron-loaded cement-based composite particle adsorption material according to claim 1, wherein in the step (2), the stirring operation: slowly stirring for 1-2min, and rapidly stirring for 1-2 min.
7. The preparation method of the iron-loaded cement-based composite particle adsorption material according to claim 5, wherein in the step (2), the rotation speed of the slow stirring is 20-25 rpm; the speed of the rapid stirring is 50-60 rpm.
8. The preparation method of the iron-loaded cement-based composite particle adsorption material according to claim 1, wherein in the step (3), the heating temperature is 45-60 ℃ and the heating time is 10-13 hours.
9. The method for preparing an iron-loaded cement-based composite particle adsorption material according to claim 8, wherein in the step (3), the heating temperature is 45 ℃ and the heating time is 12 hours.
10. A loaded iron cement-based composite particle adsorption material, which is prepared by the preparation method of any one of claims 1 to 8.
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