CN113856615A - Method for treating desulfurization circulating wastewater by ultrahigh-alumina-lime method to obtain mesoporous adsorption material - Google Patents
Method for treating desulfurization circulating wastewater by ultrahigh-alumina-lime method to obtain mesoporous adsorption material Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 35
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- 230000023556 desulfurization Effects 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 18
- 239000004571 lime Substances 0.000 title description 2
- 239000013049 sediment Substances 0.000 claims abstract description 47
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 27
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
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- 239000013335 mesoporous material Substances 0.000 claims abstract description 8
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- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000129 anionic group Chemical group 0.000 claims abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 6
- 239000003463 adsorbent Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 7
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- 238000004064 recycling Methods 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 24
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- 229910018512 Al—OH Inorganic materials 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
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- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 3
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- ZHQNSTNWSYTIKD-UHFFFAOYSA-K [Al](Cl)(Cl)Cl.[Ca] Chemical group [Al](Cl)(Cl)Cl.[Ca] ZHQNSTNWSYTIKD-UHFFFAOYSA-K 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
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- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 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
- B01J20/06—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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for treating desulfurization circulating wastewater by an ultrahigh lime-aluminum method to obtain a mesoporous adsorption material. The mesoporous adsorption material is sulfate sediment and chloride sediment. Collecting sulfate sediments: taking wastewater, sequentially adding calcium hydroxide and sodium metaaluminate to remove sulfate radicals, centrifugally filtering the mixed solution after the reaction is finished, and respectively collecting precipitates and filtrate; drying the precipitate to obtain sulfate precipitate, taking the filtrate as water sample, sequentially adding calcium hydroxide and sodium metaaluminate, reacting to remove chloride ions, centrifuging and filtering the mixed solution after the reaction is finished, collecting the precipitate, and drying the precipitateDrying to obtain the chlorine salt sediment. The primary components of the first-stage sulfate sediment and the second-stage chloride sediment are respectively CaAl-LDH-SO4And CaAl-LDH-Cl as mesoporous material. The chloride sediment has high purity and less impurities, can effectively remove anionic organic pollutants in the dye wastewater, has low secondary pollution degree, and achieves the purpose of resource recycling.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for treating desulfurization circulating wastewater by an ultrahigh lime-aluminum method to obtain a mesoporous adsorption material (sulfate sediment and chloride sediment).
Background
At present, the ultra-high lime-aluminum method is more researched to treat high-sulfate and high-chlorine wastewater, but the research on generated sediments is less. Emma-Tuulia Tolonen et al investigated the removal of sulfate from mine water precipitated as ettringite and the use of the precipitate as an adsorbent to remove arsenate. Research shows that in the ettringite precipitation process, the concentration of sulfate in the mine water is reduced by 85-90% from the initial 1400 mg/L. The solid sediment is used as an adsorbent to remove arsenate from the simulated solution, the concentration of the arsenic (V) simulated solution is reduced by 86-96% compared with the initial 1.5mg/L, and the dosage of the adsorbent is 1 g/L. Maximum arsenate adsorption capacity (qm-11.2 + -4.7 mg/g). People such as the periodic oscillation and the like invent a system and a method for treating wastewater by removing sulfate radicals and recycling sludge. The method dissolves the precipitate ettringite, recycles aluminum salt as sulfate radical to remove the precipitant for recycling, converts the ettringite into gypsum for recycling, can realize effective resource utilization of the precipitate, reduces environmental pollution and resource waste, and has remarkable economic and environmental benefits.
However, the application research of the solid sediment generated by treating the desulfurization circulating wastewater by the ultra-high lime-aluminum method is very few, so the application focuses on the research of the method and the application of the solid sediment obtained by treating the desulfurization circulating wastewater by the ultra-high lime-aluminum method.
Disclosure of Invention
The invention aims to provide a method for treating desulfurization circulating wastewater by an ultrahigh lime-aluminum method to obtain a mesoporous adsorption material.
The method for treating the desulfurization circulating wastewater by the ultrahigh-lime-aluminum method to obtain the mesoporous adsorption material adopts a two-stage ultrahigh-lime-aluminum method to treat the desulfurization circulating wastewater containing high-concentration sulfate ions and chloride ions.
The method comprises the following specific steps: collecting sulfate sediments: taking 1L of desulfurized circulating wastewater and adding Ca2+:Al3+:SO4 2-Sequentially adding calcium hydroxide and sodium metaaluminate according to the molar ratio of 4:1:1, reacting for 15-20 minutes to remove sulfate radicals, centrifugally filtering the mixed solution after the reaction is finished, and respectively collecting precipitates and filtrate; drying the precipitate to obtain sulfate precipitate;
step two, taking the filtrate obtained in the step one as a water sample and taking Ca2+:Al3+:Cl-Sequentially adding calcium hydroxide and sodium metaaluminate according to the molar ratio of 6:3:1, reacting to remove chloride ions, centrifugally filtering the mixed solution after the reaction is finished, collecting precipitates, and drying the precipitates to obtain chlorine salt sediments.
Preferably, the reaction temperature in the first step is controlled at 25-28 ℃, r is 200-.
Preferably, the drying process of the precipitate in the first step is as follows: drying the precipitate in a muffle furnace at 95-105 deg.C for 8-12h, grinding into powder, and sieving to collect sulfate precipitate.
Preferably, the reaction conditions in the second step are that T is 30-35 ℃, r is 250-300r/min, the pH of the filtrate keeps strong basicity after the first-stage reaction, and the reaction time is more than or equal to 30 min.
Preferably, the drying process of the precipitate in the second step is as follows: drying the precipitate in a muffle furnace at 95-105 ℃ for 8-12h, grinding into powder, and collecting the chloride salt precipitate through a target standard sieve.
The method for treating the desulfurization circulating wastewater by using the ultrahigh lime-aluminum method to obtain solid sediments with the main components of CaAl-LDH-SO respectively4And CaAl-LDH-Cl, which is a mesoporous material and is used as an adsorbent.
The chlorine salt sediment is applied to the removal of anionic organic pollutants in the dye wastewater.
Compared with the prior art, the invention has the beneficial effects that: the ultrahigh-lime-aluminum method can effectively remove high-concentration sulfate radicals and chloride ions in the desulfurization circulating wastewater, the obtained solid sediments are one-stage sulfate sediments and two-stage chloride-salt sediments, and the main components of the solid sediments are respectively CaAl-LDH-SO4And CaAl-LDH-Cl, which are mesoporous materials and can be used as adsorbents. And the chloride sediment has higher purity and less impurities, can effectively remove anionic organic pollutants in the dye wastewater, and has lower secondary pollution degree, thereby achieving the purpose of resource recycling.
Drawings
FIG. 1 is N of sulfate sludge and chloride sludge2Adsorption and desorption isotherm diagram;
FIG. 2 is a graph showing pore size distribution of sulfate sludge and chloride sludge;
FIG. 3 is a graph comparing the infrared of the sample before and after adsorption;
FIG. 4 is a comparison XRD of the sample before and after adsorption;
FIG. 5 is an electron micrograph of the sample before and after adsorption.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
collecting sulfate sediments: taking 1L of desulfurization circulating wastewater water sample, and adding Ca2+:Al3+:SO4 2-Sequentially adding calcium hydroxide and sodium metaaluminate according to a molar ratio of 4:1:1, reacting for 17min at a temperature of T-27 ℃, r-200 r/min and under the condition of keeping the pH of raw water constant at 6.88 to remove sulfate radicals, centrifugally filtering the mixed solution after the reaction is finished, respectively collecting precipitates and filtrate, drying the precipitates in a muffle furnace at 100 ℃ for 10h, grinding into powder, and sieving by a 100-mesh standard sieve for later use;
collecting chlorine salt sediments: the second stage uses the filtrate of the first stage as water sample and uses Ca2+:Al3+
:Cl-Sequentially adding calcium hydroxide and sodium metaaluminate according to the molar ratio of 6:3:1, reacting for 30min at the temperature of T-33 ℃ and r-280 r/min under the condition that the strong basicity of the filtrate is not changed after the pH value is kept at a stage, removing chloride ions, centrifugally filtering the mixed solution after the reaction is finished, collecting precipitates, drying the precipitates in a muffle furnace at the temperature of 100 ℃ for 10h, grinding the precipitates into powder, and screening the powder by a standard sieve of 100 meshes for later use.
In this example, N of two kinds of sulfate sludge and chloride sludge was obtained by using ASAP 2020 type volume adsorption analyzer manufactured by Micromeritics of USA2The adsorption and desorption isotherms and pore size distribution curves are shown in FIG. 1. The pore size distribution curve of the sulfate slag sediment and the chloride slag sediment is shown in figure 2,
the BET specific surface area, pore volume and pore size of the sulfate sludge and chloride sludge of this example are shown in Table 1 below.
TABLE 1
From fig. 1, it can be seen that when the relative pressure is greater than 0.9, the curve rises sharply, indicating that the material undergoes capillary condensation, indicating the existence of mesopores and tubular pores in the sediment material.
The adsorption-desorption curves of the sulphate sludge are almost parallel and the high-pressure zone curve is very steep, almost perpendicular to the X-axis, indicating that the hysteresis loop is of the H1 type, formed by cylinders or narrow holes, which is comparable to the pure substance CaAl-LDH-SO4The shapes of the two parts are identical. The adsorption-desorption curves of the chloride sediments are almost parallel and the curve of the high-pressure area is relatively slow, which indicates that the hysteresis loop is H3 type, and the hysteresis loop is formed by mesoporous pores, slits or stacking pores of the layered material, and is consistent with the structure of a pure substance CaAl-LDH-Cl.
As can be seen from fig. 2, the sulfate sludge and the chloride sludge have peaks at the apertures of 1.83nm and 2.26nm, and then gradually decrease in the range of 2-50nm, and the test points of both samples are almost accumulated in the mesoporous range, which indicates that mesopores (micropores d <2nm, mesopores d ═ 2-50nm, and macropores d >50nm) greatly contribute to the structural performance of the material. The average pore size in table 1 is greater than 2nm, also indicating that both samples are mesoporous materials.
The phases, functional groups, micro-morphologies, sample specific surface areas and pore diameters of the sulfate sediments, the chloride sediments and the corresponding pure samples are subjected to comparative characterization analysis by four characterization means of XRD, FTIR, SEM and nitrogen adsorption method. As a result, the one-stage precipitation is mainly sulfate precipitation, the rod-shaped morphology is realized, the diffraction peaks at 8.98 degrees and 15.68 degrees are strong, the O-H, H-O-H, S-O, Ca/Al-OH functional groups exist, and the main component of the one-stage sulfate precipitation can be determined to be ettringite (CaAl-LDH-SO)4) Is a mesoporous material.
The two-stage precipitation is mainly chlorine salt sediment which is in a layered shape and has a small amount of plane hexagons, a strong diffraction peak is formed at 11.258 degrees, and an O-H, H-O-H, Ca/Al-OH functional group exists, so that the main component of the two-stage chlorine salt sediment is calcium aluminum chloride layered double hydroxide (CaAl-LDH-Cl) and is also a mesoporous material.
In the embodiment, the adsorption behavior and mechanism of Congo red of chloride sediments are researched through various characterization analyses (XRD, FT-IR and SEM) of the adsorbents before and after adsorption.
The IR contrast between the pre-adsorption and post-adsorption samples is shown in FIG. 3, with the four samples being CR (Congo Red), chloride sludge, products after adsorption of 30mg/L CR and 50mg/L CR.
The infrared band distribution table of Congo red is shown in Table 2
TABLE 2
Referring to FIG. 3, the results show that-OH (3488 cm) in the chlorine salt sludge after adsorption of CR-1) Slightly lower wave number (3436 cm)-1) Shift, accounting for-SO of-OH and CR on the adsorbent surface3and-NH2The possibility of groups participating in the adsorption process through electrostatic interactions and hydrogen bonding. As shown in FIG. 3(a), at 1176 and 1064cm-1It can be seen that the asymmetric stretching vibration and the symmetric stretching vibration of the S ═ O bond respectively have no characteristic peak at the corresponding position in fig. 3(b), and have obvious characteristic peaks at the corresponding position in fig. 3(c) (d), which indicates that sulfonate groups appear on the adsorbed chloride-salt sediments. And stretching vibration (1176, 1045 cm) of sulfonate group of adsorbed sample-1And 1172, 1045cm-1) Bicongo red vibration frequency (1176, 1064 cm)-1) Slightly lower. This change indicates that there is an electrostatic interaction between the dye anion (sulfonic acid group) and the hydroxide layer and stabilizes the dye molecule.
532 and 424cm appearing in FIG. 3(b)-1The peaks indicate the bending vibration of Al-OH and Ca-OH in the chloride sediment respectively, the vibration of the characteristic peak is still kept but the strength is weakened after 30mg/L CR is absorbed, and the characteristic peak completely disappears after 50mg/L CR is absorbed. This may be due to the-SO of Congo red with the metal ions on the bulk layer3The groups undergo a complexation reaction, resulting in the metal ions being masked by Congo red, and the Congo red is completely covered at higher concentrations, so Al-OH and Ca-OH on the bulk layer cannot be detected.
As shown in FIG. 4(a), the chlorine salt sludge is mainly characterizedThe characteristic peaks are 11.258 degrees, 17.981 degrees, 22.739 degrees, 23.303 degrees and 30.959 degrees, which respectively represent (002), (001), (013), (-113) and (-311) crystal planes. Wherein, except that the (001) crystal face represents a calcium hydroxide phase, other crystal faces are identified as characteristic crystal faces of a calcium aluminum chloride layered double hydroxide (CaAl-LDH-Cl) phase, and the interlayer spacing
The graphs of 4(b) (c) respectively show XRD curves of samples adsorbing Congo red with different concentrations, wherein the intensities of three main characteristic peaks (002), (-113) and (-311) decrease with the increase of the concentration of Congo red, and basically disappear at 50mg/L CR. This indicates that the chloride sludge adsorbs and is completely covered by congo red, resulting in disappearance of characteristic peaks of CaAl-LDH-Cl.
In addition, the characteristic peak of the new layered double hydroxide does not appear in fig. 4(b), and the interlayer distance d002 is not changed, i.e., congo red is not inserted into the intermediate layer by ion exchange.
Further shows that the congo red is only fixed on the surface of the adsorbent, does not generate ion exchange effect and is consistent with the infrared analysis result. Furthermore, according to the JCPDS card number 05-0586, the peak at 29.400 ° (104) may be due to the presence of calcium carbonate in the solid waste precipitate. This is because the ultra-high lime-alumina process absorbs carbon dioxide from the air during operation to produce calcium carbonate.
The adsorption research shows that the chloride sediments have good removal effect on the anionic azo dye Congo red, and coexists with ions Cl-SO4 2-、NO3 -No influence on the reaction, CO3 2-The adding amount of the adsorbent is obviously influenced when the adding amount is low, and the chloride sediment has a wider pH adaptation range. When 100mL of Congo red solution with the concentration of 50mg/L is treated by 0.4 g/L chloride sediment, the reaction is carried out for 90 min under the conditions that the temperature is 35 ℃ and the pH value is 4, and the removal rate of the Congo red can reach 99.99%. The adsorption process of Congo red accords with a quasi-second-order kinetic model and a Langmuir model, the maximum adsorption capacity is 123.9 mg/g, the adsorption is a spontaneous and endothermic process and is driven by chemical adsorption, and the intra-particle diffusion is not the only rate-limiting mechanism in the adsorption process but is driven by chemical adsorptionCommon control of multiple diffusion mechanisms.
The infrared spectrum, XRD and scanning electron microscope images are shown in figure 5, and thermodynamic analysis further proves that the interaction of Congo red and chloride sediments is mainly the chemical complex between CaAl-LDH-Cl and Congo red, and the electrostatic attraction and hydrogen bond are assisted.
The results show that the solid sediments obtained by the ultrahigh-lime-aluminum method in the embodiment are first-stage sulfate sediments and second-stage chloride sediments when high-concentration sulfate radicals and chloride ions in the desulfurization circulating wastewater are removed, and the main components of the solid sediments are CaAl-LDH-SO4And CaAl-LDH-Cl, which are mesoporous materials and can be used as adsorbents. And the chloride sediment has higher purity and less impurities, can effectively remove anionic organic pollutants in the dye wastewater, and has lower secondary pollution degree, thereby achieving the purpose of resource recycling.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (7)
1. The method for treating desulfurization circulating wastewater by using the ultrahigh-lime-aluminum method to obtain the mesoporous adsorption material is characterized by comprising the following steps of: the method comprises the following steps: collecting sulfate sediments: taking 1L of desulfurized circulating wastewater and adding Ca2+:Al3+:SO4 2-Sequentially adding calcium hydroxide and sodium metaaluminate according to the molar ratio of 4:1:1, reacting for 15-20 minutes to remove sulfate radicals, centrifugally filtering the mixed solution after the reaction is finished, and respectively collecting precipitates and filtrate; drying the precipitate to obtain sulfate precipitate;
step two, taking the filtrate obtained in the step one as a water sample and taking Ca2+:Al3+:Cl-Sequentially adding calcium hydroxide and sodium metaaluminate according to the molar ratio of 6:3:1, reacting to remove chloride ions, centrifugally filtering the mixed solution after the reaction is finished, collecting precipitates, and drying the precipitates to obtain chlorine salt sediments.
2. The method for treating desulfurization circulating wastewater by the ultra-high lime-aluminum method to obtain the mesoporous adsorption material according to claim 1, is characterized in that: the reaction temperature in the first step is controlled at 25-28 ℃, and r is 200-.
3. The method for treating desulfurization circulating wastewater by the ultra-high lime-aluminum method to obtain the mesoporous adsorption material according to claim 1, is characterized in that: the drying process of the precipitate in the first step comprises the following steps: drying the precipitate in a muffle furnace at 95-105 deg.C for 8-12h, grinding into powder, and sieving to collect sulfate precipitate.
4. The method for treating desulfurization circulating wastewater by the ultra-high lime-aluminum method to obtain the mesoporous adsorption material according to claim 1, is characterized in that: in the second step, the reaction condition is that T is 30-35 ℃, r is 250-300r/min, the pH value of the filtrate keeps strong basicity unchanged after the first-stage reaction, and the reaction time is more than or equal to 30 min.
5. The method for treating desulfurization circulating wastewater by the ultra-high lime-aluminum method to obtain the mesoporous adsorption material according to claim 1, is characterized in that: the drying process of the precipitate in the second step comprises the following steps: drying the precipitate in a muffle furnace at 95-105 ℃ for 8-12h, grinding into powder, and collecting the chloride salt precipitate through a target standard sieve.
6. The method for treating desulfurization circulating wastewater by using the ultrahigh lime-aluminum method according to claim 1, wherein the main components of the mesoporous adsorption material are CaAl-LDH-SO4And CaAl-LDH-Cl, which is a mesoporous material and is used as an adsorbent.
7. The method for removing anionic organic pollutants in dye wastewater, wherein the mesoporous adsorption material chlorine salt sediments obtained by treating desulfurization circulating wastewater with the ultrahigh lime-aluminum method are applied to the removal of the anionic organic pollutants in the dye wastewater, according to the method disclosed by claim 1.
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