CN110314668B - Salt-tolerant ferric ion loaded D151 resin and preparation method and application thereof - Google Patents

Salt-tolerant ferric ion loaded D151 resin and preparation method and application thereof Download PDF

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CN110314668B
CN110314668B CN201910608442.7A CN201910608442A CN110314668B CN 110314668 B CN110314668 B CN 110314668B CN 201910608442 A CN201910608442 A CN 201910608442A CN 110314668 B CN110314668 B CN 110314668B
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glyphosate
resin
coo
salt
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肖谷清
吴丹
贺国文
陈昭君
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Hunan City University
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic 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
    • C02F2101/30—Organic compounds
    • C02F2101/306—Pesticides
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen

Abstract

The invention discloses salt-tolerant Fe3+A supported D151 resin, a preparation method and application thereof. Salt resistance Fe3+The loaded D151 resin is prepared from D151 resin serving as a raw material by acid washing, alkali washing and Fe sequentially3+Washing with a solution to obtain Fe with salt resistance3+The preparation method of the loaded D151 resin is simple, low in cost and beneficial to industrial production and application. And salt resistance Fe3+The loaded D151 resin can efficiently adsorb and recover glyphosate in the glyphosate production wastewater with high salt concentration through coordination chelation, not only solves the serious environmental problem caused by the direct discharge of the glyphosate production wastewater, but also efficiently recovers the glyphosate, and has important economic benefit.

Description

Salt-tolerant ferric ion loaded D151 resin and preparation method and application thereof
Technical Field
The invention relates to an adsorbing material, in particular to a D151 resin carrier Fe adsorbing material3+An adsorbing material which is an active material, preparation of the adsorbing material and application of the adsorbing material in the aspect of recovering glyphosate from glyphosate production wastewater, belonging to the technical field of chemical wastewater treatment。
Background
Glyphosate, a non-selective herbicide, is the most common herbicide variety in the world, and is only about 82.6 × 10 in 20144Tons of glyphosate are used. Due to the large amount of glyphosate used, there is a certain concentration of glyphosate in surface water, groundwater and soil. After entering human body through food chain and water, glyphosate interferes with the functions of nervous system and endocrine system, causes human body genetic toxicity and gene mutation, and has carcinogenic effect on human body. There are two industrial methods for producing glyphosate, the mother liquor for producing glyphosate by using glycine method contains about 1.5% glyphosate and 13-15% NaCl; the mother liquor for glyphosate production by the IDA process contains about 2.0% glyphosate and 4.5% NaCl. The direct discharge of the glyphosate production wastewater can cause serious environmental problems, and the glyphosate is wasted, so that the method has important environmental significance and economic benefit for recovering the glyphosate from the glyphosate wastewater.
In the prior art, a method for treating glyphosate mother liquor is to neutralize the glyphosate mother liquor with acid and alkali and then prepare a glyphosate pesticide reagent with the glyphosate content of 10% by evaporation and concentration for sale. The method for treating the glyphosate mother liquor by the evaporation solvent method to recover the glyphosate is another traditional method for treating the glyphosate mother liquor in China, and the method needs to consume a large amount of energy. Other methods such as electrochemical oxidation, biodegradation, visible light catalytic degradation, ore adsorption and the like have the defects of inapplicability to large-scale glyphosate wastewater treatment, low treatment efficiency or secondary pollution and the like.
The glyphosate has a molecular structure of (HO)2-PO-CH2-NH-CH2-COOH, the amino group in the glyphosate molecule shows alkalinity, and the carboxyl group and the phosphate group in the glyphosate molecule show acidity, so the glyphosate is an amphoteric substance. Glyphosate has a quaternary ionization constant (pK)a1＝0.78，pKa2＝2.6，pKa3＝5.6，pKa410.6). Glyphosate is ionized differently at different pH values and exists in different forms. The glyphosate ionization equation is as follows:
Figure BDA0002121533780000021
Figure BDA0002121533780000022
Figure BDA0002121533780000023
Figure BDA0002121533780000024
the solubility of the glyphosate in water is high, and the solubility of the glyphosate in an organic solvent is low, so that the styrene series adsorption resin taking the hydrophobic effect as the driving force is difficult to adsorb the glyphosate from a glyphosate aqueous solution; as can be seen from the ionization equation, the-NH-in the glyphosate molecule is mainly NH2 +Form (weak acid radical) to NH2 +Since the acting force of (a) is small, the adsorption amount of a weakly acidic resin represented by D151 resin to glyphosate is very small; the weak base resins represented by the D301 resin and the 330 resin have stronger adsorption to glyphosate under the salt-free condition, but in the presence of high-concentration salt, because the anion of the salt and the anion of the glyphosate compete for the anion exchange sites in the weak base resin, the adsorption amount of the D301 resin and the 330 resin to the glyphosate is very small or even zero. The difficulty of the research is that the glyphosate in the aqueous solution is adsorbed by a resin adsorption method under the condition of high salt concentration because the glyphosate has high solubility in water and shows acid-base amphiprotic.
Disclosure of Invention
Aiming at the problems of the method for recovering glyphosate in glyphosate production wastewater with high salt concentration by resin adsorption in the prior art, the first purpose of the invention is to provide a salt tolerance Fe3+Loaded D151 resin can be used for efficiently adsorbing and recovering high-salt-concentration glyphosate production wastewater through coordination chelationThe glyphosate not only solves the serious environmental problem caused by the direct discharge of the glyphosate production wastewater, but also efficiently recovers the glyphosate, thereby having important economic benefit.
The second purpose of the invention is to provide Fe with salt tolerance3+The preparation method of the loaded D151 resin is simple to operate, takes the existing industrial D151 resin, iron salt and the like as raw materials, is low in cost, and is beneficial to industrial production and application.
The third purpose of the invention is to provide Fe with salt tolerance3+The loaded D151 resin is applied to adsorbing and recovering glyphosate in glyphosate production wastewater as an adsorbing material, so that the glyphosate can be efficiently adsorbed from the glyphosate production wastewater such as high-concentration sodium chloride, sodium sulfate and the like, the desorption is easy, the glyphosate can be effectively recovered, and the method has important environmental protection benefits and economic benefits.
In order to achieve the technical purpose, the invention provides Fe with salt tolerance3+A method of preparing a supported D151 resin comprising the steps of:
1) carrying out cleaning pretreatment on the D151 resin;
2) washing the D151 resin treated in the step 1) with an acid solution, and then washing with water;
3) washing the D151 resin treated in the step 2) with an alkali solution, and then washing with water;
4) adopting Fe as the D151 resin after the treatment of 3)3+Washing with water after the solution is washed to obtain the product.
Preferably, in the step 1), the D151 resin is subjected to Soxhlet extraction for 8-12 hours by using ethanol as an extractant, and then washed by water. Impurities in the industrial D151 resin can be removed by alcohol washing and water washing.
In a preferable scheme, the acid solution is a hydrochloric acid solution with the concentration of 1-3 mol/L. The purpose of washing with acid solutions is to displace the foreign metal cations, for which solutions generally customary inorganic acids are theoretically suitable, preferably inexpensive hydrochloric acid. The concentration of the preferred hydrochloric acid solution is 2mol/L, and the amount of the hydrochloric acid is far excessive relative to the D151 resin.
In a preferable scheme, the alkali solution is a sodium hydroxide solution with the concentration within the range of 1-3 mol/L. The purpose of washing with an alkali solution is to neutralize the acidified D151 resin, facilitating the subsequent loading of ferric ions, and in theory the common alkali metal base solutions are generally suitable for this scheme, preferably with inexpensive sodium hydroxide. The preferred concentration of sodium hydroxide solution is 2mol/L, and the amount of sodium hydroxide used is in large excess relative to the D151 resin.
In a preferred embodiment, the Fe3+Fe in solution3+The concentration is in the range of 1-3 mol/L. Fe3+The iron ions in the solution are mainly provided by soluble iron salts, and ferric chloride solution is preferred. D151 resin bound Fe3+The capacity of (A) is limited and an excess of Fe can be used3+The solution washed the D151 resin and allowed to adsorb to saturation. The more iron ions are combined in the D151 resin, the more favorable the adsorption amount of the glyphosate is. Provided by the invention (D151-COO)3Fe in Fe type resin3+The maximum coordination ratio to glyphosate is 1: 1.
The invention also provides a salt-tolerant Fe3+A supported D151 resin obtained by the above preparation method.
The invention also provides a salt-tolerant Fe3+The loaded D151 resin is applied to the recovery of glyphosate in glyphosate production wastewater as an adsorption material.
In the preferable scheme, the pH value of the glyphosate production wastewater is controlled within the range of 2-4. Most preferably in the range of 3.0 to 3.5. The higher or lower the pH, the salt tolerance Fe3+The adsorption amount of the loaded D151 resin to the glyphosate is obviously reduced.
In the preferable scheme, the temperature of the glyphosate production wastewater is controlled to be above 283K. Preferably, it is in the range of 283K to 333K, in which the salt resistance Fe increases with increasing temperature3+The adsorption amount of the loaded D151 resin to the glyphosate is obviously increased. The temperature is properly increased, which is beneficial to improving the adsorption quantity of the glyphosate.
Preferably, the salt-resistant Fe is adopted3+After adsorbing glyphosate in glyphosate production wastewater by using loaded D151 resin, adopting sodium hydroxide solution and sulfurDesorbing the acid solution or the ferric sulfate solution to realize the recovery of the glyphosate. The concentration ranges of the sodium hydroxide solution, the sulfuric acid solution or the ferric sulfate solution are all within 1-3 mol/L. Illustrating the salt resistance of Fe3+The loaded D151 resin is easy to desorb after adsorbing glyphosate, and is beneficial to the recovery of glyphosate.
The technical scheme of the invention utilizes the electrostatic interaction between ferric ions and carboxylate radicals in D151 resin, so that the ferric ions are loaded in the D151 resin, and then Fe is utilized3+The high coordination coefficient can additionally provide the characteristic of vacant orbital energy, so that the glyphosate can form stable coordination bonds with amino, carboxyl, phosphate and the like in glyphosate molecules, and the separation and recovery of the glyphosate in wastewater can be realized.
Salt resistance Fe of the invention3+Supported D151 resin ((D151-COO)3Fe) has better salt tolerance, and still shows higher adsorption performance on glyphosate in glyphosate production wastewater with high salt concentration. When NaCl and Na are present2SO4In the presence of NaCl and Na2SO4Pair (D151-COO)3The adsorption of glyphosate by Fe-type resin has little influence. Mainly because of (D151-COO)3When the Fe-type resin adsorbs glyphosate, the Fe in the resin is mainly3+Capable of forming a complex with glyphosate, Cl-And SO4 2-With Fe3+Is not as good as the complexation of the glyphosate and the Fe3+By complexation of (D151-COO)3The Fe-type resin adsorbs glyphosate and shows good salt resistance.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the invention provides salt-resistant Fe3+The loaded D151 resin has good salt tolerance, can efficiently adsorb glyphosate in glyphosate production wastewater with high salt concentration, is easy to desorb, is easy to recover glyphosate, not only solves the serious environmental problem caused by direct discharge of the glyphosate production wastewater, but also efficiently recovers the glyphosate, and has important economic benefit.
The invention provides salt-resistant Fe3+The preparation method of the loaded D151 resin is simple to operate, the existing industrial D151 resin and ferric salt are used as raw materials, the cost is low, andis beneficial to industrial production and application.
The invention provides salt-resistant Fe3+The adsorption capacity of the loaded D151 resin to the glyphosate is far greater than that of the D151 resin loaded with other metal cations, such as (D151-COO)2Ni type resin, (D151-COO)2Cu-type resin, D151-COOH type resin, and D151-COONa type resin. And the salts NaCl and Na in the glyphosate solution2SO4At a content of up to 16%, salt pair (D151-COO)3The Fe-type resin has no obvious influence on adsorbing glyphosate. When the pH value of the glyphosate solution is 3.35, (D151-COO)3The Fe type resin has the maximum adsorption capacity to glyphosate, and the temperature is increased to be favorable (D151-COO)3Adsorbing glyphosate by Fe type resin, 10mL (D151-COO)3After adsorbing 48.5BV (bed volume) of glyphosate solution by Fe type resin, the concentration of glyphosate in effluent is 0.06mg/mL, (D151-COO)3The adsorption capacity of the Fe-type resin to the glyphosate is 28.7 mg/mL-1And (D151-COO)36.8BV 2 mol.L of glyphosate adsorbed by Fe-type resin can be used-1H2SO4And (4) desorbing, and easily recovering the glyphosate.
Drawings
FIG. 1 shows D151-COOH type resin, D151-COONa type resin, and (D151-COO)3Fe type resin, glyphosate and glyphosate-adsorbing (D151-COO)3Fe type resin (noted as (D151-COO)3Fe/glyphosate) infrared spectrum;
FIG. 2 shows D151-COOH type resin, D151-COONa type resin, and (D151-COO)3The zero charge point of Fe-type resin;
FIG. 3 is a graph of the adsorption performance of D151 resin on glyphosate for different cation loadings;
FIG. 4 is a graph of the effect of different salt contents on the performance of resins for adsorbing glyphosate;
FIG. 5 shows different pH pairs (D151-COO)3Influence of the performance of adsorbing glyphosate by Fe-type resin;
FIG. 6 shows (D151-COO)3Adsorption isotherm of Fe-type resin to glyphosate;
FIG. 7 shows (D151-COO)3The coordination ratio of Fe-type resin to glyphosate;
FIG. 8 is a graph of dynamic adsorption of glyphosate;
figure 9 is a dynamic desorption of glyphosate.
Detailed Description
The following specific examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
The following examples illustrate the detection apparatus including: nicolet iS5 fourier transform infrared spectrometer (siemer flyer, usa); u-3010 ultraviolet-visible spectrophotometer (Hitachi, Japan).
The starting materials used in the following examples are, unless otherwise specified, conventional commercial starting materials of the prior art. For example, the total exchange amounts of the D301 resin, the D151 resin and the 330 resin were measured as 4.81, 9.05 and 9.56mmol/g, respectively, as purchased from Samsung resin technologies, Inc., Anhui. Glyphosate, KBr, NaNO2Etc. are all analytically pure.
Example 1
Fe3+、Cu2+Or Ni2+Preparation of supported D151 resin:
the resin 30g D151 was placed in a Soxhlet extractor and extracted with about 250mL of absolute ethanol for 10h, and the extracted resin was washed with deionized water to remove ethanol. Transferring the washed D151 resin to a glass chromatographic column, washing the resin with about 120mL of 2mol/L hydrochloric acid solution, and then washing the resin with deionized water until no Cl-Then, the resin was discharged to obtain D151-COOH type resin.
Transferring the D151-COOH type resin to a glass chromatographic column, washing the resin with about 120mL of 2mol/L sodium hydroxide solution, and then washing the resin with deionized water to be neutral to obtain the D151-COONa type resin.
Transferring the D151-COONa type resin to a glass chromatographic column, and using about 120mL of FeCl 2mol/L3The resin is washed with the solution and then with deionized water until free of Cl-Flowing out to obtain Fe3+Loaded (D151-COO)3An Fe type resin. Respectively with Ni2+And Cu2+In place of Fe3+Obtaining Ni2+Loaded (D151-COO)2Ni-base resin and Cu2+Loaded (D151-COO)2A Cu-type resin.
Prepared (D151-COO)3Fe in Fe type resin3+Measurement of the content of (b):
taking 1.0g of (D151-COO)3The concentration of the Fe-type resin in 25mL is 2.0mol/L H2SO4In the solution, the solution was shaken at a constant temperature of 25 ℃ for 24 hours. (D151-COO)3Fe-type resin turns from brown-yellow to white, Fe3+Desorption from the resin surface, (D151-COO)3Fe type resin at 2.0mol/L H2SO4Converted into D151-COOH type resin in the solution. Determination of Fe in desorption solution by KSCN at 478nm3 +Content, calculation (D151-COO)3Fe in Fe type resin3+The content was 2.85 mmol/g.
Prepared (D151-COO)3Static adsorption of Fe-type resin to glyphosate:
taking 0.2g of wet resin, adding 25mL of 0.5-1.1mg/mL glyphosate aqueous solution, adjusting the pH value of the glyphosate solution and the content of salt in the solution, oscillating at a rotating speed of 150r/min at a set temperature to enable the glyphosate to be adsorbed by the resin to reach balance, detecting the concentration of the glyphosate in the balanced solution, and calculating the adsorption quantity q (mg/g) of the resin to the glyphosate. q is 25 (C)i-Ce)/W，CiAnd CeThe concentration of glyphosate in the solution at start and at equilibrium (mg/mL), respectively, and W is the mass of the resin (g). Freundlich equation for adsorption isotherms
Figure BDA0002121533780000061
And Langmuir equation
Figure BDA0002121533780000062
Fitting, KFAnd n is a parameter reflecting the adsorption capacity of Freundlich equation, qmAnd KLThe Langmuir equation reflects the parameters of the adsorption capacity, respectively.
Prepared (D151-COO)3Dynamic adsorption and desorption of Fe-type resin on glyphosate:
wet fill 10mL (D151-COO)3Placing Fe type resin in a glass chromatographic column with the diameter of 10mm multiplied by 350mm, adding 0.6mg/mL glyphosate aqueous solution by a constant flow pump at the constant temperature of 25 ℃ by circulating water and the flow rate of 3.2BV/h (BV is the volume of a bed)Flows through a chromatographic column. When the glyphosate concentration in the effluent is 10% of the addition concentration (0.06mg/mL), the addition of the glyphosate solution is stopped, and 2mol/L H is used2SO4And (4) regenerating.
The detection method of the glyphosate comprises the following steps:
reacting glyphosate with sodium nitrite under acidic condition to generate glyphosate nitroso derivative, wherein the glyphosate nitroso derivative has maximum absorption peak at 242nm wavelength, and measuring the glyphosate concentration by adopting an ultraviolet-visible spectrophotometer according to national standard GB 12686-2004.
Testing of D151-COOH type resin, D151-COONa type resin, (D151-COO)3Fe type resin, glyphosate and glyphosate-adsorbing (D151-COO)3Fe type resin (noted as (D151-COO)3Fe/glyphosate) as shown in fig. 1:
2930cm can be seen in the figure-1、1700cm-1Respectively correspond to C-H and carbonyl stretching vibration absorption peaks of 1450cm in D151-COOH type resin-1And 1160cm-1Respectively a-COO-asymmetric stretching vibration peak and a C-O stretching vibration peak. H atom in carboxyl group of D151-COOH type resin is Na+After substitution, the carbon-oxygen double bond and carbon-oxygen single bond in the original carboxyl group are "homogenized" into two coupled equal carbon-oxygen bonds, resulting in a bond length of 1550cm-1And 1400cm-1Strong antisymmetric stretching vibration peak and symmetric stretching vibration peak appear. Infrared spectrum of the resin is comparable to that of the resin D151-COOH, (D151-COO)3The stretching vibration absorption peaks of C-H and carbonyl in the infrared spectrum of the Fe-based resin are both red-shifted. Infrared spectrum of the resin is comparable to that of D151-COONa type resin, (D151-COO)3The 'red shift' of the symmetric stretching vibration peak of the carboxylate ions and the 'blue shift' of the antisymmetric stretching vibration peak of the carboxylate ions in the infrared spectrum of the Fe-based resin indicate that the Fe3+Substitution of Na in D151-COONa-type resin+Then, Fe3+The electron cloud distribution of carboxylate ions in the resin is influenced, which shows that Fe3+The hollow orbital portion is coordinated by electrons in the carboxylate ion. 1710cm in glyphosate infrared spectrum-1Is a characteristic absorption peak of carbonyl in glyphosate carboxyl at 1560cm-1In-plane of glyphosate N-HPeak of flexural vibration at 1155cm-1The position of the vibration peak appears as P ═ O stretching vibration peak, 1070cm-1An asymmetric stretching vibration peak of P-O appears, and the P-OH is 908cm-1An absorption peak appears. (D151-COO)3After the Fe resin adsorbs glyphosate, the stretching vibration absorption peaks of carbonyl in the resin and C-H of a resin skeleton are consistent with the infrared spectrum of the D151-COOH resin, and the characteristic absorption peaks of N-H, P ═ O and P-O in the original glyphosate molecule disappear, which shows that Fe3+Forming a coordination bond with the adsorbed glyphosate.
D151-COOH type resin, D151-COONa type resin, (D151-COO)3Zero charge point of Fe type resin:
zero Charge Point of the resin (noted as pH)PZC) The resin surface net charge is equal to the pH value of zero, and the zero charge point of the resin is determined by an inert electrolyte titration method. Preparing 0.1mol/L KNO3Solution, conditioning KNO with HCl or NaOH3pH value of the solution, initial KNO was measured with a pH meter3pH value of the solution (noted as pH)i). Adding 0.2g of resin into 100mL of KNO3In the solution, after oscillating for 48h at 25 ℃, the pH value (recorded as pH) of the solution after adsorption is measuredf). By pHiWith pHfDifference of (d) (noted as Δ pH) vs. pHiPlotted, as shown in FIG. 2, the pH corresponding to a Δ pH of zero on the curveiThe value is the zero charge point of the resin. As is clear from FIG. 2, the pH at the point of zero charge of the D151-COOH type resin was 2.05, and the pH at the point of zero charge of the D151-COONa type resin was 8.26, (D151-COO)3The pH of the Fe type resin at the zero charge point was 3.35. D151-COONa type resin, (D151-COO)3The pH values at the zero charge point of the Fe-type resin and the D151-COOH-type resin gradually decreased, demonstrating an increase in the surface acidity of the resins.
Example 2
Adsorption performance of the different cation loaded D151 resins prepared in example 1 on glyphosate, the adsorption method was operated as in example 1:
the adsorption performance of D151 resin loaded with different cations on glyphosate under the condition of no external acid and alkali is shown in figure 3. As can be seen from FIG. 3, Fe3+Loaded (D151-COO)3The adsorption capacity of the Fe type resin to the glyphosate is far greater than that of (D151-COO)2Ni type resin, (D151-COO)2Cu-type resin, D151-COOH type resin, and D151-COONa type resin.
Glyphosate pK under the condition of no external acid-base additiona1When the ratio is 0.78, the phosphate group in the glyphosate molecule ionizes hydrogen ions, the ionized hydrogen ions are combined with amino groups in the glyphosate molecule, the interaction force between the functional groups in the glyphosate molecule and the carboxyl groups in the D151-COOH type resin and the carboxylate ions in the D151-COONa type resin is small, and the solubility of the glyphosate in water is high, so that the D151-COOH type resin and the D151-COONa type resin hardly adsorb the glyphosate. Ni2+And Cu2+Ni supported on resin with central ion coordination number of 42+And Cu2+Most of the empty rail quilt (D151-COO)2Ni type resin sum (D151-COO)2Since the lone pair of electrons of the oxygen atom in the Cu-type resin is coordinated, (D151-COO)2Ni type resin sum (D151-COO)2The Cu-type resin has only weak adsorption to glyphosate. Fe3+Coordination number of central ion of 6, Fe3+Is partially covered by (D151-COO)3The lone pair electrons of the oxygen atom in the Fe type resin are coordinated, and the rest empty orbitals can form coordinate bonds with the glyphosate, so that Fe3+Loaded (D151-COO)3The adsorption capacity of the Fe type resin to the glyphosate is far greater than that of (D151-COO)2Ni type resin sum (D151-COO)2Adsorption amount of Cu-type resin to glyphosate.
Example 3
Prior Industrial resin and (D151-COO) prepared in example 1 of the present invention3The adsorption performance of Fe-type resin on glyphosate under different salt concentrations was carried out as in example 1.
The industrial wastewater for producing glyphosate contains a large amount of salt, and NaCl and Na are selected for the purpose2SO4For representation, the effect of the salt content on the glyphosate adsorption performance of the resin is studied, and the experimental results are shown in fig. 4. As can be seen from FIG. 4, the adsorption amounts of the 330 resin and the D301 resin to glyphosate were large in the absence of salt, the adsorption amount of the 330 resin to glyphosate was very small at 0.3% NaCl, the adsorption amount of the D301 resin to glyphosate was very small at 2% NaCl, and when the NaCl content in the glyphosate solution was further increased, the adsorption amounts of the 330 resin and the D301 resin were largeThe adsorption amount of the D301 resin to the glyphosate is further reduced. This is because the adsorption of glyphosate by the 330 resin and the D301 resin is such that the glyphosate anion exchanges adsorption sites with the anions in the 330 resin and the D301 resin. When NaCl is present, Cl in NaCl-Competing 330 with the glyphosate anion in solution for the anion exchange sites on the resin and on the D301 resin results in a significant reduction in the amount of glyphosate adsorbed by the 330 resin and the D301 resin.
As can be seen from FIG. 4, NaCl and Na are present in the glyphosate solution2SO4Then, NaCl pair (D151-COO)3The Fe-type resin has no obvious influence on adsorbing glyphosate, and Na2SO4Pair (D151-COO)3The effect of adsorbing glyphosate by Fe-type resin is small. This is because (D151-COO)3When the Fe-type resin adsorbs glyphosate, the Fe in the resin is mainly3+Capable of forming a complex with glyphosate, Cl-And SO4 2-With Fe3+Is not as good as the complexation of the glyphosate and the Fe3+The complexation of (a). From FIG. 4, it can be seen that the salts NaCl and Na in the glyphosate solution2SO4At a content of up to 16%, salt pair (D151-COO)3The adsorption of glyphosate by Fe-type resin has no significant influence, (D151-COO)3The Fe-type resin adsorbs glyphosate and shows good salt resistance.
Example 4
(D151-COO) prepared in example 1 of the present invention3The effect of the Fe-type resin on the performance of adsorbing glyphosate under different pH conditions, the adsorption method is operated as in example 1:
pH pair (D151-COO)3The effect of Fe-type resin adsorbing glyphosate is quite obvious, and the result is shown in figure 5. When the pH value of the glyphosate solution is 3.35, namely (D151-COO)3Zero charge point of Fe type resin, (D151-COO)3The Fe type resin shows zero net charge, (D151-COO)3The Fe type resin has the maximum adsorption amount to glyphosate. When the pH value is less than 3.35, H is reduced with the decrease of the pH value of the solution+Increased concentration of Fe3+From (D151-COO)3Desorbing the Fe resin, (D151-COO)3The Fe type resin gradually changes into D151-COOH type resin, and the adsorption amount of glyphosate becomes smaller. When the pH value is more than 3.35, (D151-COO)3The surface of the Fe type resin is negatively charged, and it is understood from FIG. 2 that (D151-COO) is formed as the pH value of the solution is increased3The negative charge on the surface of the Fe-type resin increases. From pK of glyphosateaAs can be seen from the value and the ionization equation, the ionization degree of the glyphosate is increased along with the increase of the pH value of the solution, and the negative charge carried by the ionized glyphosate anion is increased. (D151-COO)3The repulsive force between the negative charges on the surface of the Fe type resin and the negative charges on the glyphosate anion is increased, so (D151-COO)3The adsorption amount of the Fe-type resin to the glyphosate is reduced.
Example 5
(D151-COO) prepared in example 1 of the present invention3The influence of Fe type resin on the performance of adsorbing glyphosate under different temperature conditions:
FIG. 6 shows (D151-COO)3Adsorption isotherm of Fe-type resin on glyphosate. As can be seen from FIG. 6, the higher the temperature is, (D151-COO)3The larger the adsorption amount of the Fe-type resin to glyphosate. Loaded on (D151-COO)3Fe on Fe type resin3+Form coordination compound with glyphosate, and increase temperature is favorable for Fe3+With formation of glyphosate complex, it is advantageous to raise the temperature (D151-COO)3Adsorbing glyphosate by Fe-type resin.
TABLE 1 adsorption isotherm fitting parameters
Figure BDA0002121533780000101
(D151-COO)3The results of the Langmuir equation and Freundlich equation fitting of the adsorption of glyphosate by Fe-type resin are shown in Table 1. As can be seen from Table 1, (D151-COO)3Freundlich equation correlation coefficient R of adsorbing glyphosate by Fe type resin2>0.99, indicating (D151-COO)3The adsorption of the glyphosate by the Fe-type resin conforms to the Freundlich equation (D151-COO)3Adsorbing glyphosate by Fe-type resin is heterogeneous adsorption; n is>3, indicating (D151-COO)3Adsorbing glyphosate by Fe-type resin to obtain preferential adsorption; when the temperature is increased from 283K to 313K, the higher the temperature is, (D151-COO)3Adsorbing glyphosate K by Fe-type resinFThe larger the value sum n, this is in combination with (D151-C)OO)3The adsorption capacity of the Fe-type resin to the glyphosate is increased along with the increase of the temperature.
Example 6
(D151-COO) prepared in example 1 of the present invention3The coordination ratio of the Fe-type resin to glyphosate is as follows:
mixing glyphosate with (D151-COO) by a saturated capacity method3Fe in Fe type resin3+The resin and glyphosate solution were added at a ratio of amounts of 0.12:1, 0.24:1, 0.36:1, 0.48:1, 0.72:1, 0.96:1, 1.2:1, 2.4:1, 3.6:1, 4.8:1, 6.0:1, 12: 1. Adsorption to equilibrium under 298K, calculation (D151-COO)3The amount of glyphosate adsorbed by Fe-type resin was calculated (D151-COO)3Fe in Fe type resin3+The results are shown in FIG. 7 for the coordination ratio of glyphosate. As can be seen from FIG. 7, with the glyphosate pair (D151-COO)3Fe in Fe type resin3+An increased ratio of the amount of substance to (D151-COO)3Fe in Fe type resin3+The coordinated glyphosate is increased. When the glyphosate pair (D151-COO)3Fe in Fe type resin3+When the ratio of the amount of substance is increased to 2.4:1, even if glyphosate is further added, with (D151-COO)3Fe in Fe type resin3+Coordinated glyphosate invariant, glyphosate with (D151-COO)3Fe in Fe type resin3+The maximum coordination ratio is 1:1, (D151-COO)3Fe in Fe type resin3+The content is 2.85mmol/g, (D151-COO)3The saturated adsorption capacity of the Fe-type resin to the glyphosate is 481.85 mg/g.
Example 7
(D151-COO) prepared in example 1 of the present invention3Static desorption after adsorbing glyphosate by Fe type resin:
respectively by H2O、2mol/L NaOH、2mol/L H2SO4、2mol/L Fe2(SO4)3Each 25mL of the solution was used as desorbent, and four desorbent pairs (D151-COO) were examined3The desorption performance of the Fe-type resin for adsorbing glyphosate is shown in Table 2.
Table 2(D151-COO)3Static desorption of Fe-type resins
Figure BDA0002121533780000111
As can be seen from Table 2, (D151-COO)3When the glyphosate adsorbed by the Fe-type resin is used as a desorbent, the desorption rate is only 5.35 percent. Glyphosate is itself readily soluble in water, but (D151-COO)3Fe in Fe-based resin3+Has strong coordination capacity with glyphosate, so that water pair (D151-COO)3The desorption rate of the glyphosate adsorbed by the Fe-type resin is low. 2mol/L NaOH pair (D151-COO)3The glyphosate adsorbed by Fe type resin has good desorption effect because of (D151-COO)3Fe supported on Fe-based resin3+Is easy to react with OH under strong alkaline conditions-Is combined to make Fe3+No longer coordinates to glyphosate. 2mol/L H2SO4Pair (D151-COO)3The glyphosate adsorbed by Fe type resin has good desorption effect because of strong acid condition (D151-COO)3The Fe-type resin is converted into the D151-COOH type resin, and the D151-COOH type resin hardly adsorbs glyphosate. At 2mol/L Fe2(SO4)3When the solution is used as a desorbent, the glyphosate desorption rate is high. This is because of the large high concentration of Fe in the desorbent3+And (D151-COO)3Fe on Fe resin3+Competing for glyphosate, glyphosate adsorbed by resin and a large amount of Fe in desorbent3+Coordination, glyphosate from (D151-COO)3Desorbing Fe-type resin. (D151-COO)3The glyphosate adsorbed by Fe type resin can be prepared by 2mol/L NaOH and 2mol/L H2SO4、2mol/L Fe2(SO4)3And (5) desorbing the solution.
Example 8
(D151-COO) prepared in example 1 of the present invention3Dynamic adsorption and desorption of the Fe-type resin on glyphosate:
FIG. 8 shows (D151-COO)3Dynamic adsorption of Fe-type resin to glyphosate. As can be seen from FIG. 8, when the glyphosate effluent concentrations are 1%, 5% and 10% of the glyphosate injection concentration (0.6mg/mL), (D151-COO)3The volume of glyphosate solution absorbed by Fe type resin is respectively 13.6BV (136mL), 34.3BV (343mL), 48.5BV (485mL), (D151-COO)3The adsorption capacity of the Fe-type resin to the glyphosate is 8.2 mg/mL-1、20.4mg·mL-1、28.7mg·mL-1. FIG. 9 shows (D151-COO)3Dynamic desorption of glyphosate by Fe-type resin. (D151-COO)3The glyphosate adsorbed by Fe type resin can be absorbed by 6.8BV (68mL)2 mol.L-1H2SO4And (4) desorbing.
The above experiments and data show that: fe3+Loaded (D151-COO)3Fe in Fe type resin3+The content is 2.85mmol/g, (D151-COO)3The Fe-type resin has good adsorption effect on glyphosate. (D151-COO)3The Fe-type resin adsorbs glyphosate and shows good salt resistance. At a pH value of (D151-COO) of the glyphosate solution3Fe type resin at zero charge point, (D151-COO)3The Fe-type resin has the best effect of adsorbing glyphosate. Increasing the temperature favourably (D151-COO)3Adsorbing glyphosate, glyphosate and (D151-COO) by Fe type resin3Fe in Fe type resin3+The maximum coordination ratio is 1: 1. (D151-COO)3The glyphosate adsorbed by Fe type resin can be prepared by 2mol/L NaOH and 2mol/L H2SO4、2mol/L Fe2(SO4)3And (5) desorbing the solution. (D151-COO)3The Fe-based resin has good application prospect in the aspect of adsorbing and separating glyphosate in water.

Claims (8)

1. Salt-tolerant Fe3+Use of a supported D151 resin, characterized in that: the adsorbing material is used for recovering glyphosate in glyphosate production wastewater; the salt resistance of Fe3+The supported D151 resin is prepared by the following method: the method comprises the following steps: 1) carrying out cleaning pretreatment on the D151 resin; 2) washing the D151 resin treated in the step 1) with an acid solution, and then washing with water; 3) washing the D151 resin treated in the step 2) with an alkali solution, and then washing with water; 4) adopting Fe as the D151 resin after the treatment of 3)3+Washing with water after the solution is washed to obtain the product.
2. Salt-tolerant Fe according to claim 13+Use of a supported D151 resin, characterized in that: glyphosateAnd controlling the pH value of the production wastewater within the range of 2-4.
3. Salt-tolerant Fe according to claim 13+Use of a supported D151 resin, characterized in that: the temperature of the glyphosate production wastewater is controlled to be above 283K.
4. Salt-tolerant Fe according to claim 13+Use of a supported D151 resin, characterized in that: using salt-tolerant Fe3+After adsorbing glyphosate in glyphosate production wastewater by the loaded D151 resin, desorbing by using a sodium hydroxide solution, a sulfuric acid solution or a ferric sulfate solution to realize the recovery of the glyphosate.
5. Salt-tolerant Fe according to claim 13+Use of a supported D151 resin, characterized in that: in the step 1), the D151 resin is subjected to Soxhlet extraction for 8-12 h by using ethanol as an extractant, and then washed by water.
6. Salt-tolerant Fe according to claim 13+Use of a supported D151 resin, characterized in that: the acid solution is a hydrochloric acid solution with the concentration within the range of 1-3 mol/L.
7. Salt-tolerant Fe according to claim 13+Use of a supported D151 resin, characterized in that: the alkali solution is a sodium hydroxide solution with the concentration of 1-3 mol/L.
8. Salt-tolerant Fe according to claim 13+Use of a supported D151 resin, characterized in that: said Fe3+Fe in solution3+The concentration is in the range of 1-3 mol/L.
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