CN103319634B - Mesoporous composite functional resin containing quaternary amine group as well as preparation method and application thereof - Google Patents
Mesoporous composite functional resin containing quaternary amine group as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a mesoporous composite functional resin containing a quaternary amine group as well as a preparation method and an application thereof. The composite functional resin is a quaternary amine group modified mesoporous absorbing resin; the quaternary amine group content is 1.0-2.5mmol/g; the specific surface area of the composite function resin is 450-850m<2>/g; the average aperture is 4-10nm. The prepared composite function resin has three functions of physical absorption, catalytic hydrolysis and hydrolysis product absorption, so that phthalic ester pollutants in a water body can be deeply purified.
Description
Technical field
The present invention relates to a kind of mesopore composite function resin containing quaternary amine base, being specifically related to a kind of strong basicity mesopore composite function resin for removing phthalate pollutent in water body.
Background technology
Industrially mainly being used as the phthalate compound of softening agent, is a kind of environmental hormone with genotoxicity, endocrine disrupting, carinogenicity, teratogenecity, mutagenicity.In recent years, due to phthalate a large amount of production and widely use, make its constantly migration and accumulation in physical environment, in global ecological environment, reach the degree generally detected, this type of aromatic ester pollutent hydrophobicity is strong, difficult degradation, and trace level even trace level also can cause serious harm to HUMAN HEALTH and ecotope.But be difficult to the deep purifying realizing phthalate pollutent due to conventional water treatment, cause the phthalate concentration in many water bodys to be far from up to standard, therefore, in the urgent need to succinct, advanced purification technology efficiently.
Within 2006, Nanjing University has applied for " a kind of containing composite function super high crosslinked resin of quaternary amine base and preparation method thereof " (patent No. 200610039861.6), and what the method was synthesized is that a kind of pore structure is mainly micropore and contains the composite function super high crosslinked resin of quaternary amine base.And the synthetic method that pore structure mainly concentrates on the composite function resin of mesopore also containing quaternary amine base has not yet to see bibliographical information.Patent (patent No. 200610097239.0) that Nanjing University in 2006 applies for " a kind of administer diethyl phthalate waste water and therefrom reclaim the method for dimethyl phthalate ", this patent mainly utilizes the phthalate pollutent in the physisorption Adsorption water body of macroporous adsorbent resin.Patent " method of composite function resin and method for making and the process phthalate pollution of water body " patent (number of patent application 200710190974.0) of Nanjing University's application in 2007, mainly utilize the hypercrosslinked polymeric resin with sulfonic acid group of synthesis as solid acid catalyst and sorbent material, removed the phthalate pollutent in water body by physisorption and acidic catalyst Degradation.And " a kind of solid base catalyst removes the method for phthalate in water body " patent (number of patent application 200910184186.X) of Nanjing University's application in 2009, mainly utilize strongly basic anion exchange resin as solid base catalyst, first phthalate being carried out base-catalysed hydrolysis is phthalic acid, then by ion exchange by phthalic acid Adsorption, and mainly concentrate on mesopore by pore structure, and the method carrying out deep purifying phthalate pollutent as sorbent material and solid base catalyst containing quaternary amine base composite function resin at present and have no bibliographical information.
Summary of the invention
The present invention is intended to synthesize a kind of strong basicity complex function adsorption resin with having central hole structure, and uses it as phthalate pollutent in sorbent material and catalyzer removal water body.
In order to achieve the above object, the invention provides a kind of NEW TYPE OF COMPOSITE functional resin, composite function resin is quaternary amines modified mesopore nonpolar adsorption resin; Described quaternary amines is Trimethylamine or triethylamine, and content is 1.0 ~ 2.5mmol/g; Described composite function resin specific surface area is 450 ~ 850m
2/ g, mean pore size is 4-10nm.
Wherein, mesopore nonpolar adsorption resin is selected from XAD-4, XDA-1 or ZGDM 11.
Present invention also offers the preparation method of above-mentioned composite function resin, comprise the following steps:
A) get mesopore nonpolar adsorption resin and be immersed in abundant swelling 24h in chloromethyl ether, the zinc chloride or the iron(ic) chloride that add mesopore nonpolar adsorption resin weight 20 ~ 50% make catalyzer, 2 ~ 4h is reacted at 36 ~ 42 DEG C, then resin spheroid is leached, wash away mother liquor remaining in resin spheroid with ethanolic extraction, dry and obtain chloromethylation polymeric adsorbent;
B) get chloromethylation polymeric adsorbent and swell in 24h in benzene, oil of mirbane or ethylene dichloride, dropwise add the organic amine aqueous solution of chloromethylation polymeric adsorbent weight 1.5 ~ 2 times at normal temperatures, after being warming up to 30 DEG C of reaction 2 ~ 6h after dripping, resin is leached use successively distilled water, ethanol or methyl alcohol or acetone, 2% ~ 5% salt acid elution, be finally washed till neutrality with distilled water and namely obtain described composite function resin; The described organic amine aqueous solution is Trimethylamine 99 or triethylamine aqueous solution, and concentration is 22%-33%.
Present invention also offers above-mentioned composite function resin and remove the application in water body in phthalate pollutent.
Specifically comprise the following steps:
(1) water body filtration containing phthalate is removed suspended impurity;
(2) by the filtrate that obtains in step (1) at 20 ~ 40 DEG C, with the flow velocity of 5 ~ 20BV/h by being filled with the adsorption column of described composite function resin, the water body of phthalate must be removed.
Wherein, phthalate is dimethyl phthalate, diethyl phthalate, dibutyl phthalate, o-phthalic acid dibutyl ester, two-(2-ethylhexyl) phthalate; In described water body, the content of phthalate is not more than 200mg/L.
The composite function resin being adsorbed with phthalate in step (2) adopts mixing solutions, at 20-60 DEG C, carries out desorption and regeneration with 5-20BV/h flow velocity; Described mixing solutions comprises sodium hydroxide and ethanol, and sodium hydrate content is 2mol/L, and ethanol contend percentage composition is 5%.
The present invention has the following advantages compared to existing technology: 1, composite function resin terephthalic acid ester of the present invention has physisorption, catalytic hydrolysis effect and hydrolysate adsorption simultaneously; 2, the pore structure of this composite function resin mainly concentrates on mesopore region, has higher adsorption rate compared to micro-porous resin; 3, because phthalate molecule and free hydroxide ion are all enriched in resin duct, thus the alkaline hydrolysis catalytic rate of the terephthalic acid ester of resin is strengthened.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail containing the mesopore composite function resin of quaternary amine base.
Embodiment 1
Poured in 500ml there-necked flask by 30g XAD-4 polymeric adsorbent, add 100ml chloromethyl ether, abundant swelling rear (24h), adds 6g FeCl
3, be warming up to 36 DEG C of reaction 4h, filter, use dehydrated alcohol extracting, after drying at 45 DEG C, be positioned in moisture eliminator and preserve.By the resin after 30g chloromethylation, pour in the there-necked flask of 500ml, add the swelling 24h of benzene, then dropwise add the trimethylamine aqueous solution that 45g concentration is 33%, be warming up to 30 DEG C of reaction 2h.Reacted and leached by resin, used distilled water successively, ethanol, 5% salt acid elution, is finally washed till neutrality with distilled water.Products therefrom is quaternary amines modified composite function resin.This resin specific surface area is 650 m
2/ g, mean pore size is 4nm; Season, amine groups content was 1.06mmol/L.
Be in the glass adsorption column of the composite function super high crosslinked resin tape loaded chuck of quaternary amine base (Φ 12 × 160mm) by 2.4ml (about 1 gram) function base.In water inlet, dimethyl phthalate concentration is 20mg/L, and after filtration, under 25 ± 5 DEG C of conditions, pass through resin bed with the flow of 24mL/h, treatment capacity is that 2000mL/ criticizes.After resin absorption, in water outlet, dimethyl phthalate mean concns is 0.1mg/L.
Absorption is stopped when absorption reaches leakage point (in absorption water outlet, the instant concentration of dimethyl phthalate is 2% of influent concentration), by the mixing solutions containing the sodium hydroxide of 2mol/L and 5% ethanol at the temperature of 30 ± 5 DEG C, with the flow of 3mL/h downstream through resin bed, by the regeneration of this resin desorption completely.
Embodiment 2
30g XAD-4 polymeric adsorbent is poured in 500ml there-necked flask, adds 100ml chloromethyl ether, after fully swelling, add 10g FeCl
3, be warming up to 42 DEG C of reaction 2h, filter, use dehydrated alcohol extracting, after drying at 45 DEG C, be positioned in moisture eliminator and preserve.By the resin after 30g chloromethylation, pour in the there-necked flask of 500ml, add the swelling 24h of oil of mirbane, then dropwise add the trimethylamine aqueous solution that 60g concentration is 33%, be warming up to 30 DEG C of reaction 4h.Reacted and leached by resin, used distilled water successively, ethanol, 5% salt acid elution, is finally washed till neutrality with distilled water.Products therefrom is quaternary amines modified composite function resin.This resin specific surface area is 455m
2/ g, mean pore size is 4nm; Season, amine groups content was 1.52mmol/L.
Be in the glass adsorption column of the composite function super high crosslinked resin tape loaded chuck of quaternary amine base (Φ 12 × 160mm) by 2.4ml (about 1 gram) function base.In water inlet, dimethyl phthalate concentration is 100mg/L, and after filtration, under 25 ± 5 DEG C of conditions, pass through resin bed with the flow of 24mL/h, treatment capacity is that 1800mL/ criticizes.After resin absorption, in water outlet, dimethyl phthalate mean concns is 0.1mg/L.
Absorption is stopped when absorption reaches leakage point (in absorption water outlet, the instant concentration of dimethyl phthalate is 2% of influent concentration), by the mixing solutions containing the sodium hydroxide of 2mol/L and 5% ethanol at the temperature of 30 ± 5 DEG C, with the flow of 1.6mL/h downstream through resin bed, by the regeneration of this resin desorption completely.
Embodiment 3
30g XAD-4 polymeric adsorbent is poured in 500ml there-necked flask, adds 100ml chloromethyl ether, after fully swelling, add 15g FeCl
3, be warming up to 40 DEG C of reaction 2h, filter, use dehydrated alcohol extracting, after drying at 45 DEG C, be positioned in moisture eliminator and preserve.By the resin after 30g chloromethylation, pour in the there-necked flask of 500ml, add the swelling 24h of ethylene dichloride, then dropwise add the triethylamine aqueous solution that 60g concentration is 22%, be warming up to 30 DEG C of reaction 6h.Reacted and leached by resin, used distilled water successively, ethanol, 5% salt acid elution, is finally washed till neutrality with distilled water.Products therefrom is quaternary amines modified composite function resin.This resin specific surface area is 845 m
2/ g, mean pore size is 4nm; Season, amine groups content was 2.45mmol/L.
Be in the glass adsorption column of the composite function super high crosslinked resin tape loaded chuck of quaternary amine base (Φ 12 × 160mm) by 2.4ml (about 1 gram) function base.In water inlet, dimethyl phthalate concentration is 200mg/L, and after filtration, under 25 ± 5 DEG C of conditions, pass through resin bed with the flow of 24mL/h, treatment capacity is that 1600mL/ criticizes.After resin absorption, in water outlet, dimethyl phthalate mean concns is about 0.1mg/L.
Absorption is stopped when absorption reaches leakage point (in absorption water outlet, the instant concentration of dimethyl phthalate is 2% of influent concentration), by the mixing solutions containing the sodium hydroxide of 2mol/L and 5% ethanol at the temperature of 30 ± 5 DEG C, with the flow of 1.6mL/h downstream through resin bed, by the regeneration of this resin desorption completely.
Embodiment 4
30g XDA-1 polymeric adsorbent is poured in 500ml there-necked flask, adds 100ml chloromethyl ether, after fully swelling, add 15g FeCl
3, be warming up to 40 DEG C of anti-4h, filter, use dehydrated alcohol extracting, after drying at 45 DEG C, be positioned in moisture eliminator and preserve.By the resin after 30g chloromethylation, pour in the there-necked flask of 500ml, add the swelling 24h of benzene, then dropwise add the triethylamine aqueous solution that 45g concentration is 22%, be warming up to 30 DEG C of reaction 6h.Reacted and leached by resin, used distilled water successively, ethanol, 5% salt acid elution, is finally washed till neutrality with distilled water.Products therefrom is quaternary amines modified composite function resin.This resin specific surface area is 756m
2/ g, mean pore size is 7nm; Season, amine groups content was 2.04mmol/L.
Be in the glass adsorption column of the composite function super high crosslinked resin tape loaded chuck of quaternary amine base (Φ 12 × 160mm) by 2.4ml (about 1 gram) function base.In water inlet, diethyl phthalate concentration is 20mg/L, and after filtration, under 25 ± 5 DEG C of conditions, pass through resin bed with the flow of 24mL/h, treatment capacity is that 2176mL/ criticizes.After resin absorption, in water outlet, dimethyl phthalate mean concns is about 0.6mg/L.
Absorption is stopped when absorption reaches leakage point (in absorption water outlet, the instant concentration of diethyl phthalate is 2% of influent concentration), by the mixing solutions containing the sodium hydroxide of 2mol/L and 5% ethanol at the temperature of 30 ± 5 DEG C, with the flow of 16mL/h downstream through resin bed, by the regeneration of this resin desorption completely.
Embodiment 5
30g ZG DM 11 polymeric adsorbent is poured in 500ml there-necked flask, adds 100ml chloromethyl ether, after fully swelling, add 6g ZnCl
2, be warming up to 36 DEG C of anti-2h, filter, use dehydrated alcohol extracting, after drying at 45 DEG C, be positioned in moisture eliminator and preserve.By the resin after 30g chloromethylation, pour in the there-necked flask of 500ml, add the swelling 24h of oil of mirbane, then dropwise add the trimethylamine aqueous solution that 45g concentration is 33%, be then warming up to 30 DEG C of reaction 2h with the speed of 1 DEG C/5min.Reacted and leached by resin, used distilled water successively, ethanol, 5% salt acid elution, is finally washed till neutrality with distilled water.Products therefrom is quaternary amines modified composite function resin.This resin specific surface area is 805m
2/ g, mean pore size is 10nm; Season, amine groups content was 1.85mmol/L.
Be in the glass adsorption column of the composite function super high crosslinked resin tape loaded chuck of quaternary amine base (Φ 12 × 160mm) by 2.4ml (about 1 gram) function base.In water inlet, dibutyl phthalate concentration is 10mg/L, and after filtration, under 25 ± 5 DEG C of conditions, pass through resin bed with the flow of 24mL/h, treatment capacity is that 1500mL/ criticizes.After resin absorption, in water outlet, dimethyl phthalate mean concns is about 0.2mg/L.
Absorption is stopped when absorption reaches leakage point (in absorption water outlet, the instant concentration of dibutyl phthalate is 2% of influent concentration), by the mixing solutions containing the sodium hydroxide of 2mol/L and 5% ethanol at the temperature of 30 ± 5 DEG C, with the flow of 3mL/h downstream through resin bed, by the regeneration of this resin desorption completely.
Embodiment 6
30g XAD-4 polymeric adsorbent is poured in 500ml there-necked flask, adds 100ml chloromethyl ether, after fully swelling, add 10gZnCl
2, be warming up to 40 DEG C of anti-3h, filter, use dehydrated alcohol extracting, after drying at 45 DEG C, be positioned in moisture eliminator and preserve.By the resin after 30g chloromethylation, pour in the there-necked flask of 500ml, add the swelling 24h of benzene, then dropwise add the trimethylamine aqueous solution that 60g concentration is 33%, be then warming up to 30 DEG C of reaction 6h with the speed of 1 DEG C/5min.Reacted and leached by resin, used distilled water successively, ethanol, 5% salt acid elution, is finally washed till neutrality with distilled water.Products therefrom is quaternary amines modified composite function resin.This resin specific surface area is 728m
2/ g, mean pore size is 4nm; Season, amine groups content was 2.22mmol/L.
Be in the glass adsorption column of the composite function super high crosslinked resin tape loaded chuck of quaternary amine base (Φ 12 × 160mm) by 2.4ml (about 1 gram) function base.In water inlet, dioctyl phthalate (DOP) concentration is 0.8mg/L, and after filtration, under 25 ± 5 DEG C of conditions, pass through resin bed with the flow of 24mL/h, treatment capacity is that 2500mL/ criticizes.After resin absorption, in water outlet, dimethyl phthalate mean concns is about 0.008mg/L.
Absorption is stopped when absorption reaches leakage point (in absorption water outlet, the instant concentration of dioctyl phthalate (DOP) is 2% of influent concentration), by the mixing solutions containing the sodium hydroxide of 2mol/L and 5% ethanol at the temperature of 30 ± 5 DEG C, with the flow of 3mL/h downstream through resin bed, by the regeneration of this resin desorption completely.
Embodiment 7
30g XAD-4 polymeric adsorbent is poured in 500ml there-necked flask, adds 100ml chloromethyl ether, after fully swelling, add 15g ZnCl
2, be warming up to 42 DEG C of anti-4h, filter, use dehydrated alcohol extracting, after drying at 45 DEG C, be positioned in moisture eliminator and preserve.By the resin after 30g chloromethylation, pour in the there-necked flask of 500ml, add the swelling 24h of ethylene dichloride, then dropwise add the triethylamine aqueous solution that 60g concentration is 28%, be then warming up to 30 DEG C of reaction 4h with the speed of 1 DEG C/5min.Reacted and leached by resin, used distilled water successively, ethanol, 5% salt acid elution, is finally washed till neutrality with distilled water.Products therefrom is quaternary amines modified composite function resin.This resin specific surface area is 562 m
2/ g, mean pore size is 4nm; Season, amine groups content was 1.63mmol/L.
Be in the glass adsorption column of the composite function super high crosslinked resin tape loaded chuck of quaternary amine base (Φ 12 × 160mm) by 2.4ml (about 1 gram) function base.Two in water inlet-(2-ethylhexyl) phthalate concentration is 0.5mg/L, after filtration, under 25 ± 5 DEG C of conditions, pass through resin bed with the flow of 24mL/h, treatment capacity is that 3700mL/ criticizes.After resin absorption, in water outlet, dimethyl phthalate mean concns is about 0.02mg/L.
Absorption is stopped when absorption reaches leakage point (in absorption water outlet, the instant concentration of two-(2-ethylhexyl) phthalate is 2% of influent concentration), by the mixing solutions containing the sodium hydroxide of 2mol/L and 5% ethanol at the temperature of 30 ± 5 DEG C, with the flow of 10mL/h downstream through resin bed, by the regeneration of this resin desorption completely.
Claims (6)
1., containing a mesopore composite function resin for quaternary amine base, it is characterized in that: described composite function resin is quaternary amines modified mesopore nonpolar adsorption resin; Described quaternary amines is Trimethylamine or triethylamine, and content is 1.0 ~ 2.5mmol/g; Described composite function resin specific surface area is 450 ~ 850m
2/ g, mean pore size is 4-10nm; Described mesopore composite function resin is prepared by the following method:
A) get mesopore nonpolar adsorption resin and be immersed in abundant swelling 24h in chloromethyl ether, the zinc chloride or the iron(ic) chloride that add mesopore nonpolar adsorption resin weight 20 ~ 50% make catalyzer, 2 ~ 4h is reacted at 36 ~ 42 DEG C, then resin spheroid is leached, wash away mother liquor remaining in resin spheroid with ethanolic extraction, dry and obtain chloromethylation polymeric adsorbent;
B) get chloromethylation polymeric adsorbent and swell in 24h in benzene, oil of mirbane or ethylene dichloride, dropwise add the organic amine aqueous solution of chloromethylation polymeric adsorbent weight 1.5 ~ 2 times at normal temperatures, after being warming up to 30 DEG C of reaction 2 ~ 6h after dripping, resin is leached use successively distilled water, ethanol or methyl alcohol or acetone, 2% ~ 5% salt acid elution, be finally washed till neutrality with distilled water and namely obtain described composite function resin; The described organic amine aqueous solution is Trimethylamine 99 or triethylamine aqueous solution, and concentration is 22%-33%.
2. mesopore composite function resin according to claim 1, is characterized in that: described mesopore nonpolar adsorption resin is selected from XAD-4, XDA-1 or ZGDM 11.
3. mesopore composite function resin described in claim 1 or 2 is removing the application in water body in phthalate pollutent.
4. application according to claim 3, is characterized in that: described composite function resin is removed phthalate pollutent in water body and comprised the following steps:
(1) water body filtration containing phthalate is removed suspended impurity;
(2) by the filtrate that obtains in step (1) at 20 ~ 40 DEG C, with the flow velocity of 5 ~ 20BV/h by being filled with the adsorption column of described composite function resin, the water body of phthalate must be removed.
5. application according to claim 4, is characterized in that: described phthalate is dimethyl phthalate, diethyl phthalate, dibutyl phthalate, o-phthalic acid dibutyl ester, two-(2-ethylhexyl) phthalate; In described water body, the concentration of phthalate is not more than 200mg/L.
6. application according to claim 4, is characterized in that: the composite function resin being adsorbed with phthalate in described step (2) adopts mixing solutions, at 20-60 DEG C, carries out desorption and regeneration with 5-20BV/h flow velocity; Described mixing solutions comprises sodium hydroxide and ethanol, and sodium hydrate content is 2mol/L, and ethanol contend percentage composition is 5%.
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Effective date of registration: 20190530 Address after: 221300 East of Yimengshan Road, Pizhou Economic Development Zone, Xuzhou City, Jiangsu Province Patentee after: Xuzhou Da Jing new material science and Technology Group Co., Ltd. Address before: 221300 East of Yimengshan Road, Pizhou Economic Development Zone, Xuzhou City, Jiangsu Province Patentee before: Da Jing information chemicals (Xuzhou) Co., Ltd. |