CN107552005B - Ether-containing functional group metal-organic framework materials adsorb the purposes of acetic acid in acid pickle - Google Patents
Ether-containing functional group metal-organic framework materials adsorb the purposes of acetic acid in acid pickle Download PDFInfo
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- CN107552005B CN107552005B CN201710728860.0A CN201710728860A CN107552005B CN 107552005 B CN107552005 B CN 107552005B CN 201710728860 A CN201710728860 A CN 201710728860A CN 107552005 B CN107552005 B CN 107552005B
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Abstract
The invention discloses the purposes of acetic acid in ether-containing functional group metal-organic framework materials absorption acid pickle, experiments have shown that, ether-containing functional group metal-organic framework materials are high to the adsorbance of acetic acid, reach as high as 312mg/g, can be by reusing after deionized water and ethanol elution regeneration.
Description
Technical field
The present invention relates to a kind of purposes of ether-containing functional group metal-organic framework materials, more particularly to a kind of ether-containing official
The purposes of acetic acid in metal-organic framework materials absorption acid pickle can be rolled into a ball.
Background technique
Acetic acid is widely used in the industries such as medicine, chemical industry, dyestuff, food as a kind of very important industrial chemicals,
But these factories can give off industrial wastewater largely containing acetic acid during relieving haperacidity acid.For example, industrially passing through third
During alkene two-step penetration method acrylic acid synthesizing, some acetic acid by-products can be generated simultaneously, are contained in the waste water of discharge a large amount of
Acetic acid；The furfural mill of one annual output 1000t, will discharge 3 × 10 every year4T contains the waste water of acetic acid, and in these waste water
The mass fraction of acetic acid is below 30%, since the presence of acetic acid makes these industrial wastewaters that highly acid, biochemical oxygen demand all be presented
Amount COD is up to tens of thousands of to hundreds of thousands mg/L, not easily biological-degradable.Industrially generally handled using direct incineration method or neutralisation
These strongly acid wastewaters but cause the big of acetic acid although these processing methods can make industrial wastewater reach discharge standard
Amount waste.And the preparation method of industrial acetic acid is mainly the carbonylation of methanol at present, and this method is in higher temperature
It is carried out under degree and pressure condition, needs a large amount of energy resource supply, and production process will cause environmental pollution, the raw material used is not
Renewable, cost of investment is high.If acetic acid in waste water can be carried out recycling and reusing, both reduced the processing step of waste water,
Be conducive to the protection of environment, and production cost can be reduced.But the relative volatility of acetic acid and water is close to 1, industrially
It is difficult to separate, especially to quality of acetic acid score in 30% waste liquid below.
In recent years, many scientists are devoted to the technique study of low concentration of acetic acid solution recycling.Document report at present
Absorption method is most simple and easy method in the method for separating acetic acid in the slave waste water in road, and adsorbent reproducible utilization.Mesh
The treating capacity of preceding known adsorbent is relatively low, and regenerated cost is also relatively high.Therefore, a kind of suitable high-efficiency acetic acid suction is developed
Processing of the enclosure material for acetic acid waste water is to need the problem of focusing on solving on future development road.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide the absorption of ether-containing functional group metal-organic framework materials
The purposes of acetic acid in acid pickle.
Technical solution of the present invention is summarized as follows:
Ether-containing functional group metal-organic framework materials adsorb the purposes of acetic acid in acid pickle.
Preferably, ether-containing functional group metal-organic framework materials are made of following methods: in proportion, by 0.1-0.5g
Zirconium chloride, the aqueous hydrochloric acid solution that 0.1-5.0mL mass concentration is 15%-38% are added in 5-25mL n,N-Dimethylformamide,
Ultrasonic 0-30min；The 2- alkoxy terephthalic acid (TPA) of 0.1-3 times of zirconium chloride molal quantity and the N of 5-25mL, N- dimethyl methyl is added
Amide, ultrasonic 5-30min；Sealing places 10-48h, centrifugation at 50-150 DEG C, and solid is washed with n,N-Dimethylformamide,
It is washed again with dehydrated alcohol, dry 2-48h, obtains ether-containing functional group metal-organic framework in 50-200 DEG C of vacuum oven
Material.
Preferably, 2- alkoxy terephthalic acid (TPA) is 2- methoxyl group terephthalic acid (TPA)；2- ethyoxyl terephthalic acid (TPA)；2- third
Oxygroup terephthalic acid (TPA)；2- isopropoxy terephthalic acid (TPA)；2- butoxy terephthalic acid (TPA)；2- amoxy terephthalic acid (TPA) or 2-
Hexyloxy terephthalic acid (TPA).
Advantages of the present invention:
It is demonstrated experimentally that
Ether-containing functional group metal-organic framework materials are high to the adsorbance of acetic acid, reach as high as 312mg/g, can pass through
Deionized water and ethanol elution regeneration.
Detailed description of the invention
Fig. 1 is the ether-containing functional group metal-organic framework materials X-ray prepared by raw material of 2- methoxyl group terephthalic acid (TPA)
Diffraction pattern.
Fig. 2 is the ether-containing functional group metal-organic framework materials X-ray prepared by raw material of 2- ethyoxyl terephthalic acid (TPA)
Diffraction pattern.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
Embodiment 1
Ether-containing functional group metal-organic framework materials are made of following methods:
By 0.3g zirconium chloride, 15mL n,N-Dimethylformamide is added in the aqueous hydrochloric acid solution that 3.0mL mass concentration is 26%
In, ultrasonic 15min；2 times of zirconium chloride molal quantity of 2- propoxyl group terephthalic acid (TPA) and the n,N-Dimethylformamide of 15mL is added,
Ultrasonic 15min；Sealing places 30h, centrifugation, solid is washed with n,N-Dimethylformamide, then is washed with dehydrated alcohol at 100 DEG C
It washs, drying for 24 hours, obtains ether-containing functional group metal-organic framework materials in 100 DEG C of vacuum ovens.
The 2- propoxyl group of the present embodiment is substituted to benzene with 2- isopropoxy terephthalic acid (TPA) or 2- butoxy terephthalic acid (TPA)
Dioctyl phthalate, other same the present embodiment obtain corresponding ether-containing functional group metal-organic framework materials.
Embodiment 2
Ether-containing functional group metal-organic framework materials are made of following methods:
By 0.1g zirconium chloride, 5mL n,N-Dimethylformamide is added in the aqueous hydrochloric acid solution that 0.1mL mass concentration is 38%
In, ultrasonic 0min；0.1 times of zirconium chloride molal quantity of 2- methoxyl group terephthalic acid (TPA) and the n,N-Dimethylformamide of 5mL is added,
Ultrasonic 30min；Sealing places 48h, centrifugation, solid is washed with n,N-Dimethylformamide, then is washed with dehydrated alcohol at 50 DEG C
It washs, dry 48h, obtains ether-containing functional group metal-organic framework materials in 50 DEG C of vacuum ovens.
Substitute the 2- methoxyl group terephthalic acid (TPA) of the present embodiment with 2- ethyoxyl terephthalic acid (TPA), other same the present embodiment,
Obtain corresponding ether-containing functional group metal-organic framework materials.
Embodiment 3
Ether-containing functional group metal-organic framework materials are made of following methods:
By 0.5g zirconium chloride, 25mL n,N-Dimethylformamide is added in the aqueous hydrochloric acid solution that 5.0mL mass concentration is 15%
In, ultrasonic 30min；3 times of zirconium chloride molal quantity of 2- hexyloxy terephthalic acid (TPA) and the n,N-Dimethylformamide of 25mL is added,
Ultrasonic 5min；Sealing places 10h, centrifugation, solid is washed with n,N-Dimethylformamide, then is washed with dehydrated alcohol at 150 DEG C
It washs, dry 2h, obtains ether-containing functional group metal-organic framework materials in 200 DEG C of vacuum ovens.
Substitute the 2- hexyloxy terephthalic acid (TPA) of the present embodiment with 2- amoxy terephthalic acid (TPA), other same the present embodiment,
Obtain corresponding ether-containing functional group metal-organic framework materials.
Embodiment 4
Adsorption test: the ether-containing functional group metal-organic framework materials of each embodiment preparation of 0.1g are added separately to
It in the acetic acid aqueous solution of 20mL10g/L, under the conditions of 25 DEG C, adsorbs 24 hours, after absorption, supernatant is collected in centrifugation, is used
The sodium hydroxide solution of 0.01mol/L carries out parallel titration three times, is averaged as final acetic acid concentration, calculates adsorbance.
Concrete outcome is shown in Table 1.
Table 1
| Ether-containing functional group metal-organic framework materials | Acetic acid adsorbance (mg/g) |
| It is prepared by raw material of 2- methoxyl group terephthalic acid (TPA) | 80 |
| It is prepared by raw material of 2- ethyoxyl terephthalic acid (TPA) | 120 |
| It is prepared by raw material of 2- propoxyl group terephthalic acid (TPA) | 160 |
| It is prepared by raw material of 2- isopropoxy terephthalic acid (TPA) | 205 |
| It is prepared by raw material of 2- butoxy terephthalic acid (TPA) | 241 |
| It is prepared by raw material of 2- amoxy terephthalic acid (TPA) | 275 |
| It is prepared by raw material of 2- hexyloxy terephthalic acid (TPA) | 312 |
Embodiment 5
Regeneration test:
Ether-containing functional group metal-organic framework materials after absorption acetic acid are successively washed with deionized water and dehydrated alcohol
It washs, is subsequently placed in 150 DEG C of vacuum ovens dry.Ether-containing functional group metal-organic framework materials adsorption effect is shown in after regeneration
Table 2.
Table 2
| Ether-containing functional group metal-organic framework materials | Acetic acid adsorbance (mg/g) after regeneration |
| It is prepared by raw material of 2- methoxyl group terephthalic acid (TPA) | 75 |
| It is prepared by raw material of 2- ethyoxyl terephthalic acid (TPA) | 117 |
| It is prepared by raw material of 2- propoxyl group terephthalic acid (TPA) | 158 |
| It is prepared by raw material of 2- isopropoxy terephthalic acid (TPA) | 203 |
| It is prepared by raw material of 2- butoxy terephthalic acid (TPA) | 238 |
| It is prepared by raw material of 2- amoxy terephthalic acid (TPA) | 272 |
| It is prepared by raw material of 2- hexyloxy terephthalic acid (TPA) | 310 |
Claims (2)
1. ether-containing functional group metal-organic framework materials adsorb the purposes of acetic acid in acid pickle, ether-containing functional group metal-have
Machine framework material is made of following methods: in proportion, by 0.1-0.5g zirconium chloride, 0.1-5.0mL mass concentration is 15%-
38% aqueous hydrochloric acid solution is added in 5-25mL n,N-Dimethylformamide, ultrasonic 0-30min；Zirconium chloride molal quantity is added
0.1-3 times of 2- alkoxy terephthalic acid (TPA) and the n,N-Dimethylformamide of 5-25mL, ultrasonic 5-30min；Sealing, in 50-
150 DEG C, 10-48h is placed, centrifugation, solid is washed with n,N-Dimethylformamide, then is washed with dehydrated alcohol, at 50-200 DEG C
Dry 2-48h, obtains ether-containing functional group metal-organic framework materials in vacuum oven.
2. purposes according to claim 1, it is characterized in that the 2- alkoxy terephthalic acid (TPA) is 2- methoxyl group to benzene two
Formic acid；2- ethyoxyl terephthalic acid (TPA)；2- propoxyl group terephthalic acid (TPA)；2- isopropoxy terephthalic acid (TPA)；2- butoxy is to benzene
Dioctyl phthalate；2- amoxy terephthalic acid (TPA) or 2- hexyloxy terephthalic acid (TPA).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589398A (en) * | 2016-12-06 | 2017-04-26 | 首都师范大学 | Zirconium organic frame material and preparation method and application thereof |
| CN106750356A (en) * | 2017-01-10 | 2017-05-31 | 北京大学 | A kind of method that metal-organic framework materials of utilization UiO 66 purify selenium-containing wastewater |
| CN106861627A (en) * | 2017-01-20 | 2017-06-20 | 四川大学 | Metal-organic framework materials of cobalt ions and preparation method thereof in a kind of removal waste water |
| CN107029672A (en) * | 2017-05-10 | 2017-08-11 | 上海师范大学 | Based on the NH of UIO 662With the graphene synthesis adsorption photochemical catalysis composite of assembling altogether in situ |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589398A (en) * | 2016-12-06 | 2017-04-26 | 首都师范大学 | Zirconium organic frame material and preparation method and application thereof |
| CN106750356A (en) * | 2017-01-10 | 2017-05-31 | 北京大学 | A kind of method that metal-organic framework materials of utilization UiO 66 purify selenium-containing wastewater |
| CN106861627A (en) * | 2017-01-20 | 2017-06-20 | 四川大学 | Metal-organic framework materials of cobalt ions and preparation method thereof in a kind of removal waste water |
| CN107029672A (en) * | 2017-05-10 | 2017-08-11 | 上海师范大学 | Based on the NH of UIO 662With the graphene synthesis adsorption photochemical catalysis composite of assembling altogether in situ |
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