CN107469775B - Ether-containing functional group metal-organic framework materials adsorb the purposes of hydrochloric acid in acid pickle - Google Patents
Ether-containing functional group metal-organic framework materials adsorb the purposes of hydrochloric acid in acid pickle Download PDFInfo
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- CN107469775B CN107469775B CN201710728811.7A CN201710728811A CN107469775B CN 107469775 B CN107469775 B CN 107469775B CN 201710728811 A CN201710728811 A CN 201710728811A CN 107469775 B CN107469775 B CN 107469775B
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- terephthalic acid
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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Abstract
The invention discloses the purposes of hydrochloric 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 hydrochloric acid, reach as high as 420mg/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 hydrochloric acid in metal-organic framework materials absorption acid pickle can be rolled into a ball.
Background technique
With the development of industry, the purifying problem of waste water already becomes one of the hot spot of global concern, nuisance in waste water
Matter is numerous, wherein can generate a large amount of acid waste waters in the fields such as field of medicine and chemical technology, steel and iron manufacturing industry, as chemical fibre factory, food factory,
During the relieving haperacidity such as electroplating industry acid, acid waste water can largely be discharged.If by these acid waste water direct emissions, it will right
Pipeline causes to corrode, and damages to crops, and the aquatic organisms such as fish can be caused to come to harm, and causes to endanger to people's health
Evil.
By taking steel industry as an example, during steel production, a critical step is exactly " pickling " process, the mistake
Journey is that metal is immersed in descaling bath, with the oxide of acid solution removal metal surface.And from nineteen sixties
Mid-term rises, and hydrochloric acid starts gradually sulfuric acid to be replaced to become common pickling solution in industry, this way primarily to reduce cost,
And clean chlorohydric acid pickling process more fast more, the consumption of sour consumption and steam all decreases, sour benefit
It is higher with rate, the uniform quality of obtained product.Hydrochloric acid lotion needs to regularly replace, when the process of pickling cannot access
The quality of the completion of effect, the metal surface that leads to that treated starts to deteriorate, this when will be by hydrochloric acid lotion from descaling bath
It discharges, replaces with new hydrochloric acid lotion.The hydrochloric acid that one ton of steel of industrial every production will generate about 60 kilograms or so is useless
Liquid, and nearly 1,500,000,000 tons of annual crude steel output, this means that the hydrochloride waste generated every year can reach several hundred
Ten thousand tons, the hydrochloric acid in such hydrochloric acid waste water about containing mass fraction 7% or so, therefore only steel industry will generate largely
Hydrochloric acid waste water.
In addition to steel industry, there are also field such as daily chemicals fields, semiconductor work much closely bound up with our production and living
The production of industry, field of medicine and chemical technology, metallurgy etc. can also give off a large amount of hydrochloric acid waste water.A large amount of hydrochloride waste acidity is high,
If its direct emission, corrosive pipeline will cause, destroy soil acid-base equilibrium, crops damage, river pollution causes aquatic in turn
Object is compromised, and causes human health to be on the hazard indirectly.Therefore hydrochloric acid waste water has to by handling and reaching associated emissions
Just it can discharge or recycle after standard.
Absorption method is the method for hydrochloric acid in removal waste water easy to operate, but the selection there is presently no discovery to hydrochloric acid
The very high adsorbent of property.And the adsorbance of adsorbent is also relatively low, the cost of industrial adsorbent reactivation is also relatively high.Therefore,
Find that a kind of suitably to have more highly selective adsorbent to hydrochloric acid be to need the problem of focusing on solving.
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 hydrochloric 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 hydrochloric 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 hydrochloric acid, reach as high as 420mg/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 aqueous hydrochloric acid solution of 20mL1.0mol/L, under the conditions of 25 DEG C, adsorbs 24 hours, after absorption, supernatant is collected in centrifugation
Liquid carries out parallel titration three times with the sodium hydroxide solution of 0.01mol/L, is averaged as final concentration of hydrochloric acid, calculates and inhale
Attached amount.Concrete outcome is shown in Table 1.
Table 1
| Ether-containing functional group metal-organic framework materials | Hydrochloric acid adsorbance (mg/g) |
| It is prepared by raw material of 2- methoxyl group terephthalic acid (TPA) | 280 |
| It is prepared by raw material of 2- ethyoxyl terephthalic acid (TPA) | 300 |
| It is prepared by raw material of 2- propoxyl group terephthalic acid (TPA) | 320 |
| It is prepared by raw material of 2- isopropoxy terephthalic acid (TPA) | 315 |
| It is prepared by raw material of 2- butoxy terephthalic acid (TPA) | 350 |
| It is prepared by raw material of 2- amoxy terephthalic acid (TPA) | 380 |
| It is prepared by raw material of 2- hexyloxy terephthalic acid (TPA) | 420 |
Embodiment 5
Regeneration test:
Ether-containing functional group metal-organic framework materials after absorption hydrochloric 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 | Hydrochloric acid adsorbance (mg/g) after regeneration |
| It is prepared by raw material of 2- methoxyl group terephthalic acid (TPA) | 276 |
| It is prepared by raw material of 2- ethyoxyl terephthalic acid (TPA) | 295 |
| It is prepared by raw material of 2- propoxyl group terephthalic acid (TPA) | 318 |
| It is prepared by raw material of 2- isopropoxy terephthalic acid (TPA) | 312 |
| It is prepared by raw material of 2- butoxy terephthalic acid (TPA) | 344 |
| It is prepared by raw material of 2- amoxy terephthalic acid (TPA) | 372 |
| It is prepared by raw material of 2- hexyloxy terephthalic acid (TPA) | 415 |
Claims (2)
1. the purposes that ether-containing functional group metal-organic framework materials adsorb hydrochloric 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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| 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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