CN107469775A - The purposes of hydrochloric acid in the metal-organic framework materials absorption acid pickle of functional group containing ether - Google Patents
The purposes of hydrochloric acid in the metal-organic framework materials absorption acid pickle of functional group containing ether Download PDFInfo
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- CN107469775A CN107469775A CN201710728811.7A CN201710728811A CN107469775A CN 107469775 A CN107469775 A CN 107469775A CN 201710728811 A CN201710728811 A CN 201710728811A CN 107469775 A CN107469775 A CN 107469775A
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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 the metal-organic framework materials absorption acid pickle of functional group containing ether, experiment proves, the metal-organic framework materials of functional group containing ether are high to the adsorbance of hydrochloric acid, reach as high as 420mg/g, can be by being reused after deionized water and ethanol elution regeneration.
Description
Technical field
The present invention relates to a kind of purposes of the metal-organic framework materials of functional group containing ether, more particularly to a kind of official containing ether
The purposes of hydrochloric acid in metal-organic framework materials absorption acid pickle can be rolled into a ball.
Background technology
With industrial expansion, the purifying problem of waste water already becomes one of focus of global concern, nuisance in waste water
Matter is numerous, wherein can produce a large amount of acid waste waters in the field 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 be largely discharged.If these acid waste waters are directly discharged, it will right
Pipeline is caused to corrode, and crops are caused damage, and the aquatic organisms such as fish can be caused to come to harm, and the health of people is caused to endanger
Evil.
By taking steel industry as an example, during steel produces, a critical step is exactly " pickling " process, the mistake
Journey is that metal is immersed in descaling bath, and the oxide of metal surface is removed with acid solution.And from nineteen sixties
Mid-term rises, and hydrochloric acid starts gradually to turn into the pickle commonly used in industry instead of sulfuric acid, this way primarily to reduce cost,
And chlorohydric acid pickling process is set more fast more to clean, the consumption of sour consumption and steam all decreases, sour profit
It is higher with rate, the uniform quality of resulting product.Hydrochloric acid lotion needs to regularly replace, when the process of pickling can not access
The completion of effect, the quality of the metal surface after processing is caused to start to deteriorate, this when will be by hydrochloric acid lotion from descaling bath
Discharge, replace with new hydrochloric acid lotion.The hydrochloric acid that one ton of steel of industrial often production will produce about 60 kilograms or so gives up
Liquid, and nearly 1,500,000,000 tons of annual crude steel output, this means that annual caused hydrochloride waste can reaches hundreds of
Ten thousand tons, the hydrochloric acid in such hydrochloric acid waste water about containing mass fraction 7% or so, therefore only steel industry will produce largely
Hydrochloric acid waste water.
Except steel industry, also many field such as household chemicals fields, semiconductor work closely bound up with our production and living
The production of industry, field of medicine and chemical technology, metallurgy etc. can also give off substantial amounts of hydrochloric acid waste water.Substantial amounts of hydrochloride waste acidity is high,
If it is directly discharged, corrosive pipeline being caused, destroying soil acid-base equilibrium, crops damage and then causes aquatic river pollution
Thing is compromised, and causes health to be on the hazard indirectly.Therefore hydrochloric acid waste water is had to by handling and reaching associated emissions
Just it can discharge or recycle after standard.
Absorption method is the method for removing hydrochloric acid in waste water simple to operate, but there is presently no the selection found to hydrochloric acid
The very high adsorbent of property.And the adsorbance of adsorbent, also than relatively low, the cost of industrial adsorbent reactivation is also higher.Therefore,
Find it is a kind of suitably have to hydrochloric acid the adsorbent compared with high selectivity be need emphatically solve the problems, such as.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided the metal-organic framework materials absorption of functional group containing ether
The purposes of hydrochloric acid in acid pickle.
Technical scheme is summarized as follows：
The purposes of hydrochloric acid in the metal-organic framework materials absorption acid pickle of functional group containing ether.
Preferably, the metal-organic framework materials of functional group containing ether 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 concentrations are 15%-38% are added in 5-25mL DMFs,
Ultrasonic 0-30min；Add the 2- alkoxies terephthalic acid (TPA) of 0.1-3 times of zirconium chloride molal quantity and 5-25mL N, N- dimethyl methyls
Acid amides, ultrasonic 5-30min；Sealing, at 50-150 DEG C, 10-48h, centrifugation are placed, solid is washed with DMF,
Washed again with absolute ethyl alcohol, 2-48h is dried in 50-200 DEG C of vacuum drying chamber, obtains the metal-organic framework of functional group containing ether
Material.
Preferably, 2- alkoxies terephthalic acid (TPA) is 2- methoxyl group terephthalic acid (TPA)s；2- ethyoxyl terephthalic acid (TPA)s；2- third
Epoxide terephthalic acid (TPA)；2- isopropoxy terephthalic acid (TPA)s；2- butoxy terephthalic acid (TPA)s；2- amoxys terephthalic acid (TPA) or 2-
Hexyloxy terephthalic acid (TPA).
Advantages of the present invention：
It is demonstrated experimentally that
The metal-organic framework materials of functional group containing ether are high to the adsorbance of hydrochloric acid, reach as high as 420mg/g, can pass through
Deionized water and ethanol elution regeneration.
Brief description of the drawings
Fig. 1 is the metal-organic framework materials X ray of functional group containing ether prepared by raw material of 2- methoxyl groups terephthalic acid (TPA)
Diffraction pattern.
Fig. 2 is the metal-organic framework materials X ray of functional group containing ether prepared by raw material of 2- ethyoxyls terephthalic acid (TPA)
Diffraction pattern.
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
The metal-organic framework materials of functional group containing ether are made of following methods：
By 0.3g zirconium chlorides, the aqueous hydrochloric acid solution that 3.0mL mass concentrations are 26% adds 15mL DMFs
In, ultrasonic 15min；The 2- propoxyl group terephthalic acid (TPA) of 2 times of zirconium chloride molal quantity and 15mL DMF are added,
Ultrasonic 15min；Sealing, at 100 DEG C, 30h is placed, centrifugation, solid is washed with DMF, then is washed with absolute ethyl alcohol
Wash, 24h is dried in 100 DEG C of vacuum drying chambers, obtains the metal-organic framework materials of functional group containing ether.
The 2- propoxyl group of the present embodiment is substituted to benzene with 2- isopropoxies terephthalic acid (TPA) or 2- butoxy terephthalic acid (TPA)s
Dioctyl phthalate, other same the present embodiment, obtain corresponding functional group containing ether metal-organic framework materials.
Embodiment 2
The metal-organic framework materials of functional group containing ether are made of following methods：
By 0.1g zirconium chlorides, the aqueous hydrochloric acid solution that 0.1mL mass concentrations are 38% adds 5mL DMFs
In, ultrasonic 0min；The 2- methoxyl groups terephthalic acid (TPA) of 0.1 times of zirconium chloride molal quantity and 5mL DMF are added,
Ultrasonic 30min；Sealing, at 50 DEG C, 48h is placed, centrifugation, solid is washed with DMF, then is washed with absolute ethyl alcohol
Wash, 48h is dried in 50 DEG C of vacuum drying chambers, obtains the metal-organic framework materials of functional group containing ether.
Substitute the 2- methoxyl group terephthalic acid (TPA)s of the present embodiment with 2- ethyoxyl terephthalic acid (TPA)s, other same the present embodiment,
Obtain corresponding functional group containing ether metal-organic framework materials.
Embodiment 3
The metal-organic framework materials of functional group containing ether are made of following methods：
By 0.5g zirconium chlorides, the aqueous hydrochloric acid solution that 5.0mL mass concentrations are 15% adds 25mL DMFs
In, ultrasonic 30min；The 2- hexyloxies terephthalic acid (TPA) of 3 times of zirconium chloride molal quantity and 25mL DMF are added,
Ultrasonic 5min；Sealing, at 150 DEG C, 10h is placed, centrifugation, solid is washed with DMF, then is washed with absolute ethyl alcohol
Wash, 2h is dried in 200 DEG C of vacuum drying chambers, obtains the metal-organic framework materials of functional group containing ether.
Substitute the 2- hexyloxy terephthalic acid (TPA)s of the present embodiment with 2- amoxy terephthalic acid (TPA)s, other same the present embodiment,
Obtain corresponding functional group containing ether metal-organic framework materials.
Embodiment 4
Adsorption test：The metal-organic framework materials of functional group containing ether prepared by each embodiments of 0.1g are added separately to
In 20mL1.0mol/L aqueous hydrochloric acid solution, under the conditions of 25 DEG C, adsorb 24 hours, after absorption terminates, centrifugation, collect supernatant
Liquid, parallel titration three times is carried out with 0.01mol/L sodium hydroxide solution, average as final concentration of hydrochloric acid, calculate and inhale
Attached amount.Concrete outcome is shown in Table 1.
Table 1
| The metal-organic framework materials of functional group containing ether | Hydrochloric acid adsorbance (mg/g) |
| Prepared by raw material of 2- methoxyl groups terephthalic acid (TPA) | 280 |
| Prepared by raw material of 2- ethyoxyls terephthalic acid (TPA) | 300 |
| Prepared by raw material of 2- propoxyl group terephthalic acid (TPA) | 320 |
| Prepared by raw material of 2- isopropoxies terephthalic acid (TPA) | 315 |
| Prepared by raw material of 2- butoxy terephthalic acid (TPA) | 350 |
| Prepared by raw material of 2- amoxys terephthalic acid (TPA) | 380 |
| Prepared by raw material of 2- hexyloxies terephthalic acid (TPA) | 420 |
Embodiment 5
Regeneration test：
The metal-organic framework materials of functional group containing ether after absorption hydrochloric acid are washed with deionized water and absolute ethyl alcohol successively
Wash, be subsequently placed in 150 DEG C of vacuum drying chambers and dry.The metal-organic framework materials adsorption effect of functional group containing ether is shown in after regeneration
Table 2.
Table 2
| The metal-organic framework materials of functional group containing ether | Hydrochloric acid adsorbance (mg/g) after regeneration |
| Prepared by raw material of 2- methoxyl groups terephthalic acid (TPA) | 276 |
| Prepared by raw material of 2- ethyoxyls terephthalic acid (TPA) | 295 |
| Prepared by raw material of 2- propoxyl group terephthalic acid (TPA) | 318 |
| Prepared by raw material of 2- isopropoxies terephthalic acid (TPA) | 312 |
| Prepared by raw material of 2- butoxy terephthalic acid (TPA) | 344 |
| Prepared by raw material of 2- amoxys terephthalic acid (TPA) | 372 |
| Prepared by raw material of 2- hexyloxies terephthalic acid (TPA) | 415 |
Claims (3)
1. the purposes of hydrochloric acid in the metal-organic framework materials absorption acid pickle of functional group containing ether.
2. purposes according to claim 1, it is characterized in that the functional group containing ether metal-organic framework materials are with following methods
It is made：In proportion, by 0.1-0.5g zirconium chlorides, the aqueous hydrochloric acid solution that 0.1-5.0mL mass concentrations are 15%-38% adds 5-
In 25mL DMFs, ultrasonic 0-30min；Add the 2- alkoxy terephthaldehydes of 0.1-3 times of zirconium chloride molal quantity
The DMF of acid and 5-25mL, ultrasonic 5-30min；Sealing, at 50-150 DEG C, place 10-48h, centrifugation, solid
Washed with DMF, then washed with absolute ethyl alcohol, 2-48h is dried in 50-200 DEG C of vacuum drying chamber, is obtained
The metal-organic framework materials of functional group containing ether.
3. purposes according to claim 2, it is characterized in that the 2- alkoxies terephthalic acid (TPA) is 2- methoxyl groups to benzene two
Formic acid；2- ethyoxyl terephthalic acid (TPA)s；2- propoxyl group terephthalic acid (TPA)s；2- isopropoxy terephthalic acid (TPA)s；2- butoxy is to benzene
Dioctyl phthalate；2- amoxys terephthalic acid (TPA) or 2- hexyloxy terephthalic acid (TPA)s.
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Cited By (1)
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| CN109056414A (en) * | 2018-06-29 | 2018-12-21 | 湖北大学 | A kind of preparation method for the highmulti paper that can be used for lotion separation, Dye Adsorption and smoke adsorption simultaneously |
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| CN109056414A (en) * | 2018-06-29 | 2018-12-21 | 湖北大学 | A kind of preparation method for the highmulti paper that can be used for lotion separation, Dye Adsorption and smoke adsorption simultaneously |
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