It is a kind of to prepare bentonite method using acrylic acid production waste water
Technical field
The invention belongs to technical field of waste water processing, and in particular to it is a kind of using acrylic acid production waste water prepare it is organic
Bentonitic method.
Background technique
Acrylic acid is a kind of important industrial chemicals, but has a large amount of waste water to generate in its production process, is a kind of highly concentrated
Organic wastewater is spent, COD (CODcr) is up to tens of thousands of-hundreds of thousands mg/L.Acetic acid, acrylic acid, first are mainly contained in waste water
The organic matters such as aldehyde, also containing other organic matters such as a small amount of toluene, acrylate.
Tradition is mainly incineration method, catalytic oxidation, electrolysis method, biology for the processing mode of acrylic compounds production waste water
Method, reverse osmosis separation method etc., wherein energy consumption is high, operation difficulty is high for incineration method, and catalytic oxidation technique requires high, technical difficulty
Greatly, electrolysis method and bioanalysis equipment investment are big, time-consuming and efficiency is lower, and it is multiple that reverse osmosis separation method is difficult to adapt to acrylic acid wastewater
The needs of miscellaneous ingredient are easy clog reverse osmosis film.In addition, these methods be easy to cause secondary environmental pollution during processing,
And the organic components such as a large amount of acetic acid, acrylic acid are difficult to be recycled in waste water.
Some emerging treatment process trials are recycled the organic matter in waste water, but still there are biggish works
Skill defect: (1) energy consumption is high for recycling;(2) recycling product is single;(3) it introduces and consumes a large amount of third components;(4) acrylic acid and ester
The sedimentation separation mostly in a manner of polymerization, complicated component, it is difficult to be efficiently used.
Bentonite building, coating, pigment, printing and dyeing etc. industry in have very extensive application, usually as thickener,
The auxiliary agents such as anti-settling agent, binder, swelling agent be subject to using.Using montmorillonite as main mineral constituent in bentonite, basic structure
Layer structure is constituted to press from both sides one layer of alumina octahedral among two layers of oxygen-octahedron, interlayer is filled with tradable cation Na+、
Ca2+、K+Deng.Dispersibility of the bentonite with common interlayer cation in organic principle is poor, it is difficult to effectively play a role
Effect swaps modification to interlayer ion using organic molecule, and the organic modified bentonite of acquisition can effectively improve it
Dispersibility and associativity in organic matter.
Summary of the invention
The invention is to solve the problems of the prior art, provides a kind of utilization acrylic acid production waste water preparation organic bentonite
The method for moistening soil can be recycled sufficiently and using the acetic acid and acrylic acid in waste water, obtain well modified organobentonite and produce
Product.
The invention prepares bentonite method using acrylic acid production waste water, includes the following steps:
S1: carrying out electrodialysis process to acrylic acid production waste water, and operation voltage is 40-50V, drops COD in dilute phase waste water
To original 20% hereinafter, the concentration of acetic acid and acrylic acid is improved to original 2 times or more in concentrated phase waste water;
S2: taking concentrated phase waste water and adds hydroquinone thereto, steams waste water at 110-120 DEG C
Hair concentration steams acrylic acid concentration in extraction raffinate and is increased to 10-100g/L;
S3: will steam extraction raffinate and cross extraction column and carry out extraction removing hydroquinone and obtain raffinate, adjust pH to 8-10, stirring
Under be added calcium-base bentonite thereto, the mass ratio for controlling calcium-base bentonite and acrylic acid is (1.1-1.5): at 1,60-85 DEG C
It is stirred to react;
S4: calcium-base bentonite in raffinate with acrylic acid after the reaction was completed, be filtered, washed, be dried to obtain it is organic
Swelling native produce.
In above process, electrodialysis process can first be concentrated acrylic acid production waste water, make having in waste water
Machine object component content effectively improves, and effectively reduces the condensing mode bring high energy consumption issues directly evaporated, and improve production
Efficiency.Concentrated phase waste water is concentrated further in second step evaporation process, while removing light group in waste water based on acetic acid and formaldehyde
Point, make to steam acrylic acid concentration in extraction raffinate and reach modified suitable range, while the addition of hydroquinone effectively prevent it is concentrated
Auto polymerization phenomenon occurs for acrylic acid in journey.It, can using acrylic acid as main component in raffinate after steaming extraction raffinate removing hydroquinone
Effectively calcium-base bentonite is modified, between bentonite bed, obtaining modified organobentonite.
Wherein, in the step S1, the COD of acrylic acid production waste water is 100000mg/L hereinafter, organic matter forms are as follows: second
Sour 0.03%-10%, acrylic acid 0.02%-12%, formaldehyde 0.04%-4%, other organic matters 0-2%.
Wherein, in the step S1, the pole water of electrodialysis process is 15-20g/L Na2SO4Solution, dense room and light room into
Water flow is respectively 10-20L/h.Organic concentration is improved in concentrated phase after electrodialysis process, and strong voltage is conducive to organic matter
Be fully transferred in concentrated phase, in dilute phase COD concentration largely can reduce to can direct emission standard, dilute phase not up to standard on a small quantity
With circulation and stress or second level electrodialysis process can be carried out.Under normal circumstances, dilute phase waste water after the electrodialytic single treatment
Middle COD concentration can be down to 5% or less original.
Wherein, in the step S2, the additive amount of hydroquinone is the 0.1%- of acrylic acid content in concentrated phase waste water
0.5%.
Wherein, in the step S2, by the condensate liquid of the vapor condensation of evaporation, NaOH solution is added thereto, then steams
Formaldehyde is distillated, condensation-crystallization after excess sulfuric acid, the acetic acid product that can be recycled is added in the still residue of acquisition.
Wherein, in the step S3, the extractant of hydroquinone uses ether, and the extract liquor after the completion of extracting can pass through
Evaporating isolated mode separates hydroquinone and ether and is separately recovered, recycling of the realization to the two, while avoiding pair
Benzenediol influences bentonite modified obstruction.
Wherein, in the step S3, pH adjustment uses 0.1-0.5mol/L NaOH solution.
Wherein, in the step S4, calcium-base bentonite is used in raffinate with the material of acrylic acid after the reaction was completed
The mixed liquor of vacuum filtration, n-butanol and pentane is washed as cleaning solution, is repeated 2-5 times.Wherein, n-butanol and penta
The volume ratio of alkane is 1:2, and mixing, washing liquid can sufficiently remove unreacted impurity component in material.
The invention has the advantages that (1) carries out pre-concentration to waste water using electrodialytic technique, can be effectively reduced
Evaporation energy consumption improves recovery efficiency, and controls the damage reduced at low concentrations to electrodialytic membranes.It (2) can be raw by acrylic acid
Acrylic acid, acetic acid and the formaldehyde produced in waste water is recycled respectively, obtains the multinomial separation product of high-purity.(3) without drawing
Enter to influence the third component of product purity, the ingredients such as extractant, cleaning solution can recycle repeatedly.(4) organic bentonite prepared
Profit soil purity is high, the dispersibility and associativity in coating are good, can be effectively improved suspension and the durability of building coating.
Detailed description of the invention
Fig. 1 is the infrared spectrum of sample of the present invention.
Fig. 2 is the XRD diagram of sample of the present invention.
Specific embodiment
The invention is further described below.In order to describe conveniently, the equipment in the invention is omitted
Necessary or conventional operating procedure or condition, those skilled in the art can be adjusted as needed.
One, prepared by bentonite
Use the waste water of certain acrylic acid manufacturing enterprise for process object, measuring its COD is 46510mg/L, organic matter composition
Are as follows: acetic acid 3.78%, acrylic acid 6.44%, formaldehyde 1.17%, other organic matters 0.84%, surplus is water.
Electrodialysis process is carried out to above-mentioned acrylic acid production waste water, operation voltage is 40V, and pole water is 15g/L Na2SO4It is molten
The flow of inlet water of liquid, dense room and light room is respectively 15L/h.After electrodialysis single treatment, COD in dilute phase waste water is made to be down to 500mg/
L after recycling dilute phase waste water, carries out electrodialysis secondary treatment using same condition, COD in dilute phase waste water is made to be down to 50mg/L.
Acetic acid concentration is 5.27g/L, acrylic acid concentration 8.78g/L in concentrated phase waste water.
It takes concentrated phase waste water and adds the hydroquinone of the 0.1w% of acrylic acid content thereto, make waste water in the case where stirring encapsulation
It is concentrated by evaporation at 120 DEG C, makes to steam acrylic acid concentration in extraction raffinate and be increased to 15g/L.The vapor condensation of evaporation recycles to obtain condensate liquid, to
NaOH solution is wherein added, then decompression stirring distills out formaldehyde at 30 DEG C, and the still residue of acquisition is added cold after excess sulfuric acid
Condensation is brilliant, the acetic acid product recycled.
Steaming extraction raffinate is crossed extraction column to extract, extractant is ether, and hydroquinone is removed after extraction and obtains raffinate, is added
0.1mol/L NaOH solution adjusts pH to 8-10, and calcium-base bentonite is added under stirring into raffinate, controls the swelling of calcium base
The mass ratio of soil and acrylic acid is 1.2:1, is stirred to react at 80 DEG C.After the reaction was completed, by extract liquor by evaporating isolated side
Formula separates hydroquinone and ether and is separately recovered, and hydroquinone is added into concentrated phase waste water by metering again and is reused,
Ether is re-used as extractant and is reused.
It takes calcium-base bentonite to complete material in reacting for raffinate, is filtered by vacuum and using the n-butanol of volume ratio 1:2
It is washed, is repeated 3 times as cleaning solution with the mixed liquor of pentane, it is then dry to obtain organobentonite product.
Two, bentonite performance characterization
Infrared spectrum analysis is carried out to the organobentonite product of above-described embodiment, as a result as shown in Figure 1.It can from figure
Know, 3633cm-1、3429cm-1、1048cm-1The absorption peak at place is respectively the vibration of Al-O-H, H-O-H, Si-O-Si in montmorillonite
Characteristic peak, 1671cm-1、1597cm-1The absorption peak at place is respectively the vibration performance peak of C=O, C=C in acrylic acid, illustrates propylene
Acid has been successfully entered in bentonite.
X-ray diffraction analysis result is as shown in Fig. 2, θ Angle Position can be calculated at 5.32 ° according to Bragg equation in figure
D out001Interlamellar spacing be 1.66nm, the insertion of acrylic acid is so that interlamellar spacing slightly increases in bentonite.
Three, bentonite utilizes
The organobentonite product of above-described embodiment is added among dope for inner wall of architecture, concrete component is (with quality
Meter): silicone acrylic emulsion 15%, 10%PVA solution 22%, hydroxyethyl cellulose 3%, silicone oil 2%, 12 ester alcohols 0.3%, organic bentonite
Moisten native 3%, BYK-P104S dispersing agent 0.2%, ethylene glycol 0.5%, SD998 defoaming agent 0.1%, filler 40%, water surplus.It adopts
Experiment is compared with common sodium bentonite.The coating property measured is shown in Table 1.
Table 1
As can be seen from Table 1, after coating is added in the modified organobentonite of the present invention, the outstanding of coating can be effectively improved
The abrasion resistance of buoyancy energy and coating, illustrate organobentonite it is modified in coating can fine dispersion and and coating particles
It is combined, improves the suspending stabilized performance of coating, coating is made to reach prolonged stable homogeneous effect.
The foregoing is merely the preferred embodiments of the invention, are not intended to limit the invention creation, all at this
Within the spirit and principle of innovation and creation, any modification, equivalent replacement, improvement and so on should be included in the invention
Protection scope within.