CN107162266A - The method that textile waste recycling prepares submicron order calcium base rigid material - Google Patents
The method that textile waste recycling prepares submicron order calcium base rigid material Download PDFInfo
- Publication number
- CN107162266A CN107162266A CN201710447311.6A CN201710447311A CN107162266A CN 107162266 A CN107162266 A CN 107162266A CN 201710447311 A CN201710447311 A CN 201710447311A CN 107162266 A CN107162266 A CN 107162266A
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- CN
- China
- Prior art keywords
- rigid material
- base rigid
- calcium base
- textile waste
- submicron order
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses a kind of method that textile waste recycling prepares submicron order calcium base rigid material, comprise the following steps：（1）The method filtered using flocculation purification, activated carbon purifies textile waste, obtains clear liquid；（2）Sulfuric acid is added in clear liquid, pH to 3.5 4.2 is adjusted, terephthalic acid (TPA) is separated out（TA）, obtain TA emulsions；（3）TA emulsions are reacted with calcium hydroxide slurry in ultrasound-enhanced tubular reactor, and discharging can use as the functional aid of rubber-plastics material after filter cake drying through separation of solid and liquid, go out filter liquor and enter biochemical treatment system, further handle rear discharge up to standard or reuse.The present invention can not only make textile waste water outlet CODcr value reduced rates more than 82%, biodegradability is improved；Meanwhile, the submicron order calcium base rigid material that crystallization is separated out can be used for high molecular polymer, can more excellently improve the processing characteristics and comprehensive mechanical property of material.
Description
Technical field
The present invention relates to a kind of industrial wastewater resource technology, and in particular to a kind of by by the high concentration in textile waste
Organic matter is converted into the method for submicron order calcium base rigid material to realize the disposal of resources of textile waste.
Background technology
With developing rapidly for China's polyester chemical fibre industry, Alkali reduction technology has been widely used in Silk, ultra-fine conjunction
In the production of the products such as finished leather.Polyester fiber（PET）Under low temperature, without obvious chemical action in dilute NaOH solution, and highly concentrated
Spend under NaOH solution and higher temperature, PET and NaOH plays hydrolysis generation para-phthalic sodium (TA-Na) and ethylene glycol
(EG) the weightless decrements of PET, are made, hydrolysis decrement is general 3.5%~30%, that is, the PET for having 3.5%~30% is present in buck
In.From the PET that stripping is dissolved on dacron enters water, the overwhelming majority exists with TA-Na and EG states of matter, on a small quantity with difference
The oligomer of the degree of polymerization is present.It is general per 30 ~ 50 tons of myriametre woven dacron decrement discharge waste water, CODcr at concentrations up to tens thousand of mg/L,
Although the water only accounts for a few percent of dyeing and finishing composite waste to more than ten percent, mono- pollutant of the TA-Na discharged is just
The 40%~78% of total CODcr is accounted for, oneself turns into the difficult point and emphasis of current textile printing and dyeing industry environment protection treating to this effluent part, because
This, alkali decrement waste water remerges processing after should individually pre-processing.The conventional way of PET industry is first pre- to waste water progress acid out
Processing, removes TA-Na, then carries out biochemical treatment, i.e., using the biochemical combined treatment process of materialization one.
It is an effective method that acid-precipitation method, which removes TA-Na in alkali decrement waste water, but is also primarily present both sides problem：
（1）The waste water COD cr clearances of acid out processing are limited, and the load of subsequent biochemical processing is still larger；（2）The solid waste TA that acid out is reclaimed
Purity difference, particle are tiny, dehydration property is poor, no reuse value, burn or landfill disposal also easily causes secondary pollution.
Publication No. CN1935703 patent of invention discloses one kind and reclaims terephthalic acid (TPA) from colored alkali decrement waste water
Technique, the dense dilute two strands of waste water dual treatments produced to caustic reduction processing are first decolourized using decolorising agent, then pass through acid
Analysis method is combined with embrane method, and terephthalic acid (TPA) is reclaimed from alkali decrement waste water, is made the CODcr values of waste water and is reduced by 50% ~ 70%, is easy to
Follow-up biochemistry, materializing strategy.
Publication No. CN103755555 patent of invention discloses the smart terephthaldehyde of one kind alkali decrement waste water residue production
The device of acid, by reclaiming residue from alkali decrement waste water, while alkali decrement waste water residue is changed into p-phthalic acid's production
Product so that the CODcr values clearance of alkali decrement waste water is up to 75% or so.
Publication No. CN105731699 patent of invention discloses terephthaldehyde in a kind of resource reutilization alkali decrement waste water
The method of acid.The metal salt of terephthalic acid purity reclaimed using this method is high, available in the modification of product of rubber and plastic；Extraction pair
Waste water post processing load reduction after phthalic acid metal salt, the problem of solving processing cost and high cost of investment, Environmental Effect
Benefit and economic benefit are taken into account.This method can make the CODcr values of alkali decrement waste water decline more than 75%.
The CODcr of alkali decrement waste water after being handled using above method has different degrees of reduction.If alkali can be improved
The handling process of decrement waste water, makes the reduction of CODcr values more, while the stronger recycling product of feature is prepared, will
Further realize the high-valued of waste water, minimizing processing.
The content of the invention
The invention provides a kind of method that textile waste recycling prepares submicron order calcium base rigid material.Using this side
Method, can not only make textile waste water outlet CODcr value reduced rates more than 82%, biodegradability is improved；Meanwhile, crystallize the Asia separated out
Micron order calcium base rigid material can be used for high molecular polymer, can more excellently improve the processing characteristics and comprehensive mechanics of material
Performance.
To achieve these goals, the present invention is achieved through the following technical solutions：A kind of textile waste resource of the present invention
The method that change prepares submicron order calcium base rigid material, comprises the following steps：
Step one：The pH value of waste water is adjusted to 10~11, aluminium chloride is added, 3- is stirred under 400-800rpm rotating speed
10min, then 10-20min is mixed slowly under 100-300rpm rotating speed, suspension is through cinder filtration, and filtrate is again by activity
Carbon filter, obtains clear liquid；
Step 2：Sulfuric acid is added in clear liquid, pH to 3.5-4.2 is adjusted, terephthalic acid (TPA) is separated out（TA）, obtain TA emulsions；
Step 3：TA emulsions are reacted with calcium hydroxide slurry in ultrasound-enhanced tubular reactor, are discharged through separation of solid and liquid,
It can be used after 150 DEG C of drying of filter cake as the functional aid of rubber-plastics material, go out filter liquor and enter biochemical treatment system, further
Discharge or reuse after processing is up to standard.
Further, the mol ratio of TA and calcium hydroxide is preferably 1:1~1:1.1.
The application frequency of the ultrasonic wave is 55 ~ 75KHz, and power is 400 ~ 600W.
The present invention is by simple, easy method, and while advanced treating is carried out to textile waste, also recycling is obtained
Submicron order calcium base rigid material.Compared with prior art, have the following advantages that：
（1）In the presence of ultrasound-enhanced, the reaction between TA emulsions and calcium hydroxide slurry after sulfuric acid acid out can be reduced so that
TA salt in water more can fully be converted into the precipitation of calcium base rigid material, and water outlet CODcr reduced rate reaches more than 82%；
（2）In the presence of ultrasound-enhanced, the TA emulsions after sulfuric acid acid out can react completely with calcium hydroxide slurry is converted into calcium
Base rigid material；
（3）TA particles that acid out goes out are tiny, emulsion is fine and smooth, as the heterogeneous nucleation agent of crystallization reaction, while making ultrasound-enhanced
Under, submicron order calcium base rigid material is prepared.
Brief description of the drawings
Fig. 1 is the microscope pattern of TA emulsions obtained by the step 2 of embodiment 1.
Fig. 2 is the XRD spectra of calcium base rigid material prepared by embodiment 1.
Fig. 3 is the size distribution curve of calcium base rigid material prepared by embodiment 1.
Fig. 4 is the microscope pattern of TA emulsions obtained by the step 2 of comparative example 1.
Fig. 5 is the size distribution curve of calcium base rigid material prepared by comparative example 1.
Embodiment
The present invention is further illustrated by the following examples.It should be understood that these embodiments are the explainations of the present invention
And citing, the scope of the present invention is not limited in any form.
Embodiment 1
Step one：The pH value of waste water is adjusted to 10, aluminium chloride is added, 10min is stirred under 400 rpm rotating speed, then
20min is mixed slowly under 100 rpm rotating speed, suspension is through cinder filtration, and filtrate passes through active carbon filter again, obtain clear
Liquid.
Step 2：Sulfuric acid is added in clear liquid, pH to 3.5 is adjusted, terephthalic acid (TPA) is separated out（TA）, obtain TA emulsions；
Step 3：TA emulsions are reacted with calcium hydroxide slurry in ultrasound-enhanced tubular reactor, are discharged through separation of solid and liquid,
It can be used after 150 DEG C of drying of filter cake as the functional aid of rubber-plastics material, go out filter liquor and enter biochemical treatment system, further
Discharge or reuse after processing is up to standard.
The mol ratio of the TA and calcium hydroxide are 1:1.
The application frequency of the ultrasonic wave is 55KHz, and power is 400W.
The microscope pattern of TA emulsions prepared by the present embodiment step 2 is shown in Fig. 1；Using the method for experiment 1 to step 3
Go out filter liquor and carry out CODcr detections, the results are shown in Table 1；The size distribution curve of prepared calcium base rigid material is shown in Fig. 3；It is prepared
The detection of calcium hydroxide content the results are shown in Table 2 using the method for experiment 2 in calcium base rigid material；The application data of product is shown in Table
3。
The XRD spectra of prepared calcium base rigid material refers to Fig. 2, is contrasted with standard PDF cards, it is known that prepared calcium base
Rigid material is anhydrous terephthalic acid (TPA) calcium.
Embodiment 2
The difference of embodiment 2 and embodiment 1 is：
In step one, the pH value of waste water is adjusted to 11, aluminium chloride is added, 3min is stirred under 800rpm rotating speed, then
10min is mixed slowly under 300rpm rotating speed.
In step 2, sulfuric acid is added in clear liquid, pH to 4.2 is adjusted.
The mol ratio of the TA and calcium hydroxide are 1:1.1.
The application frequency of the ultrasonic wave is 75KHz, and power is 600W.
CODcr detections are carried out to the filter liquor that goes out of step 3 using the method for experiment 1,1 is the results are shown in Table.
Embodiment 3
The difference of embodiment 3 and embodiment 1 is：
In step one, the pH value of waste water is adjusted to 10.5, aluminium chloride is added, 7min is stirred under 600rpm rotating speed,
Again 15min is mixed slowly under 200rpm rotating speed.
In step 2, sulfuric acid is added in clear liquid, pH to 4.0 is adjusted.
The mol ratio of the TA and calcium hydroxide are 1:1.05.
The application frequency of the ultrasonic wave is 65KHz, and power is 500W.
CODcr detections are carried out to the filter liquor that goes out of step 3 using the method for experiment 1,1 is the results are shown in Table.
Comparative example 1
The difference of comparative example 1 and embodiment 1 is：
In step 2, emulsion is configured using fine work TA, it is ensured that identical with the component of the TA emulsions of sulfuric acid acid out.
The microscope pattern of TA emulsions prepared by this comparative example step two is shown in Fig. 4；The granularity of prepared calcium base rigid material
Distribution curve is shown in Fig. 5.
Comparative example 2
The difference of comparative example 2 and embodiment 1 is：
In step 3, TA emulsions and calcium hydroxide slurry are in batch reactor, using mechanic whirl-nett reaction to terminal.
CODcr detections are carried out to the filter liquor that goes out of step 3 using the method for experiment 1,1 is the results are shown in Table；Prepared calcium base is firm
Property material in calcium hydroxide content detection using experiment 2 method, the results are shown in Table 2.
Test 1 CODcr value detection methods
The CODcr of water sample is detected according to standard HJ 828-2017 method, and calculates corresponding CODcr reduced rates, testing result
It is shown in Table 1.
Test the detection method of calcium hydroxide content in 2 products
According to the content of calcium hydroxide in standard 25572-2010 method detection calcium base rigid material, testing result is shown in Table 2.
Experiment 3
Calcium base rigid material made from embodiment and comparative example is applied in tire tread formula, formula used is：NR 100、
Stearic acid 2, zinc oxide 4, N220 35, white carbon 8, Si69 0.8, aromatic naphtha 5, protection wax 2,4010NA 1.5, sulphur
Sulphur 1.2, NOBS 1.6, functional form auxiliary agent（Become kind） 10.
In two-roll mill, first natural rubber is plasticated, various auxiliary agents are then added, elastomeric compound is obtained, then
Vulcanized at 151 DEG C by sulfurizing time, obtain vulcanizing rubber.Tested by national standard, gained performance is shown in Table 3.
The CODcr testing results of table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 2 |
| Influent COD cr, mg/L | 17532 | 17532 | 17532 | 17532 |
| Water outlet CODcr, mg/L | 3051 | 2963 | 3068 | 4769 |
| CODcr reduced rates, % | 82.6 | 83.1 | 82.5 | 72.8 |
Find out from the data comparison of table 1：CODcr values reduction using the textile waste after the method processing of present specification is higher,
Reach more than 82%.
Calcium hydroxide residual quantity in the product of table 2
| Index | Embodiment 1 | Comparative example 2 |
| Calcium hydroxide content, % | 0 | 5.3 |
The data of analytical table 2 can be seen that：Only under ultrasound-enhanced effect, TA emulsions obtained by acid out and calcium hydroxide slurry ability
Reaction is converted into calcium base rigid material completely.
The performance data of table 3
The data of analytical table 2 can be seen that：Although adding the sizing material and addition comparative example of the submicron order calcium base rigid material of embodiment 1
There is the sizing material of 1 micron order calcium base rigid material the performance before and after identical aging coefficient, but the former aging to be much better than the latter.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, the present invention
Claimed scope is by appended claims, specification and its equivalent thereof.
Claims (3)
1. a kind of method that textile waste recycling prepares submicron order calcium base rigid material, it is characterised in that including following step
Suddenly：
Step one：The pH value of waste water is adjusted to 10~11, aluminium chloride is added, 3- is stirred under 400-800rpm rotating speed
10min, then 10-20min is mixed slowly under 100-300rpm rotating speed, suspension is through cinder filtration, and filtrate is again by activity
Carbon filter, obtains clear liquid；
Step 2：Sulfuric acid is added in clear liquid, pH to 3.5-4.2 is adjusted, terephthalic acid (TPA) is separated out（TA）, obtain TA emulsions；
Step 3：TA emulsions are reacted with calcium hydroxide slurry in ultrasound-enhanced tubular reactor, are discharged through separation of solid and liquid,
It can be used after 150 DEG C of drying of filter cake as the functional aid of rubber-plastics material, go out filter liquor and enter biochemical treatment system, further
Discharge or reuse after processing is up to standard.
2. the method that textile waste recycling as claimed in claim 1 prepares submicron order calcium base rigid material, it is characterised in that institute
The mol ratio for stating TA and calcium hydroxide is preferably 1:1~1:1.1.
3. the method that textile waste recycling as claimed in claim 1 prepares submicron order calcium base rigid material, it is characterised in that institute
The application frequency for stating ultrasonic wave is 55 ~ 75KHz, and power is 400 ~ 600W.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583813A (en) * | 2012-01-12 | 2012-07-18 | 江苏爱特恩高分子材料有限公司 | Recovery method for terephthalic acid in alkali deweighting wastewater as well as production method and application of terephthalic acid metal salt whisker |
| CN103820860A (en) * | 2014-01-27 | 2014-05-28 | 江苏爱特恩高分子材料有限公司 | Preparation method and application of terephthalic acid metal salt lamellar crystal |
| CN104671506A (en) * | 2015-03-03 | 2015-06-03 | 常州市博洋新材料科技有限公司 | Method for extracting terephthalic acid from alkali-decrement wastewater |
| CN105692952A (en) * | 2016-01-22 | 2016-06-22 | 南通海陵环境检测有限公司 | Treatment method of textile wastewater |
| CN105731699A (en) * | 2016-02-15 | 2016-07-06 | 常州市五洲化工有限公司 | Method for recycling terephthalic acid in alkali-minimization wastewater in resource mode |
-
2017
- 2017-06-14 CN CN201710447311.6A patent/CN107162266A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583813A (en) * | 2012-01-12 | 2012-07-18 | 江苏爱特恩高分子材料有限公司 | Recovery method for terephthalic acid in alkali deweighting wastewater as well as production method and application of terephthalic acid metal salt whisker |
| CN103820860A (en) * | 2014-01-27 | 2014-05-28 | 江苏爱特恩高分子材料有限公司 | Preparation method and application of terephthalic acid metal salt lamellar crystal |
| CN104671506A (en) * | 2015-03-03 | 2015-06-03 | 常州市博洋新材料科技有限公司 | Method for extracting terephthalic acid from alkali-decrement wastewater |
| CN105692952A (en) * | 2016-01-22 | 2016-06-22 | 南通海陵环境检测有限公司 | Treatment method of textile wastewater |
| CN105731699A (en) * | 2016-02-15 | 2016-07-06 | 常州市五洲化工有限公司 | Method for recycling terephthalic acid in alkali-minimization wastewater in resource mode |
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Application publication date: 20170915 |