CN106519299A - Method for directly preparing modified hydrotalcite stabilizer from alkali deweighting wastewater - Google Patents
Method for directly preparing modified hydrotalcite stabilizer from alkali deweighting wastewater Download PDFInfo
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- CN106519299A CN106519299A CN201611115531.0A CN201611115531A CN106519299A CN 106519299 A CN106519299 A CN 106519299A CN 201611115531 A CN201611115531 A CN 201611115531A CN 106519299 A CN106519299 A CN 106519299A
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- waste water
- modified hydrotalcite
- alkali decrement
- decrement waste
- hydrotalcite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention relates to a method for directly preparing a modified hydrotalcite stabilizer from alkali deweighting wastewater. The method comprises the following steps: 1, adjusting the pH value of alkali deweighting wastewater to be 4-10; 2, adding hydrotalcite into the alkali deweighting wastewater in a liquid-solid mass ratio of (5:1)-(30:1), performing stirring reaction under a heating condition, so as to obtain reaction mixed liquid; 3, performing filtering separation, feeding back obtained filtrate to the step (1) for circulation, so as to obtain a solid; and 4, washing the obtained solid with water, drying and grinding, thereby obtaining the modified hydrotalcite stabilizer which is white and odorless powder, wherein the static thermal stabilization time of PVC can be prolonged to be greater than 60 minutes by using the modified hydrotalcite stabilizer. As the modified hydrotalcite stabilizer is directly prepared from PTA (Terephthalic Acid) as a raw material in the alkali deweighting wastewater, a conventional process that crude terephthalic acid modified hydrotalcite is prepared by using an acid precipitation method can be simplified, effective resources in the alkali deweighting wastewater can be sufficiently utilized while pollution of the alkali deweighting wastewater is reduced, the energy consumption is reduced, and remarkable economic benefits can be achieved.
Description
Technical field
The present invention relates to chemical industry waste resource recovery utilizes field, and in particular to a kind of directly to utilize alkali decrement waste water system
The method of standby modified hydrotalcite heat stabilizer.
Background technology
Terylene, acrylic fibers can all produce substantial amounts of alkali decrement waste water during polyester production process, and main component is to benzene
Dioctyl phthalate（PTA）Sodium salt, ethylene glycol, a small amount of polyester oligomer and auxiliary agent etc., solution alkaline is strong（pH>12）, COD it is high, it is difficult to
Processed with common biochemical and physical chemistry method.As PTA is a kind of important raw material of industry, can make PTA as waste material reject
Into serious environmental pollution and the wasting of resources.Crude terephthalic acid is extracted from alkali decrement waste water frequently with acid-precipitation method at present, is dropped
The COD of low waste water.The crude terephthalic acid for obtaining can be thermally-stabilised for preparing plasticizer, PVC Ca Zn composites as industrial chemicals
Agent etc..But this kind of method not only needs to add substantial amounts of acid, also wastes substantial amounts of alkali resource, relatively costly.In order to solve this
Terephthalic acid (TPA) in waste water is first enriched to nanofiltration concentrate in a kind of method of the integrated process alkali decrement waste water of embrane method by problem
In, then acid out recovery terephthalic acid (TPA) is carried out to concentrate；Also someone is high using alkali decrement waste water alkalinity, and addition magnesium salts can be given birth to
The negatively charged p-phthalic bridge in positively charged hydroxide magnesium salts, strong adsorption waste water, after inorganic membrane filtration is separated
The filtrate containing a large amount of alkali can be with direct reuse to Alkali reduction link, concentrate adds inorganic acid for adjusting pH value to 3 ~ 4, can separate out
Terephthalic acid crystals.Above acid out-membrane separation process can be greatly reduced sour consumption, but need to increase membranous system, and technique is more complicated.For
Reduce acid consumption and Simplified flowsheet, have patent that the pH of alkali decrement waste water is adjusted to 7.5 ~ 8.5 first, be subsequently adding calcium chloride or
Liquor zinci chloridi, separates out terephthalic acid (TPA) calcium（Or terephthalic acid (TPA) zinc）Salt solid, can be obtained to benzene after filter washing is dried
Dioctyl phthalate calcium（Or terephthalic acid (TPA) zinc）Age resistor product.
Hydrotalcite-based compound（Layered double hydroxides, abbreviation LDHs)）It is that a class has layer structure
Anionic species, the element species and content of its main layer board, the species of interlayer anion and quantity etc. can be in wider models
Enclose interior regulation, it has also become the new material of the great application prospect of a class.Due to its special structure and composition, using LDHs as
During PVC heat stabilizer, can adsorb and neutralize HCl, eliminate the catalytic reaction that HCl degrades to PVC, significantly reduce the drop of PVC
Solution speed, can both make up the toxic contaminants problem of lead salt stabilizer, it also avoid the expensive problem of organic tin stabilizer,
Have a good application prospect.But it is thermally-stabilised that the binary hydrotalcite thermal stability industrially commonly used at present is not met by PVC
Often early stage easily turns yellow for the requirement of agent, such as magnalium hydrotalcite；Zinc-aluminum hydrotalcite early stage coloring is preferable, but the later stage easily occurs " zinc
Burn ".Research is shown, can be modified change hydrotalcite by organic anion such as dodecyl sodium sulfonate, stearic acid, maleic acid etc.
Some properties on surface, increase its interlamellar spacing and the degree of scatter in halogen polyolefine material, so as to improve its heat endurance.
Such as Lin etc. is successfully prepared maleic acid modified MgAlZn-CO by ion-exchange3- LDHs, interlamellar spacing increase from 0.75 nm
1.11nm is arrived greatly, Cl is made-It is more easy to into interlayer react.Zhu Jian is using odium stearate to MgAl-CO3- LDHs carries out surface and changes
Property, reduce modified LDHs mean particle sizes, centralized particle diameter, reunion degree in the plastic are reduced, to PVC's
Heat-stable time is slightly improved.Sun Yulian et al. is carried out organically-modified using dodecyl sodium sulfate to hydrotalcite surface, makes PVC
Initial coloring and long-term thermal stability are all improved.
The content of the invention
It is an object of the invention to provide a kind of method for directly preparing modified hydrotalcite heat stabilizer with alkali decrement waste water.
The operating procedure that a kind of direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer is as follows：
（1）PH value with acid adjustment alkali decrement waste water is 4～10, is adjusted alkali decrement waste water；
（2）It is 5 by the solid mass ratio of liquid:1~30:1 adds hydrotalcite in adjustment alkali decrement waste water, under the conditions of 60 DEG C -100 DEG C,
1～5h of stirring reaction, obtains reaction mixture；
（3）Reaction mixture is separated by filtration, gained filtrate returns to step（1）Middle recycling；
（4）By gained solids washed with water, drying, grinding, the modified hydrotalcite heat stabilizer of white tasteless powder, energy are obtained
PVC static state heat-stable times are made to improve more than 60min.
The technical scheme for further limiting is as follows：
Step（1）In, the alkali decrement waste water is terylene, the alkali decrement waste water produced by acrylic fibers industry production process, wherein
PTA contents are more than 2000mg/L.
Step（1）In, the acid is hydrochloric acid（HCl）, sulfuric acid（H2SO4）Or nitric acid（HNO3）One or more of.
Step（2）In, the hydrotalcite is binary hydrotalcite or ternary hydrotalcite.
Step（3）In, the cycle-index of the filtrate is 2～10 times.
Step（4）In, baking temperature is 60 DEG C～90 DEG C.
The Advantageous Effects of the present invention embody in the following areas：
1. the inventive method is directly to utilize industrial alkali decrement waste water to prepare modified hydrotalcite, eliminates and is first obtained with acid neutralization
Terephthalic acid (TPA), recycles the intermediate steps of terephthalic acid (TPA) modified hydrotalcite, and technical process is simple, acid consumption is low, with fine
Economic benefit and environmental benefit.
2. the present invention had both taken full advantage of PTA resources in alkali decrement waste water, had turned waste into wealth, while multiple by waste water
Recycling PTA contents therein can be made to be reduced to below discharge standard, solve the pollution problem of alkali decrement waste water.
3. the recovery utilization rate of terephthalic acid (TPA) of the present invention is high, and the waste water after separation can reduce the difficulty of follow-up biochemical treatment
Degree.
4., compared with original hydrotalcite, obtained in the present invention, the thermal stability of modified hydrotalcite heat stabilizer obtains carrying greatly very much
Height, and with PVC compatibilities more preferably, in PVC product, dispersive property is good, with good processing characteristics, is a kind of nontoxic, high
Effect, inexpensive PVC heat stabilizer.
Specific embodiment
With reference to embodiment, the present invention is further described.
Embodiment 1：
The operating procedure that a kind of direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer is as follows：
（1）160g PET productions enterprise alkali decrement waste water, wherein PTA contents is added to be about 18000mg/L in a kettle., always
Organic carbon content is about 12250mg/L, and solid content is 3.47%.Use nitric acid（HNO3）It is 4 to adjust pH value, is adjusted Alkali reduction
Waste water；
（2）By liquid-solid ratio 20:1 adds binary hydrotalcite in adjustment alkali decrement waste water（MgAl-CO3-LDHs）, at 100 DEG C
It is sufficiently stirred for reacting 4h, obtains reaction mixture；
（3）Reaction mixture is filtered, filtrate returns liquid storage tank and recycles, and obtains solid；
（4）By solid distillation water washing, and it is dried at 70 DEG C, grinds, the modified hydrotalcite for obtaining 7.71g powderies is thermally-stabilised
Agent.
Modified hydrotalcite heat stabilizer obtained by the present embodiment is white powder.It is better to the thermal stability of PVC,
Static heat-stable time brings up to more than 370min by 230min.
Embodiment 2：
The operating procedure that a kind of direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer is as follows：
（1）150g acrylic fiber production process enterprise alkali decrement waste water, wherein PTA contents is added to be about 16000mg/L in a kettle., always
Organic carbon content is about 11900mg/L, and solid content is 3.29%.Use sulfuric acid（H2SO4）It is 10 to adjust pH value, is adjusted alkali and subtracts
Amount waste water；
（2）By liquid-solid ratio 15:1 adds certain import binary hydrotalcite in adjustment alkali decrement waste water, is sufficiently stirred for anti-at 90 DEG C
5h is answered, reaction mixture is obtained；
（3）Reaction mixture is filtered, filtrate returns liquid storage tank and recycles, and obtains solid；
（4）By solid distillation water washing, and it is dried at 80 DEG C, grinds, the modified hydrotalcite for obtaining 9.52g powderies is thermally-stabilised
Agent.
Modified hydrotalcite heat stabilizer obtained by the present embodiment is white powder.It is better to the thermal stability of PVC,
Static heat-stable time brings up to more than 690min by 630min.
Embodiment 3：
The operating procedure that a kind of direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer is as follows：
（1）180g PET productions enterprise alkali decrement waste water, wherein PTA contents is added to be about 18000mg/L in a kettle., always
Organic carbon content is about 12250mg/L, and solid content is 3.47%.Use hydrochloric acid（HCl）It is 7 to adjust pH value, is adjusted Alkali reduction
Waste water；
（2）By liquid-solid ratio 30:1 adds ternary hydrotalcite CaMgAl-LDHs in adjustment alkali decrement waste water, fully stirs at 80 DEG C
Reaction 3h is mixed, reaction mixture is obtained；
（3）Reaction mixture is filtered, filtrate returns liquid storage tank and recycles, and obtains solid；
（4）By solid distillation water washing, and it is dried at 90 DEG C, grinds, the modified hydrotalcite for obtaining 5.32g powderies is thermally-stabilised
Agent.
Modified hydrotalcite heat stabilizer obtained by the present embodiment is white powder.It is better to the thermal stability of PVC,
Static heat-stable time brings up to more than 570min by 330min.
Embodiment 4：
The operating procedure that a kind of direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer is as follows：
（1）1 gained filtrate of 100g embodiments, wherein PTA contents is added to be about 10930mg/L in a kettle., total Organic carbon contains
Amount is about 7250mg/L, and solid content is 2.47%.Use nitric acid（HNO3）It is 4 to adjust pH value, is adjusted alkali decrement waste water；
（2）By liquid-solid ratio 10:1 adds binary hydrotalcite MgAl-CO3-LDHs in adjustment alkali decrement waste water, at 95 DEG C fully
Stirring reaction 2h, obtains reaction mixture；
（3）Reaction mixture is filtered, filtrate returns liquid storage tank and recycles, and obtains solid；
（4）By solid distillation water washing, and it is dried at 70 DEG C, grinds, the modified hydrotalcite for obtaining 9.67g powderies is thermally-stabilised
Agent.
Modified hydrotalcite heat stabilizer obtained by the present embodiment is white powder.It is better to the thermal stability of PVC,
Static heat-stable time brings up to more than 350min by 230min.
Described in embodiment 1-4, static heat-stable time is determined as follows：
1. gained modified hydrotalcite heat stabilizer and zinc stearate, beta-diketon, antioxidant etc. are mediated according to a certain percentage
Prepare PVC heat stabilizer；
2. PVC powder body, di-n-octyl phthalate (DOP), heat stabilizer, calcium carbonate, stearic acid are existed according to a certain percentage
Stir in agitator；
3. batch mixing is kneaded into 6-7min at 165 DEG C on twin-roll plasticator, pull into the thin slice that thickness is 1mm, cut out after cooling
It is cut into the square little print that the length of side is 15mm；
4. print is put in 190 ± 2 DEG C of baking ovens carries out static thermal ageing test, takes out sample observation face at regular intervals
The change of color.
Heat-stable time is set to the time of the complete blackening of print.
As a result find, PVC heat can be significantly improved using the modified gained modified hydrotalcite heat stabilizer of alkali decrement waste water steady
Fix time.And PTA contents therein after 5 ~ 10 times recycle can be substantially reduced, be alleviated by alkali decrement waste water
Waste water is in follow-up biochemical treatment difficulty.
Claims (6)
1. a kind of method that direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer, it is characterised in that operating procedure is such as
Under：
（1）PH value with acid adjustment alkali decrement waste water is 4～10, is adjusted alkali decrement waste water；
（2）It is 5 by the solid mass ratio of liquid:1~30:1 adds hydrotalcite in adjustment alkali decrement waste water, under the conditions of 60 DEG C -100 DEG C,
1～5h of stirring reaction, obtains reaction mixture；
（3）Reaction mixture is separated by filtration, gained filtrate returns to step（1）Middle recycling, obtains solid；
（4）By gained solids washed with water, drying, grinding, the modified hydrotalcite heat stabilizer of powdery is obtained；
The modified hydrotalcite heat stabilizer is the tasteless powder of white, PVC static state heat-stable times can be made to improve 60min with
On.
2. a kind of method that direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer according to claim 1, its
It is characterised by：Step（1）In, the alkali decrement waste water is terylene, the alkali decrement waste water produced by acrylic fibers industry production process,
Wherein PTA contents are more than 2000mg/L.
3. a kind of method that direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer according to claim 1, its
It is characterised by：Step（1）In, the acid is hydrochloric acid（HCl）, sulfuric acid（H2SO4）Or nitric acid（HNO3）One or more of.
4. a kind of method that direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer according to claim 1, its
It is characterised by：Step（2）In, the hydrotalcite is binary hydrotalcite or ternary hydrotalcite.
5. a kind of method that direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer according to claim 1, its
It is characterised by：Step（3）In, the cycle-index of the filtrate is 2～10 times.
6. a kind of method that direct utilization alkali decrement waste water prepares modified hydrotalcite heat stabilizer according to claim 1, its
It is characterised by：Step（4）In, baking temperature is 60 DEG C～90 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611115531.0A CN106519299A (en) | 2016-12-07 | 2016-12-07 | Method for directly preparing modified hydrotalcite stabilizer from alkali deweighting wastewater |
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| CN201611115531.0A CN106519299A (en) | 2016-12-07 | 2016-12-07 | Method for directly preparing modified hydrotalcite stabilizer from alkali deweighting wastewater |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257064A (en) * | 1999-12-16 | 2000-06-21 | 陈定良 | Process for recovering terephthalic acid from alkali reduced sewage |
| CN102070234A (en) * | 2010-12-14 | 2011-05-25 | 扬州市革领高科技纳米环保设备有限公司 | Method for separating sodium terephthalate and alkaline solution from alkali deweighting waste liquid |
| CN102910778A (en) * | 2011-08-01 | 2013-02-06 | 施冬梅 | Terylene alkali reduction water resource recovery process |
| CN104558775A (en) * | 2015-01-12 | 2015-04-29 | 北京化工大学 | Hydrotalcite acid acceptor for polyolefin |
| US20150218009A1 (en) * | 2012-09-02 | 2015-08-06 | Council Of Scientific & Industrial Research | Novel process for preparation of synthetic hydrotalcite from industrial waste |
| CN105802604A (en) * | 2016-04-20 | 2016-07-27 | 北京师范大学 | Intercalated structure nano material with room-temperature long-afterglow luminescence property and preparation method thereof |
-
2016
- 2016-12-07 CN CN201611115531.0A patent/CN106519299A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257064A (en) * | 1999-12-16 | 2000-06-21 | 陈定良 | Process for recovering terephthalic acid from alkali reduced sewage |
| CN102070234A (en) * | 2010-12-14 | 2011-05-25 | 扬州市革领高科技纳米环保设备有限公司 | Method for separating sodium terephthalate and alkaline solution from alkali deweighting waste liquid |
| CN102910778A (en) * | 2011-08-01 | 2013-02-06 | 施冬梅 | Terylene alkali reduction water resource recovery process |
| US20150218009A1 (en) * | 2012-09-02 | 2015-08-06 | Council Of Scientific & Industrial Research | Novel process for preparation of synthetic hydrotalcite from industrial waste |
| CN104558775A (en) * | 2015-01-12 | 2015-04-29 | 北京化工大学 | Hydrotalcite acid acceptor for polyolefin |
| CN105802604A (en) * | 2016-04-20 | 2016-07-27 | 北京师范大学 | Intercalated structure nano material with room-temperature long-afterglow luminescence property and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 李东光: "《工业废弃物回收利用实例》", 31 July 2010, 中国纺织出版社 * |
| 王军 等: "苯二甲酸插层水滑石的制备和结构表征", 《四川理工学院学报（自然科学版）》 * |
| 郑德 黄锐: "《稳定剂（2011年6月第1版）》", 30 June 2011, 国防工业出版社 * |
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