CN102660075B - Comprehensive utilization method for aromatic carboxylic acid residues - Google Patents
Comprehensive utilization method for aromatic carboxylic acid residues Download PDFInfo
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- CN102660075B CN102660075B CN 201210114480 CN201210114480A CN102660075B CN 102660075 B CN102660075 B CN 102660075B CN 201210114480 CN201210114480 CN 201210114480 CN 201210114480 A CN201210114480 A CN 201210114480A CN 102660075 B CN102660075 B CN 102660075B
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- residue
- carboxylic acid
- aromatic carboxylic
- nucleating agent
- polypropylene
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Abstract
The invention relates to a comprehensive utilization method for aromatic carboxylic acid residues. An appropriate amount of alkali compound is added into romatic carboxylic acid raffinate or the aromatic carboxylic acid residues to perform reaction till the raffinate or the residues is/are neutral, and moisture in a reaction solution is removed to obtain residue metal salt. The residue metal saltand polypropylene powder or granules are mixed according to the weight ratio of 1:5-20, an appropriate amount of white oil is added into a mixture, extrusion and granulation are performed to obtain beta-nucleating agent master-batches, the beta-nucleating agent master-batches are added during the polypropylene processing to obtain toughened polypropylene. By means of the comprehensive utilizationmethod, the residues are directly used or neutralized and converted into the metal salt. The method is simple and convenient and low in cost, 100% of comprehensive utilization of tantalum residues isachieved, no secondary pollution is caused, and energy consumption is very low.
Description
Technical field
The present invention relates to a kind of method of utilizing of aromatic carboxylic acid residue, particularly a kind of the TA residue is changed into metal-salt and salt is used for polyacrylic method for toughening as the polypropylene nucleating agent.
Background technology
Produce the polyester resin process and will produce a large amount of aromatic carboxylic acid residue (TA residue), its main component comprises phenylformic acid, terephthalic acid, m-phthalic acid, paratolunitrile etc., and complicated component is recycled difficulty.Factory by 1,000,000 tons of PTA of annual output, the level of residue in 1 year will reach 5000 tons.At present, the TA residue mainly adopts the method for burning to process, this has not only caused the pollution of environment, and has caused the waste of the industrial chemicals such as phenylformic acid, terephthalic acid and the energy in the residue, therefore, the comprehensive utilization of TA residue is chemical industry field problem demanding prompt solution always.Patent CN1278272A discloses a kind of with the method for TA residue as the boiler oil burning disposal; CN1611482A discloses a kind of terephthalic acid, m-phthalic acid and benzoic method that adopts in the reaction recovery residues such as esterification, rectifying, recrystallization and transesterify; CN1253942A discloses a kind of method that adopts underpressure distillation recovery of benzoic acid from the TA residue; CN1078738A, CN101054450A and CN1031540A disclose respectively take the TA residue as raw material by esterification, the method that step prepares stabilizer for plastics, polyurethane coating and vibrin such as have separated, these methods all provide new way for the comprehensive utilization of TA residue, these methods or process are complicated, or can not realize the fully utilization of residue.
Summary of the invention
The method of comprehensive utilization that the purpose of this invention is to provide a kind of aromatic carboxylic acid residue, easy, the easy row of the method, efficient, prepare the nucleator that can be used for polypropylene toughening by simple neutralization reaction, make simple, add easily, polypropylene there is good toughening effect, can realizes 100% recycling of TA residue, realize energy-saving and emission-reduction and utilization of waste material.
The technical scheme that the present invention takes is:
A kind of method of comprehensive utilization of aromatic carboxylic acid residue comprises that step is as follows:
(1) raffinate of getting the discharge of aromatic carboxylic acid residue or production line is surveyed its total acidity with the alkalimetric titration residue of standard on a small quantity;
(2) pending aromatic carboxylic acid residue is the water-soluble or raffinate that directly uses production line to discharge is according to what record
Total acidity is to wherein adding an amount of basic cpd reaction to neutral;
(3) filter, evaporate the moisture of removing in the reaction solution, obtain the residue metal-salt;
(4) with residue metal-salt and polypropylene powder or pellet by weight 1: 5-20 is mixed into a material grain raw material, adds a small amount of white oil, and extruding pelletization obtains the nucleating agent master batch;
(5) in the polypropylene course of processing, add the nucleating agent master batch, obtain tenacity-increased profax.
Described basic cpd is selected from oxyhydroxide, oxide compound, carbonate, supercarbonate or the subcarbonate of basic metal, alkaline-earth metal.
The add-on of described white oil is the 0.2%-1% of material grain raw materials quality.
The described nucleating agent master batch of step (5) adds in the polypropylene by quality percentage composition 0.01-20%.
Basic ideas of the present invention are the main components in conjunction with the structure of acrylic plastering nucleating agent and TA residue, take the TA residue as main raw material, adopt simple method to be translated into the salt with nucleogenesis, the mode with additive joins in the polypropylene again, is used for polyacrylic toughness reinforcing.
Compared with prior art, technology disclosed by the invention has following advantage:
1. directly use raffinate or residue dissolving neutralization is converted into metallic salt, method is easy, and cost is low, even can realize at the plant produced line;
2. utilize benzene dicarboxylic acid and benzoate on the impact of crystalling propylene behavior, induce polypropylene to form beta-crystal, crystal grain thinning, toughening effect is obvious;
3. adopt to prepare first plasticizing mother particle, the method for adding to again in the polypropylene is simple, not only can improve the dispersion effect of toughner in Pp System, also easily realizes industrialization;
4. method disclosed by the invention has realized 100% comprehensive utilization of TA residue, does not produce secondary pollution, and energy consumption is extremely low.
Embodiment
Further specify the present invention below in conjunction with embodiment, but be to be noted that the present invention is not limited to following case study on implementation.The TA raffinate that embodiment is used or residue are for to prepare the waste residue that generates in the terephthalic acid commercial run by p xylene oxidation, and other raw materials all are the industrial goods that market is buied.For the residue of different batches and producer, its total acid content might be different, should implement according to actual acidity; In addition, the reaction times that is converted into carboxylate salt and concrete operations may be relevant with the character of residue, reactant species etc., and there is different modes in concrete operation for a people that background context arranged, but final product all is carboxylate salt.
Embodiment 1
The dried residue of the used raffinate of the embodiment of the invention mainly contains phenylformic acid, phthalic acid, m-phthalic acid, terephthalic acid, p-methylbenzoic acid etc., wherein the content of each material is: phenylformic acid is 25～30%, benzene dicarboxylic acid content is 45～75%, and total acidity is 43.3969gNaOH/100g.
(1) accurately takes by weighing 0.5000g TA residue, be dissolved in the hot water (temperature 50 C), slowly use the titration of standard NaOH solution, calculate total acidity, be used for calculating the amount of the needed basic cpd of salify, be used for the preparation of carboxylate salt;
(2) take by weighing 100g TA residue, be added in 50 ℃ of hot water of 50g, stir lower to wherein adding the 111g Calcium hydrogen carbonate, abundant reaction neutralization;
(3) filter, filtrate evaporation or naturally evaporate into driedly, solid is crushed to 600 orders, obtains the residue calcium salt;
(4) get residue calcium salt 50g, polypropylene (T30S) 250g, white oil 3g stirs, and adds in the forcing machine, and extruding pelletization obtains the nucleating agent master batch;
(5) in PP produces, can add the nucleating agent master batch of quality percentage composition 0.02%, obtain tenacity-increased profax.
The shock strength of not adding the PP of nucleator is 3.75kJ/m
2, add 0.02% the present embodiment nucleating agent master batch after shock strength reach 4.51J/m
2, the PP shock strength has improved 20.27%.
Embodiment 2
With embodiment 1 described TA residue,
(1) accurately takes by weighing 0.5000g TA residue, be dissolved in the hot water, slowly use the titration of standard NaOH solution, calculate total acidity, be used for calculating the amount of the needed basic cpd of salify, be used for the preparation of carboxylate salt;
(2) take by weighing the 100.0gTA residue, be added in the 50g hot water, stir lower to wherein adding 61.3gCaO, abundant reaction neutralization;
(3) filter, filtrate evaporation or naturally evaporate into driedly, solid is crushed to 800 orders, obtains the residue calcium salt;
(4) get residue calcium salt 50g, polypropylene (T30S) 250g, white oil 3g stirs, and adds in the forcing machine, and extruding pelletization obtains the nucleating agent master batch;
(5) in PP produces, can add the nucleating agent master batch of quality percentage composition 0.4%, obtain tenacity-increased profax.
The shock strength of not adding the PP of nucleator is 3.75kJ/m
2, shock strength reaches 4.55J/m behind the nucleating agent master batch of adding the present embodiment 0.4%
2, the PP shock strength has improved 22.67%.
Embodiment 3
With embodiment 1 described TA residue,
(1) accurately takes by weighing 0.5000g TA residue, be dissolved in the hot water, slowly use the titration of standard NaOH solution, calculate total acidity, be used for calculating the amount of the needed basic cpd of salify, be used for the preparation of carboxylate salt;
(2) take by weighing 100g TA residue, be added in the 50g hot water, stir lower to wherein adding 61.5gMg (OH)
2, fully reaction;
(3) filter, filtrate evaporation or naturally evaporate into driedly, solid is crushed to 600 orders, obtains the residue magnesium salts;
(4) get residue magnesium salts 50g, polypropylene (T30S) 250g, white oil 3g stirs, and adds in the forcing machine, and extruding pelletization obtains the nucleating agent master batch;
(5) in PP produces, can add the nucleating agent master batch of quality percentage composition 0.6%, obtain tenacity-increased profax.
The shock strength of not adding the PP of nucleator is 3.75kJ/m
2, shock strength reaches 4.65J/m behind adding the present embodiment 0.6% nucleating agent master batch
2, the PP shock strength has improved 22.67%.
Embodiment 4
Step is with embodiment 1, and different is is to add 32.1g aluminium hydroxide to replace Calcium hydrogen carbonate in the step (2); The nucleating agent master batch that adds quality percentage composition 5% in the step (5).
The PP shock strength than the raising of not adding nucleator 20%.
Embodiment 5
Step is with embodiment 1, and different is is to add the 110g magnesium basic carbonate to replace Calcium hydrogen carbonate in the step (2); The nucleating agent master batch that adds quality percentage composition 10% in the step (5).
The PP shock strength than the raising of not adding nucleator 23%.
Embodiment 6
With embodiment 1 described TA residue,
(1) accurately takes by weighing 0.5000g TA residue, be dissolved in the hot water, slowly use the titration of standard NaOH solution, calculate total acidity, be used for calculating the amount of the needed basic cpd of salify, be used for the preparation of carboxylate salt;
(2) take by weighing the 100.0gTA residue, be added in the 50g hot water, stir lower to wherein adding 55.5gCaHCO
3And 30.8gMg (OH)
2Mixture, fully reaction neutralization;
(3) filter, filtrate evaporation or naturally evaporate into driedly, solid is crushed to 800 orders, obtains the residue calcium salt;
(4) get residue calcium salt 50g, polypropylene (T30S) 500g, white oil 5g stirs, and adds in the forcing machine, and extruding pelletization obtains the nucleating agent master batch;
(5) in PP produces, can add the nucleating agent master batch of quality percentage composition 20%, obtain tenacity-increased profax.
The shock strength of not adding the PP of nucleator is 3.75kJ/m
2, shock strength reaches 4.38J/m behind the nucleating agent master batch of adding the present embodiment 20%
2, the PP shock strength has improved 16.80%.
Should be noted that; adopt this residue just for concrete implementation process is described; the scope that patent is protected is not limited only to this; all are for the preparation of the residue of PTA and related products, as long as its main component is that aromatic carboxylic acid (monoprotic acid, diprotic acid, triprotic acid etc.) all can adopt the described method of this patent to fully utilize.
Claims (3)
1. the method for comprehensive utilization of an aromatic carboxylic acid residue is characterized in that, comprises that step is as follows:
(1) raffinate of getting the discharge of aromatic carboxylic acid residue or production line is surveyed its total acidity with the alkalimetric titration residue of standard on a small quantity;
(2) pending aromatic carboxylic acid residue is the water-soluble or raffinate that directly uses production line to discharge, according to the total acidity that records to wherein adding an amount of basic cpd reaction to neutral; Described basic cpd is selected from oxyhydroxide, oxide compound, carbonate, supercarbonate or the subcarbonate of basic metal, alkaline-earth metal;
(3) filter, evaporate the moisture of removing in the reaction solution, obtain the residue metal-salt;
(4) residue metal-salt and polypropylene powder or pellet are mixed into a material grain raw material by weight 1:5-20, add a small amount of white oil, extruding pelletization obtains the nucleating agent master batch;
(5) in the polypropylene course of processing, add the nucleating agent master batch, obtain tenacity-increased profax.
2. the method for comprehensive utilization of a kind of aromatic carboxylic acid residue according to claim 1 is characterized in that, the add-on of the described white oil of step (4) is the 0.2%-1% of material grain raw materials quality.
3. the method for comprehensive utilization of a kind of aromatic carboxylic acid residue according to claim 1 is characterized in that, the described nucleating agent master batch of step (5) adds in the polypropylene by quality percentage composition 0.01-20%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210114480 CN102660075B (en) | 2012-04-18 | 2012-04-18 | Comprehensive utilization method for aromatic carboxylic acid residues |
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| CN 201210114480 CN102660075B (en) | 2012-04-18 | 2012-04-18 | Comprehensive utilization method for aromatic carboxylic acid residues |
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| CN102660075A CN102660075A (en) | 2012-09-12 |
| CN102660075B true CN102660075B (en) | 2013-10-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI574925B (en) * | 2016-03-09 | 2017-03-21 | Chung-Fu Wang | Treatment of Polycarboxylic Acid Residues |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034375A (en) * | 1988-12-14 | 1989-08-02 | 中国科学院上海有机化学研究所 | Microporous polypropylene membrane and production method thereof |
| CN1611481A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid and water scrubbing residue recovery and utilization method |
-
2012
- 2012-04-18 CN CN 201210114480 patent/CN102660075B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034375A (en) * | 1988-12-14 | 1989-08-02 | 中国科学院上海有机化学研究所 | Microporous polypropylene membrane and production method thereof |
| CN1611481A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid and water scrubbing residue recovery and utilization method |
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