CN109503818A - A kind of production technology of no antimony recycled polyester slice - Google Patents
A kind of production technology of no antimony recycled polyester slice Download PDFInfo
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- CN109503818A CN109503818A CN201811226519.6A CN201811226519A CN109503818A CN 109503818 A CN109503818 A CN 109503818A CN 201811226519 A CN201811226519 A CN 201811226519A CN 109503818 A CN109503818 A CN 109503818A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 21
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000005516 engineering process Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 26
- 150000002148 esters Chemical group 0.000 claims abstract description 22
- 238000005453 pelletization Methods 0.000 claims abstract description 19
- 229920000742 Cotton Polymers 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000004744 fabric Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 174
- 239000000243 solution Substances 0.000 claims description 64
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- 238000005809 transesterification reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000003381 stabilizer Substances 0.000 claims description 14
- 150000003608 titanium Chemical class 0.000 claims description 14
- 230000000295 complement effect Effects 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000498 cooling water Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- -1 BHET small molecule Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000012790 confirmation Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 235000021050 feed intake Nutrition 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 235000012149 noodles Nutrition 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 15
- 239000005020 polyethylene terephthalate Substances 0.000 description 15
- 229940011182 cobalt acetate Drugs 0.000 description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000763 evoking effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of production technologies of no antimony recycled polyester slice, comprising the following steps: polyester disused cloth leftover pieces are 1. ground into 20cm square, are delivered to alcoholysis reaction kettle；2. alcoholysis reaction；3. polyester-cotton blend separates；4. BHET ester exchange reaction；5. DMT is crystallized；6. DMT is centrifugated；7. DMT rectifying；8. the ester exchange reaction of DMT；9. polymerization reaction；10. pelletizing.The present invention realizes recycling for waste and old resource, while solving problem of environmental pollution.
Description
Technical field
The present invention relates to polyester slice production technical fields, more particularly, to a kind of production work of no antimony recycled polyester slice
Skill.
Background technique
Polyethylene terephthalate (PET) is the current maximum of yield in the world, the widest synthetic fibers material of purposes
Material, there are shortcomings for the antimony-based catalyst that most PET are used: 1. in polyester polycondensation reaction, antimony catalyst meeting portion
Divide reduction grey；2. the polyester of synthesis is in spinning, since the reduction accumulation of heavy metal will increase the pressure of filament spinning component；3.
Heavy metal antimony has certain toxicity, is not only precipitated in PET dyeing course and causes environmental pollution, and PET end product becomes rubbish
It similarly brings annual 10,000 tons antimony into the Nature afterwards, causes expendable pollution.
As manufacturing industry environmental requirement is gradually increased in country, Textile Chain increases increasingly from the pressure of environmental protection,
Especially nearly one or two years Jiangsu and Zhejiang Provinces area printing and dyeing mill has evoked greatly due to the tide of shutting down that heavy metal " antimony " discharge beyond standards problem causes
Social repercussion, also influenced the social image for whole industrial chain of weaving.No antimony recycled polyester slice, solves weight from feed end
Metallic antimony there are problem, for " Green Development " of whole industrial chain of weaving, have especially in recycled polyester industry important
Meaning.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, a kind of production of no antimony recycled polyester slice is provided
Technique realizes recycling for waste and old resource, while solving problem of environmental pollution.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of production technology of no antimony recycled polyester slice, comprising the following steps:
1. polyester disused cloth leftover pieces are ground into 20cm square, it is delivered to alcoholysis reaction kettle；
2. alcoholysis reaction: 15m is first added in alcoholysis reaction kettle3EG, then be added 5 tons of polyester disused cloths that crushed,
It is eventually adding the potassium carbonate catalyst solution that 320kg concentration is 40%~60% and is heated to 180 DEG C~250 DEG C, alcoholysis is anti-
It answers the pressure in kettle to control in 0.2Mpa, generates BHET by reaction in 6~8 hours；
3. polyester-cotton blend separates: the cotton in BHET solution is separated；Due to containing a certain amount of cotton in polyester disused cloth, need
Cotton in BHET solution is separated to obtain purer BHET solution；
4. BHET ester exchange reaction: 18~30m being first added in transesterification reactor3Methanol solution, be then added 10
~20m3BHET solution, be eventually adding the potassium carbonate catalyst solution that 200~400kg concentration is 40%~60%, 70~
Ester exchange reaction is carried out at a temperature of 120 DEG C, obtains DMT and ethylene glycol after reaction；The reaction carries out under normal pressure；
5. DMT is crystallized: crystallization uses vacuum cooled mode, and temperature drops to 35~50 DEG C；The step is in order to DMT solution
In impurity and part colours slough；
6. DMT is centrifugated: the DMT solution of advantages of good crystallization by centrifugation by DMT solution DMT and methanol divided
From the DMT again with methanol dilution isolated is centrifuged again, obtains purer DMT；
7. DMT rectifying: under 6~13kpa pressure, temperature is controlled in 210~215 DEG C of progress rectifying DMT rectifying still, is obtained
Pure white DMT solution, the raw material as production slice；The step is relatively white pure DMT in order to obtain, and it is molten to slough DMT
Impurity and color in liquid；
8. the ester exchange reaction of DMT: 5 stages of the reaction point or less carry out: the reaction carries out in DCS process control,
A. raw material preparation, feed intake: EG, DMT, sodium acetate catalyst solution and stabilizer by flowmeter control successively plus
Enter in transesterification reactor；
B. methanol is precipitated: when reaction kettle temperature rise is to 140~180 DEG C, reaction starts and methanol is precipitated, by transesterification work
Methanol pans are flowed into after skill tower, condenser condensation；
C. react: temperature gradually rises, and methanol is constantly precipitated, and obtains BHET and methanol, methanol by ester exchange process tower,
Methanol pans are flowed into after condenser condensation, confirmation reaction is completed when temperature is to 210~240 DEG C；
D.EG extraction: continuing to be warming up to 250~260 DEG C, and extra EG is produced to EG receiving tank, add Titanium series catalyst,
Stabilizer, complementary color agent and Ti02；Titanium series catalyst can shorten the reaction time in the ester exchange reaction of DMT, while after can reducing
The reaction time of continuous polymerization reaction；Stabilizer can prevent heat deterioration；Complementary color agent can make corrections tonal quality；Ti02It is bright that product can be improved
Degree；
E. it falls: the BHET solution in transesterification reactor being sent by the filter of 25um with nitrogen pressuring method and is gathered
Close kettle；
9. polymerization reaction: polymerizeing between BHET small molecule under 50kpa~250kpa vacuum degree in polymeric kettle, detaching second
Glycol becomes macromolecular PET after small molecule BHET polymerization；
10. pelletizing: macromolecular PET melt is discharged by discharge unit in impartial noodle shape, cold through supercooled water
But after, then pelletizing carried out by pelleter, the slice after pelletizing by cooling water, be transported to dewaterer be separated into cooling water with
And slice.Pelleter is cut using pelleter in vertical-type water.
The stabilizer is any one in trimethyl phosphate, dimethyl phosphate, triphenyl phosphate or diphenyl phosphate.
The Titanium series catalyst is selected from T-436, and the additive amount of titanium is 100~150ppm of polyester quality.
The complementary color agent is cobalt acetate.
The beneficial effects of the present invention are: realizing the recycling of polyester disused cloth, while using Titanium series catalyst solution
It has determined problem of environmental pollution.
Specific embodiment
The invention will be further described With reference to embodiment:
Embodiment 1:
A kind of production technology of no antimony recycled polyester slice, comprising the following steps:
1. polyester disused cloth leftover pieces are ground into 20cm square, it is delivered to alcoholysis reaction kettle；
2. alcoholysis reaction: 15m is first added in alcoholysis reaction kettle3EG, then be added 5 tons of polyester disused cloths that crushed,
It is eventually adding the potassium carbonate catalyst solution that 320kg concentration is 40% and is heated to 180 DEG C, the pressure control in alcoholysis reaction kettle
System generates BHET in 0.2Mpa, by reaction in 8 hours；
3. polyester-cotton blend separates: the cotton in BHET solution is separated；
4. BHET ester exchange reaction: 18m being first added in transesterification reactor3Methanol solution, 10m is then added3's
BHET solution, is eventually adding the potassium carbonate catalyst solution that 200kg concentration is 40%, and it is anti-that transesterification is carried out at a temperature of 70 DEG C
It answers, DMT and ethylene glycol is obtained after reaction；
5. DMT is crystallized: crystallization uses vacuum cooled mode, and temperature drops to 35 DEG C；
6. DMT is centrifugated: the DMT solution of advantages of good crystallization by centrifugation by DMT solution DMT and methanol divided
From the DMT again with methanol dilution isolated is centrifuged again, obtains purer DMT；
7. DMT rectifying: under 6kpa pressure, temperature is controlled in 210 DEG C of progress rectifying DMT rectifying still, obtains pure white DMT
Solution, the raw material as production slice；
8. the ester exchange reaction of DMT: 5 stages of the reaction point or less carry out:
A. raw material preparation, feed intake: EG, DMT, sodium acetate catalyst solution and stabilizer by flowmeter control successively plus
Enter in transesterification reactor；
B. methanol is precipitated: when reaction kettle temperature rise is to 140 DEG C, reaction starts and is precipitated methanol, by ester exchange process tower,
Methanol pans are flowed into after condenser condensation；
C. react: temperature gradually rises, and methanol is constantly precipitated, and obtains BHET and methanol, methanol by ester exchange process tower,
Methanol pans are flowed into after condenser condensation, confirmation reaction is completed when temperature is to 210 DEG C；
D.EG extraction: continue to be warming up to 250 DEG C, extra EG is produced to EG receiving tank, adds Titanium series catalyst, stabilization
Agent, complementary color agent and Ti02；
E. it falls: the BHET solution in transesterification reactor being sent by the filter of 25um with nitrogen pressuring method and is gathered
Close kettle；
9. polymerization reaction: it is polymerizeing between BHET small molecule under 50kpa vacuum degree in polymeric kettle, is detaching ethylene glycol, it is small
Become macromolecular PET after molecule BHET polymerization；
10. pelletizing: macromolecular PET melt is discharged by discharge unit in impartial noodle shape, cold through supercooled water
But after, then pelletizing carried out by pelleter, the slice after pelletizing by cooling water, be transported to dewaterer be separated into cooling water with
And slice.
The stabilizer is trimethyl phosphate.
The Titanium series catalyst is selected from T-436, and the additive amount of titanium is the 100ppm of polyester quality.
The complementary color agent is cobalt acetate.
Embodiment 2:
A kind of production technology of no antimony recycled polyester slice, comprising the following steps:
1. polyester disused cloth leftover pieces are ground into 20cm square, it is delivered to alcoholysis reaction kettle；
2. alcoholysis reaction: 15m is first added in alcoholysis reaction kettle3EG, then be added 5 tons of polyester disused cloths that crushed,
It is eventually adding the potassium carbonate catalyst solution that 320kg concentration is 45% and is heated to 200 DEG C, the pressure control in alcoholysis reaction kettle
System generates BHET in 0.2Mpa, by reaction in 6.5 hours；
3. polyester-cotton blend separates: the cotton in BHET solution is separated；
4. BHET ester exchange reaction: 20m being first added in transesterification reactor3Methanol solution, 15m is then added3's
BHET solution, is eventually adding the potassium carbonate catalyst solution that 280kg concentration is 45%, and it is anti-that transesterification is carried out at a temperature of 90 DEG C
It answers, DMT and ethylene glycol is obtained after reaction；
5. DMT is crystallized: crystallization uses vacuum cooled mode, and temperature drops to 40 DEG C；
6. DMT is centrifugated: the DMT solution of advantages of good crystallization by centrifugation by DMT solution DMT and methanol divided
From the DMT again with methanol dilution isolated is centrifuged again, obtains purer DMT；
7. DMT rectifying: under 8kpa pressure, temperature is controlled in 212 DEG C of progress rectifying DMT rectifying still, obtains pure white DMT
Solution, the raw material as production slice；
8. the ester exchange reaction of DMT: 5 stages of the reaction point or less carry out:
A. raw material preparation, feed intake: EG, DMT, sodium acetate catalyst solution and stabilizer by flowmeter control successively plus
Enter in transesterification reactor；
B. methanol is precipitated: when reaction kettle temperature rise is to 150 DEG C, reaction starts and is precipitated methanol, by ester exchange process tower,
Methanol pans are flowed into after condenser condensation；
C. react: temperature gradually rises, and methanol is constantly precipitated, and obtains BHET and methanol, methanol by ester exchange process tower,
Methanol pans are flowed into after condenser condensation, confirmation reaction is completed when temperature is to 220 DEG C；
D.EG extraction: continue to be warming up to 255 DEG C, extra EG is produced to EG receiving tank, adds Titanium series catalyst, stabilization
Agent, complementary color agent and Ti02；
E. it falls: the BHET solution in transesterification reactor being sent by the filter of 25um with nitrogen pressuring method and is gathered
Close kettle；
9. polymerization reaction: it is polymerizeing between BHET small molecule under 150kpa vacuum degree in polymeric kettle, is detaching ethylene glycol, it is small
Become macromolecular PET after molecule BHET polymerization；
10. pelletizing: macromolecular PET melt is discharged by discharge unit in impartial noodle shape, cold through supercooled water
But after, then pelletizing carried out by pelleter, the slice after pelletizing by cooling water, be transported to dewaterer be separated into cooling water with
And slice.
The stabilizer is dimethyl phosphate.
The Titanium series catalyst is selected from T-436, and the additive amount of titanium is the 120ppm of polyester quality.
The complementary color agent is cobalt acetate.
Embodiment 3:
A kind of production technology of no antimony recycled polyester slice, comprising the following steps:
1. polyester disused cloth leftover pieces are ground into 20cm square, it is delivered to alcoholysis reaction kettle；
2. alcoholysis reaction: 15m is first added in alcoholysis reaction kettle3EG, then be added 5 tons of polyester disused cloths that crushed,
It is eventually adding the potassium carbonate catalyst solution that 320kg concentration is 50% and is heated to 230 DEG C, the pressure control in alcoholysis reaction kettle
System generates BHET in 0.2Mpa, by reaction in 7 hours；
3. polyester-cotton blend separates: the cotton in BHET solution is separated；
4. BHET ester exchange reaction: 25m being first added in transesterification reactor3Methanol solution, 18m is then added3's
BHET solution, is eventually adding the potassium carbonate catalyst solution that 350kg concentration is 50%, and it is anti-that transesterification is carried out at a temperature of 100 DEG C
It answers, DMT and ethylene glycol is obtained after reaction；
5. DMT is crystallized: crystallization uses vacuum cooled mode, and temperature drops to 45 DEG C；
6. DMT is centrifugated: the DMT solution of advantages of good crystallization by centrifugation by DMT solution DMT and methanol divided
From the DMT again with methanol dilution isolated is centrifuged again, obtains purer DMT；
7. DMT rectifying: under 10kpa pressure, temperature is controlled in 214 DEG C of progress rectifying DMT rectifying still, is obtained pure white
DMT solution, the raw material as production slice；
8. the ester exchange reaction of DMT: 5 stages of the reaction point or less carry out:
A. raw material preparation, feed intake: EG, DMT, sodium acetate catalyst solution and stabilizer by flowmeter control successively plus
Enter in transesterification reactor；
B. methanol is precipitated: when reaction kettle temperature rise is to 160 DEG C, reaction starts and is precipitated methanol, by ester exchange process tower,
Methanol pans are flowed into after condenser condensation；
C. react: temperature gradually rises, and methanol is constantly precipitated, and obtains BHET and methanol, methanol by ester exchange process tower,
Methanol pans are flowed into after condenser condensation, confirmation reaction is completed when temperature is to 230 DEG C；
D.EG extraction: continue to be warming up to 258 DEG C, extra EG is produced to EG receiving tank, adds Titanium series catalyst, stabilization
Agent, complementary color agent and Ti02；
E. it falls: the BHET solution in transesterification reactor being sent by the filter of 25um with nitrogen pressuring method and is gathered
Close kettle；
9. polymerization reaction: it is polymerizeing between BHET small molecule under 200kpa vacuum degree in polymeric kettle, is detaching ethylene glycol, it is small
Become macromolecular PET after molecule BHET polymerization；
10. pelletizing: macromolecular PET melt is discharged by discharge unit in impartial noodle shape, cold through supercooled water
But after, then pelletizing carried out by pelleter, the slice after pelletizing by cooling water, be transported to dewaterer be separated into cooling water with
And slice.
The stabilizer is triphenyl phosphate.
The Titanium series catalyst is selected from T-436, and the additive amount of titanium is the 140ppm of polyester quality.
The complementary color agent is cobalt acetate.
Embodiment 4:
A kind of production technology of no antimony recycled polyester slice, comprising the following steps:
1. polyester disused cloth leftover pieces are ground into 20cm square, it is delivered to alcoholysis reaction kettle；
2. alcoholysis reaction: 15m is first added in alcoholysis reaction kettle3EG, then be added 5 tons of polyester disused cloths that crushed,
It is eventually adding the potassium carbonate catalyst solution that 320kg concentration is 60% and is heated to 250 DEG C, the pressure control in alcoholysis reaction kettle
System generates BHET in 0.2Mpa, by reaction in 8 hours；
3. polyester-cotton blend separates: the cotton in BHET solution is separated；
4. BHET ester exchange reaction: 30m being first added in transesterification reactor3Methanol solution, 20m is then added3's
BHET solution, is eventually adding the potassium carbonate catalyst solution that 400kg concentration is 60%, and it is anti-that transesterification is carried out at a temperature of 120 DEG C
It answers, DMT and ethylene glycol is obtained after reaction；
5. DMT is crystallized: crystallization uses vacuum cooled mode, and temperature drops to 50 DEG C；
6. DMT is centrifugated: the DMT solution of advantages of good crystallization by centrifugation by DMT solution DMT and methanol divided
From the DMT again with methanol dilution isolated is centrifuged again, obtains purer DMT；
7. DMT rectifying: under 13kpa pressure, temperature is controlled in 215 DEG C of progress rectifying DMT rectifying still, is obtained pure white
DMT solution, the raw material as production slice；
8. the ester exchange reaction of DMT: 5 stages of the reaction point or less carry out:
A. raw material preparation, feed intake: EG, DMT, sodium acetate catalyst solution and stabilizer by flowmeter control successively plus
Enter in transesterification reactor；
B. methanol is precipitated: when reaction kettle temperature rise is to 180 DEG C, reaction starts and is precipitated methanol, by ester exchange process tower,
Methanol pans are flowed into after condenser condensation；
C. react: temperature gradually rises, and methanol is constantly precipitated, and obtains BHET and methanol, methanol by ester exchange process tower,
Methanol pans are flowed into after condenser condensation, confirmation reaction is completed when temperature is to 240 DEG C；
D.EG extraction: continue to be warming up to 260 DEG C, extra EG is produced to EG receiving tank, adds Titanium series catalyst, stabilization
Agent, complementary color agent and Ti02；
E. it falls: the BHET solution in transesterification reactor being sent by the filter of 25um with nitrogen pressuring method and is gathered
Close kettle；
9. polymerization reaction: it is polymerizeing between BHET small molecule under 250kpa vacuum degree in polymeric kettle, is detaching ethylene glycol, it is small
Become macromolecular PET after molecule BHET polymerization；
10. pelletizing: macromolecular PET melt is discharged by discharge unit in impartial noodle shape, cold through supercooled water
But after, then pelletizing carried out by pelleter, the slice after pelletizing by cooling water, be transported to dewaterer be separated into cooling water with
And slice.
The stabilizer is diphenyl phosphate.
The Titanium series catalyst is selected from T-436, and the additive amount of titanium is the 150ppm of polyester quality.
The complementary color agent is cobalt acetate.
The performance parameter of the polyester slice of production of the invention is as shown in table 1:
Table 1:
Execution standard: JR/PG-GL07 grade: AA
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of production technology of no antimony recycled polyester slice, which comprises the following steps:
1. polyester disused cloth leftover pieces are ground into 20cm square, it is delivered to alcoholysis reaction kettle；
2. alcoholysis reaction: 15m is first added in alcoholysis reaction kettle3EG, then be added 5 tons of polyester disused cloths that crushed, finally plus
Enter the potassium carbonate catalyst solution that 320kg concentration is 40%~60% and be heated to 180 DEG C~250 DEG C, in alcoholysis reaction kettle
Pressure control in 0.2Mpa, by the generation of reaction in 6~8 hours BHET；
3. polyester-cotton blend separates: the cotton in BHET solution is separated；
4. BHET ester exchange reaction: 18~30m being first added in transesterification reactor3Methanol solution, then be added 10~20m3
BHET solution, be eventually adding 200~400kg concentration be 40%~60% potassium carbonate catalyst solution, in 70~120 DEG C of temperature
Degree is lower to carry out ester exchange reaction, obtains DMT and ethylene glycol after reaction；
5. DMT is crystallized: crystallization uses vacuum cooled mode, and temperature drops to 35~50 DEG C；
6. DMT is centrifugated: the DMT solution of advantages of good crystallization by centrifugation by DMT solution DMT and methanol separate, divide
The DMT again with methanol dilution separated out is centrifuged again, obtains purer DMT；
7. DMT rectifying: under 6~13kpa pressure, temperature is controlled in 210~215 DEG C of progress rectifying DMT rectifying still, is obtained pure white
DMT solution, as production slice raw material；
8. the ester exchange reaction of DMT: 5 stages of the reaction point or less carry out:
A. raw material preparation, feed intake: EG, DMT, sodium acetate catalyst solution and stabilizer by flowmeter control sequentially add ester
In exchange reaction kettle；
B. methanol is precipitated: when reaction kettle temperature rise is to 140~180 DEG C, reaction starts and is precipitated methanol, by ester exchange process tower,
Methanol pans are flowed into after condenser condensation；
C. react: temperature gradually rises, and methanol is constantly precipitated, and obtains BHET and methanol, methanol is by ester exchange process tower, condensation
Methanol pans are flowed into after device condensation, confirmation reaction is completed when temperature is to 210~240 DEG C；
D.EG extraction: continue to be warming up to 250~260 DEG C, extra EG is produced to EG receiving tank, adds Titanium series catalyst, stabilization
Agent, complementary color agent and Ti02；
E. it falls: the BHET solution in transesterification reactor being sent into polymerization by the filter of 25um with nitrogen pressuring method
Kettle；
9. polymerization reaction: polymerizeing between BHET small molecule under 50kpa~250kpa vacuum degree in polymeric kettle, detaching second two
Alcohol becomes macromolecular PET after small molecule BHET polymerization；
10. pelletizing: macromolecular PET melt is discharged by discharge unit in impartial noodle shape, cooling through supercooled water
Afterwards, then by pelleter carry out pelletizing, the slice after pelletizing by cooling water, be transported to dewaterer be separated into cooling water and
Slice.
2. a kind of production technology of no antimony recycled polyester slice as described in claim 1, which is characterized in that the stabilizer is phosphorus
Any one in sour trimethyl, dimethyl phosphate, triphenyl phosphate or diphenyl phosphate.
3. a kind of production technology of no antimony recycled polyester slice as described in claim 1, which is characterized in that the Titanium series catalyst
Selected from T-436, the additive amount of titanium is 100~150ppm of polyester quality.
4. a kind of production technology of no antimony recycled polyester slice as described in claim 1, which is characterized in that the complementary color agent is vinegar
Sour cobalt.
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| CN110862520A (en) * | 2019-10-24 | 2020-03-06 | 江苏聚杰微纤科技集团股份有限公司 | Method for preparing PET (polyethylene terephthalate) by using terephthalic acid in alkali-minimization wastewater |
| CN110903616A (en) * | 2019-12-06 | 2020-03-24 | 江苏垶恒复合材料有限公司 | High-toughness regenerated PET material and preparation method thereof |
| CN110951223A (en) * | 2019-12-06 | 2020-04-03 | 江苏垶恒复合材料有限公司 | High-flame-retardant recycled PET material and preparation method thereof |
| CN110951222A (en) * | 2019-12-06 | 2020-04-03 | 江苏垶恒复合材料有限公司 | High-impact-resistance regenerated PET material and preparation method thereof |
| CN110964188A (en) * | 2019-11-25 | 2020-04-07 | 浙江佳人新材料有限公司 | Production method of cyclic regeneration cation slice |
| CN112574404A (en) * | 2020-12-27 | 2021-03-30 | 扬州普立特科技发展有限公司 | Production device for producing PBT by recycling polyester to generate DMT |
| CN114044892A (en) * | 2021-12-02 | 2022-02-15 | 浙江佳人新材料有限公司 | Process for producing film-grade copolyester chips by chemical cyclic regeneration method |
| US12522695B2 (en) | 2019-10-08 | 2026-01-13 | Eastman Chemical Company | Catalyst systems for crystallizable reactor grade resins with recycled content |
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| US12522695B2 (en) | 2019-10-08 | 2026-01-13 | Eastman Chemical Company | Catalyst systems for crystallizable reactor grade resins with recycled content |
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| CN110964188A (en) * | 2019-11-25 | 2020-04-07 | 浙江佳人新材料有限公司 | Production method of cyclic regeneration cation slice |
| CN110964188B (en) * | 2019-11-25 | 2022-10-28 | 浙江佳人新材料有限公司 | Production method of cyclic regeneration cation slice |
| CN110903616A (en) * | 2019-12-06 | 2020-03-24 | 江苏垶恒复合材料有限公司 | High-toughness regenerated PET material and preparation method thereof |
| CN110951223A (en) * | 2019-12-06 | 2020-04-03 | 江苏垶恒复合材料有限公司 | High-flame-retardant recycled PET material and preparation method thereof |
| CN110951222A (en) * | 2019-12-06 | 2020-04-03 | 江苏垶恒复合材料有限公司 | High-impact-resistance regenerated PET material and preparation method thereof |
| CN112574404A (en) * | 2020-12-27 | 2021-03-30 | 扬州普立特科技发展有限公司 | Production device for producing PBT by recycling polyester to generate DMT |
| CN114044892A (en) * | 2021-12-02 | 2022-02-15 | 浙江佳人新材料有限公司 | Process for producing film-grade copolyester chips by chemical cyclic regeneration method |
| CN114044892B (en) * | 2021-12-02 | 2022-09-16 | 浙江佳人新材料有限公司 | Process for producing film-grade copolyester chips by chemical cyclic regeneration method |
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