CN102675095A - Process for combining glycerol triacetate through acid ion liquid catalyst - Google Patents
Process for combining glycerol triacetate through acid ion liquid catalyst Download PDFInfo
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- CN102675095A CN102675095A CN2012101843104A CN201210184310A CN102675095A CN 102675095 A CN102675095 A CN 102675095A CN 2012101843104 A CN2012101843104 A CN 2012101843104A CN 201210184310 A CN201210184310 A CN 201210184310A CN 102675095 A CN102675095 A CN 102675095A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to a process for combining glycerol triacetate through an acid ion liquid catalyst. The process includes utilizing glycerol, acetic acid, a solvent and the catalyst as raw materials to conduct esterification reaction, then adding acetic anhydride to conduct acylation reaction, separating the solvent with excess acetic acid after the acylation reaction is finished, utilizing the mixture of the solvent and the acetic acid to serve as a raw material of the next batch, separating the mixture of the ion liquid catalyst and a glycerol triacetate product in remainders in a reaction kettle, using the ion liquid catalyst in circulation mode and removing micro acetic acid in glycerol triacetate to produce food-grade glycerol triacetate. Detailed process is shown in an instruction book. The process has the advantages that the ion liquid catalyst does not corrode equipment, and side reactions such as oxidation, carbonization and polymerization caused by a liquid strong acid catalyst are basically removed. The catalyst is repeatedly used, pollution of waste water to environment is removed, and production cost is reduced. Discharge of waste sludge and alkali liquor is removed. The process is short in flow and free of pollutant discharge and achieves clean production process. The yield of the glycerol triacetate is 99%, and acidity of the glycerol triacetate is lower than 0.002%.
Description
Technical field
The present invention relates to the fine chemical product technology, is the synthetic glycerine triacetate technology of acidic ionic liquid catalysts specifically.
Background technology
Glycerine triacetate is claimed vanay again, is a kind of oily liquids of no color or smell, nontoxic nonirritant.Its English name is Glycerol Triacetate, and molecular formula is C9H14O6, and molecular weight is 218.21.
Glycerine triacetate dissolves each other with organic solvents such as alcohol, ether, benzene, chloroforms, can dissolve macromolecular compounds such as soluble cotton, vinyl resin, PVA.Because glycerine triacetate has good pectisation and physiology inertia, by a large amount of plasticising solidifying agent, foodstuff additive, makeup fixative and lubricated matrix etc. as the cigarette filter FM.Glycerine triacetate is widely used in tobacco, food, metallurgy industry as a kind of safety non-toxic softening agent.
It is raw material that glycerine triacetate generally adopts glycerine and acetic acid, synthetic under an acidic catalyst catalysis.The synthesis technique of tradition three triacetins is: be catalyzer with the vitriol oil or tosic acid at first; Catalyzing glycerol and acetic acid carry out esterification; Esterification is used the band aqua constantly will react the water that generates simultaneously and is shifted out reaction system, promotes reaction to move to positive dirction; Fractionation by distillation goes out to be with aqua then, obtains the reaction product midbody; Again reaction product midbody and aceticanhydride are carried out acylation reaction, obtain head product; Head product is washed depickling and catalyzer, alkali neutralization, filtration, distillation obtain the finished product to reacting at last.
Though sulfuric acid or tosic acid can make reaction obtain esterification yields such as more satisfactory; And cheap, but in the reaction process because sulfuric acid etc. has stronger acidity and oxidisability, cause the generation of side reactions such as oxidation, carbonization, polymerization, rearrangement; Poor selectivity, product color is darker; Problems such as simultaneously, the vitriol oil also can produce corrosion to equipment, and is difficult to recycle, thereby causes production cost higher, and environmental protection pressure is big.
For this reason, both at home and abroad the scientific worker has carried out extensive work, improving technological process, as U.S. Pat P3108133 disclose a kind of under high temperature and low pressure condition the technology of purification glycerine triacetate; Disclose employing methyl alcohol or ethanol purification glycerine triacetate in the German Patent 156804 and 2900023 respectively and put forward the method that glycerine triacetate is made with extra care in depickling with carbonic acid gas or nitrogen gas; And employing charcoal absorption decoloring method is disclosed in the patents such as Chinese patent CN1022010330A, CN101973877A; Make with extra care glycerine triacetate; From patent report, its purpose is to reduce the acidity of product glycerine triacetate, but not from changing the synthesis technique of glycerine triacetate in essence; Still need adopt in washing, the alkali and etc. operation, thereby cause still having the discharging of great amount of wastewater and waste residue.In Chinese patent CN102020558A, disclosing is the method for the synthetic glycerine triacetate of catalyzer with the solid super-strong acid; From patent documentation see can reduce glycerine triacetate synthetic pollutant discharge amount; But in the reaction system of glycerine and the synthetic glycerine triacetate of acetic acid; Still exist water byproduct to catalyst stability influence and the influence of catalyzer physical strength under violent stirring, only provided the round-robin result in the patent documentation 10 times, and do not seen the report that related industries is used.
Summary of the invention
The objective of the invention is to overcome the weak point that exists in the prior art, and the synthetic glycerine triacetate technology of acidic ionic liquid catalysts of a kind of non-pollutant discharge, cleaner production is provided.
The object of the invention can realize through following measure: acidic ionic liquid catalysts is synthesized glycerine triacetate technology; With glycerine, acetic acid, solvent and catalyst quality ratio is 1:3-4:1.5-2.0:0.2-0.4; Add glass rectification process still; Carry out esterification, temperature of reaction is 100-150 ℃, and the reaction times is 3-4 hour;
After the esterification, then in reaction kettle, add aceticanhydride, the acid anhydrides add-on is pressed the 15-30% of initial reaction raw material qualities of glycerin, carries out acylation reaction, and temperature of reaction is 100-150 ℃, reaction times 1-2 hour, stirs 1 hour; After acylation reaction finished, under the vacuum tightness of 20-50KPa, with solvent and excessive acetic acid fractionation by distillation, solvent and vinegar stock were as the next batch raw material, and residuum is ionic-liquid catalyst and product glycerine triacetate mixture in the reaction kettle;
Ionic-liquid catalyst and product glycerine triacetate be separated in 0.67-1.3KPa, 130-150 ℃ of following vacuum distilling separates, ionic-liquid catalyst recycles;
Acetate in minute removes employing basic anion resin sorbent, base exchange capacity 4.8mmol/g, production food grade triacetyl glycerine in the product glycerine triacetate.
Described solvent is n-propyl acetate, vinyl acetic monomer organic solvent.
Described acidic ionic liquid catalysts is an alkyl imidazole sulphonate, and wherein: anionicsite is that alkyl imidazole, cationic moiety are the acidic ion liquid of alkylsulphonic acid, and decomposition temperature is at 250 ℃; The basic anion resin sorbent is a styrene polymer, is the opaque spherical particle of oyster white, and diameter is 0.315-1.25mm.
Water and solvent azeotropic that esterification generates shift out reaction system from the rectifying tower cat head that is connected with reaction kettle, promote reaction to move to positive dirction; Solvent and water do not dissolve each other, by rectifying tower solvent overhead and the direct recycle of water stratification jar; After reaction reaches the reaction times, in reaction kettle, add acid anhydrides by the 15-30% of initial reaction raw material qualities of glycerin, 100-150 ℃ of reaction is 1-2 hour again, makes part monoglyceride in the reaction intermediate, diester continue reaction generation glycerine triacetate with aceticanhydride.
The present invention compared with prior art has following advantage:
1, it is acid that ionic-liquid catalyst has strong catalysis, etching apparatus not, and basically eliminate adopts side reactions such as oxidation that liquid strong acid catalyst such as the vitriol oil causes, carbonization, polymerization, and product color is shallow, and the target product yield is high; The yield 99% of glycerine triacetate, acidity is lower than 0.002%;
2, owing to adopt ionic-liquid catalyst, to eliminate liquid acid catalyst such as employing sulfuric acid and removed washing step, catalyst recirculation is used, and has not only eliminated the contaminated wastewater environment, and has reduced production cost;
3, owing to adopt the basic anion resin to remove acetate in minute in the product, eliminate common process technology sodafining process, eliminated the discharging of waste soda residue and alkali lye;
4, flow process is short, and non-pollutant discharge is realized the production process cleaning.
Embodiment
Below in conjunction with embodiment the present invention is further specified, but therefore do not limit the present invention.
Embodiment 1
By glycerine: acetic acid: solvent: the ionic-liquid catalyst mass ratio is that 1:3:2:0.2 takes by weighing glycerine (CP) 50 g respectively; Acetic acid (CP) 150g; N-propyl acetate (CP) 100g, ionic-liquid catalyst (BILE-3; Alkyl imidazole sulphonate, bounties biomass fine chemistry industry Beijing key lab produces) 10g, add in the 500ml glass reaction still; Connect theoretical plate number on the glass reaction still and be 20 glass rectifying tower,, control the rectifying tower tower top temperature between 82-85 ℃ in the reaction 3 hours down of 100 ℃, agitation condition; React after 3 hours and in reaction kettle, to add the 7.5g aceticanhydride, continue down to react 1 hour at 100 ℃, agitation condition; After reaction finishes; Open the top vacuum pump; Keeping reactive system vacuum tightness is 50KPa; Reaction solvent n-propyl acetate and excessive acetic acid are steamed, and solvent n-propyl acetate and vinegar stock are as the next batch raw material, and residuum is catalyst ion liquid and product glycerine triacetate mixture in the reaction kettle; With reaction product glycerine triacetate and ionic liquid mixture 130g, be 0.67KPa, 130 ℃ of following vacuum distilling separating prod of temperature and catalyzer in vacuum tightness, obtain catalyzer 10.5g; Recycle; Glycerine triacetate product 119.4g, measuring acid number is 0.05%, purity 99.75%; With above-mentioned glycerine triacetate product by air speed 2.0h-1, under 40 ℃ of conditions with basic anion resin (D307, alkaline polystyrene resin; Hebei triumphant auspicious chemical industry stock company produces) refining depickling, glycerine triacetate 117.9g, measuring acid number is 0.001%; Purity is 99.85%; Satisfy the food grade triacetyl glycerine requirement, product yield 99.5% (with respect to theoretical yield, 118.5 grams).
Embodiment 2
By glycerine: acetic acid: solvent: the ionic-liquid catalyst mass ratio is that 1:3.5:1.5:0.3 takes by weighing glycerine (CP) 100 g respectively; Acetic acid (CP) 350g; N-propyl acetate (CP) 150g, ionic-liquid catalyst (BILE-3; Bounties biomass fine chemistry industry Beijing key lab produces) 30g, add in the 1000ml glass reaction still; Connect theoretical plate number on the glass reaction still and be 20 glass rectifying tower,, control the rectifying tower tower top temperature between 82-85 ℃ in the reaction 3 hours down of 120 ℃, agitation condition; React after 3 hours and in reaction kettle, to add the 20g aceticanhydride, continue down to react 1 hour at 120 ℃, agitation condition; After reaction finishes; Open the top vacuum pump; Keeping reactive system vacuum tightness is 20KPa; Reaction solvent n-propyl acetate and excessive acetic acid are steamed, and solvent n-propyl acetate and vinegar stock are as the next batch raw material, and residuum is catalyst ion liquid and product glycerine triacetate mixture in the reaction kettle; With reaction product glycerine triacetate and ionic liquid mixture 268g, be 1.0KPa, 140 ℃ of following vacuum distilling separating prod of temperature and catalyzer in vacuum tightness, obtain catalyzer 31.0g; Recycle; Glycerine triacetate product 237.0g, measuring acid number is 0.03%, purity 99.70%; Above-mentioned glycerine triacetate product by air speed 3.0h-1, is made with extra care depickling with basic anion resin (D307, the triumphant auspicious chemical industry in Hebei stock company produces) under 50 ℃ of conditions; Get glycerine triacetate 235.7g; Measuring acid number is 0.0008%, and purity is 99.90%, satisfies the food grade triacetyl glycerine requirement; Product yield 99.4% (with respect to theoretical yield, 236.9 grams).
Embodiment 3
By glycerine: acetic acid: solvent: the ionic-liquid catalyst mass ratio is that 1:4.0:2:0.4 takes by weighing glycerine (CP) 100 g respectively; Acetic acid (CP) 400g; N-propyl acetate (CP) 200g, ionic-liquid catalyst (BILE-3; Bounties biomass fine chemistry industry Beijing key lab produces) 40g, add in the 1000ml glass reaction still; Connect theoretical plate number on the glass reaction still and be 20 glass rectifying tower,, control the rectifying tower tower top temperature between 82-85 ℃ in the reaction 3 hours down of 140 ℃, agitation condition; React after 3 hours and in reaction kettle, to add the 30g aceticanhydride, continue down to react 1 hour at 140 ℃, agitation condition; After reaction finishes; Open the top vacuum pump; Keeping reactive system vacuum tightness is 30KPa; Reaction solvent n-propyl acetate and excessive acetic acid are steamed, and solvent n-propyl acetate and vinegar stock are as the next batch raw material, and residuum is catalyst ion liquid and product glycerine triacetate mixture in the reaction kettle; With reaction product glycerine triacetate and ionic liquid mixture 280g, be 1.3KPa, 150 ℃ of following vacuum distilling separating prod of temperature and catalyzer in vacuum tightness, obtain catalyzer 40.5g; Recycle; Glycerine triacetate product 239.5g, measuring acid number is 0.02%, purity 99.65%; Above-mentioned glycerine triacetate product by air speed 5.0h-1, is made with extra care depickling with basic anion resin (D307, the triumphant auspicious chemical industry in Hebei stock company produces) under 40 ℃ of conditions; Get glycerine triacetate 236.4g; Measuring acid number is 0.0007%, and purity is 99.95%, satisfies the food grade triacetyl glycerine requirement; Product yield 99.8% (with respect to theoretical yield, 236.9 grams).
Ionic-liquid catalyst circulation embodiment:
Press the condition of embodiment 3; Be glycerine: acetic acid: solvent: the ionic-liquid catalyst mass ratio is that 1:4.0:2:0.4 takes by weighing glycerine (CP) 100 g respectively; Acetic acid (CP) 400g; N-propyl acetate (CP) 200g, ionic-liquid catalyst (BILE-3, bounties biomass fine chemistry industry Beijing key lab produces) 40g add in the 1000ml glass reaction still; Connect theoretical plate number on the glass reaction still and be 20 glass rectifying tower,, control the rectifying tower tower top temperature between 82-85 ℃ in the reaction 3 hours down of 140 ℃, agitation condition; React after 3 hours and in reaction kettle, to add the 30g aceticanhydride, continue down to react 1 hour at 140 ℃, agitation condition; After reaction finishes; Open the top vacuum pump; Keeping reactive system vacuum tightness is 30KPa; Reaction solvent n-propyl acetate and excessive acetic acid are steamed, and solvent n-propyl acetate and vinegar stock are as the next batch raw material, and residuum is catalyst ion liquid and product glycerine triacetate mixture in the reaction kettle; With reaction product glycerine triacetate and ionic liquid mixture 280g, be 1.3KPa, 150 ℃ of following vacuum distilling separating prod of temperature and catalyzer in vacuum tightness, catalyst recirculation is used, and investigates the ionic-liquid catalyst life-span; With above-mentioned glycerine triacetate product by air speed 5.0h-1, under 40 ℃ of conditions with the refining depickling of basic anion resin (D307, the triumphant auspicious chemical industry in Hebei stock company produces), investigation basic resin deacidification effect, the test-results data see the following form.
Ionic-liquid catalyst and basic anion resin sorbent life-span are investigated the result
Claims (3)
1. acidic ionic liquid catalysts is synthesized glycerine triacetate technology; It is characterized in that: with glycerine, acetic acid, solvent and catalyst quality ratio is 1:3-4:1.5-2.0:0.2-0.4; Add glass rectification process still; Carry out esterification, temperature of reaction is 100-150 ℃, and the reaction times is 3-4 hour; After the esterification, then in reaction kettle, add aceticanhydride, the acid anhydrides add-on is pressed the 15-30% of initial reaction raw material qualities of glycerin, carries out acylation reaction, and temperature of reaction is 100-150 ℃, reaction times 1-2 hour, stirs 1 hour; After acylation reaction finished, under the vacuum tightness of 20-50KPa, with solvent and excessive acetic acid fractionation by distillation, solvent and vinegar stock were as the next batch raw material, and residuum is ionic-liquid catalyst and product glycerine triacetate mixture in the reaction kettle; Ionic-liquid catalyst and product glycerine triacetate be separated in 0.67-1.3KPa, 130-150 ℃ of following vacuum distilling separates, ionic-liquid catalyst recycles; Acetate in minute removes employing basic anion resin sorbent, base exchange capacity 4.8mmol/g, production food grade triacetyl glycerine in the product glycerine triacetate.
2. acidic ionic liquid catalysts according to claim 1 is synthesized glycerine triacetate technology, it is characterized in that: solvent is n-propyl acetate, vinyl acetic monomer organic solvent.
3. acidic ionic liquid catalysts according to claim 1 is synthesized glycerine triacetate technology; It is characterized in that: acidic ionic liquid catalysts is an alkyl imidazole sulphonate; Wherein: anionicsite is that alkyl imidazole, cationic moiety are the acidic ion liquid of alkylsulphonic acid, and decomposition temperature is at 250 ℃; The basic anion resin sorbent is a styrene polymer, is the opaque spherical particle of oyster white, and diameter is 0.315-1.25mm.
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| CN2012101843104A CN102675095A (en) | 2012-06-06 | 2012-06-06 | Process for combining glycerol triacetate through acid ion liquid catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880664A (en) * | 2014-04-08 | 2014-06-25 | 云南省玉溪市溶剂厂有限公司 | Method for producing high-purity and low-residue glycerol triacetate |
| CN106045852A (en) * | 2016-07-04 | 2016-10-26 | 宜兴市永加化工有限公司 | Preparation method of glycerol triacetate |
-
2012
- 2012-06-06 CN CN2012101843104A patent/CN102675095A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880664A (en) * | 2014-04-08 | 2014-06-25 | 云南省玉溪市溶剂厂有限公司 | Method for producing high-purity and low-residue glycerol triacetate |
| CN103880664B (en) * | 2014-04-08 | 2016-05-25 | 云南省玉溪市溶剂厂有限公司 | The production method of the triacetyl glycerine of a kind of high-purity, low-residual |
| CN106045852A (en) * | 2016-07-04 | 2016-10-26 | 宜兴市永加化工有限公司 | Preparation method of glycerol triacetate |
| CN106045852B (en) * | 2016-07-04 | 2019-01-22 | 宜兴市永加化工有限公司 | A kind of preparation method of triacetyl glycerine |
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