CN101914003A - Method for producing aromatic carboxylic acids by liquid-phase catalytic oxidation of alkyl aromatics - Google Patents
Method for producing aromatic carboxylic acids by liquid-phase catalytic oxidation of alkyl aromatics Download PDFInfo
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- CN101914003A CN101914003A CN2010102169571A CN201010216957A CN101914003A CN 101914003 A CN101914003 A CN 101914003A CN 2010102169571 A CN2010102169571 A CN 2010102169571A CN 201010216957 A CN201010216957 A CN 201010216957A CN 101914003 A CN101914003 A CN 101914003A
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Abstract
The invention discloses a method for producing aromatic carboxylic acids by the liquid-phase catalytic oxidation of alkyl aromatics, which comprises a process of oxidizing by an oxygen-containing gas in an acetic acid-containing solvent and in the presence of a cobalt-manganese-bromine ternary catalytic system. The method is characterized in that: the solvent is a mixed solvent of 2 to 4 of acetic acid, methanol, methyl acetate and water; and aromatic carboxylic acids products are obtained by the oxidation of the alkyl aromatics at 150 to 220 DEG C and under 0.5 to 1.5MPa. In the invention, cheaper methanol or methyl acetate replaces part of an acetic acid solvent, so the consumption of the acetic acid raw material is reduced, the production cost is reduced, and economic benefit is improved.
Description
Technical field
The invention belongs to and have the technical field that the oxidation of side chain arenes catalytic prepares aromatic carboxylic acid, relate to a preparation method who is connected aromatic ring with a plurality of carboxylic acid groups, relate to the technology of liquid phase catalytic oxidation simultaneously.
Background technology
Since (US 2245528) of producing aromatic carboxylic acids by liquid-phase catalytic oxidation of alkyl aromatics occurred, this method was extensive use of industrial.This method adopts cobalt-manganese-bromine ternary complex catalyst, and employing acetic acid is solvent, and temperature of reaction is 100～320 ℃.Using the product that this method commercially produces has a lot, as terephthalic acid, m-phthalic acid, phthalic acid, naphthalic acid, 4,4 '-biphenyl carboxylic acids two and phenylformic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic anhydride, 1,3,5-benzenetricarboxylic acid, pyromellitic dianhydride, benzene pentacarbonic acid and benzene hexacarboxylic acid.Wherein that the industrial scale maximum is pure terephthalic acid (PTA).
In pure terephthalic acid (PTA) production process, the acetate solvate of a part can be become carbonic acid gas, carbon monoxide, ritalin and water etc. by deep oxidation by decarboxylic reaction, and the acetic acid consumption that this burning reaction causes is referred to as " acetic acid consumption " in industry." acetic acid consumption " can increase raw material consumption and the cost in the PTA production, is the important indicator that should strictly control in the PTA production process, also is the key of PTA production cost control.
In order to reduce " acetic acid consumption " in the aromatic carboxylic acid production process, a large amount of technological improvement measure and novel method have appearred at present.The method that has is to reduce the burning reaction of acetic acid by the change of reaction conditions, as reduce temperature of reaction, reduce the tail gas oxygen concn, improve agitation condition, adjust cobalt-manganese-bromine catalyst ratio and concentration etc., though these methods can reduce " acetic acid consumption ", but the amplitude that reduces is limited but also can influence other indicator reactions, as speed of reaction, quality product, catalyst consumption etc.To reduce that acetic acid burning consumes also be a kind of effective means by adding the 4th kind of catalyst component, discloses by adding nitrogenous compound as patent CN200310106324.5, CN200310106325.X, CN200610085515.1 and reduced the method that the acetic acid burning consumes.The method that also has reduces " acetic acid consumption " by reclaiming acetic acid burning consumption product ritalin component exactly, as CN200610124556.7, CN200510019677.0, CN200510094162.7, CN200510038560.7 and CN00813072.8 etc.The method of these patent disclosures is exactly the ritalin component that at first generates by the method enrichment side reaction of washing or adsorbing; Can reclaim the ritalin straight product by rectifying then; Returning oxidation reactor also can directly circulate the ritalin crude product that reclaims; The hydrolysate rectifying of ritalin crude product can also be used as solvent with the acetic acid Returning reactor that reclaims wherein.
Yet the aforesaid method effect is all not satisfactory, can't obviously and effectively reduce the burning reaction of acetic acid, cuts down the consumption of raw materials and production cost.
Summary of the invention
The objective of the invention is to improve existing aromatic carboxylic acid production method, propose a kind of method that acetate solvate consumes that reduces.
The present invention relates to a kind of method that acetate solvate consumes in the liquid phase catalytic oxidation production aromatic carboxylic acid process that reduces.This method adopts methyl alcohol or ritalin partly to substitute acetate solvate, and general acetic acid-water solvent is become acetic acid, methyl alcohol, ritalin and water multiple mixed solvent; Adopt cobalt-manganese-bromine three-element catalytic system; Adopting the gas of oxygen-containing molecules is oxygenant, and the alkyl aromatics oxidation obtains the aromatic carboxylic acid product under 150～220 ℃, 0.5～1.5MPa.This method can effectively reduce the acetic acid burning and consume, and reduces aromatic carboxylic acid's production cost.
Among the present invention, said multiple mixed solvent is the binary mixture of acetic acid+methyl alcohol, the binary mixture of acetic acid+ritalin, the tertiary mixture of acetic acid+methyl alcohol+water, the tertiary mixture of acetic acid+ritalin+water or the quaternary mixture of acetic acid+methyl alcohol+ritalin+water, wherein the tertiary mixture of the tertiary mixture of acetic acid+methyl alcohol+water or acetic acid+ritalin+water preferably.
Among the present invention, said mixed solvent consists of: the mass percent of methyl alcohol is 0～10%, and the mass percent of ritalin is 0～40%, and the mass percent of water is 0～10%, and all the other are acetic acid.Methyl alcohol, ritalin and water can not be 0 simultaneously.In fact also produce water when the alkylaromatic hydrocarbon oxidation, this can see in the analysis of producing mother liquor.
Among the present invention, said cobalt-manganese-bromine three-element catalytic system is the mixture of Cobaltous diacetate, manganese acetate and hydrogen bromide.Wherein: the Co/Mn mol ratio is 0.2～20, and the Br/Co+Mn mol ratio is 0.5～2.0, and the concentration of cobalt is 100～2000ppm of solvent quality.The gas of said oxygen-containing molecules comprises air, oxygen-rich air and pure oxygen.
Among the present invention, said alkyl aromatics reactant can be selected from toluene, p-Xylol, m-xylene, o-Xylol, dimethylnaphthalene, 4,4 '-dimethyl diphenyl, pseudocumol (1,2,4-Three methyl Benzene), sym-trimethylbenzene (1,3, the 5-trimethylbenzene), durene (1,2,4,5-tetramethyl-benzene), pentamethylbenzene or hexamethyl-benzene.
Among the present invention, said aromatic carboxylic acid product can be selected from phenylformic acid, terephthalic acid, m-phthalic acid, phthalic acid, naphthalic acid, 4,4 '-diphenyl dicarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic dianhydride, benzene pentacarbonic acid or benzene hexacarboxylic acid.
Beneficial effect of the present invention is: the present invention adopts more cheap methyl alcohol or ritalin partly to substitute acetate solvate, can also reduce acetic acid raw material consumption, reduces production costs, and increases economic efficiency.
Below the invention will be further described with embodiment.
Embodiment
The experiment of the p xylene oxidation of related employing methyl alcohol, ritalin, acetic acid and water mixed solvent is all carried out in same batch-type experimental installation among the following embodiment.Autoclave in this dress system is the titanium material, and volume is 500ml, and the reaction solution that each experiment is packed into is about 300ml mutually.The outer wall of reactor and bottom be by electrically heated, 1.2 kilowatts of heating powers, and the outside of electrically heated cover is surrounded by thermal insulation material, to reduce the heat radiation of still wall.Spiral coil cooling tube is installed in the still, interior admittance deep fat, the flow of thermal oil is by the rotating speed control of peristaltic pump.Stirring rake is the flat oars of four leaves, disperses and the mass transfer requirement to guarantee good bubble, and stirring velocity is about 900rpm in the experiment.Inlet pipe is below blade, and the flow of air is by the micrometering valve hand control at reactor inlet place, and flow is generally 10L/min.Reaction pressure is controlled by back pressure valve, and reaction end gas will be through multi-stage condensing and deep cooling before being discharged by the back pressure valve decompression, and lime set is back in the reactor.The tail gas of being discharged by back pressure valve enters oxygen concn, CO and CO in online magnetic oxygen analyser and the infrared on line analyzer analysis tail gas respectively behind further cryodrying
2Concentration, the tail gas concentration data carries out data acquisition-and-recording by computer.Can obtain the index of correlation of main reaction and burning reaction according to these data.
Embodiment 1
In the present embodiment, be the reaction mass that 500 milliliters of titanium material autoclaves add about 300ml earlier to volume, feed nitrogen as protection gas, with reaction solution heat temperature raising to 190 ℃, pressure rises to 2.0MPa in stirring.Mainly consisting of of the reaction mass of 308g (promptly about 300ml reaction mixture): the methyl alcohol of the p-Xylol of 28.0g (263mmol), 14.0g (438mmol) and the acetic acid of 266.0g (4.43mol), wherein the mass ratio of p-Xylol and mixed solvent is 1/10, and methyl alcohol accounts for 5.0% (wt%) of mixed solvent.The catalyst concn of Tian Jiaing is the cobalt of 400ppm, the manganese of 373ppm and the bromine (ppm is a benchmark with the mixed solvent total mass all, and wherein the mol ratio of cobalt, manganese, bromine is 1: 1: 1) of 542ppm simultaneously.Use Cobalt diacetate tetrahydrate, four water acetic acid manganese and hydrogen bromide as catalyzer.It is that 190 ℃, pressure are to carry out under the condition of 2.0MPa that p xylene oxidation is reflected at temperature, feeds high-pressure air in the reaction process continuously, and the constant air flow is 10L/min.When reaching 21%, finishes the reaction end gas oxygen concn reaction (, illustrating that reaction finishes), cooling, step-down, cooling because reaction process does not have oxygen consumption.By taking out reacted liquid-solid mixture in the reactor, filter to isolate terephthalic acid solid product and mother liquor, solid and mother liquor sample are used for further sign.Colourity by solid sample can be estimated the terephthalic acid solid quality product.Acetic acid in the mother liquor sample, methyl alcohol, ritalin, xylene concentration are drawn by gas chromatographic analysis, water concentration Ka Er-take and stop titration measuring.The chromatographic instrument that is adopted is GC-1690 dawn of section, and Ka Er-taking not, volumetry adopts the KF-1 moisture determination instrument.Can calculate the oxygen consumption rate and different total oxygen-consumption constantly of reaction process by tail gas oxygen concn data and exhaust flow, by tail gas CO and CO
2Concentration data can calculate reaction process CO and CO respectively
2Generating rate and total growing amount.Time of 95% of generally getting oxygen-consumption and be theoretical oxygen-consumption (789mmol), getting this time was main reaction speed index, is called " reaction concluding time " as the response feature time; Get CO in this time
2Generate total amount as the burning reaction index with CO, be referred to as " CO
XGrowing amount ".
Oxygen-consumption is 18.3 minutes to " the reaction concluding time " of theoretical total oxygen-consumption 95% among this embodiment; " CO
XGrowing amount " be 88.3mmol; Consisting of of reaction mother liquor: methyl alcohol 0.10%, ritalin 4.14%, acetate concentration are 85.9%, water concentration is 9.77%.All experimental results are summarized in table 1 and table 2.
Embodiment 2
The mode identical with embodiment 1 carried out the oxidizing reaction of p-Xylol, just adopting acetic acid separately in embodiment 2 is solvent, be mainly the consisting of of reaction mass of 308g: the acetic acid of the p-Xylol of 28.0g (263mmol) and 280.0g (4.67mol), wherein the mass ratio of p-Xylol and pure acetate solvate is 1/10.The reaction concluding time is 17.5 minutes; CO
XGrowing amount is 108mmol; After reaction finished, water concentration was 4.65% in the reaction mother liquor, and other are acetic acid, do not detect ritalin and methyl alcohol.Experimental result is summarized in table 1 and table 2.
Embodiment 3
Method is that the mixed solvent composition that is adopted makes the methyl alcohol of 28.0g (875mmol) and the acetic acid of 252g (4.20mol) into embodiment 1, and correlated results in contrast to table 1 and table 2.
Embodiment 4
Method is that the mixed solvent composition that is adopted makes the ritalin of 32.4g (438mmol) and the acetic acid of 247.6g (4.126mol) into embodiment 1, and correlated results in contrast to table 1 and table 2.
Embodiment 5
Method is that the mixed solvent composition that is adopted makes the water of 14.0g (438mmol) and the acetic acid of 266g (4.43mol) into embodiment 1, and correlated results in contrast to table 1 and table 2.
Reaction times and CO under the table 1. different blended bonding solvent
xGrowing amount
| Embodiment | Acetic acid (g) | Methyl alcohol (g) | Ritalin (g) | Water (g) | Reaction times (min) | COx growing amount (mmol) |
| 1 | 266 | 14.0 | 0 | 0 | 18.5 | 88.5 |
| 2 | 280 | 0 | 0 | 0 | 17.5 | 108 |
| 3 | 252 | 28.0 | 0 | 0 | 19.2 | 60.0 |
| 4 | 247.6 | 0 | 32.4 | 0 | 18.1 | 90.5 |
| 5 | 266 | 0 | 0 | 14.0 | 18.7 | 101 |
Solid product color under the table 2 different blended bonding solvent and mother liquor are formed
In comparative example 1,2 and 3 the table 1 result as can be known, high concentration methanol partly substitutes acetic acid can significantly reduce COx growing amount in the p xylene oxidation process, reduces the burning consumption of acetate solvate.If methyl alcohol substitutes acetic acid excessive (being substituted by methyl alcohol as 10% acetic acid among the embodiment 3), though the COx growing amount reduces significantly, also can reduce main reaction speed simultaneously, and can cause the terephthalate product blackening.To analyzing with surperficial X diffraction method after the black precipitate filtering separation, the discovery main component is MnO
2, this is the product of the precipitation generation of catalyzer manganese.
The result adopts methyl alcohol to substitute acetic acid as can be known in 1,2 and 3 the table 2 in conjunction with the embodiments, and most of methyl alcohol finally can combine with acetic acid and generate water and ritalin, and the concentration that methyl alcohol exists is very low.
Comparative example 1,2 and 4 result also as can be known, high density acetic acid methyl esters partly substitutes acetic acid also can significantly reduce COx growing amount in the p xylene oxidation process, reduces the burning consumption of acetate solvate, but also can not influence the color of product.
Comparative example 1,2 and 5 result also can reduce COx growing amount in the oxidising process by a small margin though adopt 5% water to substitute acetate solvate also as can be known, can observe solid phase prod color burnt hair.
In sum, methyl alcohol partly substitutes acetic acid can effectively reduce COx growing amount in the p xylene oxidation process, thereby reaches the purpose of the burning consumption that reduces acetate solvate.Because methyl alcohol and acetic acid combination easily generate ritalin and water, and adopt ritalin or water all can reduce the COx growing amount separately, so can think that it is the coefficient effect of ritalin and water that methyl alcohol reduces the effect that consumes of burning.
The ritalin that the alternative acetic acid of a large amount of methyl alcohol produces can reduce water significantly and may bring two kinds of effects: can reduce COx growing amount in the reaction process significantly on the one hand, reduce the burning consumption of acetic acid; Too high on the other hand water can cause catalyzer manganese precipitation to make the product blackening.So methyl alcohol substitutes the acetic acid amount can not be excessive, should be controlled at low water gaging and put down.
Embodiment 6
Method is that the mixed solvent composition that is adopted makes the methyl alcohol of 5.60g (175mmol) and the acetic acid of 274.4g (4.573mol) into embodiment 1, and correlated results in contrast to table 3 and table 4.
Embodiment 7
Method is that the mixed solvent composition that is adopted makes the methyl alcohol of 2.80g (87.5mmol) and the acetic acid of 277.2g (4.62mol) into embodiment 1, and correlated results in contrast to table 3 and table 4.
Table 3 lower concentration methyl alcohol replaces reaction times and the COx growing amount under the acetic acid condition
| Embodiment | Acetic acid (g) | Methyl alcohol (g) | Reaction times (min) | COx growing amount (mmol) |
| 1 | 266 | 14.0 | 18.5 | 88.5 |
| 2 | 280 | 0 | 17.5 | 108 |
| 6 | 274.4 | 5.60 | 17.8 | 86.6 |
| 7 | 277.2 | 2.80 | 17.6 | 98.1 |
Table 4. lower concentration methyl alcohol replaces solid product color and the mother liquor under the acetic acid condition
Comparative example 1,2,6 and 7 results as can be known, it is not only less to the influence of main reaction speed that a spot of methyl alcohol partly substitutes acetic acid, and can reduce COx growing amount in the tail gas in the p xylene oxidation process in various degree, reduces the consumption of acetic acid incendiary.On low water gaging was flat, methyl alcohol replacement amount was many more, and it is just big more that the COx growing amount reduces amplitude, and the partly alternative acetic acid of lower concentration methyl alcohol does not influence the TA quality product.
In a word, the invention discloses a kind of method that acetate solvate consumes in the aromatic carboxylic acid production that reduces.This method adopts methyl alcohol or ritalin partly to substitute acetate solvate, can reduce the burning reaction of acetic acid, reduces acetate solvate consumption.This method can be used in oxidation or purification of alkyl aromatic hydrocarbon comes in the various industrial application processes of production aromatic acid product, and carries out condition optimizing at different reaction process.
Claims (7)
1. an alkyl aromatics liquid phase catalytic oxidation is produced aromatic carboxylic acid's method, be included in the solvent that contains acetic acid, the technology of carrying out oxidation with oxygen-containing gas under cobalt-manganese-bromine three-element catalytic system catalysis, it is characterized in that described solvent is 2～4 kinds a mixed solvent in acetic acid, methyl alcohol, ritalin and the water, the alkyl aromatics oxidation obtains the aromatic carboxylic acid product under 150～220 ℃, 0.5～1.5MPa.
2. produce aromatic carboxylic acid's method according to the described a kind of alkyl aromatics liquid phase catalytic oxidation of claim 1, it is characterized in that described mixed solvent is a kind of in the quaternary mixture of the tertiary mixture of tertiary mixture, acetic acid+ritalin+water of binary mixture, the acetic acid+methyl alcohol+water of binary mixture, the acetic acid+water of binary mixture, the acetic acid+ritalin of acetic acid+methyl alcohol or acetic acid+methyl alcohol+ritalin+water.
3. produce aromatic carboxylic acid's method according to the described a kind of alkyl aromatics liquid phase catalytic oxidation of claim 1, it is characterized in that described mixed solvent consists of: the mass percent of methyl alcohol is 0～10%, the mass percent of ritalin is 0～40%, the mass percent of water is 0～10%, and all the other are acetic acid; Methyl alcohol, ritalin and water can not be 0 simultaneously.
4. produce aromatic carboxylic acid's method according to the described a kind of alkyl aromatics liquid phase catalytic oxidation of claim 1, it is characterized in that the gas of described oxygen-containing molecules comprises air, oxygen-rich air or oxygen.
5. produce aromatic carboxylic acid's method according to the described a kind of alkyl aromatics liquid phase catalytic oxidation of claim 1, it is characterized in that described cobalt-manganese-bromine three-element catalytic system is the mixture of Cobaltous diacetate, manganese acetate and hydrogen bromide;
Wherein: the Co/Mn mol ratio is 0.2～20, and the Br/Co+Mn mol ratio is 0.5～2.0, and the concentration of cobalt is 100～2000ppm of solvent quality.
6. produce aromatic carboxylic acid's method according to the described a kind of alkyl aromatics liquid phase catalytic oxidation of claim 1, it is characterized in that described alkyl aromatics can be selected from toluene, p-Xylol, m-xylene, o-Xylol, dimethylnaphthalene, 4,4 '-dimethyl diphenyl, pseudocumol (1,2,4-Three methyl Benzene), sym-trimethylbenzene (1,3, the 5-trimethylbenzene), durene (1,2,4,5-tetramethyl-benzene), pentamethylbenzene or hexamethyl-benzene.
7. produce aromatic carboxylic acid's method according to the described a kind of alkyl aromatics liquid phase catalytic oxidation of claim 1, it is characterized in that described aromatic carboxylic acid product can be phenylformic acid, terephthalic acid, m-phthalic acid, phthalic acid, naphthalic acid, 4,4 '-diphenyl dicarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic dianhydride, benzene pentacarbonic acid or benzene hexacarboxylic acid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012121A (en) * | 2011-09-21 | 2013-04-03 | 北京理工大学 | Method for synthesizing biphenyl 4,4'-dicarboxylic acid from p-chlorotoluene |
| CN103420909A (en) * | 2012-05-16 | 2013-12-04 | 中国中化股份有限公司 | Liquid-phase catalytic oxidation quinclorac preparation method |
| CN106349048A (en) * | 2016-08-26 | 2017-01-25 | 浙江大学 | Method and apparatus for producing isophthalic acid by m-xylene oxidization |
| CN106423294A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidization |
| CN108299182A (en) * | 2018-02-02 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of method that meta-xylene and paraxylene mixed oxidization prepare phthalic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1551865A (en) * | 2001-09-07 | 2004-12-01 | ¡ | Process for the production of 2,6-naphthalenedicarboxylic acid |
| CN1751015A (en) * | 2003-02-21 | 2006-03-22 | 三菱化学株式会社 | Method for producing aromatic carboxylic acid |
-
2010
- 2010-07-02 CN CN2010102169571A patent/CN101914003A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1551865A (en) * | 2001-09-07 | 2004-12-01 | ¡ | Process for the production of 2,6-naphthalenedicarboxylic acid |
| CN1751015A (en) * | 2003-02-21 | 2006-03-22 | 三菱化学株式会社 | Method for producing aromatic carboxylic acid |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012121A (en) * | 2011-09-21 | 2013-04-03 | 北京理工大学 | Method for synthesizing biphenyl 4,4'-dicarboxylic acid from p-chlorotoluene |
| CN103420909A (en) * | 2012-05-16 | 2013-12-04 | 中国中化股份有限公司 | Liquid-phase catalytic oxidation quinclorac preparation method |
| CN103420909B (en) * | 2012-05-16 | 2016-05-18 | 中国中化股份有限公司 | A kind of liquid phase catalytic oxidation is prepared the method for dichloro quinolinic acid |
| CN106423294A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidization |
| CN106423294B (en) * | 2015-08-12 | 2019-01-25 | 中国石油化工股份有限公司 | Liquid phase oxidation prepares catalyst used in polycarboxylic aromatic acids |
| CN106349048A (en) * | 2016-08-26 | 2017-01-25 | 浙江大学 | Method and apparatus for producing isophthalic acid by m-xylene oxidization |
| CN106349048B (en) * | 2016-08-26 | 2019-03-15 | 浙江大学 | A kind of method and device of meta-xylene oxidation production M-phthalic acid |
| CN108299182A (en) * | 2018-02-02 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of method that meta-xylene and paraxylene mixed oxidization prepare phthalic acid |
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Application publication date: 20101215 |