CN103121942A - Method for hydrofining crude terephthalic acid - Google Patents
Method for hydrofining crude terephthalic acid Download PDFInfo
- Publication number
- CN103121942A CN103121942A CN2011103695757A CN201110369575A CN103121942A CN 103121942 A CN103121942 A CN 103121942A CN 2011103695757 A CN2011103695757 A CN 2011103695757A CN 201110369575 A CN201110369575 A CN 201110369575A CN 103121942 A CN103121942 A CN 103121942A
- Authority
- CN
- China
- Prior art keywords
- isophthalic acid
- activated carbon
- modified activated
- hydrofinishing
- coarse isophthalic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for hydrofining crude terephthalic acid, and the method is mainly used for solving a poor hydrogenation effect problem caused by easily lost metal pd in a catalyst of the prior art. The method adopts a technical scheme that modified activated carbon which is obtained after treatment, contains a silicon compound and is shown in the following formula is taken as a carrier and contains Si and N, Si in the modified activated carbon accounts for 0.10-0.35% in weight percent, the molar ratio of Si to N is (0.5-1.0):1, wherein R1 is-CH3 or-CH2CH3, R2 is selected from-(CH2) n1-NH2 or-(CH2) n2-NH-(CH2) n3-NH2, wherein n1, n2 and n3 are integers between 1 and 3. The method can be utilized for better solving the problem and used for refined crude terephthalic acid industrial production.
Description
Technical field
The present invention relates to a kind of method of hydrofinishing of coarse isophthalic acid.
Background technology
The Pd/C catalyzer is a kind of hydrogenation catalyst commonly used, is mainly used in the selective hydrogenation of unsaturated compounds.Contain a certain amount of by-product impurities in the coarse isophthalic acid that is obtained by the m-xylene oxidation, in the middle of it, existence of carboxyl benzaldehyde (3-CBA) affect quality and the color and luster of polyester, and is difficult to common crystallization method removal.Carry out selective hydrogenation with palladium/charcoal (being called for short Pd/C) catalyzer, make the 3-CBA selective hydrogenation change m-methyl benzoic acid into, then through Crystallization Separation, obtain 3-CBA less than the fibre-grade PTA of 25ppm, what play a major role is the palladium active ingredient.
Patent CN101347729A discloses a kind of hydrofinishing of coarse isophthalic acid method, the Pd/C catalyzer that the method adopts is in preparation process, absorbent charcoal carrier is flooded with the aqueous solution that contains nitrite ion, for example with the sodium nitrite solution of nitrite ion, then prepare palladium mixed solution dipping or spray the catalyzer that this carrier active carbon obtains the hydrofining coarse isophthalic acid, the catalyzer that this hydrofinishing process adopts in use metal Pd easily runs off, cause catalyst activity low, the hydrogenation weak effect.
Summary of the invention
Technical problem to be solved by this invention is the problem of the hydrogenation weak effect that exists in prior art, a kind of hydrofinishing of coarse isophthalic acid method is provided, and the Pd/C catalyzer that the method adopts in use has the characteristics that metal Pd is difficult for running off, activity is high, hydrogenation is effective.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of hydrofinishing of coarse isophthalic acid method, take the coarse isophthalic acid slurry as reaction raw materials, contact with the Pd/C catalyzer to react under the 210 ℃～temperature of reaction of 250 ℃ and the reaction pressure of 2.3～3.2MPa under hydrogen exists and obtain hydrotreated product; Wherein said Pd/C catalyzer contains Pd 0.20～2.50% by weight percentage, and surplus is the modified activated carbon carrier; Wherein said modified activated carbon carrier contains Si and N, and the content of Si in the modified activated carbon carrier is 0.10～0.35% by weight percentage, and the mol ratio of Si/N is 0.5～1.0: 1, and described modified activated carbon carrier adopts the following steps preparation:
A) take water as solvent, the silicon-containing compound shown in formula I is made into steeping fluid II,
Wherein, R
1For-CH
3Perhaps-CH
2CH
3, R
2Be selected from-(CH
2) n
1-NH
2Perhaps-(CH
2) n
2-NH-(CH
2) n
3-NH
2, n wherein
1, n
2, n
3It is 1～3 integer;
B) with steeping fluid II dipping cocoanut active charcoal, 60～150 ℃ of lower thermal treatments 0.5～12 hour, drying got described modified activated carbon carrier.
R in technique scheme
2Be preferably-(CH
2) n
2-NH-(CH
2) n
3-NH
2, the mol ratio of Si/N is preferably 0.5: 1, more preferably n
2=2, n
3=3; Step b) thermal treatment temp in is preferably 80～110 ℃; Step b) heat treatment time in is preferably 0.5～4 hour; Described coarse isophthalic acid contains by weight 3-CBA and is preferably 3.0～3.5%; By weight the feed ratio of described coarse isophthalic acid and pure water be preferably 1: 8～10; By weight the feed ratio of described Pd/C catalyzer and coarse isophthalic acid be preferably 1: 10～15.
In order to investigate the Pd/C catalyst performance of above-mentioned modified activated carbon carrier preparation, with catalyzer Hanging Basket 10 months in production equipment, and the catalyst performance after to Hanging Basket carries out activity rating with autoclave.
Key of the present invention is that it is the catalyzer of carrier that hydrofining reaction has adopted by modified activated carbon, described modified activated carbon contains Si and amino, Si and gac matrix have the grappling effect, and amino has complexing action to Pd, Pd/C catalyzer in use metal Pd is difficult for running off, thereby has improved the hydrofining effect.Experiment shows, after the catalyzer that the inventive method adopts is tested through 10 months Hanging Baskets, the Pd turnover rate is not more than 16%, the 3-CBA transformation efficiency of catalyzer is up to 99.8%, and the catalyzer that art methods adopts after Hanging Basket experiment in 10 months the Pd turnover rate up to 24%, the 3-CBA transformation efficiency of catalyzer is only 66.7%, so the present invention has obtained technique effect preferably.
The invention will be further elaborated below by embodiment.Described silicon-containing compound all can be buied from market, and for sake of convenience, the numbering of silicon-containing compound described in embodiment is as follows: R
1For-CH
3, n
1Be designated as compd A at=2 o'clock; R
1For-CH
2CH
3, n
2=2, n
3Be designated as compd B at=2 o'clock; R
1For-CH
3, n
2=2, n
3Be designated as Compound C at=3 o'clock.
Embodiment
[embodiment 1]
(1) modified activated carbon preparation
Get 1.80 and digest compound A and be dissolved in 50 ml waters, 1000 meters of dipping 100 gram 4～8 orders, specific surfaces
2The cocoanut active charcoal of/gram, 110 ℃ of thermal treatments of temperature 4 hours, drying was 6 hours under 120 ℃, gets modified activated carbon carrier of the present invention.Adopt the N element in German Vario EL III type elemental analyser mensuration modified activated carbon carrier, using plasma Atomic Emission SpectrometerAES (ICP-AES) is measured the Si element in the modified activated carbon carrier.Table 1 has provided the main preparation condition of modified activated carbon and Si content, the Si/N mol ratio of modified activated carbon.
(2) catalyzer preparation
Get chlorine palladium acid solution 3.13 grams that contain palladium 16% (weight) and be diluted with water to 50 milliliters, with 8% (weight) sodium carbonate solution be adjusted to pH be 3.0 palladium mixed liquor I II.With the 100 gram modified activated carbons that obtain in palladium mixed liquor I II impregnation steps (1), using the ratio (being called for short Si/Pd (mol ratio)) of the mole number of Pd when in modified activated carbon, the mole number of Si is with Kaolinite Preparation of Catalyst at this moment is 2.5, makes catalyst precursor.Catalyst precursor was placed aging 24 hours, and then under 200 ℃, in hydrogen, reduction is 6 hours, is cooled to room temperature, washs extremely without CL with pure water at last
-Till, namely get the Pd/C catalyzer after drying.In catalyzer, Pd content is recorded by plasma atomic emission spectrometer (ICP-AES) analysis, and table 2 has provided main preparation condition and the catalyst P d content of catalyzer.
(3) experiment of the Hanging Basket of catalyzer and activity rating
The evaluating catalyst method that the inventive method obtains is: the live catalyst sample is carried out Hanging Basket experiment 10 months on the refining production equipment of coarse isophthalic acid, the cradle test processing condition are 220 ℃ of temperature of reaction, pressure 2.8MPa, take off the Hanging Basket rear catalyst after 10 months and carry out palladium assay and autoclave activity rating, the activity rating condition is:
Catalyzer: 2.0 grams
Coarse isophthalic acid (by weight, containing 3-CBA 3.3%): 30.0 grams, namely the feed ratio of catalyzer and coarse isophthalic acid is 1: 15 by weight
Pure water: 270 grams, namely the feed ratio of coarse isophthalic acid and pure water is 1: 9 by weight
Reaction pressure: 2.5MPa
Temperature of reaction: 220 ℃
Adopt 3-CBA content after the high pressure liquid chromatographic analysis reaction, the activity of Hanging Basket rear catalyst represents with the transformation efficiency of 3-CBA, and the transformation efficiency calculation formula of 3-CBA is as follows:
Catalyst P d content after Hanging Basket is recorded by plasma atomic emission spectrometer (ICP-AES) analysis.Table 3 has provided the 3-CBA transformation efficiency of Pd content, Pd turnover rate, activity rating pressure, activity rating temperature and the Hanging Basket rear catalyst of catalyst P d content, Hanging Basket rear catalyst.
[embodiment 2～15]
(1) modified activated carbon preparation
Except adopting 1300 meters
2Beyond the cocoanut active charcoal of/gram, silicon-containing compound kind and consumption variation, thermal treatment temp and time changed, all the other operation stepss were with embodiment 1.Table 1 has provided the main preparation condition of modified activated carbon and Si content, the Si/N mol ratio of modified activated carbon.
(2) catalyzer preparation
Except adopting the modified activated carbon in step (1), beyond the pH of Pd compound, the Pd compound solution consumption that contains palladium 16% (weight), palladium mixed liquor I II and mode difference that catalyst precursor is reduced, all the other operation stepss are with embodiment 1.The mode that catalyst precursor reduces is: the precursor of catalyzer is mixed with reduced liquid with hydrazine hydrate 20 grams and pure water 200 grams of 5% (weight), catalyst precursor is immersed in reduced liquid at room temperature reductase 12 hour, then with the pure water washing to neutral and in addition after drying catalyst prod.Table 2 has provided main preparation condition and the catalyst P d content of catalyzer.
(3) experiment of the Hanging Basket of catalyzer and activity rating
Except catalyzer, activity rating pressure and the activity rating temperature that adopts changed, all the other operation stepss were with implementing 1.Table 3 has provided the 3-CBA transformation efficiency of Pd content, Pd turnover rate, activity rating pressure, activity rating temperature and the Hanging Basket rear catalyst of catalyst P d content, Hanging Basket rear catalyst.
[embodiment 16～18]
(1) modified activated carbon preparation
Except silicon-containing compound kind and consumption variation, all the other operation stepss are with embodiment 1.Table 1 has provided the main preparation condition of modified activated carbon and elements Si content, the Si/N mol ratio of modified activated carbon.
(2) catalyzer preparation
Adopting above-mentioned modified activated carbon is carrier, and Si/Pd (mol ratio) is 4.5, and the pH of palladium mixed liquor I II is beyond 5.8, and all the other preparation processes are with embodiment 1.Table 2 has provided main preparation condition and the catalyst P d content of catalyzer.
(3) experiment of the Hanging Basket of catalyzer and activity rating
Except the catalyzer that adopts changed, all the other operation stepss were with implementing 1.Table 3 has provided the 3-CBA transformation efficiency of Pd content, Pd turnover rate, activity rating pressure, activity rating temperature and the Hanging Basket rear catalyst of catalyst P d content, Hanging Basket rear catalyst.
[comparative example 1]
According to CN101347729A
(1) gac preparation
With 1000 meters of 100 gram 4～8 orders, specific surfaces
2The cocoanut active charcoal of/gram washed 4 hours with the nitric acid of 0.1 mol/L, then was washed till neutrality with deionized water, drained, and drying is 6 hours under 120 ℃, then is mixed with NO with 1.49 gram Sodium Nitrites and water
2 -50 milliliters of steeping fluids, flood this gac, 110 ℃ of thermal treatments of temperature 4 hours, under 120 ℃ dry 6 hours, get absorbent charcoal carrier.
(2) catalyzer preparation
Except the pH that adopts above-mentioned gac, palladium mixed liquor I II be 5.8 change, all the other preparation processes are with embodiment 1.Table 2 has provided main preparation condition and the catalyst P d content of catalyzer.
(3) experiment of the Hanging Basket of catalyzer and activity rating
Except the catalyzer that adopts changed, all the other operation stepss were with implementing 1.Table 3 has provided the 3-CBA transformation efficiency of Pd content, Pd turnover rate, activity rating pressure, activity rating temperature and the Hanging Basket rear catalyst of catalyst P d content, Hanging Basket rear catalyst.
Table 1
The ☆ Sodium Nitrite is non-silicon-containing compound.
Table 2
Table 3
★ wherein, Pd turnover rate=(catalyst P d content-Hanging Basket rear catalyst Pd content)/catalyst P d content.
Claims (8)
1. the method for a hydrofinishing of coarse isophthalic acid, take coarse isophthalic acid as reaction raw materials, take water as reaction medium, contact with the Pd/C catalyzer to react under the 210 ℃～temperature of reaction of 250 ℃ and the reaction pressure of 2.3～3.2MPa under hydrogen exists and obtain hydrotreated product; Wherein said Pd/C catalyzer contains Pd 0.20～2.50% by weight percentage, and surplus is the modified activated carbon carrier; Wherein said modified activated carbon carrier contains Si and N, and the content of Si in the modified activated carbon carrier is 0.10～0.35% by weight percentage, and the mol ratio of Si/N is 0.5～1.0: 1, and described modified activated carbon carrier adopts the following steps preparation:
A) take water as solvent, the silicon-containing compound shown in formula I is made into steeping fluid II,
Wherein, R
1For-CH
3Perhaps-CH
2CH
3, R
2Be selected from-(CH
2) n
1-NH
2Perhaps-(CH
2) n
2-NH-(CH
2) n
3-NH
2, n wherein
1, n
2, n
3It is 1～3 integer;
B) with steeping fluid II dipping cocoanut active charcoal, 60～150 ℃ of lower thermal treatments 0.5～12 hour, drying got described modified activated carbon carrier.
2. the method for hydrofinishing of coarse isophthalic acid according to claim 1, is characterized in that the R in described modified activated carbon preparation process
2For-(CH
2) n
2-NH-(CH
2) n
3-NH
2, the mol ratio of Si/N is 0.5: 1.
3. the method for hydrofinishing of coarse isophthalic acid according to claim 2, is characterized in that n
2=2, n
3=3.
4. the method for hydrofinishing of coarse isophthalic acid according to claim 1, is characterized in that described modified activated carbon preparation process b) in thermal treatment temp be 80～110 ℃.
5. the method for hydrofinishing of coarse isophthalic acid according to claim 1, is characterized in that described modified activated carbon preparation process b) in heat treatment time be 0.5～4 hour.
6. the method for hydrofinishing of coarse isophthalic acid according to claim 1, is characterized in that it is 3.0～3.5% that described coarse isophthalic acid contains 3-CBA by weight.
7. the method for hydrofinishing of coarse isophthalic acid according to claim 6 is characterized in that the feed ratio of described coarse isophthalic acid and pure water is 1: 8～10 by weight.
8. the method for hydrofinishing of coarse isophthalic acid according to claim 6 is characterized in that the feed ratio of described Pd/C catalyzer and coarse isophthalic acid is 1: 10～15 by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110369575.7A CN103121942B (en) | 2011-11-18 | 2011-11-18 | Method for hydrofining crude terephthalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110369575.7A CN103121942B (en) | 2011-11-18 | 2011-11-18 | Method for hydrofining crude terephthalic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103121942A true CN103121942A (en) | 2013-05-29 |
| CN103121942B CN103121942B (en) | 2015-04-08 |
Family
ID=48453129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110369575.7A Active CN103121942B (en) | 2011-11-18 | 2011-11-18 | Method for hydrofining crude terephthalic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103121942B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966893A (en) * | 2017-04-01 | 2017-07-21 | 来安县万博丰环保科技有限公司 | A kind of method of hydrofining crude terephthalic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006198503A (en) * | 2005-01-19 | 2006-08-03 | Hiroshima Univ | Catalyst composition which carries inorganic catalytic component and organic compound, and its utilization |
| CN101347729A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for preparing Pd/carbon catalyst for hydrofinishing of coarse isophthalic acid |
-
2011
- 2011-11-18 CN CN201110369575.7A patent/CN103121942B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006198503A (en) * | 2005-01-19 | 2006-08-03 | Hiroshima Univ | Catalyst composition which carries inorganic catalytic component and organic compound, and its utilization |
| CN101347729A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for preparing Pd/carbon catalyst for hydrofinishing of coarse isophthalic acid |
Non-Patent Citations (1)
| Title |
|---|
| SENLIN TIAN ET AL.,: "Enhanced removal of hydrogen sulfide from a gas stream by 3-aminopropyltriethoxysilane-surface-functionalized activated carbon", 《ADSORPTION》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966893A (en) * | 2017-04-01 | 2017-07-21 | 来安县万博丰环保科技有限公司 | A kind of method of hydrofining crude terephthalic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103121942B (en) | 2015-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101121127A (en) | Method for preparing supported palladium/carbon catalyst | |
| CN103664524B (en) | The method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol | |
| CN104923240A (en) | Sepiolite-loaded nickel-based catalyst modified by two metals, as well as preparation method and application of sepiolite-loaded nickel-based catalyst | |
| CN104163764B (en) | A kind of method of hydrogenation synthesizing halogen aromatic amines under condition of no solvent | |
| CN103752316A (en) | Iron catalyst for preparing butadiene through n-butene oxydehydrogenation and preparation method and application of iron catalyst | |
| CN103372441B (en) | Preparation method of methanol synthesis catalyst | |
| CN103191730A (en) | High-selectivity iridium carbon catalyst as well as preparation and application thereof | |
| CN105921164A (en) | Preparation method and application of nitrogen-doped activated carbon supported alkali metal modified nickel-based catalyst | |
| CN1436591A (en) | Pretreating process of active carbon carrier for noble metal catalyst | |
| CN104941634A (en) | Palladium-carbon catalyst for preparing furan through furfural decarbonylation process, and preparation method thereof | |
| CN101347728B (en) | Process for preparing Pd/carbon catalyst of high activity | |
| CN101637724A (en) | Method for preparing high-activity palladium/carbon catalyst | |
| CN103121942B (en) | Method for hydrofining crude terephthalic acid | |
| CN102205248B (en) | Preparation method of high-selectivity DSD (4,4'-Diaminodiphenylethylene-2,2'-disulfonic acid) hydrogenation catalyst | |
| CN113926458B (en) | Preparation method of copper hydrogenation catalyst, catalyst prepared by preparation method and application of catalyst | |
| CN102614935A (en) | Surface modification method of aluminum oxide carrier | |
| CN103121944A (en) | Hydrofining method of crude terephthalic acid | |
| CN104549251A (en) | Catalyst for synthesizing 1, 4-cyclohexanedimethanol and preparation method of catalyst | |
| CN103120963B (en) | Modified activated carbon carrier for Pd/C catalyst | |
| CN101486000A (en) | Catalyst for synthesizing MIBK and preparation method thereof | |
| CN103120937A (en) | Method for preparing Pd/C catalyst for refining terephthalic acid | |
| CN103120936A (en) | Preparation method of Pd/C catalyst | |
| CN101816935B (en) | Carbon-carried palladium catalyst and preparation method thereof | |
| CN104549240A (en) | Crude terephthalic acid hydrofining catalyst and preparation method thereof | |
| CN102302938B (en) | Catalyst for dehydrogenation and purification of bimetallic synthesis gas and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |