CN1672787A - Rosin-disproportionating high activity Pd/C catalyst preparing process - Google Patents
Rosin-disproportionating high activity Pd/C catalyst preparing process Download PDFInfo
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Abstract
The rosin-disproportionating high-activity Pd/C catalyst is prepared through simple and fast wet reduction process with palladium acetate as the precursor compound of active component palladium, active carbon as carrier and n-butylamine as solvent. The prepared catalyst has granularity of 300-350 mesh, and Pd content of 1.5-10 wt%. The catalyst may be used in the rosin disproportionating reaction to produce high quality disproportionated rosin.
Description
Technical field
The present invention relates to a kind of high activity Pd/C Preparation of catalysts method, particularly relate to a kind of rosin-disproportionating high activity Pd/C Preparation of catalysts method.
Background technology
Palladium carbon catalyst is widely used in the catalytic hydrogenation reaction of intermediates such as medicine, agricultural chemicals, spices, macromolecular material and liquid product material, catalytic hydrogenation dehalogenation.Especially be applied to the aspects such as disproportionated reaction of the catalytic hydrogenation and the rosin of terephthalic acid (TPA), rosin.
Up till now, have much about the research of rosin-disproportionating reaction with catalyst, kind is also many, rough be divided into non-precious metal catalyst and palladium carbon catalyst.In the research of non-precious metal catalyst, relatively success has transition metal simple substance class catalyst (comprising the skeletal nickel catalyst without carrier), iodine catalyst and a sulfide catalyst: transition metal simple substance class catalyst mainly is to be active component with Fe, Co, Ni, Cu etc., TiO
2Or active carbon etc. is carrier, obtains through certain processing, and such catalyst is used for the rosin-disproportionating reaction, and activity is not high, and the transition metal consumption is big, and the reaction time is long, and reaction temperature is also than higher, so not be ready to adopt this kind catalyst on the industrial production; Iodide catalyst comprises ferric iodide, magnesium iodide, calcium iodide, sodium iodide etc., and their catalytic activity is higher, and selectivity is also better, consersion unit is fairly simple, the catalytic reaction that can be used for the Starex disproportionation, but its shortcoming is that the product color is darker, also very serious to the corrosion of equipment; Sulfide catalyst is meant that with elemental sulfur or metal sulfide be catalyst, and when rosin-disproportionating reacted, such catalyst consumption was big, and the reaction time is long, and metal sulfide also can be emitted H in course of reaction simultaneously
2S or SO
2Gas is contaminated environment both, again etching apparatus.
For the non-precious metal catalyst of front, palladium carbon catalyst is because advantage such as it is active high in the rosin-disproportionating catalytic reaction, selectivity is good, the reaction time is short, reaction temperature is low, consumption is few and by the industrial production wide-scale adoption.Although costing an arm and a leg of palladium, technology is simple, the rate of recovery is high, does not increase the cost of user and producer because it reclaims.A variety of methods are arranged on the Pd/C Study of Catalyst at present both at home and abroad, because the varying of the difference of solvent, preparation technology, the activity of the Pd/C for preparing is also different, and the dispersiveness of palladium on active carbon is also different.At rosin-disproportionating with on the Pd/C catalyst, Japan, the U.S. and Korea S leading, domestic most of users are often from their there import.
Summary of the invention
The purpose of this invention is to provide a kind of rosin-disproportionating reaction high activity Pd/C Preparation of catalysts method, this method is easy, quick, and reaction has high catalytic activity and high selectivity to rosin-disproportionating, and catalyst consumption is less.
The present invention is to be the lead compound of the palladium of active component with the palladium, with the active carbon is carrier, n-butylamine is a solvent, obtain highly active Pd/C catalyst by wet reducing, its advantage is the catalytic activity height of this catalyst to the rosin-disproportionating reaction, selectivity is good, nor can introduce harmful impurity.The quality percentage composition of palladium is 1.5～10% in the catalyst.Used specific area greater than 1000m
2/ g, micropore is less, the mesopore prosperity, granularity is 300～350 purpose wood activated charcoals.Use n-butylamine to be solvent.The amount ranges of palladium lead compound and solvent is that the palladium salt that contains the 100g palladium is dissolved in the n-butylamine solvent of 120～200mL, and regulating the pH value with distilled water again after the dissolving fully is 7～8.Used wet reducing.Under the effect of solvent, obtain the Pd/C catalyst of high degree of dispersion.The wet reducing method is, feeds hydrogen while stirring, and the pore layout that feeds hydrogen is wanted rationally, and the time that feeding hydrogen reduces, the longer the better, produces in batches for pilot scale, and duration of ventilation got final product in 8～14 hours.Catalyst prod washing back is directly used or wet method is preserved.
The concrete steps of its preparation method are as follows:
The first step: the cleaning process of active carbon.Take by weighing a certain amount of active carbon, add distilled water, stirred 3 hours, repeat cleaning process after leaching again one time, obtain material A;
Second step: the course of dissolution of active component lead compound.Will be in palladium (in palladium content): n-butylamine=1 gram: 1.2～2 milliliters ratio be dissolved, and dissolving back fully is 7～8 with the pH value of distilled water regulator solution, obtains solution B;
The 3rd step: the dipping process of palladium.The solution B that configures is added drop-wise in the material A slowly, stirs, drip fully while dripping
After stirred again 10 hours, carry out centrifugation then and remove moisture and n-butylamine etc., obtain material C, the water accounts 45～65% (percentage by weight) among the material C;
The 4th step: wet reducing process.Material C is put into the wet reducing reactor, and after adding 4～8 times distilled water (for the moisture among the material C), earlier logical nitrogen changed logical hydrogen 8～14 hours after 30 minutes, the longer the better the time certainly.Change logical nitrogen at last, close gas after 30 minutes, obtain semi-finished product catalyst D;
The 5th step: D emits postprecipitation the semi-finished product catalyst, and suction filtration removes and anhydrates, and washs 10～17 times, then water usefulness gas is discharged, and obtains the finished catalyst (being the Pd/C catalyst) of required palladium content.
Pd/C catalyst activity evaluation method for rosin-disproportionating reaction usefulness.Elder generation's weighing 100 restrains the not raw material rosin of disproportionation; be placed on logical nitrogen protection and heat fused in the there-necked flask; be warming up to and open the mixer stirring about 180 ℃; can pour 80 milligrams moisture 73% Pd/C catalyst (be rate of charge for son 2～3) very much until completely melted into; when slowly being warming up to 220 ℃, voltage is adjusted to 100V, but just below the constant temperature to 280 ℃; and kept 2～3 hours, the centre disproportionated rosin that can take a morsel is estimated active quality.The real reaction temperature is 280 ℃, and the Industry Control temperature is 270 ℃～290 ℃, reacts after 2～3 hours (to be generally 3 hours), and the content of abietic acid and dehydrogenation abietic acid is analyzed in sampling.Abietic acid content is few more good more, and dehydrogenation abietic acid content 65% is relatively good.
Table 1 for the Pd/C catalyst of we oneself preparation with from Japanese import activity of such catalysts comparative result.The content of palladium is 3% in the catalyst, from rate of charge (catalyst and raw material rosin percentage by weight) for son two five and sub very much 3 two consumptions compare very much, catalytic disproportionation reaction back is analyzed abietic acid in the product and dehydrogenation abietic acid content, require the content of abietic acid in the product few more good more, dehydrogenation abietic acid content is high more good more.
Table 1
| The catalyst place of production | The tenor of catalyst | Lot number | Catalyst amount | Abietic acid content (%) | Dehydrogenation abietic acid content (%) | The quality situation |
| Japan | ?3％ | ??1 | ??0.25‰ | 0.49 | ?50.3 | Meet national standard (one-level) |
| ??2 | ??0.25‰ | 0.49 | ?48.02 | Meet national standard (one-level) | ||
| ??3 * | ??0.25‰ | 0.08 | ?45.0 | Meet national standard (one-level) | ||
| ??4 * | ??0.3‰ | 0 | ?51.3 | Meet national standard (one-level) | ||
| Self-control | ?3％ | ??1 | ??0.25‰ | 0 | ?54.5 | Meet national standard (superfine) |
| ??2 | ??0.25‰ | 0 | ?55.6 | Meet national standard (superfine) | ||
| ??3 | ??0.3‰ | 0 | ?57.7 | Meet national standard (superfine) | ||
| ??4 * | ??0.3‰ | 0 | ?54.8 | Meet national standard (superfine) | ||
| ??5 * | ??0.25‰ | 0 | ?58.4 | Meet national standard (superfine) | ||
| ??6 * | ??0.25‰ | 0 | ?63.3 | Meet national standard (superfine) |
The superfine standard of disproportionated rosin: dehydrogenation abietic acid content 〉=52%, abietic acid≤0.05%
Annotate: band
*Be pilot-scale experiment
Primary standard: dehydrogenation abietic acid content 〉=45%, abietic acid≤0.1%
The specific embodiment
The material source: wood activated charcoal (production of Jiangxi Xin Gangshan Co., Ltd), granule size is 300～350 orders, specific area is 1621m
2/ g; Palladium (Kunming Institute of Precious Metals is synthetic); N-butylamine is pure for analyzing; Raw material rosin (Yunnan Jing Gu secondary rosin).
Example 1: accurately take by weighing the 5Kg active carbon, add 50L distilled water, stirred 3 hours, (its process for preparation is the n-butylamine that the palladium that contains the 100g palladium is dissolved in 120～200mL to drip the palladium solution that contains palladium 100g prepared then, regulating the pH value with distilled water then is 7～8 to get final product), stir while dripping, stirred again after dripping 10 hours; Moisture and n-butylamine etc. are removed in centrifugation, are about 60%; Add 120L left and right sides distilled water again, earlier logical nitrogen changes logical hydrogen and is about 7 hours after 30 minutes, change logical nitrogen at last, closes after 30 minutes; Catalyst is emitted postprecipitation, and suction filtration removes and anhydrates, and washs 10 times, then water usefulness gas is discharged, and obtains finished catalyst.Being used for the reacted evaluation result of rosin-disproportionating is: abietic acid content is 0%, and the dehydrogenation abietic acid is 55.4%.
Example 2: accurately take by weighing the 5Kg active carbon, add 50L distilled water, stirred 3 hours, (its process for preparation is the n-butylamine that the palladium that contains the 100g palladium is dissolved in 120～200mL to drip the palladium solution that contains palladium 150g prepared then, regulating the pH value with distilled water then is 7～8 to get final product), stir while dripping, stirred again after dripping 12 hours; Moisture and n-butylamine etc. are removed in centrifugation, are about 55%; Add 125L left and right sides distilled water again, earlier logical nitrogen changes logical hydrogen and is about 9 hours after 30 minutes, change logical nitrogen at last, closes after 30 minutes; Catalyst is emitted postprecipitation, and suction filtration removes and anhydrates, and washs 12 times, then water usefulness gas is discharged, and obtains finished catalyst.Being used for the reacted evaluation result of rosin-disproportionating is: abietic acid content is 0%, and the dehydrogenation abietic acid is: 64.3%.
Example 3: accurately take by weighing the 5Kg active carbon, add 50L distilled water, stirred 3 hours, (its process for preparation is the n-butylamine that the palladium that contains the 100g palladium is dissolved in 120～200mL to drip the palladium solution that contains palladium 200g prepared then, regulating the pH value with distilled water then is 7～8 to get final product), stir while dripping, stirred again after dripping 13 hours; Moisture and n-butylamine etc. are removed in centrifugation, are about 55%; Add 130L left and right sides distilled water again, earlier logical nitrogen changes logical hydrogen and is about 12 hours after 30 minutes, change logical nitrogen at last, closes after 30 minutes; Catalyst is emitted postprecipitation, and suction filtration removes and anhydrates, and washs 13 times, then water usefulness gas is discharged, and obtains finished catalyst.Being used for the reacted evaluation result of rosin-disproportionating is: abietic acid content is 0%, and the dehydrogenation abietic acid is 68.1%.
Example 4: accurately take by weighing the 5Kg active carbon, add 50L distilled water, stirred 3 hours, (its process for preparation is the n-butylamine that the palladium that contains the 100g palladium is dissolved in 120～200mL to drip the palladium solution that contains palladium 250g prepared then, regulating the pH value with distilled water then is 7～8 to get final product), stir while dripping, stirred again after dripping 13 hours; Moisture and n-butylamine etc. are removed in centrifugation, are about 50%; Add 140L left and right sides distilled water again, earlier logical nitrogen changes logical hydrogen and is about 14 hours after 30 minutes, change logical nitrogen at last, closes after 30 minutes; Catalyst is emitted postprecipitation, and suction filtration removes and anhydrates, and washs 14 times, then water usefulness gas is discharged, and obtains finished catalyst.Being used for the reacted evaluation result of rosin-disproportionating is: abietic acid content is 0%, and the dehydrogenation abietic acid is 67.8%.
Claims (6)
1. rosin-disproportionating high activity Pd/C Preparation of catalysts method is characterized in that with the palladium being the lead compound of active component palladium, is carrier with the active carbon, and n-butylamine is a solvent, obtains highly active Pd/C catalyst by wet reducing.
2. by the described rosin-disproportionating high activity Pd of claim 1/C catalyst, the quality percentage composition that it is characterized in that palladium in the described catalyst is 1.5～10%.
3. by the described rosin-disproportionating high activity Pd of claim 1/C catalyst, it is characterized in that described active carbon is that specific area is greater than 1000m
2/ g, micropore is less, the mesopore prosperity, granularity is 300～350 purpose wood activated charcoals.
4. by the described rosin-disproportionating high activity Pd of claim 1/C catalyst, the amount ranges that it is characterized in that palladium lead compound and solvent is that the palladium salt that contains the 100g palladium is dissolved in the n-butylamine solvent of 120～200mL, and regulating the pH value with distilled water again after the dissolving fully is 7～8.
5. by the described rosin-disproportionating high activity Pd of claim 1/C catalyst, it is characterized in that described is to feed hydrogen while stirring, and the pore layout that feeds hydrogen is wanted rationally, and the time that feeding hydrogen reduces, the longer the better, produce in batches for pilot scale, duration of ventilation got final product in 8～14 hours.Catalyst prod washing back is directly used or wet method is preserved.
6. by each described rosin-disproportionating high activity Pd/C catalyst of claim 1 to 5, it is characterized in that concrete preparation process is as follows:
The first step: the cleaning process of active carbon: take by weighing a certain amount of active carbon, add distilled water, stirred 3 hours, repeat cleaning process after leaching again one time, obtain material A;
Second step: the course of dissolution of active component lead compound: will be in palladium (in palladium content): the ratio of n-butylamine=1g: 1.2～2mL is dissolved, and dissolving back fully is 7～8 with the pH value of distilled water regulator solution, obtains solution B;
The 3rd step: the dipping process of palladium: be added drop-wise to the solution B that configures in the material A slowly, stir while dripping, stirred again 10 hours after the dropping fully, carry out centrifugation then and remove moisture and n-butylamine etc., obtain material C, the water accounts 45～65% (percentage by weight) among the material C;
The 4th step: wet reducing process: material C is put into the wet reducing reactor, and after adding 4～8 times distilled water (for the moisture among the material C), earlier logical nitrogen is after 30 minutes, change logical hydrogen 8～14 hours, certain time, the longer the better, change logical nitrogen at last, close gas after 30 minutes, obtain semi-finished product catalyst D;
The 5th step: D emits postprecipitation the semi-finished product catalyst, and suction filtration removes and anhydrates, and washs 10～17 times, then water usefulness gas is discharged, and obtains the finished catalyst (being the Pd/C catalyst) of required palladium content.
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| CN100428989C (en) * | 2006-09-06 | 2008-10-29 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN102029151A (en) * | 2010-10-27 | 2011-04-27 | 贵研铂业股份有限公司 | Modified polyol method for preparing Pt/C catalyst |
| CN102659572A (en) * | 2012-04-12 | 2012-09-12 | 浙江工业大学 | Preparation method of dehydroabietic acid |
| CN103436175A (en) * | 2013-08-27 | 2013-12-11 | 广西梧州松脂股份有限公司 | Method for increasing content of dehydroabietic acid in disproportionated rosin |
| CN104194637A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Method for preparing disproportionated rosin with high softening point |
| CN104190440A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Palladium carbon catalyst reactivation method |
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| CN105478110A (en) * | 2016-01-27 | 2016-04-13 | 莫晓丽 | Preparing method of palladium-charcoal catalyst for producing disproportionation rosin |
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| CN105709723A (en) * | 2016-01-27 | 2016-06-29 | 莫晓丽 | Method for preparing palladium-carbon catalyst for producing disproportionated rosin |
| CN105709722A (en) * | 2016-01-27 | 2016-06-29 | 莫晓丽 | Method for preparing palladium-carbon catalyst for producing disproportionated rosin |
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| JPS5959760A (en) * | 1982-09-29 | 1984-04-05 | Harima Kasei Kogyo Kk | Photocurable resin |
| JPS614779A (en) * | 1984-06-19 | 1986-01-10 | Harima Kasei Kogyo Kk | Production of rosin which has pale color and good stability |
| JPS6381181A (en) * | 1986-09-22 | 1988-04-12 | Arakawa Chem Ind Co Ltd | Production of heterogeneous |
| CN1149142C (en) * | 2001-03-23 | 2004-05-12 | 中国石油化工股份有限公司 | Combined extruding-out and shape-fixating machine of plastic products and its application |
| CN1475475A (en) * | 2002-08-15 | 2004-02-18 | 李宽义 | Method of producing hydroquinone by palladium carbon low pressure catalytic hydrogenation |
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| CN100428989C (en) * | 2006-09-06 | 2008-10-29 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN102029151A (en) * | 2010-10-27 | 2011-04-27 | 贵研铂业股份有限公司 | Modified polyol method for preparing Pt/C catalyst |
| CN102029151B (en) * | 2010-10-27 | 2012-09-19 | 贵研铂业股份有限公司 | Modified polyol method for preparing Pt/C catalyst |
| CN102659572A (en) * | 2012-04-12 | 2012-09-12 | 浙江工业大学 | Preparation method of dehydroabietic acid |
| CN102659572B (en) * | 2012-04-12 | 2014-06-11 | 浙江工业大学 | Preparation method of dehydroabietic acid |
| CN103436175A (en) * | 2013-08-27 | 2013-12-11 | 广西梧州松脂股份有限公司 | Method for increasing content of dehydroabietic acid in disproportionated rosin |
| CN104194637A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Method for preparing disproportionated rosin with high softening point |
| CN104190440A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Palladium carbon catalyst reactivation method |
| CN105107552A (en) * | 2015-09-07 | 2015-12-02 | 广西梧州通轩林产化学有限公司 | Reactivation method of palladium-carbon catalyst for preparation of disproportionated rosin |
| CN105478110A (en) * | 2016-01-27 | 2016-04-13 | 莫晓丽 | Preparing method of palladium-charcoal catalyst for producing disproportionation rosin |
| CN105688896A (en) * | 2016-01-27 | 2016-06-22 | 莫晓丽 | Method for preparing palladium-carbon catalyst for producing nilox resin |
| CN105709723A (en) * | 2016-01-27 | 2016-06-29 | 莫晓丽 | Method for preparing palladium-carbon catalyst for producing disproportionated rosin |
| CN105709722A (en) * | 2016-01-27 | 2016-06-29 | 莫晓丽 | Method for preparing palladium-carbon catalyst for producing disproportionated rosin |
| CN107142024A (en) * | 2017-07-20 | 2017-09-08 | 广西容县宏旺树脂有限公司 | A kind of disproportionated rosin production technology of high dehydrogenation abietic acid |
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| CN115555014A (en) * | 2021-07-01 | 2023-01-03 | 谷育英 | High-activity palladium-carbon catalyst and preparation method and application thereof |
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