CN103349984B - Preparation method of coal columnar palladium-carbon catalyst used for hydrogenation of masson pine - Google Patents
Preparation method of coal columnar palladium-carbon catalyst used for hydrogenation of masson pine Download PDFInfo
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Abstract
The invention relates to a preparation method of coal columnar palladium-carbon catalyst used for hydrogenation of a masson pine, which mainly solves the problem that in the preparation process, metal Pd metal complex ion is wrapped with alumina gel dissolved in the process of adjusting pH value by impurity aluminum of coal columnar activated charcoal, so as to affect the reduction of active component palladium and dispersion of active component palladium on coal carrier. Through the adoption of technical scheme that coal columnar activated charcoal carrier is soaked in triethanolamine solution, palladium polymeric pecursor solution is slowly and dropwise added to water solution with coal columnar activated charcoal, and sodium boro-hydride is used for reduction after stirring, columnar palladium-carbon catalyst with well activity and durability is obtained. The method can be used indiscriminately and continuously for 12 times in hydrogenation reaction of masson pine, and the abietic acids are all less than or equal to 1.5%, dehydroabietic acids are all less than or equal to 9%, and the content of tetrahydroabietic acids reach up to 54.71 % of obtained hydrogenated rosins, and therefore, superfine standard of hydrogenated rosin is satisfied.
Description
Technical field
The preparation method who the present invention relates to a kind of ature of coal column palladium carbon catalyst for hydrogenation reaction, this catalyst is specially adapted to the hydrogenation reaction of masson pine.
Background technology
Foral, because its antioxygenic property is good, fragility is little, heat endurance is high, lighter color, is widely used in the industrial circles such as adhesive, scaling powder, rubber, coating, ink, papermaking, electronics, food.The manufacture method of Foral is to adopt fusion method dissolving rosin or rosin, and under the effect of catalyst, through industrialization fixed bed continously hydrogen adding, and then separation is made.At this palladium carbon catalyst used, need to there be certain intensity and shape, granular, the column palladium carbon catalyst of ature of coal as good in intensity or coconut husk matter.
Current domestic rosin deep-processing factory palladium carbon catalyst majority used is self-control, the carrier majority adopting is ature of coal column-shaped active carbon, adopt conventional infusion process that chlorine palladium acid precursor is adsorbed on absorbent charcoal carrier, then carry out the method preparation of simple reduction, but after rosin hydrogenation reaction, this catalyst is not only active and service life is poor, and also very high by palladium amount.Although have much patent and the document prepared about absorbent charcoal carrier modification and charcoal supported noble metal catalyst, but for ature of coal column palladium carbon catalyst, for the research of precious metal catalyst agent carrier and the impurity aluminum of ature of coal column-shaped active carbon, the impact research of catalyst performance is not also seen to relevant report, so the ature of coal column-shaped active carbon that output is large, price is low, intensity is high is restricted in the application of catalyst carrier.We think that this is mainly because coal mass active carbon contains more Si, Al, Mg, Fe, Ca, S impurity etc., except Si, all the other impurity all can affect the dispersion of noble metal on charcoal carrier surface, finally affect the activity and selectivity (Chen Renhui of catalyst, Shao Suhua. the impact of the inorganic constituents of the inorganic constituents of active carbon-active carbon on its manufacture process and performance. charcoal element, 1995 (03) 28-35.).Impurity element Mg, Fe, Ca and S can remove by acid-washed active carbon, but impurity A l is difficult to remove.The preparation technology of palladium carbon catalyst often adopts liquid-phase precipitation reducing process, presoma and carrier impregnation completely after, need to regulate pH value to alkalescence, presoma to be deposited on carrier.In regulating the process of pH, the impurity aluminum in coal mass active carbon can stripping generate colloid substance, and its existence has a strong impact on the reduction of active carbon to the absorption of palladium and palladium, and finally affects the activity and selectivity of column palladium carbon catalyst.
Summary of the invention
1. the object of this invention is to provide the preparation method of ature of coal column palladium carbon catalyst for a kind of masson pine hydrogenation, its technical problem to be solved is to make the impurity element aluminium in ature of coal column-shaped active carbon under alkali condition, not generate aluminium glue, efficiently solve the phenomenon of aluminium glue parcel palladium, improve the decentralization of active component palladium on carrier.
2. the triethanolamine of mentioning in the present invention, it is the screening agent of aluminium, in alkaline environment, can stop the impurity element aluminium in ature of coal column-shaped active carbon to generate aluminium glue, adopt the method after dipping completes simultaneously, do not need precipitation, can directly reduce, this is because triethanolamine is strong basicity solvent, after citric acid palladium solution is added dropwise to complete, the pH value of absorption system is in 8 left and right.In addition, adopt mode that first Immesion active carbon carrier adsorbs palladium precursor again to contribute to the dispersion of active component palladium.
3. the technique of mentioning in the present invention, hydrogenation mainly for masson pine, preparation method is immersed in the ature of coal column-shaped active carbon carrier after pickling in a certain amount of triethanolamine solution, then citric acid palladium solution is slowly added drop-wise in above-mentioned active carbon suspension, after stirring, adopts sodium borohydride to reduce.
Concrete steps are as follows:
The first step: the modification of ature of coal column-shaped active carbon: (conventional method is that active carbon is soaked after 24h in 10% salpeter solution first ature of coal column-shaped active carbon to be carried out to pretreatment, extremely neutral with deionized water washing, drying for standby at 120 ℃), then pretreated ature of coal column-shaped active carbon carrier is immersed in and contains in a certain proportion of triethanolamine deionized water solution (by the addition of triethanolamine solution with the amount of column-shaped active carbon than adding for 1:25 (weight ratio)), stirring 5h mixes it and substantially reaches adsorption equilibrium, obtain the column-shaped active carbon water solution system A after modification,
Second step: dipping process.By the palladium content ratio of finished catalyst, a certain amount of citric acid palladium is slowly added drop-wise in system A, stir on dropping limit, limit, after dropping completely, stirs 24 hours again, obtains system B;
The 3rd step: reduction process.In sodium borohydride: NaOH=4 gram: the ratio preparation reductant solution of 1 gram, be then slowly added drop-wise in system B, stir on dropping limit, limit, drip completely after stirring 2 hours, obtain system C;
The 4th step: washing dry run.System C suction filtration is removed to water, and with deionized water washing 8-10 time, then in vacuum drying chamber, at 80 ℃, dry, obtain the ature of coal column palladium carbon catalyst of required palladium content.
The preparation method of ature of coal column palladium carbon catalyst for masson pine hydrogenation of the present invention.Mainly solve in preparation process the aluminium glue that impurity aluminum in ature of coal column-shaped active carbon is dissolved out generation in the process that regulates pH value metal Pd complex ion packet has been wrapped, affected reduction and the scattering problem on charcoal carrier thereof of active component palladium.By adopting, ature of coal column-shaped active carbon carrier is immersed in triethanolamine solution, then palladium precursor solution is slowly added drop-wise to above-mentioned containing in the aqueous solution of ature of coal column-shaped active carbon, after stirring, by the technical scheme of sodium borohydride reduction, active and the good column palladium carbon catalyst of durability have been obtained.In masson pine hydrogenation reaction, can apply mechanically continuously 12 times, in gained Foral, all≤1.5%, all≤9%, tetrahydroabietic acid content, up to 54.71%, meets the superfine standard of Foral to dehydrogenation abietic acid to abietic acid.
The specific embodiment
The present invention is described in detail by following example:
Material source: ature of coal column-shaped active carbon (active carbon Co., Ltd of Shanxi Xinhua, diameter is 3-4mm, specific area is 1032m
2/ g); Citric acid palladium (Guiyan Catalyst Co., Ltd., Kunming); Triethanolamine is pure for analyzing; Sodium borohydride is pure for analyzing; NaOH is pure for analyzing; One-level masson pine (Chongzuo Sen Long silvichemical Co., Ltd).And ature of coal column-shaped active carbon is carried out to pretreatment, be about to active carbon and soak after 24h in 10% salpeter solution, with deionized water washing to neutral, drying for standby at 120 ℃.
Embodiment 1: accurately measure the triethanolamine solution of heavy 400g in 100L water, stir, then the dry weight 10kg ature of coal column-shaped active carbon weighing up is added, stir 5 hours, then slowly add the citric acid palladium containing palladium 100g, stir on dropping limit, limit, dripping rear continuation stirs 24 hours, then drip the reductant solution (its process for preparation is that 200g sodium borohydride and 50g NaOH are dissolved in 10L deionized water) preparing, stir on dropping limit, limit, after dripping, stir again 2 hours, then catalyst suction filtration is anhydrated, and with after deionized water washing 10 times, in vacuum drying chamber, at 80 ℃, dry, obtain finished catalyst.For the evaluation result after rosin hydrogenation reaction, be: abietic acid content is 0%, and dehydrogenation abietic acid content is 9.06%, and dihydroabietic acid's content is 41.52%, and tetrahydroabietic acid content is 34.94%, is height one-level Foral.
Embodiment 2: accurately measure the triethanolamine solution of heavy 400g in 100L water, stir, then the dry weight 10kg ature of coal column-shaped active carbon weighing up is added, stir 5 hours, then slowly add the citric acid palladium containing palladium 200g, stir on dropping limit, limit, dripping rear continuation stirs 24 hours, then be added dropwise to the reductant solution (its process for preparation is that 400g sodium borohydride and 100g NaOH are dissolved in 16L deionized water) preparing, stir on dropping limit, limit, after dripping, stir again 2 hours, then catalyst suction filtration is anhydrated, and with after deionized water washing 10 times, in vacuum drying chamber, at 80 ℃, dry, obtain finished catalyst.For the evaluation result after rosin hydrogenation reaction, be: abietic acid content is 0%, and dehydrogenation abietic acid content is 5.45%, and dihydroabietic acid's content is 47.38%, and tetrahydroabietic acid content is 42.54%, is highly superfine Foral.
Embodiment 3: accurately measure the triethanolamine solution of heavy 400g in 100L water, stir, then the dry weight 10kg ature of coal column-shaped active carbon weighing up is added, stir 5 hours, then slowly add the citric acid palladium containing palladium 300g, stir on dropping limit, limit, dripping rear continuation stirs 24 hours, then be added dropwise to the reductant solution (its process for preparation is that 600g sodium borohydride and 150g NaOH are dissolved in 16L deionized water) preparing, stir on dropping limit, limit, after dripping, stir again 2 hours, then catalyst suction filtration is anhydrated, and with after deionized water washing 10 times, in vacuum drying chamber, at 80 ℃, dry, obtain finished catalyst.For the evaluation result after rosin hydrogenation reaction, be: abietic acid content is 0%, and dehydrogenation abietic acid content is 5.05%, and dihydroabietic acid's content is 48.25%, and tetrahydroabietic acid content is 43.2%, is highly superfine Foral.
Embodiment 4: accurately measure the triethanolamine solution of heavy 400g in 100L water, stir, then the dry weight 10kg ature of coal column-shaped active carbon weighing up is added, stir 5 hours, then slowly add the citric acid palladium containing palladium 400g, stir on dropping limit, limit, dripping rear continuation stirs 24 hours, then be added dropwise to the reductant solution (its process for preparation is that 800g sodium borohydride and 200g NaOH are dissolved in 16L deionized water) preparing, stir on dropping limit, limit, after dripping, stir again 2 hours, then catalyst suction filtration is anhydrated, and with after deionized water washing 10 times, in vacuum drying chamber, at 80 ℃, dry, obtain finished catalyst.For the evaluation result after rosin hydrogenation reaction, be: abietic acid content is 0%, and dehydrogenation abietic acid content is 4.52%, and dihydroabietic acid's content is 40.46%, and tetrahydroabietic acid content is 45.73%, is highly superfine Foral.
Embodiment 5: accurately measure the triethanolamine solution of heavy 400g in 100L water, stir, then the dry weight 10kg ature of coal column-shaped active carbon weighing up is added, stir 5 hours, then slowly add the citric acid palladium containing palladium 500g, stir on dropping limit, limit, dripping rear continuation stirs 24 hours, then be added dropwise to the reductant solution (its process for preparation is that 1kg sodium borohydride and 250g NaOH are dissolved in 16L deionized water) preparing, stir on dropping limit, limit, after dripping, stir again 2 hours, then catalyst suction filtration is anhydrated, and with after deionized water washing 10 times, in vacuum drying chamber, at 80 ℃, dry, obtain finished catalyst.For the evaluation result after rosin hydrogenation reaction, be: abietic acid content is 0%, and dehydrogenation abietic acid content is 3.29%, and dihydroabietic acid's content is 38.22%, and tetrahydroabietic acid content is 48.36%, is highly superfine Foral.
The evaluation of catalyst activity:
The column palladium carbon catalyst that is 50g by 500g masson pine, dry weight is successively placed in hydrogenation reaction kettle, dries sealing surface, covers kettle cover.Pass into nitrogen, displaced air 2-3 time, then replace nitrogen 2-3 time with a small amount of hydrogen.Pass into a certain amount of hydrogen, be warming up to predetermined temperature (473K), Hydrogen Vapor Pressure is adjusted to reaction pressure (10Mpa), regulate stir speed (S.S.) to 600r/min, start reaction.Temperature, pressure and the rotating speed suitably controlled in course of reaction remain constant, react after 4 hours, finish reaction.When temperature in the kettle is down to about 423K, open atmospheric valve and make still internal pressure to normal pressure discharging, filter while hot filtration catalizer.Obtain Foral product, the product that takes a morsel carries out gas chromatographic analysis.
Activity and the life-span comparative result of the catalyst that the column palladium carbon catalyst that table 1 is prepared for us and producer oneself produce.After catalytic hydrogenation, the content of abietic acid, dehydrogenation abietic acid, dihydroabietic acid and tetrahydroabietic acid in product is analyzed to (quality condition of stipulating in GB GB/T 14020-2006 Foral is in Table 2).
The palladium carbon catalyst hydrogenation activity of the homemade catalyst of table 1 and manufacturer production and selective contrast
Table 2: Foral technical indicator
Claims (4)
1. a preparation method for ature of coal column palladium carbon catalyst for masson pine hydrogenation, is characterized in that containing following processing step:
1) modification of ature of coal column-shaped active carbon: first ature of coal column-shaped active carbon is carried out to pretreatment, be about to active carbon soaks after 24h in 10% salpeter solution, extremely neutral with deionized water washing, drying for standby at 120 ℃, then pretreated ature of coal column-shaped active carbon carrier is immersed in triethanolamine deionized water solution, stir 5h and it is mixed and substantially reach adsorption equilibrium, obtain the column-shaped active carbon water solution system A after modification;
2) in system A dipping process: a certain amount of palladium precursor solution is slowly added drop-wise to 1 by the palladium content ratio of finished catalyst), stir after dipping 24h, obtain system B;
3) reduction process: with reducing agent, system B is reduced to processing, stir on dropping limit, limit, stirs 2 hours after dripping completely again, obtains system C;
4) washing dry run: system C suction filtration is removed to water, and with deionized water washing 8-10 time, then dry at 80 ℃ in vacuum drying chamber, obtain the ature of coal column palladium carbon catalyst of required palladium content.
2. preparation method according to claim 1, it is characterized in that: described step 1), use the modification of triethanolamine deionized water solution to ature of coal column-shaped active carbon, the addition that the ratio of employing is triethanolamine solution and the weight ratio of column-shaped active carbon are 1:25.
3. preparation method according to claim 1, is characterized in that: step 2) in palladium presoma be citric acid palladium.
4. preparation method according to claim 1, is characterized in that: reducing agent described step 3) is the mixed solution of sodium borohydride and NaOH, and the weight ratio of sodium borohydride and NaOH is 4:1.
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| CN102463124A (en) * | 2010-11-11 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing phenol from benzene through one-step process |
| CN102553584A (en) * | 2011-12-26 | 2012-07-11 | 西安凯立化工有限公司 | Modified palladium-carbon catalyst for producing chloroacetic acid and preparation method for catalyst |
| CN102658133A (en) * | 2012-05-09 | 2012-09-12 | 杭州凯大催化金属材料有限公司 | Method for preparing active carbon carrying precious metal catalyst |
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| CN102463124A (en) * | 2010-11-11 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing phenol from benzene through one-step process |
| CN102553584A (en) * | 2011-12-26 | 2012-07-11 | 西安凯立化工有限公司 | Modified palladium-carbon catalyst for producing chloroacetic acid and preparation method for catalyst |
| CN102658133A (en) * | 2012-05-09 | 2012-09-12 | 杭州凯大催化金属材料有限公司 | Method for preparing active carbon carrying precious metal catalyst |
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| 陈仁辉,等."活性炭的无机成分 活性炭的无机成分对其制造过程和性能的影响".《碳素》.1995,(第3期),第28-35页. * |
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Address after: 650106 No. 669, high road, hi tech Industrial Development Zone, Yunnan, Kunming, China Patentee after: Guiyan Catalyst Co., Ltd., Kunming Patentee after: Guangxi Hualin Chemical Co., Ltd. Address before: 650106 No. 669, high road, hi tech Industrial Development Zone, Yunnan, Kunming, China Patentee before: Guiyan Catalyst Co., Ltd., Kunming Patentee before: Senlong Chemical Co., Ltd. |