CN102294240A - Pd/C catalyst for producing 2,3,5-trimethylhydroquinone (TMHQ) by virtue of hydrogenation of 2,3,5-trimethylbenzoquinone (TMBQ) and preparation method thereof - Google Patents
Pd/C catalyst for producing 2,3,5-trimethylhydroquinone (TMHQ) by virtue of hydrogenation of 2,3,5-trimethylbenzoquinone (TMBQ) and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a Pd/C catalyst for producing 2,3,5-trimethylhydroquinone (TMHQ) by virtue of hydrogenation of 2,3,5-trimethylbenzoquinone (TMBQ) and a preparation method thereof. In the Pd/C catalyst provided by the invention, a noble metal Pd supported on a carrier activated carbon exists in a nano particle form, the dispersion degree of Pd is not less than 30%, and the carrier activated carbon has micropores and mesopores. The preparation method comprises the following steps: (1) carrying out acid treatment on the carrier activated carbon, and adding an acid solution in activated carbon for carrying out water bath reflux treatment; (2) washing activated carbon treated by the acid with deionized water to be neutral, and drying so as to obtain the activated carbon carrier; (3) infiltrating the activated carbon carrier with an infiltration liquid in advance; (4) slowly dropwise adding a 0.01-0.3mol/L Pd source solution in the activated carbon carrier which is infiltrated in advance, so that Pd is supported on the activated carbon, thus a catalyst precursor is obtained; and (5) drying the catalyst precursor and then treating the dried catalyst precursor by a reduction method so as to obtain the Pd/C catalyst for producing TMHQ by virtue of hydrogenation of TMBQ. The Pd/C catalyst provided by the invention has the characteristics of being simple and efficient, and having high catalysis property in BTOP (benzene to phenol) reaction.
Description
Technical field
The present invention relates to a kind of loaded noble metal catalyst that is used for the liquid phase catalytic hydrogenation reaction and preparation method thereof, particularly relate to a kind of TMBQ of being used for (2,3, the 5-trimethylbenzoquinone) hydrogenation and produce TMHQ (2,3,5-TMHQ) Pd/C catalyst and preparation method.
Background technology
Vitamin E (VE) not only should be used as the additive of medicine, health products, food, cosmetics, and more and more as industrial antioxidant, becomes the focus product that receives much attention in recent years.The domestic and international market sharply increases the demand of VE, and price constantly rises, thereby the production of in good time operation and expansion VE all can bring favorable economic benefit.
TMHQ (2,3, the 5-TMHQ) is a kind of organic substance of white powder, is the important intermediate of synthesising complex E, and VE is synthesized in itself and different vegetable alcohol reaction.But the production technology of this class intermediate is always by the monopolization of external major company for a long time, makes the production of China VE be subjected to the restriction of raw material and intermediate, lacks competitiveness in the international market.Though in recent years, domestic units such as Zhejiang chemical research institute have successfully developed the synthetic TMHQ technology of metacresol method, promoted the production of China VE, but because this technological development ground zero, technical advance is compared with external similar enterprise with maturity and is had obvious gap.Therefore, it is significant to the production that develops domestic VE further to carry out the study on the synthesis of TMHQ.
The method that with TMBQ is the synthetic TMHQ of raw material mainly contains chemical reduction method and catalytic hydrogenating reduction method.Chemical reduction method generally is with raw material 2,3, and 6-trimethyl phenol (TMP) earlier sulfonation generates 4-sulfonic group-2,3, the 6-pseudocuminol, then through oxidant (as MnO
2) oxidation generation TMBQ, be reduced to TMHQ through reducing agent (as sodium hydrosulfite) then.China enterprise adopts this production technology to produce TMHQ basically.In actual production, the solid 4-sulfonic group-2,3 that generates after the TMP sulfonation, 6-pseudocuminol tend to caking, use MnO
2Solid dissolving that must these are block before the oxidation, complex operation is time-consuming.In addition, reduction process not only produces a large amount of waste liquids, and unavoidably introduces impurity and cause the TMHQ quality to reduce.The catalytic hydrogenation method is meant in hydrogen atmosphere, under the catalyst action, TMBQ is carried out the process that hydrogenation reaction directly is reduced into TMHQ, and this method has characteristics such as product quality height, cost are low, is the production method that at present external major company generally adopts.
Because VE is mainly used in medicine and food additives field, as the important source material TMHQ that produces VE, its production purity affects the performance and the quality of downstream product.Prepare the TMHQ process based on the TMBQ catalytic hydrogenating reduction, present difficulty is in suitable solvent, develops the effective catalyst that a kind of TMBQ orientation changes into TMHQ.
U.S. Pat 3839468 has been investigated under the catalyst based effect of Pd, and solvent becomes the influence of TMHQ to the TMBQ hydrogenating reduction.Discovery is with C
3-C
5Alcohol is as solvent, and product is colored (air oxidation) degree and is lower than with C
1-C
2Alcohol is the situation of solvent, and painted is formation quinhydrone compound because TMBQ and TMHQ mutually combine, and quinhydrone is black when solid state, makes TMHQ painted just because of the existence of this material.With aliphatic ketone (C
3-C
6) during as solvent, the catalyst based life-span of Pd obtains prolonging, and TMHQ purity is higher.U.S. Pat 4769500 is mentioned the heterogeneous catalytic hydrogenation catalyst that a kind of precious metals pd loads to the alkali metal containing alumino-silicate, under normal pressure, 40 ℃ of reaction temperatures, the conversion ratio of TMBQ reaches 100%, and the selectivity of TMHQ also is higher than 99%, and catalyst can be reused.But this patent does not have the structure and concrete composition of clear and definite carrier alumino-silicate, does not mention the concrete preparation process of catalyst yet.
Because catalytic hydrogenation reaction is to carry out on the surface of metal Pd, therefore usually for the identical catalyst of precious metals pd load capacity, the decentralization of Pd is high more in the catalyst, and activity is then high more.If directly with the Pd compound (as the acid of chlorine palladium, or chlorine palladium acid sodium) solution loads on the active carbon, activated carbon surface can the very thin glossiness metal Pd layer of very fast appearance, this mainly is that these groups are easy to make the Pd cation to be reduced into the metal Pd of zeroth order because activated carbon surface contains oxy radicals such as hydroxyl, aldehyde radical.Therefore, the decentralization of precious metals pd is generally all very low in the catalyst that so prepares.One of effective ways that overcome this technical problem are that the Pd ion that will contain in the maceration extract of Pd compound before dipping is transformed into insoluble compound.For example, at room temperature the water soluble compound hydrolysis of Pd is changed into insoluble Pd (OH)
2Or PdO, and then load on the active carbon, then with the reducing agent reduction, can prevent that like this migration of Pd and particle from growing up.U.S. Pat 3138560 adds hydrogen peroxide in maceration extract makes the water soluble compound hydrolysis of Pd generate insoluble compound, floods then.But because hydrogen peroxide itself also has oxidisability, can be with the activated carbon surface radical oxidation, thus will change the physico-chemical property of carrier surface, promptly change the surface group structure of carrier, thereby catalyst is caused uncertain negative effect.The maceration extract that contains the Pd compound is prepared in 4476242 propositions of U.S. Pat with organic matters such as methyl alcohol or pyridines; this grows up very effective to the migration and the particle that suppress Pd; but preparation process is used methyl alcohol or this harmful compound of pyridine, is disadvantageous from point of view of environment protection.In addition, European patent EP 08150726.1 has been reported under the effect of surfactant, by regulating the colloidal sol that the pH value is reduced into the Pd cation zero-valent metal Pd, load to preparation Pd/C catalyst on the active carbon again, but because colloidal stability is not high, cause Pd on carrier active carbon, to be difficult to be evenly distributed, thereby cause the decentralization of Pd to reduce.
In sum, though existing P d/C catalyst can show high selectivity, it is low that it exists the precious metals pd decentralization, the not high weak point of catalytic activity in the process of the synthetic TMHQ of catalysis TMBQ hydrogenation.
Summary of the invention
It is low to the present invention is directed to the existing precious metals pd decentralization of existing P d/C catalyst, the not high weak point of catalytic activity in the process of the synthetic TMHQ of catalysis TMBQ hydrogenation, a kind of precious metals pd decentralization height is provided, in TMBQ catalytic hydrogenation production TMHQ process, not only has high selectivity, and in the TMBQ catalytic hydrogenation reaction, have a high catalytic activity be used for TMBQ (2,3, the 5-trimethylbenzoquinone) hydrogenation is produced Pd/C catalyst and the preparation method of TMHQ (2,3, the 5-TMHQ).
The present invention finishes by following technical scheme, a kind of Pd/C catalyst that is used for TMBQ hydrogenation production TMHQ, the precious metals pd that wherein is carried on the carrier active carbon exists with nanoparticle form, the Pd decentralization is not less than 30%, carrier active carbon is a coconut husk type active carbon, have micropore and mesoporous on the carrier active carbon, wherein mesoporous pore volume is 5～6 times of micropore pore volume.
At described a kind of Pd/C catalyst that the TMBQ hydrogenation is produced TMHQ that is used for, the Pd nano-particles size is 2.0～5.0nm.
At described a kind of Pd/C catalyst that the TMBQ hydrogenation is produced TMHQ that is used for, the specific area of described carrier active carbon is greater than 1000m
2/ g, the mesoporous 2～10nm that is of a size of on the carrier active carbon.
A kind of Pd/C Preparation of catalysts method that is used for TMBQ hydrogenation production TMHQ of the present invention may further comprise the steps:
(1) acid treatment of carrier active carbon adds acid solution in the active carbon, and water-bath reflow treatment 2～4h, acid solution adopt a kind of in hydrochloric acid, phosphoric acid or the salpeter solution;
(2) with deionized water that the active carbon cyclic washing of above-mentioned acid treatment is extremely neutral, in 80～120 ℃ of drying 0.5～10h, get pretreated absorbent charcoal carrier;
(3) pretreated carried by active carbon body and function infiltrate is soaked into 0.2～5h in advance, the concentration of infiltrate is 0.1～2mol/L, and the infiltrate quality is 0～4 with the ratio of quality of activated carbon;
(4) be that the Pd source solution of 0.01～0.3mol/L is added drop-wise in the absorbent charcoal carrier that soaks in advance lentamente with concentration, Pd is carried on the active carbon, promptly obtain catalyst precarsor, wherein the quality that adds of metal Pd is counted 1.0～5.0wt.% by the catalyst gross mass;
(5) adopt method of reducing to handle after drying catalyst precarsor, promptly obtain being used for the Pd/C catalyst that the TMBQ hydrogenation is produced TMHQ.
In described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for, the concentration of used acid solution is 5wt.%～10wt.% in step (1).
In described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for, the granularity of carrier active carbon is 180～220 orders, preferred 200 orders.
In described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for, be preferably 0.5～4h the drying time after the carrier active carbon acid treatment.
In described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for, used infiltrate is a kind of in sodium carbonate liquor or the oxalic acid solution in step (3).
In described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for, the Pd source of used Pd source solution is a kind of in acetate, nitrate, hydrochloride, the acid of chlorine palladium, palladium amine complex or the organic palladium of Pd in step (4), a kind of in preferred chlorine palladium acid or the chlorine palladium acid sodium.
In described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for, used method of reducing is a kind of in hydrogen reducing, formaldehyde reduction, reduction of ethylene glycol, formic acid reduction, the sodium formate reduction in step (5), a kind of in preferred hydrogen reducing or the formaldehyde reduction.
The present invention compares with the method for existing preparation Pd/C catalyst, characteristics of the present invention are: the present invention is before dipping Pd compound, carrier active carbon is after sour preliminary treatment, having added suitable infiltrate modifies, because infiltrate can interact with the oxy radical on the carrier active carbon, has improved the reduction potential of carrier.When Pd loaded on the active carbon, the Pd cation just can not reduced by the carrier surface group of modified, thereby Pd can be distributed in the surface of carrier active carbon very equably.In addition, the present invention also has: the precious metals pd catalyst of preparation has the decentralization height, the Pd nano particle is even, used carrier infiltrate wide material sources, cheap, catalyst preparation process is simple, and the catalyst of preparation has the outstanding feature of very high catalytic activity in the TMBQ catalytic hydrogenation reaction.
Among the present invention, the decentralization of precious metals pd that adopted CO pulse titration measuring, decentralization calculates by following formula:
Decentralization=(V
Inhale* M
Pd)/(22400 * W
Pd) * 100%
In the formula: V
InhaleCO adsorbance (ml) under the expression standard state,
M
PdAtomic weight 106.4gmol for Pd
-1,
W
PdBe Pd quality (g) in the catalyst.
Among the present invention, the precious metals pd particle size of prepared Pd/C catalyst adopts transmission electron microscope (TEM) technology to analyze.
Catalyst activity appreciation condition: reactant TMBQ:10～20g; The ratio that catalyst amount accounts for reactant is 0.05～0.12wt.%; Reaction dissolvent ethyl acetate: 35～65ml; Hydrogen initial pressure: 0.5～0.8MPa; Reaction temperature: 65～95 ℃.
Measure the still internal pressure and reduce 0.1MPa Δ t of needed time, with initial hydrogen-absorption speed
The TMBQ hydrogenation activity of evaluate catalysts.
Characteristics of the present invention are: by changing the alkali treatment condition, as NaOH concentration, temperature and time etc., can change micropore and mesoporous ratio in the microporous mesoporous composite molecular sieve catalyst of Fe-ZSM-5, thus the catalytic performance of catalyst in BTOP before and after the modulation alkali treatment.Sign and reaction evaluating result from sample, the mode of the present invention by alkali treatment is with in the mesoporous introducing micropore Fe-ZSM-5 molecular sieve crystal, the gained sample topography is complete, crystal structure is constant, and the molecular sieve mass-transfer performance significantly improves, and its catalytic activity and stability in the BTOP catalytic reaction also are significantly improved.Under the alkali treatment condition of optimizing, the catalyst after the modification reacts 3h under 320 ℃ of reaction temperatures, and the conversion ratio of benzene still maintains 20%, and apparently higher than the catalytic activity without the alkali treatment sample, and the selectivity of phenol reaches 100% under reaction condition.Compared with prior art, the present invention is to provide a kind of simply, effectively, in the BTOP reaction, have the microporous mesoporous compound Fe-ZSM-5 zeolite molecular sieve catalyst preparation method of high catalytic performance.
Description of drawings
Fig. 1 is the TEM figure and the particle diameter distribution map thereof of 5wt.%Pd/C catalyst among the embodiment 1.
Fig. 2 is the TEM figure and the particle diameter distribution map thereof of 2wt.%Pd/C catalyst among the embodiment 4.
The specific embodiment
Below by embodiment the present invention is made further and to specify, but the present invention is not limited to following example.
Embodiment 1
20g is Powdered, and specific area is greater than 1000m
2The coconut husk type active carbon concentration of/g is 60 ℃ of following water-bath backflow 2h of nitric acid of 5wt.%, uses the deionized water cyclic washing to neutral then, and is standby in 80 ℃ of following forced air drying 4h.
The preparation of Pd source maceration extract takes by weighing the PdCl about about 3g
2Solid joins in the 7.29ml concentrated hydrochloric acid, treats to dissolve fully the back and adds deionized water and be diluted in the volumetric flask of 50ml standby.
Get pretreated active carbon 3g, adding 10ml concentration is that the sodium carbonate of 0.9mol/L soaks into active carbon 0.5h in advance.Load capacity according to Pd is 5.0wt.%, pipettes PdCl
2The about 14ml of solution adds in the active carbon that soaks in advance behind the dipping 6h, after then putting into 50 ℃ of baking ovens and spending the night, in 10vol.%H
2(overall flow rate: 30ml/min) the following 200 ℃ of reductase 12 h of atmosphere get catalyst to/Ar, by CO pulse titration catalyst are carried out decentralization and characterize, and by analysis, its decentralization is 50%.
Catalyst activity appreciation condition: reactant TMBQ:15g; Reaction dissolvent ethyl acetate: 50ml; Hydrogen initial pressure: 0.6MPa; Reaction temperature: 80 ℃; Catalyst: 0.012g.
The catalyst activity evaluation result: it is 4.5min that record reduces the 0.1MPa required time, and its hydrogen-absorption speed is 648ml (min g)
-1
Embodiment 2
20g is Powdered, and specific area is greater than 1000m
2The active carbon concentration of/g is 60 ℃ of following water-bath backflow 2h of nitric acid of 5wt.%, uses the deionized water cyclic washing to neutral then, and is standby in 80 ℃ of following forced air drying 4h.
The preparation of Pd source maceration extract takes by weighing the PdCl about about 3g
2Solid joins in the 7.29ml concentrated hydrochloric acid, treats to dissolve fully the back and adds deionized water and be diluted in the volumetric flask of 50ml standby.
Get pretreated active carbon 3g, adding 10ml concentration is that the oxalic acid of 0.1mol/L soaks into active carbon 0.5h in advance.Load capacity according to Pd is 5.0wt%, pipettes PdCl
2The about 14ml of solution adds in the active carbon that soaks in advance behind the dipping 6h, after then putting into 50 ℃ of baking ovens and spending the night, in 10vol.%H
2(overall flow rate: 30ml/min) the following 200 ℃ of reductase 12 h of atmosphere get catalyst to/Ar, by CO pulse titration catalyst are carried out decentralization and characterize, and by analysis, its decentralization is 45%.
Catalyst activity appreciation condition: reactant TMBQ:15g; Reaction dissolvent ethyl acetate: 50ml; Hydrogen initial pressure: 0.6MPa; Reaction temperature: 80 ℃; Catalyst: 0.012g.
The catalyst activity evaluation result: it is 4.9min that record reduces the 0.1MPa required time, and its hydrogen-absorption speed is 595ml (min g)
-1
Embodiment 3
20g is Powdered, and specific area is greater than 1000m
2The coconut husk type active carbon concentration of/g is 60 ℃ of following water-bath backflow 2h of nitric acid of 10wt.%, uses the deionized water cyclic washing to neutral then, and is standby in 80 ℃ of following forced air drying 4h.
The preparation of Pd source maceration extract takes by weighing the PdCl about about 3g
2Solid joins in the 7.29ml concentrated hydrochloric acid, treats to dissolve fully the back and adds deionized water and be diluted in the volumetric flask of 50ml standby.
Get pretreated active carbon 3g, adding 10ml concentration is that the oxalic acid of 0.1mol/L soaks into active carbon 0.5h in advance.Load capacity according to Pd is 5.0wt%, pipettes PdCl
2The about 14ml of solution adds in the active carbon that soaks in advance behind the dipping 6h, after then putting into 50 ℃ of baking ovens and spending the night, in 10vol.%H
2(overall flow rate: 30ml/min) the following 200 ℃ of reductase 12 h of atmosphere get catalyst to/Ar, by CO pulse titration catalyst are carried out decentralization and characterize, and by analysis, its decentralization is 43%.
Catalyst activity appreciation condition: reactant TMBQ:15g; Reaction dissolvent ethyl acetate: 50ml; Hydrogen initial pressure: 0.6MPa; Reaction temperature: 80 ℃; Catalyst: 0.012g.
The catalyst activity evaluation result: it is 10.5min that record reduces the 0.1MPa required time, and its hydrogen-absorption speed is 648ml (min g)
-1
Embodiment 4
20g is Powdered, and specific area is greater than 1000m
2The active carbon concentration of/g is 60 ℃ of following water-bath backflow 2h of nitric acid of 10wt.%, uses the deionized water cyclic washing to neutral then, and is standby in 80 ℃ of following forced air drying 4h.
The preparation of Pd source maceration extract takes by weighing the PdCl about about 3g
2Solid joins in the 7.29ml concentrated hydrochloric acid, treats to dissolve fully the back and adds deionized water and be diluted in the volumetric flask of 50ml standby.
Get pretreated active carbon 3g, adding 2.8ml concentration is 1.62mol/L Na
2CO
3Stir.Load capacity according to Pd is 2.0wt%, pipettes PdCl
2The about 1ml of solution is simultaneously to thin up PdCl wherein
2Behind the solution, add in the active carbon that soaks in advance and flood 6h, after then putting into 50 ℃ of baking ovens and spending the night, in 10vol.%H
2(overall flow rate: 30ml/min) the following 200 ℃ of reductase 12 h of atmosphere get catalyst to/Ar, by CO pulse titration catalyst are carried out decentralization and characterize, and by analysis, its decentralization is 35%.
Catalyst activity appreciation condition: reactant TMBQ:15g; Reaction dissolvent ethyl acetate: 50ml; Hydrogen initial pressure: 0.6MPa; Reaction temperature: 80 ℃; Catalyst: 0.012g.
The catalyst activity evaluation result: it is 6.2min that record reduces the 0.1MPa required time, and its hydrogen-absorption speed is 470ml (min g)
-1
Comparative example 1
5.0wt.%Pd/C catalyst from domestic Pd/C Catalyst Production producer buys carries out decentralization by CO pulse titration to catalyst and characterizes, and by analysis, its decentralization is 26%.
Catalyst activity appreciation condition: reactant TMBQ:15g; Reaction dissolvent ethyl acetate: 50ml; Hydrogen initial pressure: 0.6MPa; Reaction temperature: 80 ℃; Catalyst: 0.012g.
The catalyst activity evaluation result: it is 11.5mm that record reduces the 0.1MPa required time, and its hydrogen-absorption speed is 254ml (min g)
-1
Claims (10)
1. one kind is used for the Pd/C catalyst that the TMBQ hydrogenation is produced TMHQ, it is characterized in that the precious metals pd that described Pd/C catalyst wherein is carried on the carrier active carbon exists with nanoparticle form, the Pd decentralization is not less than 30%, carrier active carbon is a coconut husk type active carbon, have micropore and mesoporous on the carrier active carbon, wherein mesoporous pore volume is 5～6 times of micropore pore volume.
2. according to the described a kind of Pd/C catalyst that the TMBQ hydrogenation is produced TMHQ that is used for of claim 1, it is characterized in that the Pd nano-particles size is 2.0～5.0nm.
3. according to the described a kind of Pd/C catalyst that the TMBQ hydrogenation is produced TMHQ that is used for of claim 1, the specific area that it is characterized in that described carrier active carbon is greater than 1000m
2/ g, the mesoporous 2～10nm that is of a size of on the carrier active carbon.
4. according to claim 1 or 2 or 3 described a kind of Pd/C Preparation of catalysts methods that the TMBQ hydrogenation is produced TMHQ that are used for, it is characterized in that this preparation method may further comprise the steps:
(1) acid treatment of carrier active carbon adds acid solution in the active carbon, and water-bath reflow treatment 2～4h, acid solution adopt a kind of in hydrochloric acid, phosphoric acid or the salpeter solution;
(2) with deionized water that the active carbon cyclic washing of above-mentioned acid treatment is extremely neutral, in 80～120 ℃ of drying 0.5～10h, preferred 0.5～4h gets pretreated absorbent charcoal carrier;
(3) pretreated carried by active carbon body and function infiltrate is soaked into 0.2～5h in advance, the concentration of infiltrate is 0.1～2mol/L, and the infiltrate quality is 0～4 with the ratio of quality of activated carbon;
(4) be that the Pd source solution of 0.01～0.3mol/L is added drop-wise in the absorbent charcoal carrier that soaks in advance lentamente with concentration, Pd is carried on the active carbon, promptly obtain catalyst precarsor, wherein the quality that adds of metal Pd is counted 1.0～5.0wt.% by the catalyst gross mass;
(5) adopt method of reducing to handle after drying catalyst precarsor, promptly obtain being used for the Pd/C catalyst that the TMBQ hydrogenation is produced TMHQ.
5. according to the described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for of claim 4, the concentration that it is characterized in that acid solution used in described step (1) is 5wt.%～10wt.%.
6. according to the described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for of claim 4, the granularity that it is characterized in that described carrier active carbon is 180～220 orders, preferred 200 orders.
7. according to the described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for of claim 4, it is characterized in that in step (3) used infiltrate is a kind of in sodium carbonate liquor or the oxalic acid solution.
8. according to the described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for of claim 4, the Pd source that it is characterized in that Pd source solution used in step (4) is a kind of in acetate, nitrate, hydrochloride, the acid of chlorine palladium, palladium amine complex or the organic palladium of Pd, a kind of in preferred chlorine palladium acid or the chlorine palladium acid sodium.
9. according to the described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for of claim 4, it is characterized in that method of reducing used in step (5) is a kind of in hydrogen reducing, formaldehyde reduction, reduction of ethylene glycol, formic acid reduction, the sodium formate reduction, a kind of in preferred hydrogen reducing or the formaldehyde reduction.
10. according to the described a kind of Pd/C Preparation of catalysts method that the TMBQ hydrogenation is produced TMHQ that is used for of claim 5, it is characterized in that this preparation method comprises following concrete steps:
(1) acid treatment of carrier active carbon adds acid solution in the active carbon, and water-bath reflow treatment 2～4h, acid solution adopt a kind of in hydrochloric acid, phosphoric acid or the salpeter solution, and the granularity of carrier active carbon is 180～220 orders, preferred 200 orders;
(2) with deionized water that the active carbon cyclic washing of above-mentioned acid treatment is extremely neutral, in 80～120 ℃ of drying 0.5～10h, preferred 0.5～4h gets pretreated absorbent charcoal carrier;
(3) pretreated carried by active carbon body and function infiltrate is soaked into 0.2～5h in advance, the concentration of infiltrate is 0.1～2mol/L, and the infiltrate quality is 0～4 with the ratio of quality of activated carbon, and infiltrate adopts a kind of in sodium carbonate liquor or the oxalic acid solution.
(4) be that the Pd source solution of 0.01～0.3mol/L is added drop-wise in the absorbent charcoal carrier that soaks in advance lentamente with concentration, Pd is carried on the active carbon, promptly obtain catalyst precarsor, wherein the quality of metal Pd adding is counted 1.0～5.0wt.% by the catalyst gross mass, the Pd source of Pd source solution is a kind of in acetate, nitrate, hydrochloride, the acid of chlorine palladium, palladium amine complex or the organic palladium of Pd, a kind of in preferred chlorine palladium acid or the chlorine palladium acid sodium.
(5) after drying with catalyst precarsor, adopt a kind of method of reducing in hydrogen reducing, formaldehyde reduction, reduction of ethylene glycol, formic acid reduction, the sodium formate reduction, a kind of method of reducing in preferred hydrogen reducing or the formaldehyde reduction is handled, and promptly obtains being used for the Pd/C catalyst that the TMBQ hydrogenation is produced TMHQ.
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| CN103506115A (en) * | 2012-06-21 | 2014-01-15 | 陕西天卓材料技术有限公司 | Preparation method of bimetallic catalyst used for carbapenem drug synthesis |
| CN105916803A (en) * | 2013-11-06 | 2016-08-31 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | A method for storage and release of hydrogen |
| CN107684921A (en) * | 2017-09-11 | 2018-02-13 | 浙江师范大学 | It is a kind of to be converted into TMHQ catalyst and preparation method thereof for TMBQ |
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| CN103506112A (en) * | 2012-06-21 | 2014-01-15 | 陕西天卓材料技术有限公司 | Preparation method of palladium carbon catalyst used for lisinopril drug synthesis |
| CN103506115A (en) * | 2012-06-21 | 2014-01-15 | 陕西天卓材料技术有限公司 | Preparation method of bimetallic catalyst used for carbapenem drug synthesis |
| CN103357423A (en) * | 2013-07-29 | 2013-10-23 | 西安凯立化工有限公司 | Preparation method of modified palladium-carbon catalyst for aromatic amine preparation, and application of catalyst |
| CN103357423B (en) * | 2013-07-29 | 2015-02-11 | 西安凯立化工有限公司 | Preparation method of modified palladium-carbon catalyst for aromatic amine preparation, and application of catalyst |
| CN105916803A (en) * | 2013-11-06 | 2016-08-31 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | A method for storage and release of hydrogen |
| US10207921B2 (en) | 2013-11-06 | 2019-02-19 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Method for storage and release of hydrogen |
| CN105916803B (en) * | 2013-11-06 | 2019-12-10 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | Method for storing and releasing hydrogen |
| CN110980638A (en) * | 2013-11-06 | 2020-04-10 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | Method for storing and releasing hydrogen |
| US10618807B2 (en) | 2013-11-06 | 2020-04-14 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Method for storage and release of hydrogen |
| CN107684921A (en) * | 2017-09-11 | 2018-02-13 | 浙江师范大学 | It is a kind of to be converted into TMHQ catalyst and preparation method thereof for TMBQ |
| CN107684921B (en) * | 2017-09-11 | 2020-02-07 | 浙江师范大学 | Catalyst for converting TMBQ into TMHQ and preparation method thereof |
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