CN104368358A - Catalyst applicable to succinic acid hydrogenation reaction, and preparation method and hydrogenation reaction method thereof - Google Patents
Catalyst applicable to succinic acid hydrogenation reaction, and preparation method and hydrogenation reaction method thereof Download PDFInfo
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Abstract
A Pd-M double metal or multi-metal catalyst and application thereof to succinic acid hydrogenation. Succinic acid is subjected to hydrogenation reaction for preparing gamma-butyrolactone, tetrahydrofuran, 1,4-butanediol; and the ratio of reaction products can be adjusted according to different components of the catalyst. The catalyst comprises 0.05-5wt% of an active component Pd and 0.1-30 wt% of a second metal M. The preparation method mainly comprises the following steps: preparing a stable nano palladium colloid solution by a chemical reduction process; introducing the second metal component M into the carrier, adsorbing the palladium colloid by the carrier, washing and drying to obtain the high-dispersion Pd-M nano catalyst.
Description
Technical field
The present invention relates to butanedioic acid hydrogenation reaction, specifically a kind of be applicable to butanedioic acid hydrogenation reaction catalyst and preparation and process for selective hydrogenation.
Background technology
Gamma-butyrolacton, oxolane, 1,4-butanediol is very important industrial chemicals, still mainly fossil fuel is come from present, fossil fuel non-renewable and utilize in process and produce a large amount of environmental pollutions and make people must find a kind of alternate resources.Butanedioic acid can prepare gamma-butyrolacton, oxolane, BDO through a step hydrogenation reaction, but traditional production of succinic acid mainly relies on petrochemical technology.Along with developing rapidly of biofermentation technique, the output of future biological base butanedioic acid will roll up, and be that raw material has a high potential to produce high valuable chemicals with butanedioic acid, lot of domestic and international scholar has carried out correlative study to butanedioic acid hydrogenation.
Song etc. have prepared Pd/Al
2o
3, Pd/STC and Cu-C catalyst is used for butanedioic acid hydrogenation reaction, product mainly contains gamma-butyrolacton, oxolane and a small amount of BDO.Result explanation, the effect of the degree of scatter of Pd metal on carrier on catalyst butanedioic acid hydrogenation has significant impact, by improving the degree of scatter of metal active constituent on carrier surface of load, effectively can promote the hydrogenation reaction of butanedioic acid, improve the yield of target product, the hydrogenation of mesoporous carbon carrier (STC) load Ru to butanedioic acid prepared by surfactants' templating has good activity, 240 DEG C, react 8 hours under 6MPa hydrogen, the conversion ratio of butanedioic acid is 90%, and the selective of gamma-butyrolacton reaches 74%.But the preparation process of meso-porous carbon material is relatively complicated, need the roasting of a lot of step, washing process.Luque etc. are at the porous carrier prepared by renewable raw materials (starch)
upper load multiple noble metal active component Pd, Pt, Ru, Rh etc., the load type gold metal nano-particle that infusion process is prepared has less average particle size particle size, this load type gold metal nano-particle is applied to the hydrogenation process of butanedioic acid, 100 DEG C, react under 1Mpa hydrogen after 24 hours, use the butanedioic acid conversion ratio of 5%Pd-Starbon to reach 75%, BDO and the selective of gamma-butyrolacton are respectively 70% and 30%; Use the butanedioic acid conversion ratio of 5%Pt-Starbon to reach 78%, BDO and the selective of gamma-butyrolacton are respectively 85% and 15%.Deshpande etc. use the hydrogenation reaction of Ru-Co Catalyzed by Pt/M Bimetallic Nano butanedioic acid to prepare gamma-butyrolacton and BDO.Its experimental result shows, and the Ru that adulterates in Co can make catalytic hydrogenation activity have significant enhancing (3-4 doubly), and this is mainly owing to creating very strong synergy between Co and Ru.At 250 DEG C, the product under 10MPa hydrogen is mainly oxolane, selective poor to BDO, there is butanols, the dehydration of propyl alcohol even depth, hydroformylation product solution in reaction.Ru-Co bimetallic catalyst is compared with Ru/C catalyst with Co catalyst, and the distribution of product also has obvious difference.The above results proves, we can control the distribution of product in butanedioic acid hydrogenation reaction, to realize the optimization to target product yield by regulating active component in catalyst.Besson etc. find the Pd/TiO in Re doping
2be applied to the reaction of butanedioic acid catalytic hydrogenation, find the Pd/TiO at 2wt%
2the Re metal that adulterates in catalyst can significantly promote that butanedioic acid hydrogenation generates BDO, and the hydrogenation reaction that the synergy produced between Pd and Re can strengthen butanedioic acid and gamma-butyrolacton simultaneously generates BDO.Use 1.9%Ru-3.6%Re/C catalyst when 150 DEG C, levulic acid is converted into the selective of Isosorbide-5-Nitrae-pentanediol can reach 82%, but does not mention in detail the concrete data of butanedioic acid hydrogenation.This team has also carried out monometallic Pd/TiO prepared by distinct methods
2the reaction of catalysis butanedioic acid hydrogenation, experimental result display Pd catalyst has higher selective for gamma-butyrolacton, the degree of scatter of Pd and Pd/TiO
2preparation method on the conversion ratio of butanedioic acid by larger impact.But this Pd/TiO
2the higher Hydrogen Vapor Pressure of reaction needed.US Patent No. 4940805 reports the hydrogenation reaction under Co-Cu and Co-P catalyst such as maleic anhydride, succinyl oxide, maleic acid, butanedioic acid, reaction is solvent with fatty alcohol, carry out in fixed bed reactors, product is mainly BDO and oxolane.But the temperature that shortcoming is mainly used is higher, reaction temperature is more than 230 DEG C.US Patent No. 4609636 and US4550185 describe a kind of carbon supported palladium, rhenium catalyst catalysis maleic acid, maleic anhydride Hydrogenation for 1, the method of 4-butanediol and oxolane, on prepared catalyst, the palladium grain size of load is 10-25nm rhenium grain size is 2.5nm, preparation method is that palladium is carried on active carbon prior to rhenium, and the carrying method of palladium and rhenium is the precipitation method.US Patent No. 4985572 provides a kind of method of the rhenium, palladium, silver catalyst catalysis carboxylic acid or the carboxylic acid anhydrides preparing alcohol by hydrogenating relative class that use charcoal load, first palladium or galactic longitude are crossed precipitation method load on the activated carbon, after high-temperature heat treatment, and then by rhenium precipitation on the activated carbon.European patent EP 0722923 B1 use infusion process prepare palladium, silver, rhenium catalyst for maleic acid, maleic anhydride Hydrogenation for oxolane, 1,4-butanediol by-product gamma-butyrolacton, activated carbon supported palladium, silver, rhenium catalyst use infusion process preparation, and palladium average crystal grain is less than 10nm.Although Pd catalyst can well be applied to butanedioic acid hydrogenation reaction, but because the stability of Pd catalyst is not good, easily there is agglomerated particle change ambassador hydrogenation activity after using a period of time easily to reduce, adding of the second component, the deactivation phenomenom of Pd catalyst can well be suppressed.
Summary of the invention
The object of the invention be to provide a kind of be applicable to butanedioic acid hydrogenation reaction catalyst and preparation and process for selective hydrogenation.
For achieving the above object, the technical solution used in the present invention is:
Be applicable to a catalyst for butanedioic acid hydrogenation reaction, being applicable to active component Pd content in the Pd-M catalyst of hydrogenation reaction is 0.05-5wt%, and metal M content is 0.1-30wt%; Metal M is selected from VI
b, VII
b, VIII, I
bin one or more metallic elements; Carrier is active carbon, aluminium oxide, zirconia, titanium oxide, silica, acidic molecular sieve or metal oxide compounds carrier.
In described catalyst, active component Pd content is 0.05-3wt%, and metal M content is 0.5-20wt%; One or more in metal M chosen from Fe, tin, copper, cobalt, manganese, molybdenum, tin, gold, silver, rhenium; Carrier is active carbon, activated alumina, zirconia, titanium oxide or acidic molecular sieve.
One or both mixing in described metal M chosen from Fe, copper, cobalt, tungsten, molybdenum, rhenium.
Be applicable to a preparation method for the catalyst of butanedioic acid hydrogenation reaction,
1) aqueous surfactant solution and pH are that the palladium salting liquid of 0.5-5 mixes, and reduction after mixing, forms the Technique of Nano Pd colloidal solution A of surfactants stabilize;
2) carrier to be immersed in M metallic solution 0.5 hour-24 hours, then the carrier B of dry carried metal M;
Or, carrier to be immersed in M metallic solution 0.5 hour-24 hours, then dry, reduce to obtain the carrier B of carried metal M;
Or, carrier to be immersed in M metallic solution 0.5 hour-24 hours, then drying, roasting, the carrier B of carried metal M of reducing to obtain;
3) carrier B of carried metal M joined in Technique of Nano Pd colloidal solution A, fully stir contact, after filtration, washing obtains catalyst;
Or,
1) aqueous surfactant solution and pH are that the palladium salting liquid of 0.5-5 mixes, and form the Technique of Nano Pd colloidal solution A of surfactants stabilize;
2) carrier to be immersed in M metallic solution 0.5 hour-24 hours, then the carrier B of dry carried metal M;
Or, carrier to be immersed in M metallic solution 0.5 hour-24 hours, then dry, reduce to obtain the carrier B of carried metal M;
Or, carrier to be immersed in M metallic solution 0.5 hour-24 hours, then drying, roasting, the carrier B of carried metal M of reducing to obtain;
3) carrier B of carried metal M joined in Technique of Nano Pd colloidal solution A, fully stir contact, reduction after mixing, filtration, washing obtains catalyst.
Reducing agent liquid-phase reduction can be adopted further or carry out reduction treatment in atmosphere of hydrogen before the catalyst use of above-mentioned acquisition.
Above-mentioned carrier immerses in M metallic solution, adopts existing infusion process or the precipitation method to be carried on carrier by metal M; The carrier of carried metal M, 50-200 DEG C of dry 0.5-24 hour, roasting under 200-700 DEG C of condition after dry process, adopts the mode of liquid-phase reduction or vapour phase reduction to carry out reduction treatment, obtains catalyst after roasting, wherein, preferred H during reduction treatment
2vapour phase reduction, reduction temperature is 200-700 DEG C, and preferred reduction temperature is 300-550 DEG C.
Described aqueous surfactant solution be the 1-500 of critical micelle concentration doubly, mean molecule quantity is the aqueous solution of the non-ionic surface active agent between 500-5000.
Described non-ionic surface active agent is one or more in sapn type surfactant, tween type surfactant, hydrogenated rosin glyceride, AEO methyl-monosilane, polyethylene glycols or APG.
Described palladium salting liquid is the mixing of one or more in palladium bichloride, the acid of chlorine palladium, palladium nitrate, palladium, preferred palladium bichloride.
Described reduction reaction, adopts reducing agent, liquid-phase reduction or vapour phase reduction;
Wherein reducing agent is the mixing of one or more in formaldehyde, hydrazine hydrate, ascorbic acid, sodium borohydride, sodium formate, ethylene glycol, hydrogen.
When above-mentioned liquid-phase reduction or vapour phase reduction, preferred H
2vapour phase reduction, reduction temperature is 200-700 DEG C, and preferred reduction temperature is 300-550 DEG C.
A method for catalyst hydrogenation reaction, take butanedioic acid as raw material, adds described catalyst wherein, and under polar solvent effect, hydrogenation reaction obtains one or more in gamma-butyrolacton, oxolane and BDO; Wherein, catalyst amount is the 1/10000-1/10 of butanedioic acid quality, and hydrogenation reaction temperature is 100-260 DEG C, and initial hydrogen pressure is 0.5-12MPa.
10. by the method utilizing catalyst hydrogenation to react described in claim 9, it is characterized in that: described hydrogenation reaction temperature is 160-230 DEG C, initial hydrogen pressure is 5-10MPa, and polar solvent is water, alcohols, Isosorbide-5-Nitrae-dioxane; Preferred water.
The advantageous effect that the present invention has is:
1. the raw material selected by hydrogenation reaction of the present invention is bio-based butanedioic acid, can by biofermentation, and wide material sources, raw material is renewable.
2. hydrogenation reaction of the present invention prepares high valuable chemicals product is gamma-butyrolacton, oxolane, 1,4-butanediol, product distribution can form according to catalyst that Pd-M active component composition, proportioning and carrier are different differently with preparation method carries out modulation, advantage can obtain gamma-butyrolacton, oxolane, 1, one or both products in 4-butanediol, can use after being separated, be widely used.
3. use the palladium in non-ionic surface active agent rugged catalyst during Kaolinite Preparation of Catalyst of the present invention, the palladium nano-particles of preparation, grain graininess is homogeneous adjustable; After simultaneously the carrier of catalyst adds the second component M, catalyst noble metal component not only not easily runs off, and can the composition distribution of modulation product, and catalytic activity is high, and the life-span is long.The preparation method of catalyst is simple, favorable repeatability.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.Should be understood that following examples only for illustration of the present invention but not for limiting scope of the present invention.
The present invention take butanedioic acid as raw material, gamma-butyrolacton, oxolane is obtained through hydrogenation reaction, specifically comprise the following steps: with butanedioic acid: water=1:10-100 adds in hydrogenation reactor, and add aM-bPd/ carrier (a=0.1-30%, b=0.0.5-5%) catalyst, at certain temperature and Hydrogen Vapor Pressure, carry out a step hydrogenation, reaction time is 10min-72h, then catalyst separation is carried out, product isolates volatile product gamma-butyrolacton, oxolane through rectifying, and yield is 50-98%.In described method, catalyst selects palladium and one or two kinds of Metal Supporteds on carrier, and catalyst amount is the 1/1000-1/10 of butanedioic acid.Hydrogenation reaction temperature is 100-260 DEG C.Initial hydrogen pressure is greater than 0.5MPa and is less than or equal to 12MPa.Polar solvent as reaction dissolvent, as water, Isosorbide-5-Nitrae-dioxane, alcohols, preferred water.
In butanedioic acid hydroconversion process, the difference of catalyst, product is different, when in Pd-M catalyst, M is Fe, Co, Ni component, product is butyrolactone and oxolane, extend the reaction time, the amount of butyrolactone product reduces, and the yield of oxolane increases, and be primary product with oxolane, yield can reach more than 90%, modulation Pd/M ratio, and the distribution of product butyrolactone and oxolane also can change.When M is Cu, W, Mo, Re component time, initial reaction stage primary product is butyrolactone and butanediol, extend the reaction time, the amount of butyrolactone product reduces, the yield of butanediol increases, and is primary product with butanediol, and yield also can reach more than 90%, modulation Pd/M ratio, the distribution of product butyrolactone and butanediol also can change.In this conversion process, acid carrier is conducive to the raising of initial activity, and improves the yield of reaction starting stage butyrolactone.
Catalyst preparation example
Embodiment 1
Get 0.12g frerrous chloride, be dissolved in 20mL water and add 1g active carbon wherein, regulate pH=8 with sodium acid carbonate, stir 40min, filter, fully wash, then for subsequent use through hydrogen 300 DEG C reduction after dried overnight at 110 DEG C.Take 5.0g polysorbas20 to be dissolved in 30mL water, stir, get 0.0548g palladium bichloride in flask, add 1mL 15wt% sodium chloride solution and make it dissolve, add NaHCO
3adjustment pH value of solution is to 3.5.Mixed with Tween solution by palladium salting liquid, add 0.12g formalin wherein, orange solution becomes black rapidly, obtains palladium colloidal solution.The active carbon above-mentioned load being crossed iron adds in palladium colloidal solution, stirs 1h, filters, fully washes, obtained 5%Fe-3%Pd/C.
Embodiment 2
Get 0.12g frerrous chloride, be dissolved in 4mL water, dissolve in backward solution and add in load weighted 1g active carbon, leave standstill 24 hours, evaporate to dryness liquid, drying for standby at 80 DEG C.Take 5.0g hydrogenated rosin glyceride to be dissolved in 30mL water, stir, get 0.0548g palladium bichloride in flask, add 1mL 15wt% sodium chloride solution and make it dissolve, add NaHCO
3adjustment pH value of solution is to 3.By palladium salting liquid and hydrogenated rosin glyceride aqueous solution, stir 1 hour at adding 0.12g ascorbic acid solution 70 DEG C wherein, orange solution becomes black rapidly, obtains palladium colloidal solution.The active carbon above-mentioned load being crossed iron adds in palladium colloidal solution, stirring at room temperature 1h, filters, fully washes, obtained 5%Fe-3%Pd/C.
Embodiment 3
Get 0.26g frerrous chloride, be dissolved in 20mL water and add 1g active carbon wherein, regulate pH=8 with sodium acid carbonate, stir 40min, filter, fully washing is for subsequent use.Take 5.3g polysorbas20 to be dissolved in 30mL water, stir, get 0.058g palladium bichloride in flask, add 1mL 15wt% sodium chloride solution and make it dissolve, add NaHCO
3adjustment pH value of solution is to 4.Mixed with Tween solution by palladium salting liquid, add 0.13g formalin wherein, orange solution becomes black rapidly, obtains palladium colloidal solution.The active carbon above-mentioned load being crossed iron adds in palladium colloidal solution, stirs 1h, filters, fully washes, obtained 10%Fe-3%Pd/C.
Embodiment 4
Get 0.59g frerrous chloride, be dissolved in 20mL water and add 1g active carbon wherein, regulate pH=8 with sodium acid carbonate, stir 40min, filter, fully washing is for subsequent use.Take 6.0g polysorbas20 to be dissolved in 30mL water, stir, get 0.066g palladium bichloride in flask, add 1mL 15wt% sodium chloride solution and make it dissolve, add NaHCO
3adjustment pH value of solution is to 4.Mixed with Tween solution by palladium salting liquid, add 0.15g formalin wherein, at 80 DEG C, react 1h, orange solution becomes black rapidly, obtains palladium colloidal solution.The active carbon above-mentioned load being crossed iron adds in palladium colloidal solution, and room temperature continues to stir 1h, filters, fully washes, obtained 20%Fe-3%Pd/C.
Embodiment 5
Get 2.23g copper nitrate, be dissolved in 20mL water and add 1g active carbon wherein, regulate pH=8 with sodium acid carbonate, stir 40min, filter, fully washing is for subsequent use.Take 6.0g polysorbas20 to be dissolved in 30mL water, stir, get 0.066g palladium bichloride in flask, add 1mL 15wt% sodium chloride solution and make it dissolve, add NaHCO
3adjustment pH value of solution is to 4.Mixed with Tween solution by palladium salting liquid, add 0.15g formalin 80 DEG C reaction 1h wherein, orange solution becomes black rapidly, obtains palladium colloidal solution.The active carbon above-mentioned load being crossed iron adds in palladium colloidal solution, stirs 1h, filters, fully washes, obtained 20%Cu-3%Pd/C.
Embodiment 6
Get 1.74g stannic chloride pentahydrate, be dissolved in 4mL water, solution is added in load weighted 1g active carbon, leave standstill 24 hours, evaporate to dryness liquid, drying for standby at 80 DEG C.Take 6.0g polysorbas20 to be dissolved in 30mL water, stir, get 0.066g palladium bichloride in flask, add 1mL 15wt% sodium chloride solution and make it dissolve, add NaHCO
3adjustment pH value of solution is to 4.Mixed with Tween solution by palladium salting liquid, add 0.15g formalin wherein, orange solution becomes black rapidly, obtains palladium colloidal solution.The active carbon above-mentioned load being crossed iron adds in palladium colloidal solution, stirs 1h, filters, fully washes, obtained 20%Sn-3%Pd/C.
Embodiment 7
Get 0.12g frerrous chloride, 1.74g stannic chloride pentahydrate is dissolved and is gone in 10mL water, solution is added load weighted 1g and lives in aluminium oxide, leave standstill 24 hours, evaporate to dryness liquid, drying for standby at 80 DEG C.Take 5.0g polysorbas20 to be dissolved in 30mL water, stir, get 0.0548g palladium bichloride in flask, add 1mL 15wt% sodium chloride solution and make it dissolve, add NaHCO
3adjustment pH value of solution is to 3.5.Mixed with Tween solution by palladium salting liquid, stir 1 hour at adding 0.12g formalin 70 DEG C wherein, orange solution becomes black rapidly, obtains palladium colloidal solution.The active carbon above-mentioned load being crossed iron adds in palladium colloidal solution, stirring at room temperature 1h, filters, fully washes, obtained 5%Fe-20%Sn-3%Pd/ aluminium oxide.
Hydrogenation reaction embodiment
Embodiment 8
20mL 1wt% succinic acid solution is added in 50mL stainless steel autoclave, adds the 5%Fe-3%Pd/C catalyst of preparation in 0.04g embodiment 1.After passing into hydrogen exchange three times, fill initial hydrogen pressure 5MPa, stir with the speed of 1000 turns/min, 35min temperature programming to 200 DEG C, in reactor and microcomputer linkage record course of reaction, the change of temperature and pressure, reacts 10 minutes to 72 hours.Reaction terminate after, be cooled to room temperature, get centrifugal after supernatant fluid, cross 0.22 μm of filter membrane, with gas-chromatography (GC) and high performance liquid chromatography (HPLC) carry out analysis detection.By gas chromatography mass spectrometry (GC-MS) and the contrast of reference material GC retention time, qualitative analysis is carried out to low-boiling products, determine that product (low boiling) is mainly: gamma-butyrolacton, oxolane, a small amount of propionic acid.Quantitatively carrying out in Varian 450-GC gas-chromatography of low-boiling point material; The quantitative of reactant butanedioic acid carries out on Waters high performance liquid chromatography, by carrying out qualitative, quantitative with reference material retention time and the comparison of peak area size.The yield of product liquid calculates with (mole of target product)/(butanedioic acid mole) × 100%, and correlation computations formula is as follows:
At initial H
25MPa, 35min are from room temperature to 200 DEG C for pressure, and when reacting 3h under target temperature, the conversion ratio of butanedioic acid on palladium-iron catalyst can reach 100%, and butyrolactone yield reaches 92.5%, and oxolane yield reaches 2.6%; When reacting 5h under target temperature, conversion ratio can reach 100%, and butyrolactone yield reaches 80.3%, and oxolane yield reaches 19.7%; Reaction 10h, conversion ratio is 100%, and butyrolactone yield reaches 60.5%, and oxolane yield reaches 39.5%.
Embodiment 9
20mL 1wt% succinic acid solution is added in 50mL stainless steel autoclave, adds the 5%Fe-3%Pd/C catalyst of preparation in 0.04g example 2.After passing into hydrogen exchange three times, fill initial hydrogen pressure 5MPa, stir with the speed of 1000 turns/min, 35min temperature programming to 200 DEG C, in reactor and microcomputer linkage record course of reaction, the change of temperature and pressure, reacts 10 minutes to 72 hours.After reaction terminates, sample thief gas-chromatography (GC) and high performance liquid chromatography (HPLC) carry out analysis and detect, and detection method is with example 8.
Press 5MPa, 35min from room temperature to 200 DEG C at initial H2, when reacting 3h under target temperature, the conversion ratio of butanedioic acid on palladium-iron catalyst can reach 100%, and butyrolactone yield reaches 95.6%, and oxolane yield reaches 2.1%; When reacting 5h under target temperature, conversion ratio can reach 100%, and butyrolactone yield reaches 76.5%, and oxolane yield reaches 22.5%; Reaction 10h, conversion ratio is 100%, and butyrolactone yield reaches 55.2%, and oxolane yield reaches 43.4%.
Embodiment 10
20mL 1wt% succinic acid solution is added in 50mL stainless steel autoclave, adds the 10%Fe-3%Pd/C catalyst of preparation in 0.04g example 3.After passing into hydrogen exchange three times, fill initial hydrogen pressure 5MPa, stir with the speed of 1000 turns/min, 35min temperature programming to 200 DEG C, in reactor and microcomputer linkage record course of reaction, the change of temperature and pressure, reacts 10 minutes to 72 hours.After reaction terminates, sample thief gas-chromatography (GC) and high performance liquid chromatography (HPLC) carry out analysis and detect, and detection method is with example 8.
At initial H
25MPa, 35min are from room temperature to 200 DEG C for pressure, and when reacting 5h under target temperature, the conversion ratio of butanedioic acid on palladium-iron catalyst can reach 100%, and butyrolactone yield reaches 60.4%, and oxolane yield reaches 35.6%; Reaction 10h, conversion ratio is 100%, and butyrolactone yield reaches 50.3%, and oxolane yield reaches 46.4%.
Embodiment 11
20mL 1wt% succinic acid solution is added in 50mL stainless steel autoclave, adds the 20%Fe-3%Pd/C catalyst of preparation in 0.04g example 4.After passing into hydrogen exchange three times, fill initial hydrogen pressure 5MPa, stir with the speed of 1000 turns/min, 35min temperature programming to 200 DEG C, in reactor and microcomputer linkage record course of reaction, the change of temperature and pressure, reacts 10 minutes to 72 hours.After reaction terminates, sample thief gas-chromatography (GC) and high performance liquid chromatography (HPLC) carry out analysis and detect, and detection method is with example 8.
At initial H
25MPa, 35min are from room temperature to 200 DEG C for pressure, and when reacting 5h under target temperature, the conversion ratio of butanedioic acid on palladium-iron catalyst can reach 100%, and butyrolactone yield reaches 48.3%, and oxolane yield reaches 50.6%; Reaction 10h, conversion ratio is 100%, and butyrolactone yield reaches 32.8%, and oxolane yield reaches 65.4%, and extend the reaction time further to 20h, butyrolactone yield is 15.1%, and oxolane yield reaches 73.9%.
Embodiment 12
20mL 1wt% succinic acid solution is added in 50mL stainless steel autoclave, adds the 20%Fe-3%Pd/C catalyst of preparation in 0.04g example 4.After passing into hydrogen exchange three times, fill initial hydrogen pressure 5MPa, stir with the speed of 1000 turns/min, 35min temperature programming to 200 DEG C, in reactor and microcomputer linkage record course of reaction, the change of temperature and pressure, reacts 10 minutes to 72 hours.After reaction terminates, sample thief gas-chromatography (GC) and high performance liquid chromatography (HPLC) carry out analysis and detect, and detection method is with example 8.
Press 2MPa, 35min from room temperature to 200 DEG C at initial H2, when reacting 5h under target temperature, the conversion ratio of butanedioic acid on palladium-iron catalyst can reach 91%, and butyrolactone yield reaches 56.4%, and oxolane yield reaches 35.6%; Reaction 10h, conversion ratio is 100%, and butyrolactone yield reaches 43.5%, and oxolane yield reaches 55.4%; The further prolongation reaction time, butyrolactone yield was 9.5%, and oxolane yield reaches 70.9%, and BDO yield reaches 8.2% to 30h.
Embodiment 13
20mL 1wt% succinic acid solution is added in 50mL stainless steel autoclave, adds the 20%Cu-3%Pd/C catalyst of preparation in 0.04g example 5.After passing into hydrogen exchange three times, fill initial hydrogen pressure 5MPa, stir with the speed of 1000 turns/min, 35min temperature programming to 200 DEG C, in reactor and microcomputer linkage record course of reaction, the change of temperature and pressure, reacts 10 minutes to 72 hours.After reaction terminates, sample thief gas-chromatography (GC) and high performance liquid chromatography (HPLC) carry out analysis and detect, and detection method is with example 8.
At initial H
25MPa, 35min are from room temperature to 180 DEG C for pressure, and when reacting 5h under target temperature, the conversion ratio of butanedioic acid on palladium-iron catalyst can reach 100%, and butyrolactone yield reaches 61.5%, and BDO yield reaches 30.2%; Reaction 10h, conversion ratio is 100%, and butyrolactone yield reaches 40.1%, and BDO yield reaches 50.4%, and extend the reaction time further to 20h, butyrolactone yield is 10.2%, and BDO yield reaches 83.2%.
Embodiment 14
20mL 1wt% succinic acid solution is added in 50mL stainless steel autoclave, adds the 20%Sn-3%Pd/C catalyst of preparation in 0.04g example 5.After passing into hydrogen exchange three times, fill initial hydrogen pressure 5MPa, stir with the speed of 1000 turns/min, 35min temperature programming to 200 DEG C, in reactor and microcomputer linkage record course of reaction, the change of temperature and pressure, reacts 10 minutes to 72 hours.After reaction terminates, sample thief gas-chromatography (GC) and high performance liquid chromatography (HPLC) carry out analysis and detect, and detection method is with example 8.
At initial H
25MPa, 35min are from room temperature to 180 DEG C for pressure, and when reacting 5h under target temperature, the conversion ratio of butanedioic acid on palladium-iron catalyst can reach 100%, and butyrolactone yield reaches 72%, and BDO yield reaches 22%; Reaction 10h, conversion ratio is 100%, and butyrolactone yield reaches 53.4%, and BDO yield reaches 40.7%, and extend the reaction time further to 30h, butyrolactone yield is 3.0%, and BDO yield reaches 90.7%.
Claims (10)
1. be applicable to a catalyst for butanedioic acid hydrogenation reaction, it is characterized in that: being applicable to active component Pd content in the Pd-M catalyst of hydrogenation reaction is 0.05-5wt%, and metal M content is 0.1-30wt%; Metal M is selected from VI
b, VII
b, VIII, I
bin one or more metallic elements; Carrier is active carbon, aluminium oxide, zirconia, titanium oxide, silica, acidic molecular sieve or metal oxide compounds carrier.
2. by the catalyst being applicable to butanedioic acid hydrogenation reaction according to claim 1, it is characterized in that: in described catalyst, active component Pd content is 0.05-3wt%, metal M content is 0.5-20wt%; One or more in metal M chosen from Fe, tin, copper, cobalt, manganese, molybdenum, tin, gold, silver, rhenium; Carrier is active carbon, activated alumina, zirconia, titanium oxide or acidic molecular sieve.
3. by the catalyst being applicable to butanedioic acid hydrogenation reaction according to claim 2, it is characterized in that: one or both the mixing in described metal M chosen from Fe, copper, cobalt, tungsten, molybdenum, rhenium.
4. the preparation method being applicable to the catalyst of butanedioic acid hydrogenation reaction according to claim 1, is characterized in that:
1) aqueous surfactant solution and pH are that the palladium salting liquid of 0.5-5 mixes, and reduction after mixing, forms the Technique of Nano Pd colloidal solution A of surfactants stabilize;
2) carrier to be immersed in M metallic solution 0.5 hour-24 hours, then the carrier B of dry carried metal M;
Or, carrier to be immersed in M metallic solution 0.5 hour-24 hours, then dry, reduce to obtain the carrier B of carried metal M;
Or, carrier to be immersed in M metallic solution 0.5 hour-24 hours, then drying, roasting, the carrier B of carried metal M of reducing to obtain;
3) carrier B of carried metal M joined in Technique of Nano Pd colloidal solution A, fully stir contact, after filtration, washing obtains catalyst;
Or,
1) aqueous surfactant solution and pH are that the palladium salting liquid of 0.5-5 mixes, and form the Technique of Nano Pd colloidal solution A of surfactants stabilize;
2) carrier to be immersed in M metallic solution 0.5 hour-24 hours, then the carrier B of dry carried metal M;
Or, carrier to be immersed in M metallic solution 0.5 hour-24 hours, then dry, reduce to obtain the carrier B of carried metal M;
Or, carrier to be immersed in M metallic solution 0.5 hour-24 hours, then drying, roasting, the carrier B of carried metal M of reducing to obtain;
3) carrier B of carried metal M joined in Technique of Nano Pd colloidal solution A, fully stir contact, reduction after mixing, filtration, washing obtains catalyst.
5., by the preparation method being applicable to the catalyst of butanedioic acid hydrogenation reaction according to claim 4, it is characterized in that: described aqueous surfactant solution be the 1-500 of critical micelle concentration doubly, mean molecule quantity is the aqueous solution of the non-ionic surface active agent between 500-5000.
6. by the preparation method being applicable to the catalyst of butanedioic acid hydrogenation reaction according to claim 5, it is characterized in that: described non-ionic surface active agent is one or more in sapn type surfactant, tween type surfactant, hydrogenated rosin glyceride, AEO methyl-monosilane, polyethylene glycols or APG.
7. by the preparation method being applicable to the catalyst of butanedioic acid hydrogenation reaction according to claim 4, it is characterized in that: described palladium salting liquid is the mixing of one or more in palladium bichloride, the acid of chlorine palladium, palladium nitrate, palladium.
8. by the preparation method being applicable to the catalyst of butanedioic acid hydrogenation reaction according to claim 4, it is characterized in that: described reduction reaction, adopt reducing agent, liquid-phase reduction or vapour phase reduction;
Wherein reducing agent is the mixing of one or more in formaldehyde, hydrazine hydrate, ascorbic acid, sodium borohydride, sodium formate, ethylene glycol, hydrogen.
9. the method utilizing claim 1 catalyst hydrogenation to react, it is characterized in that: take butanedioic acid as raw material, add described catalyst wherein, under polar solvent effect, hydrogenation reaction obtains one or more in gamma-butyrolacton, oxolane and BDO; Wherein, catalyst amount is the 1/10000-1/10 of butanedioic acid quality, and hydrogenation reaction temperature is 100-260 DEG C, and initial hydrogen pressure is 0.5-12MPa.
10. by the method utilizing catalyst hydrogenation to react described in claim 9, it is characterized in that: described hydrogenation reaction temperature is 160-230 DEG C, initial hydrogen pressure is 5-10MPa, and polar solvent is water, alcohols, Isosorbide-5-Nitrae-dioxane.
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| CN104888802A (en) * | 2015-05-21 | 2015-09-09 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing butyric acid and preparation method and application of catalyst |
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