CN104368358B - It is a kind of suitable for the catalyst of butanedioic acid hydrogenation reaction and its preparation and process for selective hydrogenation - Google Patents
It is a kind of suitable for the catalyst of butanedioic acid hydrogenation reaction and its preparation and process for selective hydrogenation Download PDFInfo
- Publication number
- CN104368358B CN104368358B CN201410532878.XA CN201410532878A CN104368358B CN 104368358 B CN104368358 B CN 104368358B CN 201410532878 A CN201410532878 A CN 201410532878A CN 104368358 B CN104368358 B CN 104368358B
- Authority
- CN
- China
- Prior art keywords
- carrier
- catalyst
- butanedioic acid
- palladium
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A kind of Pd M bimetallics or multimetal reforming catalyst are prepared and its for the method for butanedioic acid hydrogenation, and butanedioic acid prepares gamma butyrolactone, tetrahydrofuran, Isosorbide-5-Nitrae butanediol by hydrogenation reaction, can be different according to the composition of catalyst, modulation product ratio.Catalyst load active component Pd contents are 0.05 5wt%, and the second metallized metal M contents are 0.1 30wt%, and preparation method mainly includes：The Technique of Nano Pd colloidal solution of stabilization is prepared by chemical reduction method, the second metal component M is introduced into carrier, with carrier adsorption palladium colloid, then by washing, drying and other steps can obtain the nano Pd particle M catalyst of high dispersive.
Description
Technical field
The present invention relates to butanedioic acid hydrogenation reaction, specifically a kind of catalyst suitable for butanedioic acid hydrogenation reaction and
It is prepared and process for selective hydrogenation.
Background technology
Gamma-butyrolacton, tetrahydrofuran, BDO are very important industrial chemicals, are still mostly come from present
Fossil fuel, substantial amounts of environmental pollution is produced so that people have to look for during the non-renewable and its utilization of fossil fuel
A kind of alternate resources.Butanedioic acid can prepare gamma-butyrolacton, tetrahydrofuran, BDO by a step hydrogenation reaction, but
Traditional production of succinic acid relies primarily on petrochemical technology.With developing rapidly for biofermentation technique, future biological base amber
The yield of amber acid will roll up, and produce high valuable chemicals with butanedioic acid as raw material and have a high potential, lot of domestic and international
Scholar has carried out correlative study to butanedioic acid hydrogenation.
Song etc. is prepared for Pd/Al2O3, Pd/STC and Cu-C catalyst be used for butanedioic acid hydrogenation reaction, product mainly has
Gamma-butyrolacton, tetrahydrofuran and a small amount of 1,4- butanediols.Result illustrates that degree of scatter of the Pd metals on carrier is to catalyst
The effect of catalysis butanedioic acid hydrogenation has significant impact, by improving dispersion of the metal active constituent of load on carrier surface
Degree, can be effectively promoted the hydrogenation reaction of butanedioic acid, improve the yield of target product, prepared by surfactants' templating
Mesoporous high-area carbon (STC) load Ru has preferably activity to the hydrogenation of butanedioic acid, 240 DEG C, is reacted 8 hours under 6MPa hydrogen,
The conversion ratio of butanedioic acid is 90%, and the selectivity of gamma-butyrolacton is up to 74%.But the preparation process of meso-porous carbon material is relatively
Complexity is, it is necessary to the roastings of many steps, washing process.Luque etc. is in the porous carrier prepared by renewable raw materials (starch)On loaded various noble metal active components Pd, Pt, Ru, Rh etc., the load type metal that infusion process is prepared is received
Rice grain has less average particle size particle size, and the load type gold metal nano-particle is applied to the hydrogenation process of butanedioic acid, 100
DEG C, after being reacted 24 hours under 1Mpa hydrogen, 75%, BDO are reached using the butanedioic acid conversion ratio of 5%Pd-Starbon
70% and 30% are respectively with the selectivity of gamma-butyrolacton；78% is reached using the butanedioic acid conversion ratio of 5%Pt-Starbon,
The selectivity of 1,4- butanediols and gamma-butyrolacton is respectively 85% and 15%.Deshpande etc. uses Ru-Co bimetallic catalytics
The hydrogenation reaction of agent catalysis butanedioic acid prepares gamma-butyrolacton and 1,4- butanediols.Its experimental result shows that adulterate Ru in Co
Catalytic hydrogenation activity can be made significant enhancing (3-4 times), and this very strong cooperates with work mainly due to being generated between Co and Ru
With.At 250 DEG C, the product under 10MPa hydrogen is mainly tetrahydrofuran, and the selectivity to BDO is poor, reaction
In exist butanol, propyl alcohol even depth dehydration, hydroformylation product solution.Ru-Co bimetallic catalysts and Co catalyst and Ru/C catalyst
Compare, also there is obvious difference in the distribution of product.The above results prove, we can be living in catalyst by adjusting
Property component controls the distribution of product in butanedioic acid hydrogenation reaction, to realize the optimization to target product yield.Besson etc. sends out
The Pd/TiO of present Re doping2The reaction of butanedioic acid catalytic hydrogenation is applied to, the Pd/TiO in 2wt% is found2Adulterated in catalyst
Re metals can remarkably promote butanedioic acid and be hydrogenated to BDO, and the synergy produced between Pd and Re can simultaneously strengthen amber
Amber acid and the hydrogenation reaction generation 1,4- butanediols of gamma-butyrolacton.1.9%Ru-3.6%Re/C catalyst, second are used at 150 DEG C
Acyl propionic acid can reach 82% for the selectivity of Isosorbide-5-Nitrae-pentanediol, but the specific data of butanedioic acid hydrogenation are not carried in detail
And.The team has been also carried out the monometallic Pd/TiO of distinct methods preparation2The reaction of catalysis butanedioic acid hydrogenation, experimental result shows
Pd catalyst has selectivity higher, the degree of scatter and Pd/TiO of Pd for gamma-butyrolacton2Preparation method to butanedioic acid
Conversion ratio by large effect.But the Pd/TiO2Reaction need Hydrogen Vapor Pressure higher.United States Patent (USP) US 4940805
Report the hydrogenation reaction under Co-Cu and Co-P catalyst such as maleic anhydride, succinyl oxide, maleic acid, butanedioic acid, reaction with
Fatty alcohol is solvent, is carried out in fixed bed reactors, and product is mainly BDO and tetrahydrofuran.But shortcoming is main
It is that used temperature is higher, reaction temperature is more than 230 DEG C.United States Patent (USP) US4609636 and US4550185 describe one kind
Carbon supported palladium, rhenium catalyst catalysis maleic acid, maleic anhydride Hydrogenation are prepared for BDO and the method for tetrahydrofuran
Catalyst on the palladium grain size that loads for 10-25nm rheniums grain size is 2.5nm, preparation method is carried on for palladium prior to rhenium
On activated carbon, the carrying method of palladium and rhenium is the precipitation method.United States Patent (USP) US4985572 provides a kind of load of use charcoal
The method of rhenium, palladium, silver catalyst catalysis carboxylic acid or carboxylic acid anhydrides preparing alcohol by hydrogenating relative class, first crosses precipitation method load by palladium or galactic longitude
On the activated carbon, after high-temperature heat treatment, rhenium is precipitated on the activated carbon again then.The B1 of European patent EP 0722923 uses leaching
Stain method prepare palladium, silver, rhenium catalyst be used for maleic acid, maleic anhydride Hydrogenation for tetrahydrofuran, 1,4- butanediol by-products γ-
Butyrolactone, activated carbon supported palladium, silver, rhenium catalyst are prepared using infusion process, and palladium average crystal grain is less than 10nm.Though Pd catalyst
So can be very good to be applied to butanedioic acid hydrogenation reaction, but because the stability of Pd catalyst is not good, use a period of time
After be susceptible to agglomerated particle become ambassador's hydrogenation activity be easily reduced, the addition of the second component, can be very good suppress Pd catalysis
The deactivation phenomenom of agent.
The content of the invention
It is a kind of suitable for the catalyst of butanedioic acid hydrogenation reaction and its preparation and hydrogenation reaction present invention aim at providing
Method.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of catalyst suitable for butanedioic acid hydrogenation reaction, it is adaptable to active component in the Pd-M catalyst of hydrogenation reaction
Pd contents are 0.05-5wt%, and metal M content is 0.1-30wt%；Metal M is selected from VIB、VIIB、VIII、IBIn one kind or several
Plant metallic element；Carrier is multiple for activated carbon, aluminum oxide, zirconium oxide, titanium oxide, silica, acidic molecular sieve or metal oxide
Compound carrier.
Active component Pd contents are 0.05-3wt% in the catalyst, and metal M content is 0.5-20wt%；Metal M is selected
One or more from iron, tin, copper, cobalt, manganese, molybdenum, tin, gold, silver, rhenium；Carrier be activated carbon, activated alumina, zirconium oxide,
Titanium oxide or acidic molecular sieve.
The metal M is selected from one or two the mixing in iron, copper, cobalt, tungsten, molybdenum, rhenium.
A kind of preparation method of the catalyst suitable for butanedioic acid hydrogenation reaction,
1) aqueous surfactant solution is reduced with pH for the palladium salt solution of 0.5-5 is well mixed after mixing, is formed surface and is lived
Property agent stabilization Technique of Nano Pd colloidal solution A；
2) carrier is immersed -24 hours 0.5 hour in M metallic solutions, the carrier B of then dry carried metal M；
Or, by carrier immerse M metallic solutions in -24 hours 0.5 hour, then dry, reduce carried metal M carrier
B；
Or, carrier is immersed -24 hours 0.5 hour in M metallic solutions, carried metal M is then dried, is calcined, reducing and to obtain
Carrier B；
3) carrier B of carried metal M is added in Technique of Nano Pd colloidal solution A, is sufficiently stirred for contact, through filtering, washing
Obtain catalyst；
Or,
1) aqueous surfactant solution forms surfactant stabilization with pH for the palladium salt solution of 0.5-5 is well mixed
Technique of Nano Pd colloidal solution A；
2) carrier is immersed -24 hours 0.5 hour in M metallic solutions, the carrier B of then dry carried metal M；
Or, by carrier immerse M metallic solutions in -24 hours 0.5 hour, then dry, reduce carried metal M carrier
B；
Or, carrier is immersed -24 hours 0.5 hour in M metallic solutions, carried metal M is then dried, is calcined, reducing and to obtain
Carrier B；
3) carrier B of carried metal M is added in Technique of Nano Pd colloidal solution A, is sufficiently stirred for contact, reduced after mixing,
Filtering, washing obtains catalyst.
The catalyst of above-mentioned acquisition further can be entered before using reducing agent liquid-phase reduction or in atmosphere of hydrogen
Row reduction treatment.
In above-mentioned carrier immersion M metallic solutions, metal M is carried on carrier using existing infusion process or the precipitation method；
The carrier of carried metal M, 50-200 DEG C dries 0.5-24 hours, is calcined under the conditions of 200-700 DEG C after dried process, after roasting
Reduction treatment is carried out by the way of liquid-phase reduction or vapour phase reduction, catalyst is obtained final product, wherein, preferred H during reduction treatment2Gas
Mutually reduce, reduction temperature is 200-700 DEG C, preferably reduction temperature is 300-550 DEG C.
The aqueous surfactant solution is 1-500 times of critical micelle concentration, mean molecule quantity is between 500-5000
Nonionic surfactant the aqueous solution.
The nonionic surfactant is sapn type surfactant, tween type surfactant, hydrogenated rosin glycerine
One or more in ester, AEO methyl-monosilane, polyethylene glycols or APG.
The palladium salt solution is the mixing of one or more in palladium bichloride, the acid of chlorine palladium, palladium nitrate, palladium, preferably chlorine
Change palladium.
The reduction reaction, using reducing agent, liquid-phase reduction or vapour phase reduction；
Wherein reducing agent is the one kind in formaldehyde, hydrazine hydrate, ascorbic acid, sodium borohydride, sodium formate, ethylene glycol, hydrogen
Or several mixing.
When above-mentioned liquid-phase reduction or vapour phase reduction, preferably H2Vapour phase reduction, reduction temperature is 200-700 DEG C, is preferably reduced
Temperature is 300-550 DEG C.
A kind of method of catalyst hydrogenation reaction, with butanedioic acid as raw material, is added thereto to the catalyst, molten in polarity
One or more in hydrogenation reaction acquisition gamma-butyrolacton, tetrahydrofuran and 1,4- butanediols are descended in agent effect；Wherein, catalyst
Consumption 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. using the method for catalyst hydrogenation reaction as described in claim 9, it is characterised in that：The hydrogenation reaction temperature
It is 160-230 DEG C to spend, and initial hydrogen pressure is 5-10MPa, and polar solvent is water, alcohols, Isosorbide-5-Nitrae-dioxane；It is preferred that water.
Advantage for present invention effect is：
1. the raw material selected by hydrogenation reaction of the present invention be bio-based butanedioic acid, can by biofermentation, wide material sources,
Raw material is renewable.
2. hydrogenation reaction of the present invention prepares high valuable chemicals product for gamma-butyrolacton, tetrahydrofuran, 1,4- fourths two
Alcohol, product distribution can according to catalyst constitute Pd-M active components composition, with when carrier it is different it is different with preparation method enter
Row modulation, can obtain one or two products in gamma-butyrolacton, tetrahydrofuran, BDO with advantage, can be through undue
Used after, be widely used.
3. the palladium in nonionic surfactant rugged catalyst, the palladium nanometer of preparation are used when the present invention prepares catalyst
Particle, grain graininess is homogeneous adjustable；After the carrier of catalyst adds the second component M simultaneously, catalyst noble metal component is not only not
It is easy to run off, and can be distributed with the composition of modulation product, catalysis activity is high, long lifespan.The preparation method of catalyst is simple,
Favorable repeatability.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.It should be understood that following examples are merely to illustrate this
Invention is not for restriction the scope of the present invention.
The present invention obtains gamma-butyrolacton, tetrahydrofuran with butanedioic acid as raw material by hydrogenation reaction, specifically includes following
Step：With butanedioic acid：Water=1:10-100 is added in hydrogenation reactor, and adds aM-bPd/ carriers (a=0.1-30%, b=
0.0.5-5%) catalyst, at certain temperature and Hydrogen Vapor Pressure, carries out a step hydrogenation, and the reaction time is 10min-72h, so
After carry out catalyst separation, product isolates volatile product gamma-butyrolacton, tetrahydrofuran through rectifying, and yield is 50-
98%.In described method, from palladium and one or two kinds of Metal Supported on carrier, catalyst amount is amber to catalyst
The 1/1000-1/10 of acid.Hydrogenation reaction temperature is 100-260 DEG C.Initial hydrogen pressure is less than or equal to 12MPa more than 0.5MPa.
Polar solvent is used as reaction dissolvent, such as water, preferably Isosorbide-5-Nitrae-dioxane, alcohols, water.
In butanedioic acid hydroconversion process, the difference of catalyst, product is different, when in Pd-M catalyst M be Fe,
When Co, Ni component, product is butyrolactone and tetrahydrofuran, extends the reaction time, and the amount of butyrolactone product is reduced, tetrahydrofuran
Yield increases, and with tetrahydrofuran as primary product, yield is up to more than 90%, modulation Pd/M ratios, product butyrolactone and four
The distribution of hydrogen furans can also produce change.When M is Cu, W, Mo, Re component, initial reaction stage primary product is butyrolactone and fourth
Glycol, extends the reaction time, and the amount of butyrolactone product is reduced, and the yield of butanediol increases, and with butanediol as primary product, receives
Also up to more than 90%, modulation Pd/M ratios, the distribution of product butyrolactone and butanediol can also produce change to rate.It is transformed at this
Cheng Zhong, acid carrier is conducive to the raising of initial activity, and improves the yield of reaction starting stage butyrolactone.
Catalyst preparation example
Embodiment 1
0.12g frerrous chlorides are taken, is dissolved in 20mL water and is added thereto to 1g activated carbons, pH=8 is adjusted with sodium acid carbonate, stirred
40min is mixed, filtering, fully washing are standby through 300 DEG C of reduction of hydrogen after being then dried overnight at 110 DEG C.Weigh 5.0g tweens
20 are dissolved in 30mL water, stir, and take 0.0548g palladium bichlorides in flask, add 1mL 15wt% sodium chloride solutions to make it
Dissolving, adds NaHCO3Adjust pH value of solution to 3.5.Palladium salt solution is mixed with Tween solution, 0.12g formaldehyde is added thereto to
Solution, orange solution quickly becomes black, obtains palladium colloidal solution.Add palladium colloid molten the above-mentioned activated carbon for loading iron
In liquid, 1h is stirred, filtering, fully washing are obtained 5%Fe-3%Pd/C.
Embodiment 2
0.12g frerrous chlorides are taken, is dissolved in 4mL water, dissolved in add in backward solution load weighted 1g activated carbons, it is quiet
Put 24 hours, be evaporated liquid, drying for standby at 80 DEG C.Weigh 5.0g hydrogenated rosin glycerides to be dissolved in 30mL water, stir,
0.0548g palladium bichlorides are taken in flask, adds 1mL 15wt% sodium chloride solutions to dissolve it, add NaHCO3Adjustment pH value of solution
To 3.Palladium salt solution is mixed with the hydrogenated rosin glyceride aqueous solution, is added thereto to be stirred at 70 DEG C of 0.12g ascorbic acid solutions
Mix 1 hour, orange solution quickly becomes black, obtain palladium colloidal solution.The above-mentioned activated carbon for loading iron is added into palladium glue
In liquid solution, 1h is stirred at room temperature, filtering, fully washing are obtained 5%Fe-3%Pd/C.
Embodiment 3
0.26g frerrous chlorides are taken, is dissolved in 20mL water and is added thereto to 1g activated carbons, pH=8 is adjusted with sodium acid carbonate, stirred
40min is mixed, filtered, fully washed standby.Weigh 5.3g polysorbas20s to be dissolved in 30mL water, stir, take 0.058g palladium bichlorides
In flask, add 1mL 15wt% sodium chloride solutions to dissolve it, add NaHCO3Adjust pH value of solution to 4.By palladium salt solution
Mix with Tween solution, be added thereto to 0.13g formalins, orange solution quickly becomes black, obtain palladium colloid molten
Liquid.By in the above-mentioned activated carbon addition palladium colloidal solution for loading iron, 1h, fully filtering, washing, prepared 10%Fe-3% are stirred
Pd/C。
Embodiment 4
0.59g frerrous chlorides are taken, is dissolved in 20mL water and is added thereto to 1g activated carbons, pH=8 is adjusted with sodium acid carbonate, stirred
40min is mixed, filtered, fully washed standby.Weigh 6.0g polysorbas20s to be dissolved in 30mL water, stir, take 0.066g palladium bichlorides
In flask, add 1mL 15wt% sodium chloride solutions to dissolve it, add NaHCO3Adjust pH value of solution to 4.By palladium salt solution
Mix with Tween solution, be added thereto to 0.15g formalins, 1h is reacted at 80 DEG C, orange solution quickly becomes black
Color, obtains palladium colloidal solution.By in the above-mentioned activated carbon addition palladium colloidal solution for loading iron, room temperature continues to stir 1h, filter,
Fully washing, is obtained 20%Fe-3%Pd/C.
Embodiment 5
2.23g copper nitrates are taken, is dissolved in 20mL water and is added thereto to 1g activated carbons, pH=8, stirring are adjusted with sodium acid carbonate
40min, filters, fully washes standby.Weigh 6.0g polysorbas20s to be dissolved in 30mL water, stir, take 0.066g palladium bichlorides in
In flask, add 1mL 15wt% sodium chloride solutions to dissolve it, add NaHCO3Adjust pH value of solution to 4.By palladium salt solution with
Tween solution mixes, and is added thereto to 80 DEG C of reaction 1h of 0.15g formalins, and orange solution quickly becomes black, obtains
Palladium colloidal solution.By in the above-mentioned activated carbon addition palladium colloidal solution for loading iron, 1h is stirred, filtering, fully washing are prepared
20%Cu-3%Pd/C.
Embodiment 6
1.74g stannic chloride pentahydrates are taken, is dissolved in 4mL water, during solution added into load weighted 1g activated carbons, stand 24
Hour, it is evaporated liquid, drying for standby at 80 DEG C.Weigh 6.0g polysorbas20s to be dissolved in 30mL water, stir, take 0.066g chlorinations
Palladium adds 1mL 15wt% sodium chloride solutions to dissolve it in flask, adds NaHCO3Adjust pH value of solution to 4.Palladium salt is molten
Liquid mixes with Tween solution, is added thereto to 0.15g formalins, and orange solution quickly becomes black, obtains palladium colloid
Solution.By in the above-mentioned activated carbon addition palladium colloidal solution for loading iron, 1h, fully filtering, washing, prepared 20%Sn- are stirred
3%Pd/C.
Embodiment 7
0.12g frerrous chlorides are taken, the dissolving of 1.74g stannic chloride pentahydrates is gone in 10mL water, and solution is added into load weighted 1g
In aluminum oxide living, 24 hours are stood, be evaporated liquid, drying for standby at 80 DEG C.Weigh 5.0g polysorbas20s to be dissolved in 30mL water, stir
Uniformly, 0.0548g palladium bichlorides are taken in flask, adds 1mL 15wt% sodium chloride solutions to dissolve it, add NaHCO3Adjustment
PH value of solution is to 3.5.Palladium salt solution is mixed with Tween solution, stirring 1 is small at being added thereto to 70 DEG C of 0.12g formalins
When, orange solution quickly becomes black, obtains palladium colloidal solution.The above-mentioned activated carbon for loading iron is added into palladium colloidal solution
In, 1h is stirred at room temperature, filtering, fully washing are obtained 5%Fe-20%Sn-3%Pd/ aluminum oxide.
Hydrogenation reaction embodiment
Embodiment 8
To add and make in 0.04g embodiments 1 during 20mL 1wt% succinic acid solutions add 50mL stainless steel autoclaves
Standby 5%Fe-3%Pd/C catalyst.Be passed through hydrogen replace three times after, initial hydrogen pressure 5MPa is filled, with 1000 turns/min's
Speed is stirred, 35min temperature programmings to 200 DEG C, reactor and temperature and pressure in microcomputer linkage record course of reaction
Change, reacts 10 minutes to 72 hours.After reaction terminates, room temperature is cooled to, takes the supernatant fluid after centrifugation, cross 0.22 μm of filter
Film, detection is analyzed with gas-chromatography (GC) and high performance liquid chromatography (HPLC).By gas chromatography mass spectrometry (GC-MS) and reference material
The control of GC retention times carries out qualitative analysis to low-boiling products, determines that product (low boiling) is mainly：Gamma-butyrolacton,
Tetrahydrofuran, a small amount of propionic acid.Quantifying for low-boiling point material is carried out in Varian 450-GC gas-chromatographies；Reactant amber
The quantitative of amber acid is carried out on Waters high performance liquid chromatography, is carried out by being compared with reference material retention time and peak area size
Qualitative, quantitative.The yield of product liquid is calculated with (mole of target product)/(butanedioic acid mole) × 100%, phase
Close computing formula as follows：
In initial H2, from room temperature to 200 DEG C, when reacting 3h under target temperature, butanedioic acid is urged in palladium-iron for pressure 5MPa, 35min
Conversion ratio in agent can reach 100%, and butyrolactone yield reaches 92.5%, and tetrahydrofuran yield reaches 2.6%；Target temperature
During lower reaction 5h, conversion ratio can reach 100%, and butyrolactone yield reaches 80.3%, and tetrahydrofuran yield reaches 19.7%；Reaction
10h, conversion ratio is 100%, and butyrolactone yield reaches 60.5%, and tetrahydrofuran yield reaches 39.5%.
Embodiment 9
To add and prepare in 0.04g examples 2 during 20mL 1wt% succinic acid solutions add 50mL stainless steel autoclaves
5%Fe-3%Pd/C catalyst.Be passed through hydrogen replace three times after, initial hydrogen pressure 5MPa is filled, with the speed of 1000 turns/min
Degree is stirred, 35min temperature programmings to 200 DEG C, the change of reactor and temperature and pressure in microcomputer linkage record course of reaction
Change, react 10 minutes to 72 hours.After reaction terminates, take sample is carried out with gas-chromatography (GC) and high performance liquid chromatography (HPLC)
Analysis detection, detection method is with example 8.
5MPa is pressed in initial H2,35min from room temperature to 200 DEG C, when reacting 3h under target temperature, in palladium-iron urge by butanedioic acid
Conversion ratio in agent can reach 100%, and butyrolactone yield reaches 95.6%, and tetrahydrofuran yield reaches 2.1%；Target temperature
During lower reaction 5h, conversion ratio can reach 100%, and butyrolactone yield reaches 76.5%, and tetrahydrofuran yield reaches 22.5%；Reaction
10h, conversion ratio is 100%, and butyrolactone yield reaches 55.2%, and tetrahydrofuran yield reaches 43.4%.
Embodiment 10
To add and prepare in 0.04g examples 3 during 20mL 1wt% succinic acid solutions add 50mL stainless steel autoclaves
10%Fe-3%Pd/C catalyst.Be passed through hydrogen replace three times after, initial hydrogen pressure 5MPa is filled, with the speed of 1000 turns/min
Degree is stirred, 35min temperature programmings to 200 DEG C, the change of reactor and temperature and pressure in microcomputer linkage record course of reaction
Change, react 10 minutes to 72 hours.After reaction terminates, take sample is carried out with gas-chromatography (GC) and high performance liquid chromatography (HPLC)
Analysis detection, detection method is with example 8.
In initial H2, from room temperature to 200 DEG C, when reacting 5h under target temperature, butanedioic acid is urged in palladium-iron for pressure 5MPa, 35min
Conversion ratio in agent can reach 100%, and butyrolactone yield reaches 60.4%, and tetrahydrofuran yield reaches 35.6%；Reaction
10h, conversion ratio is 100%, and butyrolactone yield reaches 50.3%, and tetrahydrofuran yield reaches 46.4%.
Embodiment 11
To add and prepare in 0.04g examples 4 during 20mL 1wt% succinic acid solutions add 50mL stainless steel autoclaves
20%Fe-3%Pd/C catalyst.Be passed through hydrogen replace three times after, initial hydrogen pressure 5MPa is filled, with the speed of 1000 turns/min
Degree is stirred, 35min temperature programmings to 200 DEG C, the change of reactor and temperature and pressure in microcomputer linkage record course of reaction
Change, react 10 minutes to 72 hours.After reaction terminates, take sample is carried out with gas-chromatography (GC) and high performance liquid chromatography (HPLC)
Analysis detection, detection method is with example 8.
In initial H2, from room temperature to 200 DEG C, when reacting 5h under target temperature, butanedioic acid is urged in palladium-iron for pressure 5MPa, 35min
Conversion ratio in agent can reach 100%, and butyrolactone yield reaches 48.3%, and tetrahydrofuran yield reaches 50.6%；Reaction
10h, conversion ratio is 100%, and butyrolactone yield reaches 32.8%, and tetrahydrofuran yield reaches 65.4%, further extension reaction
Time, butyrolactone yield was 15.1%, and tetrahydrofuran yield reaches 73.9% to 20h.
Embodiment 12
To add and prepare in 0.04g examples 4 during 20mL 1wt% succinic acid solutions add 50mL stainless steel autoclaves
20%Fe-3%Pd/C catalyst.Be passed through hydrogen replace three times after, initial hydrogen pressure 5MPa is filled, with the speed of 1000 turns/min
Degree is stirred, 35min temperature programmings to 200 DEG C, the change of reactor and temperature and pressure in microcomputer linkage record course of reaction
Change, react 10 minutes to 72 hours.After reaction terminates, take sample is carried out with gas-chromatography (GC) and high performance liquid chromatography (HPLC)
Analysis detection, detection method is with example 8.
2MPa is pressed in initial H2,35min from room temperature to 200 DEG C, when reacting 5h under target temperature, in palladium-iron urge by butanedioic acid
Conversion ratio in agent can reach 91%, and butyrolactone yield reaches 56.4%, and tetrahydrofuran yield reaches 35.6%；Reaction 10h,
Conversion ratio is 100%, and butyrolactone yield reaches 43.5%, and tetrahydrofuran yield reaches 55.4%；Further extend the reaction time
To 30h, butyrolactone yield is 9.5%, and tetrahydrofuran yield reaches 70.9%, and BDO yield reaches 8.2%.
Embodiment 13
To add and prepare in 0.04g examples 5 during 20mL 1wt% succinic acid solutions add 50mL stainless steel autoclaves
20%Cu-3%Pd/C catalyst.Be passed through hydrogen replace three times after, initial hydrogen pressure 5MPa is filled, with the speed of 1000 turns/min
Degree is stirred, 35min temperature programmings to 200 DEG C, the change of reactor and temperature and pressure in microcomputer linkage record course of reaction
Change, react 10 minutes to 72 hours.After reaction terminates, take sample is carried out with gas-chromatography (GC) and high performance liquid chromatography (HPLC)
Analysis detection, detection method is with example 8.
In initial H2, from room temperature to 180 DEG C, when reacting 5h under target temperature, butanedioic acid is urged in palladium-iron for pressure 5MPa, 35min
Conversion ratio in agent 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 further extension is anti-
To 20h between seasonable, butyrolactone yield is 10.2%, and BDO yield reaches 83.2%.
Embodiment 14
To add and prepare in 0.04g examples 5 during 20mL 1wt% succinic acid solutions add 50mL stainless steel autoclaves
20%Sn-3%Pd/C catalyst.Be passed through hydrogen replace three times after, initial hydrogen pressure 5MPa is filled, with the speed of 1000 turns/min
Degree is stirred, 35min temperature programmings to 200 DEG C, the change of reactor and temperature and pressure in microcomputer linkage record course of reaction
Change, react 10 minutes to 72 hours.After reaction terminates, take sample is carried out with gas-chromatography (GC) and high performance liquid chromatography (HPLC)
Analysis detection, detection method is with example 8.
In initial H2, from room temperature to 180 DEG C, when reacting 5h under target temperature, butanedioic acid is urged in palladium-iron for pressure 5MPa, 35min
Conversion ratio in agent 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%, further during extension reaction
Between to 30h, butyrolactone yield is 3.0%, and BDO yield reaches 90.7%.
Claims (8)
1. a kind of method that butanedioic acid is hydrogenated with, it is characterised in that：With butanedioic acid as raw material, the catalyst is added thereto to,
One or more in hydrogenation reaction acquisition gamma-butyrolacton, tetrahydrofuran and 1,4- butanediols are descended in polar solvent effect；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；
Active component Pd contents are 0.05-5wt% in the catalyst, and metal M content is 0.1-30wt%；Metal M is selected from VIB、
VIIB、VIII、IBIn one or more metallic elements；Carrier is activated carbon, aluminum oxide, zirconium oxide, titanium oxide, silica, acid
Property molecular sieve or metal oxide compounds carrier；
The preparation method of catalyst is：1) aqueous surfactant solution is well mixed with the palladium salt solution that pH is 0.5-5, after mixing
Reduction, forms the Technique of Nano Pd colloidal solution A of surfactant stabilization；
2) carrier is immersed -24 hours 0.5 hour in M metallic solutions, the carrier B of then dry carried metal M；
Or, by carrier immerse M metallic solutions in -24 hours 0.5 hour, then dry, reduce carried metal M carrier B；
Or, will carrier immerse M metallic solutions in -24 hours 0.5 hour, then dry, be calcined, reducing carried metal M load
Body B；
3) carrier B of carried metal M is added in Technique of Nano Pd colloidal solution A, is sufficiently stirred for contact, through filtering, washing is obtained
Catalyst；
Or,
1) aqueous surfactant solution forms the nanometer of surfactant stabilization with pH for the palladium salt solution of 0.5-5 is well mixed
Palladium colloidal solution A；
2) carrier is immersed -24 hours 0.5 hour in M metallic solutions, the carrier B of then dry carried metal M；
Or, by carrier immerse M metallic solutions in -24 hours 0.5 hour, then dry, reduce carried metal M carrier B；
Or, will carrier immerse M metallic solutions in -24 hours 0.5 hour, then dry, be calcined, reducing carried metal M load
Body B；
3) carrier B of carried metal M is added in Technique of Nano Pd colloidal solution A, is sufficiently stirred for contact, reduced after mixing, filtered,
Washing obtains catalyst.
2. the method that the butanedioic acid as described in claim 1 is hydrogenated with, it is characterised in that：Active component Pd contents in the catalyst
It is 0.05-3wt%, metal M content is 0.5-20wt%；Metal M is selected from iron, tin, copper, cobalt, manganese, molybdenum, tin, gold, silver, rhenium
One or more；Carrier is activated carbon, activated alumina, zirconium oxide, titanium oxide or acidic molecular sieve.
3. the catalyst suitable for butanedioic acid hydrogenation reaction as described in claim 2, it is characterised in that：The metal M is selected from
One or two mixing in iron, copper, cobalt, tungsten, molybdenum, rhenium.
4. the method that the butanedioic acid as described in claim 1 is hydrogenated with, it is characterised in that：The aqueous surfactant solution is critical
1-500 times, the aqueous solution that mean molecule quantity is the nonionic surfactant between 500-5000 of micellar concentration.
5. the method that the butanedioic acid as described in claim 4 is hydrogenated with, it is characterised in that：The nonionic surfactant is sapn
Type surfactant, tween type surfactant, hydrogenated rosin glyceride, AEO methyl-monosilane, poly- second two
One or more in alcohols or APG.
6. the method that the butanedioic acid as described in claim 1 is hydrogenated with, it is characterised in that：The palladium salt solution is palladium bichloride, chlorine palladium
The mixing of one or more in acid, palladium nitrate, palladium.
7. the method that the butanedioic acid as described in claim 1 is hydrogenated with, it is characterised in that：The reduction reaction using liquid-phase reduction or
Person's vapour phase reduction；
Wherein reducing agent is the one kind or several in formaldehyde, hydrazine hydrate, ascorbic acid, sodium borohydride, sodium formate, ethylene glycol, hydrogen
The mixing planted.
8. the method that the butanedioic acid as described in claim 1 is hydrogenated with, it is characterised in that：The hydrogenation reaction temperature is 160-230
DEG C, initial hydrogen pressure is 5-10MPa, and polar solvent is water, alcohols, Isosorbide-5-Nitrae-dioxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410532878.XA CN104368358B (en) | 2014-10-11 | 2014-10-11 | It is a kind of suitable for the catalyst of butanedioic acid hydrogenation reaction and its preparation and process for selective hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410532878.XA CN104368358B (en) | 2014-10-11 | 2014-10-11 | It is a kind of suitable for the catalyst of butanedioic acid hydrogenation reaction and its preparation and process for selective hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104368358A CN104368358A (en) | 2015-02-25 |
| CN104368358B true CN104368358B (en) | 2017-06-06 |
Family
ID=52547704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410532878.XA Active CN104368358B (en) | 2014-10-11 | 2014-10-11 | It is a kind of suitable for the catalyst of butanedioic acid hydrogenation reaction and its preparation and process for selective hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104368358B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888802B (en) * | 2015-05-21 | 2017-03-01 | 中国科学院青岛生物能源与过程研究所 | A kind of for preparing catalyst of butanoic acid as well as preparation method and application thereof |
| CN104923218A (en) * | 2015-05-28 | 2015-09-23 | 中国科学院青岛生物能源与过程研究所 | Catalyst for itaconic acid hydrogenation as well as preparation method and use of catalyst, and method for preparing high value-added products from itaconic acid |
| CN107245026A (en) * | 2017-06-22 | 2017-10-13 | 江苏飞翔化工股份有限公司 | The solvent-free method that glycol is prepared by lactone |
| CN110862302B (en) * | 2018-08-27 | 2022-10-28 | 中国石化扬子石油化工有限公司 | Method for preparing 1, 4-butanediol by combining slurry bed hydrogenation and fixed bed hydrogenation |
| CN109317140B (en) * | 2018-10-19 | 2021-10-15 | 江苏清泉化学股份有限公司 | Catalyst for preparing gamma-acetyl propanol and application thereof |
| CN111097411B (en) * | 2018-10-25 | 2024-01-23 | 中国石油化工股份有限公司 | Liquid-phase hydrogenation synthesis method of 1, 5-pentanediol based on modified palladium supported catalyst |
| CN110882695A (en) * | 2019-12-17 | 2020-03-17 | 江苏欣诺科催化剂有限公司 | Palladium-carbon catalyst and method and application thereof |
| CN111203217B (en) * | 2020-03-11 | 2022-08-05 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method and application thereof in p-tert-butylphenol hydrogenation |
| CN112642441B (en) * | 2020-12-10 | 2022-12-02 | 西安凯立新材料股份有限公司 | Catalyst for preparing 1,2, 4-butanetriol through catalytic hydrogenation and preparation method and application thereof |
| CN114345335B (en) * | 2022-01-18 | 2023-09-26 | 北京工业大学 | Ternary metal catalyst with excellent chlorine resistance and high-efficiency catalytic oxidation mixed VOCs |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1534136A (en) * | 1975-04-18 | 1978-11-29 | Gaf Corp | Hydrogenation catalyst composition process of producing same and production of gamma-butyrolactone from maleic anhydride therewith |
| US4083809A (en) * | 1976-08-20 | 1978-04-11 | Gaf Corporation | Hydrogenation catalyst and method of producing same |
| US4480115A (en) * | 1983-03-17 | 1984-10-30 | Celanese Corporation | Direct hydrogenation of carboxylic acids to alcohol and esters |
| JPH0641106A (en) * | 1992-02-10 | 1994-02-15 | Tosoh Corp | Production of lactones |
| DE10225929A1 (en) * | 2002-06-11 | 2003-12-24 | Basf Ag | Two-stage process for the production of butanediol with intermediate separation of succinic anhydride |
| JP5442776B2 (en) * | 2009-02-26 | 2014-03-12 | サソール テクノロジー（プロプライエタリー）リミテッド | Preparation of Fischer-Tropsch catalyst and use thereof |
| KR101088100B1 (en) * | 2010-06-04 | 2011-11-29 | 서울대학교산학협력단 | PALLADIUM CATALYST SUPPORTED ON ALUMINA XEROGEL SUPPORT WITH CONTROLLED ACIDITY AND PRODUCTION METHOD OF γ-BUTYROLACTONE BY HYDROGENATION OF SUCCINIC ACID USING SAID CATALYST |
| CN102311332B (en) * | 2010-07-07 | 2013-11-20 | 中国石油化工股份有限公司 | Method for producing succinic acid |
| KR101303898B1 (en) * | 2011-07-27 | 2013-09-05 | 한국생산기술연구원 | The palladium supported tungsten alumina catalyst for hydrogenation, preparing method thereof and an application of the same |
| CN103288596B (en) * | 2012-02-27 | 2015-08-26 | 中国科学院大连化学物理研究所 | A kind of organic acid Hydrogenation is for the method for monohydroxy-alcohol or dibasic alcohol |
| CN102659724B (en) * | 2012-04-12 | 2016-01-20 | 中科合成油技术有限公司 | A kind of preparation method of succinyl oxide |
| CN103007929B (en) * | 2012-12-07 | 2018-01-12 | 上海华谊（集团）公司 | The Pd bases catalyst of colloidal deposition method preparation, preparation method and application |
| CN103113325A (en) * | 2013-02-27 | 2013-05-22 | 大连理工大学 | Method for preparing gamma-butyrolactone and tetrahydrofuran through water-phase catalytic hydrogenation of biomass-based succinic acid |
| CN103769094B (en) * | 2014-01-20 | 2015-09-23 | 中国科学院宁波材料技术与工程研究所 | A kind of egg-shell catalyst for selective hydrogenation, preparation method and application |
-
2014
- 2014-10-11 CN CN201410532878.XA patent/CN104368358B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104368358A (en) | 2015-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104368358B (en) | It is a kind of suitable for the catalyst of butanedioic acid hydrogenation reaction and its preparation and process for selective hydrogenation | |
| Mishra et al. | Selective hydrogenation of d-glucose to d-sorbitol over HY zeolite supported ruthenium nanoparticles catalysts | |
| Li et al. | A Ce-promoted Ni–B amorphous alloy catalyst (Ni–Ce–B) for liquid-phase furfural hydrogenation to furfural alcohol | |
| Dabbawala et al. | Selective hydrogenation of D-glucose using amine functionalized nanoporous polymer supported Ru nanoparticles based catalyst | |
| Mishra et al. | Liquid phase hydrogenation of d-glucose to d-sorbitol over the catalyst (Ru/NiO–TiO2) of ruthenium on a NiO-modified TiO2 support | |
| Wang et al. | Catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol with formic acid as hydrogen donor over CuCs-MCM catalyst | |
| CN105833864B (en) | A kind of support type nano spherical particle palladium catalyst and its preparation method and application | |
| CN103977819A (en) | Method for activating adiponitrile hydrogenation catalyst | |
| Tian et al. | Synthesis of nitrogen-doped carbon coated TiO2 microspheres and its application as metal support in cinnamaldehyde hydrogenation | |
| CN110240578A (en) | A kind of plus hydrogen prepares the method for tetrahydrofurfuryl alcohol and nickel catalyst carried | |
| Huang et al. | Active ruthenium catalysts prepared by Cacumen Platycladi leaf extract for selective hydrogenation of maleic anhydride | |
| CN104801299A (en) | Plant reduction preparation method of ruthenium-on-carbon catalyst, ruthenium-on-carbon catalyst and application | |
| CN109647394B (en) | Catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof | |
| CN114054034B (en) | Multi-element copper-based non-noble metal hydrogenation catalyst, and preparation method and application thereof | |
| CN101711982B (en) | Supported nano Au catalyst for preparing crotyl alcohol and preparation method thereof | |
| CN102553592A (en) | High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof | |
| CN111135828B (en) | Catalyst and application, preparation and performance test method of catalyst | |
| Ma et al. | Liquid phase hydrogenation of biomass-derived ethyl lactate to propane-1, 2-diol over a highly active CoB amorphous catalyst | |
| CN106861689A (en) | A kind of Pd bases catalyst and its preparation and application | |
| CN102861573A (en) | Carrier type platinum-ruthenium catalyst and application to hydrogenation of halide-containing nitro compound | |
| CN108114727B (en) | Hydrogenation catalyst, preparation method and application thereof | |
| CN108144618B (en) | Hydrogenation catalyst, preparation method and application thereof | |
| CN112264028B (en) | Boron-multi-metal alloy catalyst, preparation method and application in preparation of cyclopentanone through furfuryl alcohol hydrogenation rearrangement | |
| CN104888802A (en) | Catalyst for preparing butyric acid and preparation method and application of catalyst | |
| CN115043708A (en) | Method for synthesizing 1,4-butanediol by catalytic hydrogenation of maleic anhydride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |