CN1004791B - Pd/re hydrogenation catalyst and process for making same - Google Patents
Pd/re hydrogenation catalyst and process for making same Download PDFInfo
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- CN1004791B CN1004791B CN85101672.3A CN85101672A CN1004791B CN 1004791 B CN1004791 B CN 1004791B CN 85101672 A CN85101672 A CN 85101672A CN 1004791 B CN1004791 B CN 1004791B
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Abstract
The present invention relates to a Pd/Re catalyst on a carbon carrier, a method for preparing tetrahydrofuran, 1, butanediol-1, 4, or the mixture thereof by various reactant raw materials (with selected ratios) with the catalyst, and a method for preparing a Pd/Re/C catalyst with the catalyst.
Description
The present invention relates to a kind of tetrahydrofuran (THF), 1 that is used to make, the palladium of 4-two butanols and composition thereof/rhenium composite catalyst and manufacture method thereof.
United States Patent (USP) 4176088 discloses a kind of many metal composite catalytic material of going back ortho states, it is to be combined with the porous carrier materials that contains the platinum-group component of effective catalytic amount by the ADSORPTION STATE rhenium oxide component with effective catalytic amount to form, the platinum component exists with the metal element attitude, and is dispersed in the solid support material.This patent also discloses the manufacture method of this compound catalyze material.In the method, the predetermined rhenium oxide reagent of use is introduced the rhenium component in catalyzer before, a kind of material (handling through halogen usually) that contains predetermined oxidation state platinum metals is stood anhydrous basically reduction treatment step.This patent is also addressed usefulness " platinum " and is represented any platinum group metal, but only mentions platinum in actual the giving an example.
United States Patent (USP) 4157989 discloses a kind of many metal composite catalytic material that hydrocarbon transforms that is used for.It is to be combined to form by pyrolysis rhenium carbonyl component with effective catalytic amount and the porous carrier materials that contains the platinum-group component of effective catalytic amount, and the platinum component is dispersed in this porous carrier materials with the metal element state.When this compound catalyze material is applied to need to use when having the hydrocarbon technology of catalyzer that hydrogenation/dehydrogenation function and carbon ion form function, it is said have good activity, selectivity and anti-inactivation.This patent also discloses the manufacture method of this compound catalyze material, wherein the predetermined rhenium carbonyl reagent of use is introduced the rhenium component in catalyzer before, to contain predetermined oxidation state platinum metals and material that handle through halogen usually, stand anhydrous basically reduction treatment step.
Opposite with above-mentioned patent, the present invention is stated from palladium/rhenium compound catalyze material on the carbon support.Catalyzer of the present invention can provide: a) tetrahydrofuran (THF) and 1, the transformation efficiency of the precursor of 4-butyleneglycol is near 100%, b) produce tetrahydrofuran (THF) and 1, the selectivity height of 4-butyleneglycol, c) have and to control tetrahydrofuran (THF) and 1, the advantage of the proportion of products of 4-butyleneglycol is as long as change the space time of temperature, duration of contact and/or hydrogen.
The present invention touch upon palladium and rhenium composite catalyst on the carbon support, this catalyzer contains the palladium of the 0.5%-10% that has an appointment and the rhenium of about 1%-10% (by weight).This catalyzer contains the palladium of 1%-6% and the rhenium of 3%-6% usually, preferably contains 3% palladium and 3% rhenium.
Contained palladium is the crystal grain form in palladium/rhenium of the present invention/C catalyst, and its median size is the 10-25 millimicron, and rhenium is the crystal grain form of high dispersive phase, and its particle diameter is less than 2.5 millimicrons, preferably less than 1.5 millimicrons.Use H
2/ O
2Volumetry can be measured the grain size of palladium, can measure the grain size of rhenium with scanning transmission electron microscope (STEM).The rhenium crystal grain of high dispersive is too little so can not measure with X-ray diffraction or with STEM.
Also the touch upon manufacture method of above-mentioned catalyzer of the present invention, this manufacture method in turn includes the following steps:
(1) with palladium source (solution of palladium) impregnated carbon carrier and except that desolvating;
(2) under the temperature of 150 ℃-550 ℃ (being preferably in 200 ℃-300 ℃), under reductive condition, heating is generally 2-5 hour heat-up time through the carbon of palladium dipping;
(3) on the carbon of palladium dipping, be coated with rhenium source (solution of rhenium), removing and desolvate to make palladium/rhenium/C catalyst.
Under the temperature of 150 ℃-550 ℃ (being preferably in 200 ℃-300 ℃), under reductive condition, the palladium/rhenium/C catalyst that makes in the heating above-mentioned steps (3) is generally 2-5 hour heat-up time.Reduction reaction can carry out immediately after the step (3) just reacting preceding or begin to react in hydrogenator, carry out.
In the catalyzer building-up process, preferably have I
AOr II
AFamily's metal such as potassium, sodium, lithium, calcium or magnesium, its amount are about the mole number of 0.1-1 mol %(based on carbon in the carrier).The surface-area of carrier is usually greater than 650 meters
2/ gram is (more preferably greater than 900 meters
2/ gram).
The present invention also touches upon and makes hydrogenatable parent hydrogenation and selectivity manufacturing tetrahydrofuran (THF), 1, the method of 4-butyleneglycol or its mixture, hydrogenatable parent such as maleic anhydride, toxilic acid, fumaric acid, succsinic acid, oxysuccinic acid, succinate such as dimethyl succinate, the mixture of r-butyrolactone or two or more above-claimed cpds, these hydrogenatable parents are in water medium or in organic solvent medium, temperature of reaction is about 130 ℃-285 ℃, hydrogen pressure is about 300Psig(2MPa-5000Psig(35Mpa), the space-time of hydrogen is about 1-10 minute, under the situation that the palladium on the above-mentioned carbon support-rhenium catalyst exists, reaction raw materials and catalyzer are about 0.5-7 hour duration of contact.Typical organic medium comprises diox, r-butyrolactone and similar compounds.Parent is preferably toxilic acid and maleic anhydride.
Catalyzer of the present invention has following feature: parent 100% is transformed basically; (b) tetrahydrofuran (THF)/1 to generating, the selectivity of 4-butyleneglycol product is good; (c) just can control tetrahydrofuran (THF)/1 by changing temperature, duration of contact and/or the space-time of hydrogen being adjusted to desired operating restraint or the like, the productive rate of 4-butyleneglycol, in general, temperature is high more, duration of contact is long more and/or hydrogen space-time is big more, the tetrahydrofuran (THF) that obtains/1, the ratio of 4-butyleneglycol is high more, and vice versa.So-called hydrogen space-time is meant that under reaction conditions, reaction volume is divided by the flow velocity of hydrogen.
The present invention also touches upon and uses positive C
4Hydrocarbon or aromatic hydrocarbons are made tetrahydrofuran (THF) continuously, and 1, the method for 4-butyleneglycol or its mixture, this method comprises the following steps:
(1) oxygenated hydrocarbon is to generate maleic anhydride;
(2) maleic anhydride that makes in the step (1) is collected in the aqueous solution;
(3) under above-mentioned reaction conditions, under the situation that palladium/rhenium of the present invention/C catalyst is arranged, make the toxilic acid aqueous solution and H-H reaction.
In above-mentioned reaction,, in the aqueous medium that makes, toxilic acid is gone up fully substantially transformed with the palladium-rhenium catalyst on the carbon support, and tetrahydrofuran (THF)/1, the production selectivity of 4-butyleneglycol is good.Palladium-rhenium catalyst on the carbon support of the present invention is very effective to continuous production processes.
Detailed description of the invention
Catalyzer:
A kind of method for making of catalyzer is as follows: (a) be coated with palladium compound solution also except that desolvating on carbon support; (b) 150 ℃-550 ℃ (being preferably in 200 ℃-300 ℃), under reductive condition, the carbon that obtains in the heating steps (a), the composite palladium catalyzer (Pd/C) on the carbon support that makes in the cooling step (b) with the palladium compound dipping; (c) on this composite palladium catalyzer, be coated with the solution of rhenium compound also except that desolvating.
150 ℃-550 ℃ (being preferably in 200 ℃-300 ℃), under reductive condition, the palladium/carbon with the rhenium compound dipping that makes in the heating above-mentioned steps (c) is preferably 2-5 hour heat-up time.Can after step (c), heat immediately, also can in hydrogenator, before reaction just takes place or in the reaction beginning, heat.
Be preferably in I
AOr II
APrepare palladium/rhenium/C catalyst under the situation of family's metal such as potassium, sodium, lithium, calcium or magnesium.Above-mentioned metal can be included in the carbon support that makes or can add in addition.If no above-mentioned metal in the carbon support, available I
AOr II
AFamily's solution of metal compound impregnated carbon carrier, these metallic compounds such as Licl, Nacl, Kcl, KOH, NaOH, Cacl
2Or Mgcl
2, 6H
2O.Can believe I
AOr II
AThe microstructure of family's metal pair catalyzer is good.
Add I
AOr II
AThe another kind of method of family's metal is as follows: with I
AOr II
AFamily's metallic compound is added in the solution of palladium compound or with also containing I
AOr II
AThe palladium compound of family's metal such as K
2PdCl
4Or Na
2Pdcl
4, can add I by palladium like this
AOr II
AFamily's metal.Preferably with I
AOr II
AFamily's metal is added on the carbon support and before with palladium source impregnated carbon carrier, under 200 ℃-400 ℃ temperature, calcined impregnated carbon 2-6 hour.
The method of solution that is coated with palladium compound and rhenium compound on carbon is as follows: carbon support material can be immersed or be suspended in the solution or spray solution on carbon.The acidic aqueous media that contains the normally hydrochloric and a certain amount of palladium compound of the solution of palladium compound, thereby the catalyzer that makes contains the palladium of specified amount.Palladium compound is Pdcl normally
2, but also can be following palladium compound: nitrate, carbonate, carboxylate salt, acetate, acetyl pyruvate or amine.The solution that contains rhenium compound normally contains the water medium of certain rhenium compound, thereby the catalyzer that makes contains the rhenium of specified amount.Rhenium compound is generally Re
2O
7, but also can be the perrhenate or the alkali-metal perrhenate of ammonium.
What is called heats under reductive condition, and the meaning is meant in reductant (being preferably hydrogen) and heats.Usually make sample reductive method as follows:, in the He air-flow, sample to be heated about 1 hour, then at 150 ℃, at He/H earlier at 150 ℃
2(He/H in the air-flow
2Mole ratios be 50: 50) about 1 hour of heated sample, at last at 150 ℃-550 ℃ at He/H
2(He/H in the air-flow
2Mole ratios be 50: 50) heated at the most 3 hours.
In catalyst preparation process, in carbon support if contain I
AOr II
AFamily's metal, then available X-ray diffraction and scanning transmission electron microscope are observed contained ReO in the catalyzer
- 4The big crystal grain of salt (about 0.2 micron).If this catalyzer is placed (as in the hydrogenation of maleic acid process) under the reductive condition once more, and then measure, just do not detect ReO
- 4Salt or contain I
AOr II
AThe phase of family's metal-salt.And still contain the above-mentioned palladium and the crystal grain of rhenium in the catalyzer.
Catalysis process:
If use positive C
4Hydrocarbon is as reaction raw materials, and this method does not have particular requirement (and requiring to separate and the purifying maleic anhydride) to equipment, the energy and time in relevant hydrogenant look-ahead technique.Catalysis process generally includes following steps: (a) in oxygen-containing gas, just make under the situation of the mixed oxide catalyst that vanadium/phosphorus is arranged-butane or benzene reaction, thereby make the n butane oxidation in the vapor phase become maleic anhydride; (b) collect maleic anhydride, the water quenching is to make the toxilic acid aqueous solution, and strength of solution is about 40%(by weight); (c) under the situation that palladium/rhenium/hydrocarbonize catalyzer is arranged, make the solution and the H-H reaction that make in the step (b).
Above-mentioned oxidation step (a) is preferably under 300 ℃-600 ℃ the temperature, operates under the pressure of 0.5-20 normal atmosphere (50-2000KPa), and the service temperature of step of hydrogenation (c) is about 150 ℃-275 ℃, and hydrogen pressure is about 300 pounds/inch
2(MPa-5000 pound/inch
2(35MPa).
With common instrument and technology, in the agitated pool reactor or in fixed-bed reactor, can carry out liquid phase hydrogenation of the present invention.Hydrogen adds continuously, makes the hydrogen add-on substantially exceed stoichiometry with non-inert dilution gas usually.Unreacted hydrogen can be got back in the reactor with the round-robin air-flow, and mother solution such as maleic acid solution also add continuously, and its concentration range can be about 30%-40%(by weight usually from dilute solution near maxima solubility).The catalyst carbon carrier particle diameter of using in the agitated pool reactor is about 200 orders, the carrier particle diameter of in fixed-bed reactor, using big [for by 60 sieve apertures 1/4 " (0.64 centimetre)].Catalyst levels can be according to the size and the structure of multiple factor such as reactor.Change with similar other factors duration of contact, for example, for the reactor of 60 ml volumes, the most handy 25 gram catalyzer.Used catalyst content is the rhenium/carbon of 3% palladium/3%.
Following example can further specify the present invention, temperature in the example is degree centigrade (unless otherwise indicated), all hydrogenation experiment all is to be (unless otherwise indicated) of carrying out in the reactor of 0.5 " (1.27 centimetres), length are 30 " (76 centimetres) at diameter, structure of reactor is as follows: " " (0.09 centimetre), internal diameter are 0.430 to anti-corrosion, Chlorimet carbon pipe; wall thickness is 0.035 to uncle's Framingham wire gauge (BWG) 20.1/2 " (1.1 centimetres).Calculate the volume of reactor according to the catalyst volume of filling.In all examples, packed bed length is 25 " (63 centimetres).With inertia silicon carbide filling space.The calculated value of the reaction volume of the catalyzer that generates is 59.49 centimetres, and it is duration of contact that this value can be used for measuring the surface reaction residence time.
Reactor is with following current, the mode of upstream is operated, measure the add-on of aqueous toxilic acid or other parent and hydrogen respectively, be added to then in the T shape mixing tube of reactor bottom, make the reaction raw materials thorough mixing, and carry out preheating, partly finish reaction at the inert packed bed, add excessive hydrogen, discharge product by valve, the pressure of valve drops to normal atmosphere from reaction pressure.The most of aqueous product of collecting contains tetrahydrofuran (THF) (THF) and 1,4-butyleneglycol (BDO) and small amounts of by-products.The vapour stream of reaction is by a succession of vapor/liquid separation container: at first the separator of usefulness at room temperature, water/ice trap is used two (placed in-line) dry ice/acetone traps more then.Main gleanings is tetrahydrofuran (THF) and a small amount of monohydroxy-alcohol and butyrolactone.Because a spot of liquid/vapor is difficult to separate, so adopt above-mentioned trap.
The method for making of used toxilic acid (unless otherwise indicated) is as follows in the following example: add 500 grams through the qualified maleic anhydride of purity checking (sale of Fisher Scientific company) in 1190 gram distilled water.From purity is 99% hydrogen cylinder, hydrogen-pressure is reduced to about 2500 pounds/inch of reaction pressure
2(17MPa) hydrogen adding speed is 1000 ml/min (standard temperature and pressure), and this speed and reaction conditions (are that pressure is 2500 pounds/inch
2(17MPa) and temperature be 200 ℃) down the space-time (being 6 minutes) of hydrogen equate.The space-time of hydrogen is 6 minutes (unless otherwise indicated).Catalyzer is granular, and particle diameter is less than 20 orders.Rate unit was gram (product)/kilogram-hour (catalysis time) when " Space Time Yield " was empty in all titles and example.
Example 1
Prepare catalyzer (being 3%Pd/3%Re/C) on 3% palladium/3% rhenium/carbon support with Sodium hexametaphosphate 99 polychlorobiphenyl detergent wash carbon (size is 12 * 30) with following method, 200 ℃ of calcinings 2 hours, and then 400 ℃ of calcinings 2 hours, the surface-area of treated carbon was a 1000-1300 rice
2/ gram, voidage is 0.6 centimetre
3/ gram.Depositing Pd and rhenium successively on treated carbon, concrete steps are as follows: with 2.5 gram PdCl
2With 10 milliliters of concentrated hydrochloric acids and 80 ml distilled water wiring solution-formings, in this solution, add the treated carbon of 50 grams, at room temperature stir frequently, after 3 hours, with slurries 110 ℃ of dryings 18 hours.
Make the sample reduction through the following steps, earlier at 150 ℃, (flow velocity is 1000 centimetres in the He air-flow
3/ minute) heated 1 hour, then at 150 ℃, at He/H
2(He/H in the air-flow
2Mole ratios is 50: 50, and flow velocity is 1000 centimetres
3/ minute) heated 1 hour; At last at 300 ℃ at He/H
2(He/H in the air-flow
2Mole ratios be 50: 50, flow velocity is 1000 centimetres
3/ minute) heated 3 hours.At He/H
2Make sample be chilled to 50 ℃ rapidly in the atmosphere, add ammonia, make sample be cooled to room temperature simultaneously.At N
2After 30 minutes, at room temperature add O in the air-flow
2/ N
2Air-flow (O
2/ N
2Mole ratios be 1: 99), made the sample purifying 2 hours.
Then, in 50 ml distilled waters, add 5 gram Re
2O
7, the distilled water of 19.7 milliliters rhenium solution and the 70 milliliters palladium/carbon catalysts with 50 grams are added in 1000 ml flasks.At room temperature stir frequently, after 3 hours, make slurry dried, reduction also makes the product passivation with the method for above-mentioned palladium/carbon catalyst passivation.Product is 3% palladium/3% rhenium/C catalyst.
With X-ray diffraction, scanning transmission electron microscope and H
2/ O
2Palladium/rhenium that this example of titration measuring makes/C catalyst, measurement result show that the median size of palladium crystal grain is about the 150*-200*(15-20 millimicron).The crystal grain of rhenium is too little, can not measure with X-ray diffraction or scanning transmission electron microscope, therefore, can only estimate that the particle diameter of rhenium is less than the 25*(2.5 millimicron).
Record KReO with microscope and crystal analysis technology
4The median size of crystal grain is about 0.2 micron.Arrive with microscopic examination, the rhenium of the high dispersing of above-mentioned little crystal grain contacts with the crystal grain of some palladium.Carbon support can be used for preparing the catalyzer that contains 0.36 mol %K.
Example 2-14
Method by example 1 prepares the 3%Pd/3%Re/C catalyzer, it is 0.5 that this catalyzer is added to diameter " reactor in; regulate the adding speed of toxilic acid; making duration of contact is 0.9 hour-5.5 hours (for example; the adding speed of toxilic acid is 0.5 ml/min; obtaining reaction or duration of contact is 2.0 hours), regulates the flow velocity of hydrogen, and the space-time that makes hydrogen is 3 or 6 minutes.Under the temperature of reaction of 175 °, 180 °, 190 °, 200 °, 215 ° and 225 °, carry out hydrogenation, reaction product serial sampling.Under various reaction conditionss, tetrahydrofuran (THF) and 1 in the product, the mol percentage composition (based on the amount of carbon) of 4-butyleneglycol and monohydroxy-alcohol byproduct such as butanols, propyl alcohol etc. and r-butyrolactone intermediate product is as shown in table 1.These data are to get the mean value of measuring several times after reaching stable condition.
Because do not measure the amount of toxilic acid, this shows that toxilic acid is gone up substantially and finished conversion.Therefore, mole percent can be represented the content of the special component of product selectivity and generation.Also listed rate when empty in the table.Rate is when adding the metal catalyst of unit weight in the unit time and the amount of the product that obtains when empty.The result shows, present method is good to the selectivity of producing tetrahydrofuran (THF)/1.4-butyleneglycol, the productive rate of tetrahydrofuran (THF)/1.4-butyleneglycol increases when empty with the increase of temperature, the increase of duration of contact and/or hydrogen, and the above-mentioned reaction conditions of may command makes reaction yield be adjusted to and only generate tetrahydrofuran (THF) basically from only generating the 1.4-butyleneglycol basically.
(seeing Table 1)
Example 15-18
Method by example 1 prepares the 1%Pd/3%Re/C catalyzer, and institute's difference is: PdCl
2Consumption be in the example 1 consumption 1/3, carrying out the reductive top temperature after palladium deposition is 350 ℃, carrying out the reductive top temperature after the rhenium deposition is 150 ℃.
As described in routine 2-14, under 180 ℃ temperature of reaction, carry out hydrogenation, regulate the flow velocity of toxilic acid, making duration of contact is 2.1-3.5 hour.Table 2 routine test-results show, tetrahydrofuran (THF)/1, the productive rate of 4-butyleneglycol increases with the increase of duration of contact.
(seeing Table 2)
Example 19-24
Method by example 1 prepares the 3%Pd/1%Re/C catalyzer, and institute's difference is: Re
2O
7Amount be in the example 1 consumption 1/3.As routine 2-14, under various temperature of reaction and reaction contact time, carry out hydrogenation, the result shown in the table 3 shows, improves temperature of reaction and/or increases reaction contact time, the result can increase tetrahydrofuran (THF)/1, the productive rate of 4-butyleneglycol.Measurement result is not found toxilic acid yet, and this shows that toxilic acid is gone up substantially fully and transformed.
(seeing Table 3)
Example 25
Method by example 1 prepares the 10%/Pd/3%Re/C catalyzer, and institute's difference is: PdCl
2Amount be in the example 1 consumption 10/3.In pressurized vessel, add 53.76 gram Succinic acid dimethylesters and 6.0 gram water, under 285 ℃ temperature, at 2500 pounds/inch
2Under the hydrogen pressure, contact 2 hours with 30 gram 10%Pd/3%Re/C catalyzer, by the amount of carbon, reaction product contains tetrahydrofuran (THF) 62.2 mol %, butanols 18.6 mol %, propyl alcohol 4.7 mol % and r-butyrolactone 14.5 mol %.
Example 26-27
Method by example 1 prepares the 3%Pd/3%Re/C catalyzer, and institute's difference is that two top temperatures in the reduction step are 200 ℃ rather than 300 ℃, as routine 2-14, with in the table 4 given reaction conditions carry out hydrogenation.The result shows that duration of contact is long, tetrahydrofuran (THF)/1, and the productive rate of 4-butyleneglycol is just high.
(seeing Table 4)
Example 28-32
Method by example 1 prepares the 3%Pd/3%Re/C catalyzer, and institute's difference is: the post-depositional reactions steps of palladium compound is to be 500 ℃ rather than 300 ℃ in top temperature to carry out.As routine 2-14, the reaction conditions given with table 5 carries out hydrogenation.The result proves-advantage of catalyzer of the present invention.
(seeing Table 5)
Example 33
Method by example 1 prepares the 6%Pd/3%Re/C catalyzer, and institute's difference is: PdCL
2Consumption be the twice of example 1.As routine 2-14, under 180 ℃ temperature of reaction, be 2.1 hours duration of contact, carries out hydrogenation.The mole percent proportioning of product ∥ byproduct is: tetrahydrofuran (THF) 67/1, and 4-butyleneglycol 19 ∥ monohydroxy-alcohol 8/r-butyrolactone 5, succsinic acid 1, rate is 239 when empty.
Example 34
Method by example 1 prepares the 6%Pd/3%Re/C catalyzer, and institute's difference is: PdCL
2Consumption be the twice of example 1, Re
2O
7Consumption also be 2 times of example 1.As routine 2-14,180 ℃ temperature of reaction, be 2.0 hours duration of contact, carries out hydrogenation, and the mole percent proportioning of product ∥ byproduct is: tetrahydrofuran (THF) 40/1, and 4-butyleneglycol 50 ∥ monohydroxy-alcohol 9/r-butyrolactone 1, rate is 300 when empty.
Example 35
As routine 2-14, the catalyzer of use-case 1 in hydrogenation experiment, institute's difference is: add concentration and be 9%(by weight) the fumaric acid aqueous solution.Temperature of reaction is 180 ℃, and the reaction times is 2.0 hours, and the mole percent of product (proportioning) is: tetrahydrofuran (THF)/1,4-butyleneglycol ∥ monohydroxy-alcohol/r-butyrolactone is 19/71 ∥ 8/2.Rate is 72 when empty.
Example 36
With just-butane, make tetrahydrofuran (THF)/1 continuously through unsegregated toxilic acid intermediate product, the method for 4-butyleneglycol is as follows: at 2%(by weight) SiO
2In in advance activatory V/P/OX be that 3%(is in atomicity), catalyzer in pelletized form, particle diameter is 1/8 "; the catalyzer of heavy 70 grams are added in the axial No. 316 stainless steel fixed-bed reactor; the diameter of reactor is 1 ", height is 12 ", and reactor heating is to reach controlled temperature in the fluidizing sand-bath.This reactor is connected with transfer canal, the acting as of transfer canal: (1) multichannel adds is containing 1.5% just-and the airflow of butane, through the preheater induction coil in the sand-bath, the bottom that enters reactor then is to contact with catalyst bed; (2) the product gas exhaust duct (gas exhaust duct being heated to more than 200 ℃, to avoid maleic anhydride deposition) of flowing through enters separator then, and to absorb maleic anhydride, maleic anhydride can be used for the hydrogenation of back to 80% waste gas by water.
Remaining product flow is sent into binary gas chromatographic analysis device to do product analysis through the pipeline of heating.The heating check valve is installed, so that the working pressure of system is raised to 125 pounds/inch of peak pressures from normal atmosphere (100KPa) in the gas off-take of chromatographic analysis device front end
2(870KPa).Service temperature is 380 ℃-450 ℃, and be 1-7 second duration of contact (under standard temperature and pressure (STP)).This analytical system can be measured N
2, O
2, CO, CO
2, H
2O, just-butane, maleic anhydride, ethene, furans, methyl ethyl ketone, acetic acid and vinylformic acid.Maleic acid solution is colourless.
By the method for routine 2-14, the 3%Pd/3%Re/C catalyzer that makes in the use-case 1 makes thick toxilic acid intermediate product generation hydrogenation.The concentration of toxilic acid is 33%, and the adding speed of toxilic acid is 0.5 ml/min, and be 2 hours corresponding duration of contact, and temperature of reaction is 200 ℃.The mole percent proportioning of product ∥ byproduct (being tetrahydrofuran (THF)/1,4-butyleneglycol ∥ monohydroxy-alcohol) is 30/58 ∥ 12.The space-time rate is 280.
Example 37 and Comparative examples A and B
This example and Comparative examples A and B are compared, and purpose is that two kinds of activity of such catalysts among ratio A and the B are not poor for the activity of such catalysts that will prove the present invention's (example 37).In this example and Comparative examples A and B, the catalyzer on carbon support contains %Pd and 3%Re.The present invention's's (example 37) catalyzer is by the preparation of the method for example 1.
The catalyzer method for making of Comparative examples A is as follows: under atmospheric pressure, calcining 100 gram activated carbon are earlier 200 ℃ of calcinings 2 hours, then 400 ℃ of calcinings 2 hours.Make the carbon cooling, sieve then, obtain the carbon of incinerating of 54.0 grams, 20 order granularities.In 50 ml distilled waters, add 5.0 gram Re
2O
7Can make concentration is the rhenium solution of 0.076 grams per milliliter.Then, 19.7 milliliters of rhenium solution, 10 milliliters of concentrated hydrochloric acids, 50 ml distilled waters, 2.5 are restrained PdCl
2And the burnt carbon of 50 grams is added in 1000 ml flasks, stir frequently, after 3 hours with slurries 110 ℃ of dryings 18 hours.Then with following method reduction Pd/Re/C catalyzer: at 150 ℃, heating is 1 hour in nitrogen, again at 150 ℃, at N
2/ H
2(N
2/ H
2Ratio be 50%/50%) in the heating 1 hour, at last at 300 ℃, at N
2/ H
2(ratio is 50%/50%) heating 3 hours, after the cooling, the O 1%
2/ N
2In the atmosphere, made catalyst deactivation 3 hours.
The method for making of the catalyzer of comparative example B is as follows: under atmospheric pressure, calcining 100 gram activated carbon are earlier 200 ℃ of calcinings 2 hours, then 400 ℃ of calcinings 2 hours.Make the carbon cooling, sieve then, obtain the carbon of incinerating of 61.0 grams, 20 order granularities.In 50 ml distilled waters, add 5.0 gram Re
2O
7Can make concentration is the rhenium solution of 0.076 grams per milliliter.Then, 19.7 milliliters of rhenium solution are added in 1000 ml flasks, and in flask, add 50 burnt carbon of gram and 70 ml distilled waters, stir frequently, after four hours with slurries 110 ℃ of dryings 18 hours.
The method of reducing of Re/C material is as follows: at 150 ℃, add 1 hour in nitrogen, again at 150 ℃, at N
2/ H
2(50%50%) heating is 1 hour in, then at 300 ℃, at N
2/ H
2Heating is 3 hours in (50%/50%).At 1%O
2/ H
2In make Re/C material passivation 3 hours.Then, with 2.5 gram PdCL
2, 70 ml distilled waters and 10 milliliters of dense HCl are added in 1000 ml flasks together.The Re/C material is added in the solution, slurries were placed room temperature following 3 hours, made slurry dried 18 hours at 110 ℃.Reducing under the following condition: under 150 ℃, heating is 1 hour in nitrogen, again at 150 ℃, at 50%/50%N
2/ H
2In heating 1 timely, then at 300 ℃, the N 50%/50%
2/ H
2Middle heating 3 hours.After the cooling, at 1%O
2/ H
2In made catalyst deactivation 3 hours.
Carry out hydrogenation under the following conditions: in all cases, the catalyzer on the carbon support contains 3% palladium and 3% rhenium, weighs 18 grams, and catalyzer is added to 0.37 inch diameter, anti-corrosion, Chlorimet carbon, is about in 2 feet the reaction under high pressure pipe.
With the upright electric furnace reacting by heating pipe of three sections of branches, the nitrogen in the reaction system is removed totally, make the pressure of reactor be raised to 2500 pounds/inch with hydrogen
2Keep stable hydrogen flow rate (being 2 liters/minute) (standard temperature and pressure), reactor slowly is heated to the temperature that reacts, continues 1 hour, catalyst warm-up is adapted to, after preheating is finished, add concentration and be 30%(by weight) maleic acid solution (with certain flow velocity).Reagent adds with downbeam, to the upper reaches.Reaction product and excessive hydrogen are discharged by back pressure regulator.The sample interval of reaction product is half an hour.
The microstructure of the catalyzer of Comparative examples A is as follows: this catalyzer all deposits rhenium and palladium, and the median size of the palladium crystal grain that it is contained has only 7 millimicrons, and rhenium is the high dispersing phase.After the use, the crystal grain that records palladium by X-ray diffraction is bigger, but does not detect rhenium metal.Find out deposition rhenium earlier from the microstructure of the catalyzer of comparative example B, depositing Pd then, the median size of its contained palladium crystal grain has only 8 millimicrons before using, and the median size of the big crystal grain of rhenium is about 50 millimicrons.And the connection between palladium and the rhenium phase is not obvious.After the use, palladium is unbodied with rhenium mutually, therefore surveys not come out with X-ray diffraction.
The ratio of temperature of reaction, duration of contact and the product ∥ byproduct that obtains is as shown in table 6, the result shows, catalyzer of the present invention can make toxilic acid transform fully, to making tetrahydrofuran (THF)/1,4-butyleneglycol selectivity is good, and the catalyzer among Comparative examples A and the B can not make toxilic acid transform fully and poor selectivity.
(seeing Table 6)
Example 38-47
Following example is by adding different reagents, and the solution of different concns and water and organic solvent have been done test, and the catalyzer of use-case 1 reacts.The reaction soln, reaction conditions and the result that add are shown in table 7 and 8.In all cases, it is 6 minutes during hydrogen empty.
(seeing Table 7 tables 8)
Comparative example C
Repeat the step of example 1, institute's difference is: before palladium and rhenium deposition, embathe carbon support with hydrochloric acid, to reduce the content (being lower than 0.001 mol %) of potassium in the carbon support.Change the microstructure of catalyzer, the size of palladium crystal grain is changed, use H
2/ O
2The particle diameter of titration measuring palladium crystal grain only is 5 millimicrons.At 180 ℃, carry out hydrogenation with the general method that is listed as 2-14, the hydrogenation time length was respectively 2 hours and 2.2 hours, and test-results is as follows: the tetrahydrofuran (THF) that the catalyst selectivity of use-case 1 obtains/1,4-butyleneglycol are 13/29, and rate is 325 when empty; And obtain tetrahydrofuran (THF)/1 with the catalyzer alternative of flush away potassium, and the 4-butyleneglycol is 33/19, rate is 210 when empty.
Example 48
The method for making of 3%Pd/3%Re/C catalyzer (adding 0.5 mol % sodium in the carbon of flush away potassium) is as follows: with size is 12 * 30, with the carbon of Sodium hexametaphosphate 99 polychlorobiphenyl detergent wash 200 ℃ of calcinings 2 hours, then 400 ℃ of calcinings 2 hours.With eyelet is that 20 purpose sieves screen, and removes carbon dust and fine-grained carbon, and 20 purpose carbon, 200 grams that will obtain then are added in 4 liters of 1M hydrochloric acid.Slurries were left standstill 24 hours, then carbon is collected in the clinkering funnel,, use sour repetitive scrubbing again, made carbon dry 18 hours at 110 ℃ then, obtain carbon 190.3 grams of flush away potassium with 4 liters of distilled water washs.In 70 ml distilled waters, add 1.3 gram sodium-chlor with wiring solution-forming, add the not potassic carbon of 50.0 grams in the Nacl solution, at room temperature stir frequently, after 3 hours, with slurries 110 ℃ of dryings 18 hours.With 2.5 gram PdCl
2With 10 milliliters of concentrated hydrochloric acids, 65 ml distilled water wiring solution-formings, in this solution, add the carbon that contains sodium, at room temperature stir frequently, after 3 hours,, made slurry dried 18 hours at 110 ℃.Then, at 150 ℃, it is 100 centimetres at flow velocity
3/ minute the He air-flow in heating Pd/C sample 1 hour, again at 150 ℃, at He/H
2(flow velocity is 100 centimetres to air-flow
3/ minute) the middle heating 1 hour, at last at 300 ℃, at He/H
2Heating is 3 hours in the air-flow (flow velocity is the same).Then in the He/H air-flow, cool off, use 1.5% then.Oxygen (in nitrogen) made the solid passivation that makes 18 hours.
The pd/C solid of 48.3 gram passivation is added to 19 milliliters of 0.2MRe
2O
7Solution (this solution is mixed with 51 ml waters), at room temperature stir frequently, after 3 hours,, made slurry dried 18 hours at 110 ℃, make the sample reduction then, passivation under these conditions obtains 47.8 gram Pd/Re/C catalyzer.
With 27 gram catalyzer, 35%(is by weight) the toxilic acid aqueous solution carries out hydrogenation, and the hydrogenation condition is as follows: temperature is 190 ℃, H
2Atmospheric pressure is 2500 pounds/inch
2(17MPa), be 2.2 hours duration of contact, and hydrogen space-time is 6 minutes.The mol percentage composition of reaction product (based on the amount of carbon) is THF-55/BDO-34 ∥ monohydroxy-alcohol-8/r-butyrolactone-3, and rate is 240 when empty.
Example 49-51
Prepare the 3%Pd/3%Re/C catalyzer by following method: in 86 ml distilled waters, add 9.6 gram NaPdCl
43H
2O adds 100 gram carbon (CC-521-G through embathing) in this solution, at room temperature placed 1 hour, under stirring state, makes slurry dried by steam bath then.Add 4.0 gram NaOH in 88 ml distilled waters, with this NaOH solution impregnation carbon 2 hours, till no muriate, the recovery of dry back obtained 150 palladiums that restrain on the carbon sample with distilled water wash carbon; With the palladium of 45 grams on carbon support 110 ℃ of dryings 18 hours.Heat again; At 150 ℃, (flow velocity of He is 100 centimetres at the He air-flow earlier
3/ minute) the middle heating 1 hour, then at 150 ℃, at He/H
2(flow velocity is 100 centimetres to air-flow
3/ minute) the middle heating 1 hour, last, at 300 ℃, at He/H
2Heating is 3 hours in the air-flow.At He/H
2After the cooling, made the sample passivation 18 hours in the air-flow with 1.5% oxygen (in nitrogen).Then at 11.5 milliliters 0.2MRe
2O
7With add the as-reduced Pd/C of 29.38 grams in the solution of 38.5 ml distilled waters, at room temperature place 3 hours after, at 110 ℃, made slurry dried 18 hours.Make Pd/Re/C catalyst reduction and the passivation that makes with aforesaid method, obtain 29.44 gram catalyzer.
Method by routine 2-14 is carried out hydrogenation, and temperature of reaction and duration of contact are as shown in table 9, and in three examples, hydrogen pressure is 2500 pounds/inch
2(17MPa), hydrogen space-time is 6.0 minutes.
(seeing Table 9)
Comparative Example D-H
Depositing Pd and rhenium and do not have intermediate product successively
Prepare the 3%Pd/3%Re/C catalyzer by following method: 100 gram carbon (size is 12 * 30, with six inclined to one side phosphorus ferment sodium polychlorobiphenyl detergent wash) 200 ℃ of calcinings 2 hours, were calcined 2 hours at 400 ℃ then.Sub-elect 20 purpose carbon, 65.25 grams.At depositing Pd and rhenium successively on the carbon of calcining and screening, deposition method is as follows: containing 25 gram PdCl
2With add 50 in the solution of 10 milliliters of concentrated hydrochloric acids and 75 ml distilled waters and restrain incinerating carbon, at room temperature stir frequently, after 3 hours, made slurry dried 18 hours at 110 ℃, take out a gram exsiccant Pd/C sample and be used for analyzing, remaining sample (50.31 gram) is added to 19.86 milliliters of 0.2MRe
2O
7In the solution of 65 ml distilled waters, at room temperature stir frequently, after 3 hours,, made slurry dried 18 hours at 110 ℃.Get a gram exsiccant Pd/Re/C sample and be used for analyzing, remaining sample heats, and earlier at 150 ℃, (flow velocity is 100 centimetres in the He air-flow
3/ minute) heated 1 hour, again at 150 ℃, at He/H
2(flow velocity is 100 centimetres in the air-flow
3/ minute) heating 1 hour, then at 300 ℃ at He/H
2Heating is 3 hours in the air-flow.Making sample be cooled to room temperature, in 1.5% oxygen (containing nitrogen), make as-reduced Pd/Re/C sample passivation 18 hours, is 46.68 grams through the output of passivation reductive Pd/Re/C catalyzer.
Method by routine 2-14 is carried out hydrogenation, and reduction temperature, reaction contact time and test-results are as shown in table 10.The result shows that reactant can not transform fully, and the poor selectivity of reaction product.
(seeing Table 10)
Example 52-56
In 1M hydrochloric acid, add 400 gram carbon (the carbon size is 12 * 30, with Sodium hexametaphosphate 99 polychlorobiphenyl detergent wash), after 24 hours, carbon is collected in the cementing funnel, use distilled water wash then till no muriate.With acid treatment and wash with water, made carbon dry 48 hours at 110 ℃ more repeatedly.Recovery obtains carbon 385.3 grams of pickling to be used for the following step.
The catalyzer (in the catalyzer of example 52, also containing 0.30 mol % magnesium) for preparing 3%Pd/3%Re/C by following method: 96.0 grams are added to through the carbon of pickling contain 4.82 gram MgCl earlier
2, 6H
2In the solution of O and 150 ml distilled waters, at room temperature stir frequently, after 3 hours, under continuous condition of stirring, made slurry dried 18 hours at 110 ℃, the Mg/C sample was calcined 2 hours at 200 ℃, calcined again 2 hours at 400 ℃ then, with the Mg/C sample after the 20 purpose sieves screening calcining.
With 2.5 gram PdCl
2Add 75 ml distilled water wiring solution-formings with 10 milliliters of concentrated hydrochloric acids, in this solution, add 50.0 grams through incinerating Mg/C, at room temperature place 3 hours after, under continuous condition of stirring, made slurry dried 18 hours at 110 ℃.Making the reduction of Pd/C-M sample by heating then, earlier at 150 ℃, is 100 centimetres at flow velocity
3/ minute the He air-flow in the heating 1 hour, again at 150 ℃, at He/H
2(flow velocity is 100 centimetres to air-flow
3/ minute) the middle heating 1 hour, at last at 300 ℃, at He/H
2Heating is 3 hours in the air-flow.At He/H
2In the air-flow, sample is chilled to room temperature, then at 1.5%O
2/ N
2Middle passivation 18 hours.
At 19 milliliters of 0.2MRe
2O
7With add the as-reduced Pd/C-Mg sample of 47.95 grams in the solution of 60 ml distilled waters, at room temperature placed 3 hours, then at 110 ℃, made slurry dried 18 hours, after adding palladium, reduce the Pd/Re/C-Mg sample as stated above, make as-reduced Pd/Re/C catalyst deactivation 18 hours in 1.5% oxygen nitrogen * gas, passivation reductive Pd/Re/C-Mg catalyst yield is 48.34 grams.
The catalyzer of example 53 also contains 0.30 mol % calcium except that containing 3%Pd/3%Re/C, the method for making of this catalyzer is as follows: add earlier 2.66 gram CaCl in 150 ml distilled waters
2With wiring solution-forming, in this solution, add the carbon of 96.0 gram pickling, at room temperature stir frequently, after 3 hours, under continuous condition of stirring, made slurry dried 18 hours at 110 ℃.At 200 ℃, make Ca/C sample calcining 2 hours, and then, screen burnt Ca/C sample with 20 purpose sieves 400 ℃ of calcinings 2 hours.
In 75 ml distilled waters, add 2.5 gram PdCl
2With 10 milliliters of concentrated hydrochloric acids with wiring solution-forming, in this solution, add 50.0 and restrain incinerating Ca/C sample, at room temperature placed 3 hours, then under continuous condition of stirring, made slurry dried 18 hours at 110 ℃, make the reduction of Pd/C-Ca sample by heating, earlier at 150 ℃, (flow velocity is 100 centimetres at the He air-flow
3/ minute) the middle heating 1 hour, again at 150 ℃, at He/H
2(flow velocity is 100 centimetres to air-flow
3/ minute) the middle heating 1 hour, at last at 300 ℃, at He/H
2Heating is 3 hours in the air-flow, at He/H
2In the air-flow, make sample be chilled to room temperature, then at 1.5%O
2/ N
2Middle passivation 18 hours.
Then, 49.0 grams are added to 19.35 milliliters of 0.2MRe through reductive Pd/C-Ca sample
2O
7In the solution of 65 ml distilled waters.After at room temperature placing 3 hours, made slurry dried 18 hours, after adding palladium, with aforesaid method reduction Pd/Rc/C-Ca sample, at 1.5%O at 110 ℃
2/ N
2In make as-reduced Pd/Re/C-Ca catalyst deactivation 18 hours.Output through passivation reductive Pd/Re/C-Ca catalyzer is 50.28 grams.
The catalyzer of example 54 is except that containing 3%Pd/3%Re/C, the K that also contains 0.30 mol %, the method for making of this catalyzer is as follows: add 1.38 gram KOH with wiring solution-forming in 150 ml distilled waters, in this solution, add 96.0 grams through the carbon of pickling, at room temperature stir 3 hours frequently after, under continuous condition of stirring, made slurry dried 18 hours at 110 ℃, the K/C sample 200 ℃ of calcinings 2 hours, 400 ℃ of calcinings 2 hours, is screened incinerating K/C sample with 20 purpose sieves again.
In 75 ml distilled waters, add 2.5 gram PdCl
2With 10 milliliters of concentrated hydrochloric acid wiring solution-formings, in this solution, add 50.0 grams at incinerating K/C, at room temperature place 3 hours after, under continuous condition of stirring, made slurry dried 18 hours at 110 ℃, make the reduction of Pd/C-K sample by heating then, at 150 ℃, it is 100 centimetres earlier at flow velocity
3/ minute the He air-flow in the heating 1 hour, again at 150 ℃, at He/H
2(flow velocity is 100 centimetres to air-flow
3/ minute) in the heating 1 hour, at last at 300 ℃ at He/H
2Heating is 3 hours in the air-flow, then at 1.5%O
2/ N
2Middle passivation 18 hours.
Then, the as-reduced Pd/C-K sample of 48.4 grams is added to 19.10 milliliters of 0.2MRe
2O
7In the solution of 65 ml distilled waters, at room temperature place 3 hours after, slurries 110 ℃ of dryings 18 hours, then after adding palladium, are reduced the Pd/Re/C-K sample with above-mentioned method, at 1.5%O
2/ N
2In make as-reduced Pd/Re/C-K catalyst deactivation 18 hours.Output through passivation reductive pd/Re/C-K catalyzer is 48.67 grams.
The catalyzer of example 55 is except that containing 3%Pd/3%Re/C, also contain 0.36 mol %Li, the method for making of this catalyzer is as follows: add 1.17 gram LiCl with wiring solution-forming in 150 ml distilled waters, in LiCl solution, add the carbon of 96.0 grams, at room temperature stir frequently, after 3 hours through pickling, under continuous condition of stirring, made slurry dried 18 hours at 110 ℃, make Li/C sample calcining 2 hours, calcined again 2 hours at 400 ℃ then at 200 ℃.Screen through incinerating Li/C sample with 20 purpose sieves.
In 80 ml distilled waters, add 2.5 gram PdCl and 10 milliliters of concentrated hydrochloric acids with wiring solution-forming, in this solution, add 50.0 grams through incinerating Li/C sample, at room temperature place 3 hours after, under continuous condition of stirring, made slurry dried 18 hours at 110 ℃.By adding thermal reduction Pd/C-Li sample, earlier at 150 ℃, (flow velocity is 100 centimetres at the He air-flow then
3/ minute) heated 1 hour, again at 150 ℃, at He/H
2(flow velocity is 100 centimetres to air-flow
3/ minute) the middle heating 1 hour, at last at 300 ℃, at He/H
2Heating is 3 hours in the air-flow.At He/H
2Make sample be chilled to room temperature in the air-flow, then at 1.5%O
2/ N
2Middle passivation 18 hours.
The as-reduced Pd/C-Li sample of 49.5 grams is added to 19.5 milliliters of 0.2MRe
2O
7In 60 ml distilled water solution, at room temperature place 3 hours after, at 110 ℃ with slurry dried 18 hours.After adding palladium, with aforesaid method reduction Pd/Re/C-Li sample, at 1.5%O
2/ N
2In make as-reduced Pd/Re/C-Li catalyst deactivation 18 hours.Output through passivation reductive Pd/Re/C-Li catalyzer is 49.97 grams.
The catalyzer of example 56 also contains 0.5 mol %Na except that containing 3%Pd/3%Re/C, its method for making is identical with example 48.The method of the equal use-case 2-14 of above-mentioned catalyzer is carried out hydrogenation, and hydrogenation temperature, reaction contact time and experimental result are as shown in table 11.
(seeing Table 11)
Claims (7)
1, a kind ofly is used to make tetrahydrofuran (THF), 1, the palladium of 4-butyleneglycol and composition thereof/rhenium composite catalyst, form by the palladium of 0.5%-10%, the rhenium of 1%-10% (all in gross weight) and the carbon support of surplus, wherein palladium is the crystal grain form, its median size is the 10-25 millimicron, rhenium is the crystal grain form of high dispersive phase, and its median size is less than 2.5 millimicrons.
2, make the method for the palladium/rhenium composite catalyst of claim 1, form by the following step successively:
(1) with palladium source (being palladium solution) impregnated carbon carrier;
(2) except that desolvating, under 150 ℃-550 ℃ temperature, heating is through the carbon of palladium dipping under reductive condition;
(3) on the carbon of palladium dipping, be coated with rhenium source (being the solution of rhenium);
(4) except that desolvating;
(5) under 150 ℃-550 ℃ temperature, under reductive condition, the composite catalyst that heating steps (4) obtains.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101672.3A CN1004791B (en) | 1983-12-22 | 1985-04-01 | Pd/re hydrogenation catalyst and process for making same |
| CN 88104938 CN1021224C (en) | 1985-04-01 | 1988-08-06 | Process for making tetrahydrofuran and 1,4-butanediol using pd/re hydrogenation catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/564,372 US4550185A (en) | 1983-12-22 | 1983-12-22 | Process for making tetrahydrofuran and 1,4-butanediol using Pd/Re hydrogenation catalyst |
| CN85101672.3A CN1004791B (en) | 1983-12-22 | 1985-04-01 | Pd/re hydrogenation catalyst and process for making same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88104938 Division CN1021224C (en) | 1985-04-01 | 1988-08-06 | Process for making tetrahydrofuran and 1,4-butanediol using pd/re hydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101672A CN85101672A (en) | 1987-01-24 |
| CN1004791B true CN1004791B (en) | 1989-07-19 |
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|---|---|---|---|
| CN85101672.3A Expired CN1004791B (en) | 1983-12-22 | 1985-04-01 | Pd/re hydrogenation catalyst and process for making same |
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| US7019155B2 (en) * | 2001-11-13 | 2006-03-28 | Invista North America S.A.R.L. | Hydrogenation of tetrahydroxybutane to tetrahydrofuran |
| US10023549B2 (en) * | 2014-12-04 | 2018-07-17 | Shell Oil Company | Process for the production of 1,4-butanediol and tetrahydrofuran from furan |
| CN113304747B (en) * | 2021-05-07 | 2022-07-12 | 万华化学集团股份有限公司 | Catalyst for preparing 2-methylpyridine, preparation method and method for preparing 2-methylpyridine by using same |
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