CN106694010A - Catalyst for preparation of enol through alkynol semi-hydrogenation and preparation method of catalyst - Google Patents
Catalyst for preparation of enol through alkynol semi-hydrogenation and preparation method of catalyst Download PDFInfo
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- CN106694010A CN106694010A CN201611223191.3A CN201611223191A CN106694010A CN 106694010 A CN106694010 A CN 106694010A CN 201611223191 A CN201611223191 A CN 201611223191A CN 106694010 A CN106694010 A CN 106694010A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention discloses a catalyst for preparation of enol through alkynol semi-hydrogenation and a preparation method of the catalyst. The preparation method is characterized in that Pd is taken as an active component, CaCO3 is taken as a carrier, acetate of Fe, Mg, Ca and Zn is taken as an additive, the mass content of the active component is 1%-10%, the content of the additive is 3%-7%, and the catalyst is prepared with a thermal filtration method. The catalyst shows higher reaction conversion rate as well as high product selectivity and yield in reactions for preparation of enol through alkynol semi-hydrogenation such as preparation of 1,4-butylene glycol from 1,4-butynediol, preparation of methyl butenol from methyl butynol, preparation of vinyl isopropanol from acetenyl isopropanol and the like, the catalyst has longer service life, particularly shows better catalytic performance in the reaction for preparation of 1,4-butylene glycol through 1,4-butynediol semi-hydrogenation and has high industrial application value.
Description
Technical field
The invention belongs to fine chemistry industry catalyst and new chemical materialses field, and in particular to a kind of height unsaturation alkynol half
Catalyst of Hydrogenation enol and preparation method thereof.
Background technology
Enol is widely used in the fields such as medicine, agricultural chemicals and new material as important chemical synthesis intermediate.Due to alkene
Alcohol matter is unstable, while being confined to unintelligible to the understanding of its structural relation, result in enols used synthesis hair
Exhibition receives serious limitation.Until 20th century mid-term, Fuson etc. is found that a series of enol of big steric hindrance aryl substitutions can be with
Stable existence, such reacting middle catalyst plays a decisive role, and how to prepare high conversion, high selectivity, long service life
Synthesizing stable enol class catalyst becomes one of important focus of Alcohols compound.Wherein, the hydrogenation synthesis alkene of alkynol half
Alcohol technique is a preferable technology path, therefore has important meaning to studying for the hydrogenation synthesis enol catalyst of alkynol half
Justice.
The hydrogenation catalyst of alkynol half mainly has noble metal catalyst and non-precious metal catalyst.For example, can be work with Cu, Ni
Property component or with Pd as active component, catalyst hydrogenation performance is improved by adding different auxiliary agents.Cu bases catalyst is used to select
When selecting acetylene hydrogenation, reaction temperature is of a relatively high, and alkene easily occurs polymer deposits and shows to form tar in catalyst with alkynes,
Catalyst is caused to inactivate, service life is short.When Ni bases catalyst choice is hydrogenated with, reaction conversion ratio and selectivity be not relatively low.Pd
The activity of base catalyst reaction is higher, and condition is gentleer, and there is reaction-ure conversion-age higher and reactant to select under low-temp low-pressure
Selecting property.Due to Pd, activity is too high in hydrogenation reaction, to prevent deep hydrogenation from generating alkanol, is typically both needed to environmentally undesirable
Heavy metal ion (such as Pb) poisons to Pd catalyst.
Document [1] " Partial Hydrogenation of 1,4-Butynediol [J] .Bulletin of the
Chemical Society of Japan,1958,31(3):339-342. " discloses a kind of using Pb (Ac)2, pyridine, piperidines
Or quinoline poisons Pa/CaCO3Catalyst is prepared, the catalysis Hydrogenation of Isosorbide-5-Nitrae-butynediols half obtains Isosorbide-5-Nitrae-butylene glycol, Isosorbide-5-Nitrae-butine
The conversion ratio of glycol is 52%~89%, and product distribution is sufficiently complex, and the selectivity to Isosorbide-5-Nitrae-butylene glycol is relatively low.
Document [2] " A novel stereospecific reduction of alkynes to alkenes [J]
.Tetrahedron Letters,1980,21(11):1069-1070. " discloses a kind of Zn-Cu catalyst in methyl alcohol boiling system
Lower catalysis Isosorbide-5-Nitrae-butynediols half Hydrogenation Isosorbide-5-Nitrae-butylene glycol, but its yield is only 57%.
Patent CN1966480A, discloses a kind of Pd/C using lead poisoning as urging that catalysis Isosorbide-5-Nitrae-butynediols half is hydrogenated with
Agent, synthesizes Isosorbide-5-Nitrae-butylene glycol under 35-45 DEG C and 0.6-1.7MPa, and this catalyst contains heavy metal lead, and environment is produced
Adverse effect, is not suitable for carrying out industrialization promotion.
East China University of Science in sieve into professor "《Chemistry world》, supplementary issue in 2006, the 143-144 pages " disclose one kind and adopt
Use Pd/SiO2The method that methyl butynol is selected catalyst Hydrogenation methyl butenol, the conversion ratio of methyl butynol is
100%, the selectivity of methyl butenol is 96.5%.
European patent EP 0941979A3 discloses a kind of Pd/C catalyst for adding alkali metal promoter, and the catalyst is in second
Acetenyl iso-propanol conversion rate is more than 95%, the choosing of vinyl isopropanol in the Hydrogenation vinyl isopropanol reaction of alkynyl isopropanol half
Selecting property is more than 98%.
European patent EP 1611072A2 disclose it is a kind of with Pd-Bi-Pb/CaCO3 catalyst by dehydrogenation linalool (3,7-
Dimethyl -1,6 pungent diine -3- alcohol) half Hydrogenation linalool (3,7- dimethyl -1,6 octadiene -3- alcohol) method, dehydrogenation virtue
Camphor tree alcohol conversion is 99.75%, and linalool is selectively 96.85%.
It remains desirable, however, that a kind of excellent hydrogenation catalyst of alkynol half, does not only have hydrogenation activity higher, preferably choosing
Selecting property, it is often more important that there is good stability and environmentally friendly.
The content of the invention
It is an object of the invention to provide a kind of catalyst that can be used for the hydrogenation synthesis enol of alkynol compound half, the catalysis
Agent has the advantages that high conversion, high selectivity, long service life, environment-friendly, therefore with obvious industrial application value.
In order to achieve this, the present invention provides following technical scheme.
1st, a kind of catalyst for the Hydrogenation enol of alkynol half, including calcium carbonate granule carrier, and positioned at the carbon
The palladium element and the other elements as electronic auxiliary on sour calcium particulate vector surface, wherein the palladium element is substantially with noncrystal
Form is present in the surface of the calcium carbonate granule, and the other elements are selected from Fe, Mg, Zn and Ca.
In some embodiments, in the catalyst as electronic auxiliary other elements mass content be 1-
10%, preferably 2-8%, such as 3-7%, 4-6%, about 5% etc..
2nd, according to the catalyst for the Hydrogenation enol of alkynol half of technical scheme 1, wherein palladium element in the catalyst
Mass content be 1-10%, preferably 2-5%, more preferably from about 3%.
Herein, " the palladium element is substantially present in the surface of the calcium carbonate granule with the amorphous form " meaning
Be the mass content of the palladium simple substance and its compound existed with crystal form in the palladium element less than 5%, preferably smaller than 4%,
More preferably less than 3%, less than 2%, less than 1%, less than 0.5%.
3rd, according to the catalyst for the Hydrogenation enol of alkynol half of any one of preceding solution, wherein the catalysis
The XRD characterization results of the surface crystalline phase of agent are as shown in Figure 1.
4th, according to the catalyst for the Hydrogenation enol of alkynol half of any one of preceding solution, wherein it is described other
Element is the Zn-ef ficiency that zinc oxide form is present, and mass content is 3-7%.
5th, the preparation method of a kind of catalyst for the Hydrogenation enol of alkynol half, including：With Pd as active component,
CaCO3It is carrier, the acetate of Fe, Mg, Ca, Zn is electronic auxiliary, is prepared by hot filter method.
In some cases, the active component of catalyst is Pd, and mass content is 1~10%, and carrier accounts for catalyst quality
80~98%, electronic auxiliary accounts for the 3~7% of catalyst quality.In other cases, the electronic auxiliary be Fe, Mg,
The acetate of Ca, Zn.
6th, the preparation method of the catalyst for the Hydrogenation enol of alkynol half according to technical scheme 5, comprises the following steps：
The solution A that a, offer are mixed to get by palladium salt and acid solution；Wherein described palladium salt can be selected from following species：
Palladium acetate, palladium halide salt, palladium nitrate, palladium phosphate, palladium sulfate, palladium chlorate, palladium borate, palladium iodate, palladium carbon
Hydrochlorate, palladium perchlorate, palladium tartrate, palladium formates, palladium grape hydrochlorate, palladium lactate, palladium sulfamate, above chemical combination
Hydrate and mixture of thing etc.；The acid solution can be：Hydrochloric acid, hydrobromic acid, hydroiodic acid, acetic acid, formic acid, acetic acid, sulfuric acid,
Nitric acid or its mixture；Preferably, the palladium salt is palladium bichloride, and acid solution is concentrated hydrochloric acid, and the ratio of palladium bichloride and concentrated hydrochloric acid is
1:0.5~1.5 (g:Ml), preferably 1:0.8~1.2 (g:ml)；
The emulsion B that b, offer are mixed to get by calcium carbonate granule and water, the wherein ratio of calcium carbonate granule and water are 1:1
~5 (g:Ml), preferably 1:1~3, more preferably 1:1~2；Preferably, the particle diameter of calcium carbonate granule is 50-400 mesh, preferably 100-
200 mesh；In some cases, calcium carbonate granule is the white powder of technical grade calcium carbonate granule, and particle diameter is for about 200 mesh；
C, offer reductant solution C；Wherein described reducing agent is selected from the aqueous solution of aqueous sodium formate solution and hydrazine hydrate；
D, under agitation solution A is added into emulsion B, obtain emulsion AB；
E, will reductant solution C add emulsion AB in reduction reaction is carried out at 50~95 DEG C, stir 10-60 minutes,
Solid powder D is filtered to obtain while hot；
F, powder D is mixed with water, add the salt of alkali and the other elements as electronic auxiliary, stirred 10-60 minutes, mistake
Filter, obtains the catalyst after filtration cakes torrefaction；Preferably, the alkali is selected from ammoniacal liquor or NaOH；Preferably, described other yuan
Element is selected from Fe, Mg, Zn and Ca；Preferably, the salt of the other elements be selected from zinc acetate, ferric acetate, magnesium acetate, calcium acetate and its
Any mixture.
In some cases, step a includes：It is the concentrated hydrochloric acid of 30-37% to be added to concentration to palladium bichloride powder solid, is stirred
Mix lower heating to dissolve for 1-9 minutes, the ratio of palladium bichloride and concentrated hydrochloric acid is 1:0.5~1.5 (g:Ml), plus thermostatic stirring, system
Brown color clear solution is obtained, the solution A containing active component is designated as.
In some cases, step b includes：To CaCO3Add deionized water in particle, stirring 10-60min to uniform,
Milky white color cloud liquid, CaCO is obtained3With H2The ratio of O is 1:1~5 (g:Ml), it is designated as the emulsion B containing carrier.
In some cases, step c includes：It is then slow to drip to deionized water dissolving is added in natrium carbonicum calcinatum solid
Plus formic acid, until being released without gas, the colourless transparent solution containing sodium formate is obtained, it is designated as reductant solution C.
In some cases, step d includes：Solution A is slowly added into emulsion B at room temperature, strong agitation 5-
10min, then heats to 50-100 DEG C, and constant temperature stirring 5-60min obtains pale brown color cloud liquid, is designated as emulsion AB.
In some cases, step e includes：Solution C by temperature for 50-80 DEG C disposably quickly adds with vigorous stirring
Enter into emulsion AB, be then warmed up to 65~90 DEG C, and constant temperature stirs 10~60min, is released to without gas, filters while hot,
Filter cake is washed with deionized to without Cl-, through drying, black powder solid is obtained, it is designated as powder D.In step e, in solution C
The reducing agent of such as sodium formate or hydrazine hydrate there is reduction, for by the activity in carrier particle surface in emulsion AB
Component palladium salt is reduced to Metal Palladium；Additionally, solution C and emulsion AB are under conditions of step e, Rapid contact reaction and while hot mistake
Filter so that the palladium simple substance from palladium salt reduction generation is ultra-dispersed in carrier surface, without Pd metallic atom agglomerations, improves catalysis
Agent Adsorption, increases catalysis activity.
In some cases, step f includes：At room temperature, powder D is mixed with deionized water stirring, adds and be selected from acetic acid
The ratio of the powder solid E of zinc, ferric acetate, magnesium acetate, calcium acetate and its any mixture, powder D and powder solid E is
1000：50-250(g:G), preferably 1000：80-200(g:G), more preferably 1000：100-180(g:g)；Be subsequently adding ammoniacal liquor or
Sodium hydroxide solution is 7-10 to pH, and 50-100 DEG C is heated under stirring, and preferably 60-90 DEG C, constant temperature stirring 10-60min takes out
Filter, filter cake is placed in dried in vacuum overnight, and final catalyst is obtained.
Preferably, in step a, solution temperature is 50~100 DEG C.
Preferably, in stepb, mixing time is 20~60min.
Preferably, in step c, when sodium formate solution is prepared, the ratio of sodium carbonate, formic acid and water is 1~10:0.5
~8:5~400 (g:g:Ml), preferably 5~10:4~8:100~400 (g:g:ml).
Preferably, in step d, active component is supported on when on carrier, and thermostat temperature is 70-90 DEG C.
Preferably, in step d, active component is supported on when on carrier, and constant temperature mixing time is 5-15min.
Preferably, in step f, auxiliary agent is added under agitation, 75-85 DEG C of the temperature of constant temperature stirring.
In the present invention, described " alkynol " refers to arbitrarily in strand containing triple carbon-carbon bonds and in triple carbon-carbon bonds phase
There is the organic compound of hydroxyl, it includes such as Isosorbide-5-Nitrae-butynediols, methyl butynol, acetenyl isopropyl on adjacent carbon atom
Alcohol, dalgol etc..
In the present invention, described " half is hydrogenated with " refers to that the triple carbon-carbon bonds in organic compound molecule are passed through into hydrogenating reduction extremely
The reaction of carbon-carbon double bond.
In the present invention, the enol refers to pass through containing in strand for " half is hydrogenated with " reaction generation by " alkynol "
There is carbon-carbon double bond and in the organic compound with hydroxyl on the adjacent carbon atom of carbon-carbon double bond, it includes such as Isosorbide-5-Nitrae-butylene
Glycol, methyl butenol, vinyl isopropanol, first pentenol etc..
In the present invention, " reducing agent " is in redox reaction, to lose electronics or have the material of electronics deviation.Reduction
Agent is said in a broad sense in itself, is also antioxidant, with reproducibility, is oxidized, and its product is oxidation product.Reduction is anti-with oxidation
Should carry out simultaneously, i other words, while with being reduced thing and carrying out reduction reaction, itself is also oxidized reducing agent, forms
It is oxide.The elevated reactant of chemical valence of certain contained material is reducing agent.Typical reducing agent has formic acid, second two
Amine, oxalic acid, formaldehyde, acetaldehyde, hydrazine hydrate, sodium borohydride etc..
In the present invention, " substantially " it is not precluded from the meaning of " complete ".Such as a composition substantially free Y, also may be used
Being to be entirely free of Y.If desired, " substantially " can delete from present invention definition.
In the present invention, " containing " both includes the factor mentioned, and also allows to include additional, uncertain factor.
In the present invention, " about ", " left and right " with represent each component concentration system in the case of, refer to the +/- of standard value
5%, +/- 4%, +/- 3%, +/- 2%, +/- 1%, +/- 0.5%.
In the present invention, example is typically illustrated by a certain scope, be intended merely to concise explanation, rather than to this
The limitation of invention.The scope of description includes subrange, is also included within all of single numerical value in the range of this.For example, 1~6
This scope, including subrange such as 1~3,1~4,1~5,2~4,2~6,3~6 etc., also including individually being counted in the range of this
Word, such as 1,2,3,4,5,6.
The technology of the present invention at least has the following advantages that：
1st, catalyst of the invention is with Pd as active component, CaCO3It is carrier, the acetate of Fe, Mg, Ca, Zn is auxiliary agent,
The mass content of active component is 1~10%, and the content of auxiliary agent is 3~7%, is prepared by hot filter method.The catalyst
XRD characterization results show, in CaCO3Carrier surface only exists ZnO crystal grain, and the crystal in the absence of Pd simple substance and its compound is deposited
.Do not constrained by any existing theory, inventor thinks that this is attributed to and uses hot filter method by PdCl2In solution Pd it is ultra-dispersed
Carrier surface, thus without Pd metallic atom agglomerations, catalyst surface active position is improve, increase catalysis activity；Adopt simultaneously
Carrier surface formation ZnO crystal grain is supported on organic zinc salt decomposition and occupies a certain amount of catalyst surface lattice defect, enhance
The selectivity of catalyst.
2nd, use mass content to replace environmentally harmful heavy metal Pb as auxiliary agent for 3~7% Zn, reduce Pd and live
Property, poisoning effect is played, cause alkynol only to carry out a step and be hydrogenated to enol, effectively control its hydrogenation step.
3rd, the Pd-Zn/CaCO prepared as auxiliary agent using Zn3Catalyst in the Hydrogenation enol of various alkynols half have compared with
Reaction-ure conversion-age high, selectivity of product and yield.The catalyst is in 1,4- butynediols 1,4- butylene glycols, methyl fourth
Shown in the reaction of the Hydrogenation enols of alkynol half such as alkynol methyl butenol, acetenyl isopropanol vinyl isopropanol higher
Reaction conversion ratio, high product selectivity and yield, catalyst service life is more long, especially in the Hydrogenation of Isosorbide-5-Nitrae-butynediols half
Preferably catalytic performance is shown in Isosorbide-5-Nitrae-butylene glycol reaction, is worth with good industrial applications.
Brief description of the drawings
Fig. 1 shows the surface crystalline phase XRD characterization results of according to embodiments of the present invention 1 catalyst.
Specific embodiment
With reference to background example, the present invention is further illustrated with embodiment.These embodiments be only given for
Descriptive purpose, can not be interpreted as limitation of the invention.Based on the embodiment in the present invention, ordinary skill people
The every other embodiment that member is obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.
The experimental technique for being used in the following embodiments unless otherwise specified, is conventional method.In following embodiments
In material, reagent used etc. unless otherwise specified, commercially obtain.Embodiment 1：
To in 0.45kg palladium bichloride powder plus 400mL concentration is 37% concentrated hydrochloric acid and is heated to 60 DEG C of dissolvings and forms solution
A；Milky emulsion B is formed to 30min is stirred in the calcium carbonate that 5kg particle diameters are 200 mesh plus after 10L deionized waters；In room
Under temperature with 7.5L deionized water dissolving 375g natrium carbonicum calcinatums and be slowly added dropwise formic acid 305mL until without gas release (now temperature
Degree is for about 60 DEG C) form solution C；Solution A is added in emulsion B at room temperature then, after stirring 5min, 80 is warmed up to
DEG C, 10min is incubated, obtain brown color emulsion AB；Then the solution C that temperature is for about 60 DEG C is disposably added rapidly to milkiness
Liquid AB, is warmed up to 85 DEG C, is then incubated and stirs 30min, until being released without gas, filters while hot, and filter cake is washed with deionized water 3
It is secondary to without Cl-, powdered black solid of weighing to obtain is dried, it is designated as powder D.At room temperature, by 1kg powder D and 100L deionizations
Water stirring mixing, adds zinc acetate 120g, and it is 7-8 to pH that appropriate ammoniacal liquor is added after having dissolved, and is warming up to 80 DEG C, insulation
30min, filtering, filter cake is placed in dried in vacuum overnight and must be final catalyst, is designated as C-1.
Embodiment 2：
To in 0.45kg palladium bichloride powder plus 400mL concentration is 37% concentrated hydrochloric acid and is heated to 60 DEG C of dissolvings and forms solution
A；Milky emulsion B is formed to 30min is stirred in the calcium carbonate that 5kg particle diameters are 200 mesh plus after 10L deionized waters；In room
Under temperature with 7.5L deionized water dissolving 375g natrium carbonicum calcinatums and be slowly added dropwise formic acid 305mL until without gas release (now temperature
Degree is for about 60 DEG C) form solution C；Solution A is added in emulsion B at room temperature then, after stirring 5min, 80 is warmed up to
DEG C, 10min is incubated, obtain brown color emulsion AB；Then the solution C that temperature is for about 60 DEG C is disposably added rapidly to milkiness
Liquid AB, is warmed up to 85 DEG C, is then incubated and stirs 30min, until being released without gas, filters while hot, and filter cake is washed with deionized water 3
It is secondary to without Cl-, powdered black solid of weighing to obtain is dried, it is designated as powder D.At room temperature, by 1kg powder D and 100L deionizations
Water stirring mixing, adds ferric acetate 152g, and it is 7-8 to pH that appropriate ammoniacal liquor is added after having dissolved, and is warming up to 80 DEG C, insulation
30min, filtering, filter cake is placed in dried in vacuum overnight and must be final catalyst, is designated as C-2.
Embodiment 3：
To in 0.45kg palladium bichloride powder plus 400mL concentration is 37% concentrated hydrochloric acid and is heated to 60 DEG C of dissolvings and forms solution
A；Milky emulsion B is formed to 30min is stirred in the calcium carbonate that 5kg particle diameters are 200 mesh plus after 10L deionized waters；In room
Under temperature with 7.5L deionized water dissolving 375g natrium carbonicum calcinatums and be slowly added dropwise formic acid 305mL until without gas release (now temperature
Degree is for about 60 DEG C) form solution C；Solution A is added in emulsion B at room temperature then, after stirring 5min, 80 is warmed up to
DEG C, 10min is incubated, obtain brown color emulsion AB；Then the solution C that temperature is for about 60 DEG C is disposably added rapidly to milkiness
Liquid AB, is warmed up to 85 DEG C, is then incubated and stirs 30min, until being released without gas, filters while hot, and filter cake is washed with deionized water 3
It is secondary to without Cl-, powdered black solid of weighing to obtain is dried, it is designated as powder D.At room temperature, by 1kg powder D and 100L deionizations
Water stirring mixing, adds magnesium acetate 140g, and it is 7-8 to pH that appropriate ammoniacal liquor is added after having dissolved, and is warming up to 80 DEG C, insulation
30min, filtering, filter cake is placed in dried in vacuum overnight and must be final catalyst, is designated as C-3.
Embodiment 4：
To in 0.45kg palladium bichloride powder plus 400mL concentration is 37% concentrated hydrochloric acid and is heated to 60 DEG C of dissolvings and forms solution
A；Milky emulsion B is formed to 30min is stirred in the calcium carbonate that 5kg particle diameters are 200 mesh plus after 10L deionized waters；In room
Under temperature with 7.5L deionized water dissolving 375g natrium carbonicum calcinatums and be slowly added dropwise formic acid 305mL until without gas release (now temperature
Degree is for about 60 DEG C) form solution C；Solution A is added in emulsion B at room temperature then, after stirring 5min, 80 is warmed up to
DEG C, 10min is incubated, obtain brown color emulsion AB；Then the solution C that temperature is for about 60 DEG C is disposably added rapidly to milkiness
Liquid AB, is warmed up to 85 DEG C, is then incubated and stirs 30min, until being released without gas, filters while hot, and filter cake is washed with deionized water 3
It is secondary to without Cl-, powdered black solid of weighing to obtain is dried, it is designated as powder D.At room temperature, by 1kg powder D and 100L deionizations
Water stirring mixing, adds calcium acetate 103.5g, and it is 7-8 to pH that appropriate ammoniacal liquor is added after having dissolved, and is warming up to 80 DEG C, insulation
30min, filtering, filter cake is placed in dried in vacuum overnight and must be final catalyst, is designated as C-4.
Embodiment 5：
To in 0.45kg palladium bichloride powder plus 400mL concentration is 30% concentrated hydrochloric acid and is heated to 70 DEG C of dissolvings and forms solution
A；Milky emulsion B is formed to 40min is stirred in the calcium carbonate that 5kg particle diameters are 400 mesh plus after 15L deionized waters；In room
Under temperature with 7.5L deionized water dissolving 375g natrium carbonicum calcinatums and be slowly added dropwise formic acid 305mL until without gas release (now temperature
Degree is for about 65 DEG C) form solution C；Solution A is added in emulsion B at room temperature then, after stirring 5min, 75 is warmed up to
DEG C, 15min is incubated, obtain brown color emulsion AB；Then the solution C that temperature is for about 65 DEG C is disposably added rapidly to milkiness
Liquid AB, is warmed up to 90 DEG C, is then incubated and stirs 20min, until being released without gas, filters while hot, and filter cake is washed with deionized water 4
It is secondary to without Cl-, powdered black solid of weighing to obtain is dried, it is designated as powder D.At room temperature, by 1kg powder D and 150L deionizations
Water stirring mixing, adds zinc acetate 140g, and it is 8-9 to pH that appropriate ammoniacal liquor is added after having dissolved, and is warming up to 80 DEG C, insulation
30min, filtering, filter cake is placed in dried in vacuum overnight and must be final catalyst, is designated as C-5.
Comparative example 1：
The preparation method of catalyst is same as Example 1, except auxiliary agent is changed into anhydrous plumbous acetate 175g from zinc acetate, system
Into catalyst D-1.
Comparative example 2：
The preparation method of catalyst is same as Example 1, the barium sulfate except carrier to be changed to 200 mesh from calcium carbonate granule
Particle, is made catalyst D-2.
Catalyst catalytic performance is evaluated：
In each evaluation experimental, by 20g catalyst and 2kg reactants input 5L autoclaves.Filled after vacuumizing
N2To 1MPa, pressurize 30min, whether observation pressure declines.Vacuumize again, fill H2To 0.7MPa, reactor design temperature is 65
DEG C, stir speed (S.S.) is 300~600rpm, and heat-insulation pressure keeping, reaction terminates after carrying out 90min.Cooling pressure release, N2Displacement, discharging is taken out
Leaching sample, gas-chromatography carries out quantitative analysis.
Product yield=reaction-ure conversion-age × selectivity of product
The catalyst of embodiment 1-4 and the catalyst of comparative example 1 react in 1,4- butynediols 1,4- butylene glycols
In specific catalytic performance test the results are shown in Table 1；Catalyst C-1 prepared by embodiment 1 should in the catalysis of various alkynol enols
Specific catalytic performance test the results are shown in Table 2 in.
Table 1：C1-C4 and D1 catalyst catalytic performance test in 1,4- butynediols systems 1,4, the reaction of-butylene glycol
As can be seen from Table 1, the catalyst of the present invention in embodiment 1-4 with Zn, Fe, Mg, Ca as auxiliary agent is in Isosorbide-5-Nitrae-butine
Glycol system 1,4, reaction-ure conversion-age and product higher is shown in the reaction of-butylene glycol than the catalyst of comparative example 1 and 2
Yield.Also, in catalyst of the present invention, compared with the catalyst of Fe, Mg, Ca for auxiliary agent, using Zn as the catalyst of auxiliary agent
Show reaction-ure conversion-age higher, selectivity of product and yield.
Catalytic performance of the C-1 catalyst of table 2 in various alkynol enol catalytic applications
As can be seen from Table 2, the Pd-Zn/CaCO for being prepared as auxiliary agent using Zn3Catalyst is in the Hydrogenation of various alkynols half
There is reaction-ure conversion-age higher, selectivity of product and yield, in Isosorbide-5-Nitrae-butynediols Isosorbide-5-Nitrae-butylene glycol, first in enol
The alkynols such as base butynol methyl butenol, acetenyl isopropanol vinyl isopropanol, dalgol first pentenol half add
Reaction conversion ratio higher, high product selectivity and yield are all shown in the reaction of hydrogen enol.
The above, is only presently preferred embodiments of the present invention, not makees any formal limitation to the present invention, it is every according to
Any simple modification, the equivalent variations made to above example according to technical spirit of the invention, each fall within protection of the invention
Within the scope of.
Claims (10)
1. a kind of catalyst for the Hydrogenation enol of alkynol half, including calcium carbonate granule carrier, and positioned at the calcium carbonate
The palladium element and the other elements as electronic auxiliary on particulate vector surface, wherein the palladium element is substantially with amorphous form
It is present in the surface of the calcium carbonate granule, the other elements are selected from Fe, Mg, Zn and Ca.
2. the catalyst for the Hydrogenation enol of alkynol half according to claim 1, wherein palladium element in the catalyst
Mass content be 1-10%.
3. the catalyst for the Hydrogenation enol of alkynol half according to claim 1, wherein as electricity in the catalyst
The mass content of the other elements of sub- auxiliary agent is 1-10%.
4. the catalyst for the Hydrogenation enol of alkynol half as claimed in one of claims 1-3, wherein it is described other
Element is the Zn-ef ficiency existed in zinc oxide form, and the XRD characterization results of the surface crystalline phase of the catalyst are as shown in Figure 1.
5. the catalyst for the Hydrogenation enol of alkynol half according to claim 4, wherein aoxidizing in the catalyst
The mass content of the Zn-ef ficiency that zinc form is present is 3-7%.
6. the preparation method of a kind of catalyst for the Hydrogenation enol of alkynol half, including：With Pd as active component, CaCO3To carry
Body, the salt selected from the other elements of Fe, Mg, Ca, Zn and combinations thereof is electronic auxiliary, and the catalysis is prepared by hot filter method
Agent.
7. the preparation method of the catalyst for the Hydrogenation enol of alkynol half according to claim 6, comprises the following steps：
The solution A that a, offer are mixed to get by palladium salt and acid solution；
The emulsion B that b, offer are mixed to get by calcium carbonate granule and water；
C, offer reductant solution C；
D, under agitation solution A is added into emulsion B, obtain emulsion AB；
E, will reductant solution C add emulsion AB in reduction reaction is carried out at 50~95 DEG C, solid is then filtered to obtain while hot
Powder D；
F, powder D is mixed with water, add the second as the other elements selected from Fe, Mg, Ca, Zn and combinations thereof of electronic auxiliary
Hydrochlorate, stirring, filtering obtains the catalyst after filtration cakes torrefaction.
8. the preparation method of the catalyst of the Hydrogenation enol of alkynol half is used for according to claim 6 or 7, wherein,
In step a, palladium salt is palladium bichloride, and acid solution is concentrated hydrochloric acid, and the ratio of palladium bichloride and concentrated hydrochloric acid is 1:0.5~1.5 (g:
ml)；
In stepb, the ratio of calcium carbonate granule and water is 1:1~5 (g:Ml), the particle diameter of calcium carbonate granule is 50-400 mesh；
In step c, the reducing agent is selected from the aqueous solution of aqueous sodium formate solution and hydrazine hydrate.
9. the preparation method of the catalyst for the Hydrogenation enol of alkynol half according to claim 8, wherein,
In step e, the solution C by temperature for 50-80 DEG C is disposably rapidly joined into emulsion AB with vigorous stirring, with
After be warmed up to 65~90 DEG C, and constant temperature stirs 10~60min, is released to without gas, filters while hot, and filter cake is washed with deionized
To without Cl-, through drying, black powder solid is obtained, it is designated as powder D.
10. the preparation method of the catalyst for the Hydrogenation enol of alkynol half according to claim 8, wherein,
Step c includes：To deionized water dissolving is added in natrium carbonicum calcinatum solid, formic acid is then slowly added dropwise, until without gas
Release, the colourless transparent solution containing sodium formate is obtained, as reductant solution C.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715893A (en) * | 2017-10-27 | 2018-02-23 | 西南化工研究设计院有限公司 | A kind of shell base catalyst of 1,4 butynediols selective hydrogenation and preparation method thereof |
| CN108043431A (en) * | 2017-12-15 | 2018-05-18 | 厦门大学 | A kind of selective hydrogenation catalyst of carbon-carbon double bond and its preparation method and application |
| CN109382100A (en) * | 2018-11-12 | 2019-02-26 | 大连理工大学 | A kind of selection plus hydrogen obtain compound catalyst and preparation method thereof between the zinc-containing metal of 1,4- butylene glycol |
| CN110124742A (en) * | 2019-05-28 | 2019-08-16 | 万华化学集团股份有限公司 | A method of by alkynol partial hydrogenation prepare enol catalyst and preparation method and utilize the catalyst preparation enol |
| CN110586081A (en) * | 2019-09-09 | 2019-12-20 | 浙江新和成股份有限公司 | Palladium-carbon catalyst and preparation method and application thereof |
| CN112408319A (en) * | 2020-10-10 | 2021-02-26 | 三峡大学 | Zn-EDTA as a hydrogen production control switch for ammonia borane |
| CN113788737A (en) * | 2021-08-25 | 2021-12-14 | 万华化学集团股份有限公司 | Triple bond partial hydrogenation method and catalyst thereof |
| CN114192161A (en) * | 2021-12-03 | 2022-03-18 | 大连理工大学 | A kind of Pt-Zn catalyst for synthesizing 1,4-butene diol, preparation method and application |
| CN115894173A (en) * | 2022-12-01 | 2023-04-04 | 西北工业大学 | A Visible Light-Driven Method for Selective Hydrogenation of Alkyne Alcohols to Enols |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3857894A (en) * | 1972-07-27 | 1974-12-31 | Snam Progetti | Hydrogenation of cyclic hydrocarbon diolefins to cyclic hydrocarbon olefins |
| CN1151725A (en) * | 1994-07-06 | 1997-06-11 | 巴斯福股份公司 | Process and catalyst for the selective hydrogenation of butine diol to butene diol |
-
2016
- 2016-12-27 CN CN201611223191.3A patent/CN106694010B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3857894A (en) * | 1972-07-27 | 1974-12-31 | Snam Progetti | Hydrogenation of cyclic hydrocarbon diolefins to cyclic hydrocarbon olefins |
| CN1151725A (en) * | 1994-07-06 | 1997-06-11 | 巴斯福股份公司 | Process and catalyst for the selective hydrogenation of butine diol to butene diol |
Non-Patent Citations (1)
| Title |
|---|
| R. V. CHAUDHARI等: ""Hydrogenation of Butynediol to Cis-Butenediol Catalyzed by Pd-Zn-CaCO3: Reaction Kinetics and Modeling of a Batch Slurry Reactor"", 《ALCHE JOURNAL》 * |
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