CN101768063A - Preparation method of isotope 13C-marked aldehyde - Google Patents
Preparation method of isotope 13C-marked aldehyde Download PDFInfo
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- CN101768063A CN101768063A CN200910198299A CN200910198299A CN101768063A CN 101768063 A CN101768063 A CN 101768063A CN 200910198299 A CN200910198299 A CN 200910198299A CN 200910198299 A CN200910198299 A CN 200910198299A CN 101768063 A CN101768063 A CN 101768063A
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Abstract
The invention relates to a preparation method of isotope 13C-marked aldehyde. The method includes the following steps that firstly, metallic carbide is generated by active metal and carbon dioxide, namely, the active metal is put in a reactor, the vacuum degree and the temperature of the reactor are controlled, 13 carbon dioxide and the active metal are put in the reactor to generate the metallic carbide; secondly, the metallic carbide is hydrolyzed to generate acetylene, and the by-product hydrogen is discharged by a vacuum pump; the acetylene is catalyzed and hydrated to generate aldehyde, namely, a catalyst system is added to the reactor provided with a cold trap and a constant flow pump and then hydrated to generate the 13C-marked aldehyde which is liquefied in the cold trap and collected. Compared with the prior art, the invention selects proper synthetic precursors, self-designs the reactor and optimizes synthetic path and technique. The method has a simple process, the preparation is easy, the purity of the product aldehyde is more than 99 percent, and the abundance of the isotope 13C is equal to or more than 98 atom percent.
Description
Technical field
The present invention relates to a kind of preparation method of acetaldehyde, especially relate to a kind of isotropic substance
13The preparation method of C marked aldehyde.
Background technology
Carbon-13 (is called for short
13C, down together) be the stable isotope of carbon, its natural abundance is 1.108atom%.Since the 1950's, along with the breakthrough of stable isotope isolation technique and the develop rapidly of testing tool, and the 13C stable isotope has and human body is not had characteristics such as radiohazard, make it can be used as tracer agent, be widely used in fields such as organic chemistry, biological chemistry, medical science and clinical diagnosis, pharmacology, agricultural sciences, especially life science and food safety field had earthshaking meaning.
Because this type of products material costliness, output is little, and purity and abundance are required height, and the mark position to label isotope in preparation also has particular requirement, usually needs to design special synthetic route, and adopts special reagent and reaction conditions.Compound isotopically labelled mainly is by chemical synthesis or biological fermentation process production at present.
Acetaldehyde has another name called acetaldehyde, is a kind of basic organic aldehydes raw material.Stable isotope
13The C marked aldehyde is a kind of important basic organic reagent, and setting out as precursor thus to obtain a series of isotropic substances
13The organic compound of C mark.
The present invention mainly was divided into for two steps to produce isotropic substance
13C marked aldehyde: 1, isotropic substance
13The carbonic acid gas of C mark prepares isotropic substance
13The acetylene of C mark; 2, isotropic substance
13The acetylene catalysis synthetic isotope of C mark
13The acetaldehyde of C mark.
From CO
2Set out and produce acetylene several different methods is arranged, industrial widely used be calcium carbide route, unslaked lime and coke at high temperature (usually above 1200 ℃) generate calcium carbide carbide of calcium (carbide of calcium) down, calcium carbide hydrolysis again generates acetylene.This process is fit to industrial-scale production acetylene, installs very highly to temperature requirement, and the productive rate and the purity of acetylene are lower, is not suitable for the synthetic of isotopic labeling acetylene.
The method that is fit to bench scale preparation isotopic labeling acetylene mainly contains magnesium method and lithium method, wherein the magnesium method adopts the ammoniacal liquor absorbing carbon dioxide to generate volatile salt, volatile salt and ebullient strontium chloride reaction precipitation are separated out Strontium carbonate powder, Strontium carbonate powder is blended in 850 ℃ of reactions with the magnesium powder of drying again and generates strontium carbides, and strontium carbide hydrolysis again prepares acetylene.It is complicated that this legal system is equipped with the acetylene process, and the chemical reagent of consumption is more, long flow path, and acetylene yield and purity are lower, are subject to topsoil, and explosion hazard is arranged; The lithium method adopts metallic lithium at 600～900 ℃ of following and CO
2Generate lithium carbide, lithium carbide hydrolysis again obtains acetylene, and purity and yield that this legal system is equipped with acetylene are the highest, simple to operate, easy to prepare, influenced by environmental pollution.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists that a kind of technology is simple, purity and the higher isotropic substance of abundance
13The preparation method of C marked aldehyde.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of isotropic substance
13The preparation method of C marked aldehyde is characterized in that, this method may further comprise the steps:
(1) reactive metal and carbonic acid gas generate metallic carbide: reactive metal is placed reactor, and the vacuum tightness of controlling reactor and temperature feed in reactor again
13CO
2With reactive metal reaction 4-10h, naturally cool to 20-25 ℃ again, obtain metallic carbide;
(2) the metallic carbide hydrolysis generates acetylene: reactor is connected to is furnished with scavenging air valve, is hydrolyzed in the hydrolysis device of cold-trap and vacuum pump, the acetylene that hydrolysis produces is collected in the liquid nitrogen cold trap, and by product hydrogen is got rid of by vacuum pump;
(3) the acetylene catalytic hydration prepares acetaldehyde: catalyst system is joined in the reactor of being furnished with cold-trap and constant flow pump, under the effect of constant flow pump acetylene is fed reactor, hydration reaction takes place generate
13The C marked aldehyde, generation
13The C marked aldehyde liquefies in cold-trap and is collected.
Reactive metal in the described step (1) comprises lithium, magnesium, sodium, potassium or strontium, preferable alloy lithium or magnesium.
The reactor vacuum tightness of described step (1) is-0.05～-0.1MPa.
The temperature of reactor of described step (1) is 600-1200 ℃, preferred 850-920 ℃.
Described step (1)
13CO
2With the mol ratio of reactive metal be 1: (1.0-25.0), preferred 1: (5.0-10.0).
The condenser temperature of described step (2) and step (3) is-30～-70 ℃.
The catalyst system of described step (3) comprises following component and content: the mol ratio of Primary Catalysts, mineral acid, promotor, water is 1: (1-100): (0-5): (50-1000), and preferred 1: (5-15): (0-2): (200-500).
Described Primary Catalysts comprises the salt of mercury, lead, zinc or molybdenum, the salt of preferred mercury or zinc; Described mineral acid comprises sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid, preferably sulfuric acid or phosphoric acid; Described promotor comprises salt or its oxide compound of the transition metal with variable valence state, comprises salt or its oxide compound of iron, nickel, vanadium, manganese or cobalt, the salt of preferred iron or vanadium.
Described Primary Catalysts comprises Mercury bisulfate, zinc chloride, and described promotor comprises ferric sulphate, ferric oxide or Vanadium Pentoxide in FLAKES.
The hydration reaction temperature of described step (3) is 30-250 ℃, preferred 60-100 ℃, and reaction times 3-10h.
Compared with prior art, the invention provides a cover isotropic substance
13The preparation method of C marked aldehyde selects suitable synthetic precursor, and reactor design is optimized synthetic route and technology voluntarily, and present method process is comparatively simple, preparation easily, and the purity of products therefrom acetaldehyde is more than 99%; Isotropic substance
13C abundance 〉=98atom%.
Description of drawings
Fig. 1 is the synoptic diagram of the reactor of step among the embodiment 1 (1);
Fig. 2 is the synoptic diagram of the reactor of step among the embodiment 1 (2);
Fig. 3 is the synoptic diagram of the reactor of step among the embodiment 1 (3).
1 is that screw clip, 2 is that stopping valve, 3 is that reactor heating, 4 is that vacuum meter, 5 is that hydrolysis reactor, 6 is that cold-trap, 7 is that reaction vessel, 8 is that well heater, 9 is that constant flow pump, 10 is that acetylene airbag, 11 is that vacuum stop,threeway, 12 is a reflux condensing tube among the figure.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
A kind of isotropic substance
13The preparation method of C marked aldehyde, this method may further comprise the steps:
(1) reactive metal and carbonic acid gas generate metallic carbide: adopt reactor as shown in Figure 1; comprise screw clip 1, stopping valve 2, reactor heating 3, vacuum meter 4; accurate weighing 15.6g (2.25mol) metallic lithium (purity is higher than 99.9%); under argon shield, put into reactor heating 1 rapidly; vacuumize and be warming up to 1200 ℃ after airtight, open screw clip and begin to feed 0.30mol
13CO
2,
13CO
2By Ba
13CO
3Quantitative yield obtains,
13C abundance 99atom%.Observe vacuum meter 4, by the vacuum tightness in the stopping valve 3 control reactor heatings 1 remain on-0.05～-0.1MPa, approximately 4h has led to
13CO
2, reaction naturally cools to room temperature after finishing, and obtains the carbide of metallic lithium.
(2) the metallic carbide hydrolysis generates acetylene: adopt reactor as shown in Figure 2, comprise screw clip 1, stopping valve 2, vacuum meter 4, hydrolysis reactor 5, cold-trap 6.Reactor in the step (1) is connected in the hydrolysis reactor 5, open vacuum pump and utilize stopping valve 2 Controlling System vacuum tightnesss at 0.05Mpa, from vacuum meter 4, read, slowly drip the about 2L of deionized water, the gas that is produced utilizes cold-trap 6 to absorb, and cold-trap 6 comprises alcohol-liquid nitrogen cold trap and liquid nitrogen cold trap.Moisture in the gas is collected by alcohol-liquid nitrogen cold trap, and acetylene product is collected in the liquid nitrogen cold trap, and hydrogen is got rid of by vacuum pump.After hydrolysis finishes, acetylene product in the liquid nitrogen cold trap is standby with airbag collection preservation, through drainage measurement gas volume, detect purity acetylene through chromatogram and be higher than 98%, proofread and correct the CO of back with consumption
2Meter, the acetylene yield is about 65%.
(3) the acetylene catalytic hydration prepares acetaldehyde: adopt reactor as shown in Figure 3, comprise cold-trap 6, reaction vessel 7, well heater 8, constant flow pump 9, acetylene airbag 10, vacuum stop,threeway 11, reflux condensing tube 12.According to following ratio preparation catalyzer mother liquor: HgSO
4(4.0g, 0.0135mol), dense H
2SO
4(12.2g, 0.124mol) and deionized water (100ml 5.55mol), adds the catalyzer mother liquor in the reaction vessel 7, and reaction vessel 7 connects reflux condensing tube 12, cold-trap 6, acetylene airbag 10 and constant flow pump 9 successively, and pipeline is provided with vacuum stop,threeway 11.At first reaction system is vacuumized, argon replaces three times, feed acetylene gas 0.223mol (proofreading and correct the back), temperature of reaction keeps 65 ℃, under the effect of constant flow pump 9, acetylene gas elder generation bubbling enters reaction vessel 7, generate acetaldehyde in reaction vessel 7, product acetaldehyde is along with unreacted acetylene enters reflux condensing tube 12 and alcohol-liquid nitrogen cold trap 6, and acetaldehyde is collected in cold-trap 6, unreacted acetylene enters once more and continues reaction in the reactor, no longer increases until generating the acetaldehyde amount.After reaction finishes, obtain
13The anhydrous acetaldehyde 6.7g of C mark (0.152mol), yield 68%, product identify through mass spectrum and nuclear-magnetism,
13The C abundance is higher than 98atom%.
Embodiment 2
(1) reactive metal and carbonic acid gas generate metallic carbide: weighing 5.47g (0.225mol) MAGNESIUM METAL; under argon shield, put into reactor heating rapidly; vacuumize after airtight; slowly heat up; when reaching 500～700 ℃, temperature stops to vacuumize; continue to be warming up to 600 ℃, open screw clip and feed 0.225molCO
2, observe vacuum meter, by the vacuum tightness in the stopping valve control reactor heating remain on-0.05～-0.1MPa, approximately 10h has led to CO
2, reaction naturally cools to 20 ℃ after finishing, and obtains the carbide of MAGNESIUM METAL.
(2) the metallic carbide hydrolysis generates acetylene: the reactor in the step (1) is connected in the hydrolysis reactor, open vacuum pump and utilize stopping valve Controlling System vacuum tightness at 0.05Mpa, slowly drip the about 2L of deionized water, the acetylene that is produced utilizes cold-trap to absorb, condenser temperature is-30 ℃, and hydrogen is got rid of by vacuum pump.After hydrolysis finishes, acetylene product in the liquid nitrogen cold trap is standby with airbag collection preservation, through drainage measurement gas volume, detect purity acetylene through chromatogram and be higher than 98%, proofread and correct the CO of back with consumption
2Meter, the acetylene yield is about 25%.
(3) the acetylene catalytic hydration prepares acetaldehyde: according to following ratio preparation catalyzer mother liquor: ZnCl
2(8.1g, 0.06mol), H
3PO
4(24.5g, 0.25mol) and deionized water (100ml, 5.55mol), the catalyzer mother liquor is added in the reaction vessel, at first reaction system is vacuumized, argon replaces three times, feed acetylene gas 0.223mol (proofreading and correct the back), temperature of reaction keeps 85 ℃, under the effect of constant flow pump, acetylene gas elder generation bubbling enters reaction vessel, generate acetaldehyde in reaction vessel, product acetaldehyde is along with unreacted acetylene enters reflux condensing tube and alcohol-liquid nitrogen cold trap, and acetaldehyde is collected in cold-trap, unreacted acetylene enters once more and continues reaction in the reactor, no longer increases until generating the acetaldehyde amount.After reaction finishes, obtain
13The anhydrous acetaldehyde 2.72g of C mark (0.059mol), yield 27%.
Embodiment 3
Step (1) is identical with embodiment 1 with step (2), prepares catalyzer mother liquor: HgSO according to following ratio in the step (3)
4(6.0g, 0.02mol), dense H
2SO
4(12.2g, 0.124mol) and deionized water (100ml, 5.55mol), (4.0g is 0.01mol) as promotor to add ferric sulphate simultaneously.
Reaction system is vacuumized, argon replaces three times, feed 0.223mol acetylene, temperature of reaction keeps 85 ℃, under the effect of constant flow pump, acetylene gas elder generation bubbling enters reaction vessel, generate acetaldehyde in reaction vessel, product acetaldehyde is along with unreacted acetylene enters reflux condensing tube and alcohol-liquid nitrogen cold trap, and acetaldehyde is collected in cold-trap, unreacted acetylene enters once more and continues reaction in the reactor, no longer increases until generating the acetaldehyde amount.After reaction finishes, obtain
13The anhydrous acetaldehyde 7.69g of C mark (0.167mol), yield 75%, product identify through mass spectrum and nuclear-magnetism,
13The C abundance is higher than 98atom%.
Embodiment 4
(1) reactive metal and carbonic acid gas generate metallic carbide: weighing 24g (1mol) MAGNESIUM METAL, under argon shield, put into reactor heating rapidly, and vacuumize after airtight, slowly be warming up to 1200 ℃, open screw clip and feed 0.25molCO
2Observe vacuum meter, by the vacuum tightness in the stopping valve control reactor heating remain on-0.05～-0.1MPa, approximately 3h has led to CO
2, reaction naturally cools to 20 ℃ after finishing, and obtains the carbide of MAGNESIUM METAL.
(2) the metallic carbide hydrolysis generates acetylene: the reactor in the step (1) is connected in the hydrolysis reactor, open vacuum pump and utilize stopping valve Controlling System vacuum tightness at 0.05Mpa, slowly drip the about 5L of deionized water, the acetylene that is produced utilizes cold-trap to absorb, condenser temperature is-70 ℃, and hydrogen is got rid of by vacuum pump.After hydrolysis finishes, preserve standby with the airbag collection acetylene product in the liquid nitrogen cold trap.
(3) the acetylene catalytic hydration prepares acetaldehyde: prepare the catalyzer mother liquor according to following ratio: 0.1mol ZnCl
2, 0.1mol HCl, V
2O
50.05mol and deionized water 20mol, the catalyzer mother liquor is added in the reaction vessel, at first reaction system is vacuumized, argon replaces three times, feed acetylene gas, temperature of reaction keeps 30 ℃, under the effect of constant flow pump, acetylene gas elder generation bubbling enters reaction vessel, generate acetaldehyde in reaction vessel, product acetaldehyde is along with unreacted acetylene enters reflux condensing tube and alcohol-liquid nitrogen cold trap, and acetaldehyde is collected in cold-trap, unreacted acetylene enters once more and continues reaction in the reactor, no longer increases until generating the acetaldehyde amount.Reaction obtains anhydrous acetaldehyde 3.05g (0.069mol), yield 31% after finishing.
Embodiment 5
(1) reactive metal and carbonic acid gas generate metallic carbide: weighing metallic lithium 5mol, under argon shield, put into reactor heating rapidly, and vacuumize after airtight, slowly be warming up to 850 ℃, open screw clip and feed 0.5molCO
2Observe vacuum meter, by the vacuum tightness in the stopping valve control reactor heating remain on-0.05～-0.1MPa, approximately 4h has led to CO
2, reaction naturally cools to 25 ℃ after finishing, and obtains the carbide of metallic lithium.
(2) the metallic carbide hydrolysis generates acetylene: the reactor in the step (1) is connected in the hydrolysis reactor, open vacuum pump and utilize stopping valve Controlling System vacuum tightness at 0.05Mpa, slowly drip the about 3L of deionized water, the acetylene that is produced utilizes cold-trap to absorb, condenser temperature is-50 ℃, and hydrogen is got rid of by vacuum pump.After hydrolysis finishes, preserve standby with the airbag collection acetylene product in the liquid nitrogen cold trap.
(3) the acetylene catalytic hydration prepares acetaldehyde: prepare the catalyzer mother liquor according to following ratio: 0.1mol ZnCl
2, 10mol HCl, V
2O
50.5mol and deionized water 100mol, the catalyzer mother liquor is added in the reaction vessel, at first reaction system is vacuumized argon replaces three times, feed acetylene gas, temperature of reaction keeps 250 ℃, and under the effect of constant flow pump, acetylene gas elder generation bubbling enters reaction vessel, in reaction vessel, generate acetaldehyde, product acetaldehyde is along with unreacted acetylene enters reflux condensing tube and alcohol-liquid nitrogen cold trap, and acetaldehyde is collected in cold-trap, and condenser temperature is-30 ℃.Unreacted acetylene enters once more and continues reaction in the reactor, no longer increases until generating the acetaldehyde amount.Reaction obtains anhydrous acetaldehyde 2.48g (0.056mol), yield 25% after finishing.
Embodiment 6
(1) reactive metal and carbonic acid gas generate metallic carbide: weighing metallic lithium 5mol, under argon shield, put into reactor heating rapidly, and vacuumize after airtight, slowly be warming up to 850 ℃, open screw clip and feed 0.5molCO
2Observe vacuum meter, by the vacuum tightness in the stopping valve control reactor heating remain on-0.05～-0.1MPa, approximately 6h has led to
13CO
2, reaction naturally cools to 25 ℃ after finishing, and obtains the carbide of metallic lithium.
(2) the metallic carbide hydrolysis generates acetylene: the reactor in the step (1) is connected in the hydrolysis reactor, open vacuum pump and utilize stopping valve Controlling System vacuum tightness at 0.05Mpa, slowly drip the about 5L of deionized water, the acetylene that is produced utilizes cold-trap to absorb, condenser temperature is-30 ℃, and hydrogen is got rid of by vacuum pump.After hydrolysis finishes, preserve standby with the airbag collection acetylene product in the liquid nitrogen cold trap.
(3) the acetylene catalytic hydration prepares acetaldehyde: according to following ratio preparation catalyzer mother liquor: 29.66gHgSO
4, 0.5mol HCl, V
2O
50.2mol and deionized water 50mol, the catalyzer mother liquor is added in the reaction vessel, at first reaction system is vacuumized argon replaces three times, feed acetylene gas, temperature of reaction keeps 100 ℃, and under the effect of constant flow pump, acetylene gas elder generation bubbling enters reaction vessel, in reaction vessel, generate acetaldehyde, product acetaldehyde is along with unreacted acetylene enters reflux condensing tube and alcohol-liquid nitrogen cold trap, and acetaldehyde is collected in cold-trap, and condenser temperature is-30 ℃.Unreacted acetylene enters once more and continues reaction in the reactor, no longer increases until generating the acetaldehyde amount.Reaction obtains anhydrous acetaldehyde 3.66g (0.083mol), yield 37% after finishing.
Claims (10)
1. isotropic substance
13The preparation method of C marked aldehyde is characterized in that, this method may further comprise the steps:
(1) reactive metal and carbonic acid gas generate metallic carbide: reactive metal is placed reactor, and the vacuum tightness of controlling reactor and temperature feed in reactor again
13CO
2With reactive metal reaction 4-10h, naturally cool to 20-25 ℃ again, obtain metallic carbide;
(2) the metallic carbide hydrolysis generates acetylene: reactor is connected to is furnished with scavenging air valve, is hydrolyzed in the hydrolysis device of cold-trap and vacuum pump, the acetylene that hydrolysis produces is collected in the liquid nitrogen cold trap, and by product hydrogen is got rid of by vacuum pump;
(3) the acetylene catalytic hydration prepares acetaldehyde: catalyst system is joined in the reactor of being furnished with cold-trap and constant flow pump, under the effect of constant flow pump acetylene is fed reactor, hydration reaction takes place generate
13The C marked aldehyde, generation
13The C marked aldehyde liquefies in cold-trap and is collected.
2. a kind of isotropic substance according to claim 1
13The preparation method of C marked aldehyde is characterized in that, the reactive metal in the described step (1) comprises lithium, magnesium, sodium, potassium or strontium, preferable alloy lithium or magnesium.
3. a kind of isotropic substance according to claim 1
13The preparation method of C marked aldehyde is characterized in that, the reactor vacuum tightness of described step (1) is-0.05～-0.1MPa.
4. a kind of isotropic substance according to claim 1
13The preparation method of C marked aldehyde is characterized in that, the temperature of reactor of described step (1) is 600-1200 ℃, preferred 850-920 ℃.
5. a kind of isotropic substance according to claim 1
13The preparation method of C marked aldehyde is characterized in that, described step (1)
13CO
2With the mol ratio of reactive metal be 1: (1.0-25.0), preferred 1: (5.0-10.0).
6. a kind of isotropic substance according to claim 1
13The preparation method of C marked aldehyde is characterized in that, the condenser temperature of described step (2) and step (3) is-30～-70 ℃.
7. a kind of isotropic substance according to claim 1
13The preparation method of C marked aldehyde, it is characterized in that, the catalyst system of described step (3) comprises following component and content: the mol ratio of Primary Catalysts, mineral acid, promotor, water is 1: (1-100): (0-5): (50-1000), and preferred 1: (5-15): (0-2): (200-500).
8. a kind of isotropic substance according to claim 7
13The preparation method of C marked aldehyde is characterized in that, described Primary Catalysts comprises the salt of mercury, lead, zinc or molybdenum, the salt of preferred mercury or zinc; Described mineral acid comprises sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid, preferably sulfuric acid or phosphoric acid; Described promotor comprises salt or its oxide compound of the transition metal with variable valence state, comprises salt or its oxide compound of iron, nickel, vanadium, manganese or cobalt, the salt of preferred iron or vanadium.
9. a kind of isotropic substance according to claim 8
13The preparation method of C marked aldehyde is characterized in that, described Primary Catalysts comprises Mercury bisulfate, zinc chloride, and described promotor comprises ferric sulphate, ferric oxide or Vanadium Pentoxide in FLAKES.
10. a kind of isotropic substance according to claim 1
13The preparation method of C marked aldehyde is characterized in that, the hydration reaction temperature of described step (3) is 30-250 ℃, preferred 60-100 ℃, and reaction times 3-10h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993576A (en) * | 2018-07-16 | 2018-12-14 | 石河子大学 | A kind of zinc catalyst and preparation method thereof for catalyzing acetylene hydration reaction |
| CN109716118A (en) * | 2016-11-02 | 2019-05-03 | 韩国电力公社 | Acetylene gas analytical equipment and analysis method for buried cable |
-
2009
- 2009-11-04 CN CN200910198299A patent/CN101768063A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109716118A (en) * | 2016-11-02 | 2019-05-03 | 韩国电力公社 | Acetylene gas analytical equipment and analysis method for buried cable |
| CN108993576A (en) * | 2018-07-16 | 2018-12-14 | 石河子大学 | A kind of zinc catalyst and preparation method thereof for catalyzing acetylene hydration reaction |
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Application publication date: 20100707 |