CN106669701A - 1,4-butyne diol catalyst preparation method - Google Patents
1,4-butyne diol catalyst preparation method Download PDFInfo
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Abstract
The invention discloses a 1,4-butyne diol catalyst preparation method, which comprises: (1) preparing a copper-silicon mixing solution, a copper-bismuth mixing solution, a precipitant solution I and a precipitant solution II; (2) adding bottom water to a reaction kettle, heating to a reaction temperature, and carrying out co-current flow adding-in-a-dropwise and co-precipitating on the copper-silicon mixing solution and the precipitant solution I; (3) adding a dispersant to the copper-bismuth mixing solution, adding the obtained solution and the precipitant solution II to the reaction liquid obtained in the step (2) in a co-current flow and dropwise manner, and aging after completing the reaction; (4) filtering the material, and adding a proper amount of distilled water according to the solid content of 10-40% after washing; and (5) carrying out spray drying on the slurry, and calcining to obtain the catalyst. According to the present invention, the catalyst is the ethynylation catalyst with characteristics of good wear resistance, uniform particles, loss resistance during the use, and the preparation method has characteristics of simpleness, easy performing, and good reproducibility.
Description
Technical field
The present invention relates to a kind of preparation method for producing Isosorbide-5-Nitrae-butynediols catalyst, belongs to technical field of chemical engineering catalysts.
Background technology
1,4- butynediols（BD）It is a kind of important organic chemical industry's intermediate, its hydrogenation products BDO（BDO）, can be used to produce gamma-butyrolacton（GBL）, tetrahydrofuran（THF）, poly- two benzene dicarboxylic acid butanediol ester（PBT）Deng.In recent years because of the demand abruptly increase of the derivants such as PBT, China increases substantially to the demand of BDO.Industrially, the production of Isosorbide-5-Nitrae-butynediols is main adopts the formaldehyde of Coal Chemical Industry production, acetylene to be bound up, and there are abundant coal resources in China so that have advantageous condition and advantage by raw material production Isosorbide-5-Nitrae-butynediols of Coal Chemical Industry Route acetylene.
The forties in 20th century, Reppe has been invented with formaldehyde and acetylene as the technique of Material synthesis Isosorbide-5-Nitrae-butynediols.The technique adopts alkynes copper catalyst, and the operational danger of acetylene and alkynes copper is increased under reaction pressure.After the seventies, new synthesis Isosorbide-5-Nitrae-butynediols catalyst is developed again, Reppe techniques is improved.The catalyst that the technique is used is malachite, and granule is little, and activity is good, is reacted in slurry bed, improves operating pressure, reduces the danger of blast.But this catalyst is not wear-resistant, easily it is lost in.Such as patent US4110249
, US4584418 and CN1118342A.Phenomenon that is not wear-resisting for malachite catalyst, being easy to run off, the ethynylation catalyst with silicon dioxide, zeolite, kieselguhr etc. as carrier was occurred in that later, such as patent US4288641 and US3920759, the ethynylation catalyst with molecular sieve and magnesium silicate as carrier is individually disclosed；Patent CN102125856A is prepared for formaldehyde using the Kaolin for especially preparing and acetylene reaction prepares 1,4- butynediols and contains carried catalyst；But such catalyst has the following disadvantages：（1）Carrier magnesium silicate is unstable, can dissolve in reaction system, short life；（2）Catalyst amount is more, and metal oxidation copper content is higher, easily reunites, it is impossible to give full play to the catalytic effect in each active center, causes the waste of copper resource.
CN201210157882.3
A kind of copper bismuth catalyst and preparation method are disclosed, its step is as follows：It is added drop-wise in the mixed liquor containing mantoquita, bismuth salt, magnesium salt and dispersant using the alcoholic solution of organic silicon source, the pH value for adjusting mixed solution with aqueous slkali obtains mixed sediment, the washing that Jing is further aging, adopt dispersant carries out precipitate for medium, and roasting is carried out using inert atmosphere.The activity of the catalyst is higher, but relatively costly, bad mechanical strength, it is difficult to realize industrialization.
CN201210397161.X discloses catalyst for Isosorbide-5-Nitrae-butynediols production and preparation method thereof, and the method adopts nano silicon for carrier, the method to precipitate deposition, and copper and bismuth are adsorbed on carrier.Catalyst prepared by the method has preferable activity and selectivity, but due to adopting carbamide for precipitant, course of reaction is slower, can produce substantial amounts of ammonia, causes environmental pollution, and the catalyst granules for preparing is less, bad filtration.
CN103170342A discloses a kind of nanometer CuO-Bi of synthesis 1,4- butynediols2O3Catalyst, it is characterised in that proper amount of surfactant and sodium hydroxide solution are separately added in copper bismuth acidic aqueous solution, pyrolysis at a certain temperature prepares nanocatalyst.Prepared 10 ~ 80nm of catalyst particle size.The catalyst reaction activity is higher, but because the granule of catalyst is little, for slurry bed or suspension bed, granule is little, sad filter.And nanometer CuO-Bi2O3Active center exposure is more, easily inactivation.
CN103157500A discloses a kind of preparation method of loaded catalyst, and the method adopts mesopore molecular sieve for carrier, and the mantoquita and bismuth salt of solubility are loaded on carrier using infusion process, and the catalyst particle size of preparation is 10 ~ 80
Nm, the catalyst activity is higher, but catalyst granules is too little, sad filter.
CN103480382A discloses a kind of production 1, catalyst of 4- butynediols and preparation method thereof, the method adopts the nano silicon after acidifying for carrier, makes copper and bismuth absorption on carrier with deposition sedimentation method to impregnate, and then dry, roasting obtains finished catalyst.Preferably, intensity is higher for catalyst activity prepared by the method.But the particle size uniformity of catalyst fines prepared by the method is bad, and little particle is more, is unfavorable for the industrial operation of catalyst.
In sum, the catalyst generally existing that Isosorbide-5-Nitrae-butynediols is produced in prior art following deficiency：The technical problems such as catalyst particle size is not moderate, catalyst wearability and stability is poor, the carrier complicated process of preparation relative costs height that active component is easily lost in and adopts.
The content of the invention
The purpose of the present invention is to overcome defect present in prior art, one kind is provided and synthesizes 1 in slurry bed system for formaldehyde and acetylene, the ethynylation catalyst that the active good, wearability of 4- butynediols is good, catalyst granules is uniform, not easily run off during use, and the preparation method of catalyst is simple, easy, reproducible.
The technical solution used in the present invention is：A kind of preparation method for producing Isosorbide-5-Nitrae-butynediols catalyst, it includes following preparation process：
（1）Prepare copper silicon mixed solution, copper bismuth mixed solution, precipitant solution I and precipitant solution II；
（2）Bottom water, intensification is added to be heated to reaction temperature toward reactor；It is 50 DEG C ~ 80 DEG C in reaction temperature, preferably 60 DEG C ~ 70 DEG C, copper silicon mixed solution and the cocurrent Deca of precipitant solution I is co-precipitated, keep precipitation system pH value to be 4 ~ 7, preferably 5 ~ 6, copper consumption used is 30% ~ 70% of the total consumption of copper in catalyst, preferably 40% ~ 60%；
（3）Dispersant is added in copper bismuth mixed solution, with the cocurrent of precipitant solution II step is added drop-wise to（2）Reactant liquor in, copper consumption used is remaining content, compares step（2）Deposition condition, coprecipitation reaction temperature reduce by 5 DEG C ~ 30 DEG C, preferably 10 DEG C ~ 20 DEG C, coprecipitation reaction pH value improve 0.2 ~ 1.5, preferably 0.5 ~ 1.2, reaction terminate after, carry out aging；
（4）By material filtering, solid content 10%-40% is pressed after washing, preferably 20% ~ 30% meter adds appropriate distilled water；
（5）Using being spray-dried, dry temperature is 100 DEG C ~ 200 DEG C to serosity, and preferably 120 DEG C ~ 180 DEG C, then in 350 DEG C ~ 650 DEG C 1 ~ 5h of roasting, preferably 400 DEG C ~ 600 DEG C 2 ~ 4h of roasting obtain producing the catalyst of Isosorbide-5-Nitrae-butynediols.
The inventive method step（1）In, one or more of the copper in copper sulfate, copper nitrate or copper chloride, preferably copper nitrate.The silicon be waterglass, Ludox, potassium silicate, the mixture of one or more in tetraethyl orthosilicate, preferably Ludox.One or more of bismuth in bismuth nitrate, bismuth sulfate or bismuth chloride, preferably bismuth nitrate.In copper silicon mixed solution, the molar concentration of copper is controlled 0.6 ~ 3.0
Mol/L, preferably 1.0 ~ 2.5 mol/L.In terms of silicon dioxide, the molar concentration of silicon is controlled to 0.2 ~ 2.5 mol/L, preferably 0.8 ~ 2.0 mol/L.In copper bismuth mixed solution, the molar concentration of copper is controlled 0.6 ~ 2.5
Mol/L, preferably 1.0 ~ 2.0 mol/L.The molar concentration of bismuth salt is controlled in 0.015 ~ 0.045 mol/L, and preferably 0.02 ~ 0.04
mol/L。
The inventive method step（1）In, selected from one or more from sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, ammonium carbonate or ammonia, the molar concentration of precipitant solution I is 1.0 ~ 8.0 to precipitant solution I
Mol/L, preferably 2.5 ~ 6.0 mol/L.One or more of precipitant solution II in sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate, the molar concentration of precipitant solution II is 0.1 ~ 2.0 mol/L, preferably 0.5 ~ 1.5 mol/L.
The inventive method step（2）In, bottom water addition is 1/6 ~ 2/3, preferably the 1/3 ~ 1/2 of reactor cumulative volume.
The inventive method step（3）In, one or more of dispersant in polyethylene glycol 200, PEG400, sodium methylene bis-naphthalene sulfonate, sodium polyacrylate, sodium sulfonate, sodium cellulose xanghate, sodium lignin sulfonate, methyl sodiosul foaliphatate, its addition is that 0.1 ~ 5.0%, preferably the 0.5 ~ 3.5% of copper mass is aoxidized in catalyst.
The inventive method step（3）In, aging condition is consistent with the reaction condition of the step, and ageing time is controlled 10 ~ 70
Min, preferably 20 ~ 50 min.
The inventive method step（4）In, it is described to wash to Na2O mass contents are less than 0.5%.
Using said method prepare production Isosorbide-5-Nitrae-butynediols catalyst, the catalyst with silicon oxide as carrier, with copper bismuth compound as active component, by mass percentage, copper oxide is 30% ~ 60%, preferably 40% ~ 55% to its composition, bismuth oxide is 2% ~ 5%, preferably 3% ~ 4%, and silicon oxide is surplus；10 ~ 40 μm of particle diameters of the catalyst at least more than 80%, preferably more than 85%, specific surface area be 20 ~ 50 m2/ g, pore volume is 0.1 ~ 0.5 cm3·g-1 ,Pore-size distribution accounts for more than 85%, preferably 80% ~ 95% between 10nm ~ 50nm, and bulk density is 1.0 ~ 1.8 gmL-1, preferably 1.2 ~ 1.6
g·mL-1。
Copper silicon solution and precipitant solution are carried out coprecipitated reaction by method for preparing catalyst of the present invention first, obtain the serosity containing copper silicon precipitate, can so make the copper for first precipitating form relatively stable homogeneous species in catalytic inner,While with certain catalytic activity, the wearability of catalyst is in turn ensure that.
Method for preparing catalyst of the present invention adds dispersant in copper bismuth mixed solution, and copper bismuth can be made equably to be deposited on established copper silicon carrier, and the distribution of sizes for making crystal grain is focused in a narrower scope.
Method for preparing catalyst of the present invention have selected precipitant I in cement copper silicon carrier, and precipitant II has been used in cement copper bismuth active component, so carrier and active component can be reacted under the conditions of each optimal, so that catalyst has suitable specific surface area, pore volume, be conducive to improving the reactivity and selectivity and stability of catalyst.
Good catalyst activity, easily separated, catalyst granules are uniform obtained in method for preparing catalyst of the present invention, distribution is concentrated, wherein granularity accounts for more than 80% in 10-40 μm of granule, not easily runs off during catalyst use, and the preparation method of catalyst is simple, easy, reproducible.The catalyst of the present invention has the specific surface area and pore volume being adapted to, and improves the reactivity and selectivity and stability of catalyst.
Specific embodiment
Technical scheme is further illustrated below by embodiment and comparative example, but protection scope of the present invention should not be limited by the examples.The anti-wear performance of catalyst is analyzed using the BT-9300ST laser particle analyzers that ultrasonication device is carried out after supersound process again using Dandong Bai Te in the present invention, and sonication treatment time is 30min, and supersonic frequency is 20KHz.Catalyst is evaluated using intermittent stirring reactor.Using formaldehyde and acetylene reaction system, reaction temperature is 90 DEG C, and reaction pressure is normal pressure, and acetylene flow velocity is 80mL/min, and catalyst amount is 35mL, and the formaldehyde addition of concentration 37wt% is 250ml.% in embodiment and comparative example if no special instructions, is mass percent.
Embodiment 1
（1）Weigh 96.64g
Cu(NO3)2.3H2O and 229.6g
30% Ludox, prepares 400ml copper silicon mixed solutions；Weigh 144.96g
Cu(NO3)2.3H2O and 10.24g
Bi(NO3)3.5H2O, prepares 600ml copper bismuth mixed solutions, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved；Prepare the Na of 3mol/L and 1mol/L2CO3Solution for standby.
（2）The bottom water of 2L is added toward 5L reactors, intensification is heated to 60 DEG C, by 400ml steps（1）The copper silicon mixed solution and the Na of 3mol/L of middle preparation2CO3Solution cocurrent Deca is co-precipitated, and keeps precipitation system pH value to be 6.
（3）2.0g polyethylene glycol 200s are added in 600ml copper bismuth mixed solutions, is stirred, then in 50 DEG C of system temperature, pH value is the Na with 1mol/L under conditions of 6.52CO3Solution co-precipitation, after reaction terminates, continues to stir 60min under this condition.
（4）Material filtering is washed to Na2O content is less than 0.5%, based on solid content 20%, adds appropriate distilled water.
（5）Using being spray-dried, dry temperature is 130 DEG C to serosity, then in 500 DEG C of roasting 3h, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Embodiment 2
（1）Weigh 120.8g
Cu(NO3)2.3H2O and 348.8g
30% Ludox, prepares 500ml copper silicon mixed solutions；Weigh 120.8g
Cu(NO3)2.3H2O and 12.49g
Bi(NO3)3.5H2O, prepares 500ml copper bismuth mixed solutions, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved；Prepare the NaOH solution of 4mol/L and the Na of 1mol/L2CO3Solution for standby.
（2）The bottom water of 1.8L is added toward 5L reactors, intensification is heated to 65 DEG C, by 500ml steps（1）The copper silicon mixed solution of middle preparation and the NaOH solution cocurrent Deca co-precipitation of 4mol/L, keep precipitation system pH value to be 5.5.
（3）1.5g sodium cellulose xanghates are added in 500ml copper bismuth mixed solutions, is stirred, then in 55 DEG C of system temperature, pH value is the Na with 1mol/L under conditions of 6.02CO3Solution co-precipitation, after reaction terminates, continues to stir 30min under this condition.
（4）Material filtering is washed to Na2O content is less than 0.5%, based on solid content 25%, adds appropriate distilled water.
（5）Using being spray-dried, dry temperature is 120 DEG C to serosity, then in 450 DEG C of roasting 3h, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Embodiment 3
（1）Weigh 144.96g
Cu(NO3)2.3H2O and 304.7g
30% Ludox, prepares 600ml copper silicon mixed solutions；Weigh 96.64g
Cu(NO3)2.3H2O and 13.71g
Bi(NO3)3.5H2O, prepares 500ml copper bismuth mixed solutions, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved；Prepare the ammonia spirit of 4.4mol/L and the Na of 1.5mol/L2CO3Solution for standby.
（2）The bottom water of 2.2L is added toward 5L reactors, intensification is heated to 70 DEG C, by 600ml steps（1）The copper silicon mixed solution of middle preparation and the ammonia spirit cocurrent Deca co-precipitation of 4.4mol/L, keep precipitation system pH value to be 5.5.
（3）1.2g PEG400s are added in 400ml copper bismuth mixed solutions, is stirred, then in 50 DEG C of system temperature, pH value is the Na with 1.5mol/L under conditions of 72CO3Solution co-precipitation, after reaction terminates, continues to stir 30min under this condition.
（4）Material filtering is washed to Na2O content is less than 0.5%, based on solid content 25%, adds appropriate distilled water.
（5）Using being spray-dried, dry temperature is 130 DEG C to serosity, then in 500 DEG C of roasting 3h, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Embodiment 4
（1）Weigh 120.8g
Cu(NO3)2.3H2O and 273.7g
30% Ludox, prepares 500ml copper silicon mixed solutions；Weigh 96.64g
Cu(NO3)2.3H2O and 12.24g
Bi(NO3)3.5H2O, prepares 500ml copper bismuth mixed solutions, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved；Prepare the Na of 3mol/L and 1.2mol/L2CO3Solution for standby.
（2）The bottom water of 2L is added toward 5L reactors, intensification is heated to 65 DEG C, by 500ml steps（1）The copper silicon mixed solution and the Na of 3mol/L of middle preparation2CO3Solution cocurrent Deca is co-precipitated, and keeps precipitation system pH value to be 6.0.
（3）0.75g sodium polyacrylate is added in 500ml copper bismuth mixed solutions, is stirred, then in 50 DEG C of system temperature, pH value is the Na with 1.2mol/L under conditions of 6.82CO3Solution co-precipitation, after reaction terminates, continues to stir 60min under this condition.
（4）Material filtering is washed to Na2O content is less than 0.5%, based on solid content 20%, adds appropriate distilled water.
（5）Using being spray-dried, dry temperature is 130 DEG C to serosity, then in 500 DEG C of roasting 3h, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Comparative example 1
It is step with the difference of embodiment 1（3）In be added without polyethylene glycol 200.
Comparative example 2
It is step with the difference of embodiment 1（3）Reaction condition and step（2）Reaction condition it is consistent.
Comparative example 3
The catalyst that there is same composition with embodiment 3 is prepared by the technical scheme of CN201210397161.X embodiments 1.
Activity rating of catalyst result and physico-chemical property prepared by above-mentioned comparative example and embodiment（Or particle size distribution）1, table 2 is shown in Table respectively.
The evaluation result of the catalyst of table 1
The physico-chemical property and distribution of particles of the catalyst of table 2
Claims (16)
1. a kind of preparation method for producing Isosorbide-5-Nitrae-butynediols catalyst, it is characterised in that：Comprise the steps：
（1）Prepare copper silicon mixed solution, copper bismuth mixed solution, precipitant solution I and precipitant solution II；
（2）Bottom water, intensification is added to be heated to reaction temperature toward reactor；It is 50 DEG C ~ 80 DEG C in reaction temperature, copper silicon mixed solution and the cocurrent Deca of precipitant solution I is co-precipitated, keep precipitation system pH value to be 4 ~ 7, copper consumption used is 30% ~ 70% of the total consumption of copper in catalyst；
（3）Dispersant is added in copper bismuth mixed solution, with the cocurrent of precipitant solution II step is added drop-wise to（2）Reactant liquor in, copper consumption used is remaining content, compares step（2）Deposition condition, coprecipitation reaction temperature reduce by 5 DEG C ~ 30 DEG C, coprecipitation reaction pH value improve 0.2 ~ 1.5, reaction terminate after, carry out aging；
（4）By material filtering, after washing based on solid content 10% ~ 40%, appropriate distilled water is added；
（5）Using being spray-dried, dry temperature is 100 DEG C ~ 200 DEG C to serosity, then in 350 DEG C ~ 650 DEG C 1 ~ 5h of roasting, obtains producing the catalyst of Isosorbide-5-Nitrae-butynediols.
2. method according to claim 1, it is characterised in that：Step（1）In, one or more of the copper in copper sulfate, copper nitrate or copper chloride, in copper silicon mixed solution, the molar concentration of copper is controlled in 0.6 ~ 3.0 mol/L.
3. method according to claim 1, it is characterised in that：Step（1）In, the silicon be waterglass, Ludox, potassium silicate, the mixture of one or more in tetraethyl orthosilicate, in terms of silicon dioxide, the molar concentration of silicon is controlled to 0.2 ~ 2.5 mol/L in copper silicon mixed solution.
4. method according to claim 1, it is characterised in that：Step（1）In, one or more of bismuth in bismuth nitrate, bismuth sulfate or bismuth chloride, in copper bismuth mixed solution, in 0.6 ~ 2.5 mol/L, the molar concentration of bismuth salt is controlled in 0.015 ~ 0.045 mol/L for the molar concentration control of copper.
5. method according to claim 4, it is characterised in that：The molar concentration control of copper is controlled in 0.02 ~ 0.04 mol/L in 1.0 ~ 2.0 mol/L, the molar concentration of bismuth salt.
6. method according to claim 1, it is characterised in that：Step（1）In, one or more of precipitant solution I in sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, ammonium carbonate or ammonia, the molar concentration of precipitant solution I is 2.5 ~ 6.0 mol/L.
7. method according to claim 1, it is characterised in that：Step（1）In, one or more of precipitant solution II in sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate, the molar concentration of precipitant solution II is 0.5 ~ 1.5 mol/L.
8. method according to claim 1, it is characterised in that：Step（2）In, reaction temperature is 60 DEG C ~ 70 DEG C, keeps precipitation system pH value to be 5 ~ 6, and copper consumption used is 40% ~ 60% of the total consumption of copper in catalyst.
9. method according to claim 1, it is characterised in that：Step（2）In, bottom water addition is the 1/6 ~ 2/3 of reactor cumulative volume.
10. method according to claim 1, it is characterised in that：Step（3）Coprecipitation reaction temperature reduces by 10 DEG C ~ 20 DEG C, and coprecipitation reaction pH value improves 0.5-1.2.
11. methods according to claim 1, it is characterised in that：Step（3）In, one or more of dispersant in polyethylene glycol 200, PEG400, sodium methylene bis-naphthalene sulfonate, sodium polyacrylate, sodium sulfonate, sodium cellulose xanghate, sodium lignin sulfonate, methyl sodiosul foaliphatate, its addition is that the 0.1% ~ 5.0% of copper mass is aoxidized in catalyst.
12. methods according to claim 1, it is characterised in that：Step（3）In, aging condition is consistent with reaction condition, and ageing time is controlled in 10 ~ 70 min.
13. methods according to claim 1, it is characterised in that：Step（4）In, it is described to wash to Na2O mass contents are less than 0.5%.
14. methods according to claim 1, it is characterised in that：Step（4）In, dry temperature is 120 DEG C ~ 180 DEG C, then in 400 DEG C ~ 600 DEG C 2 ~ 4h of roasting.
Catalyst prepared by a kind of 15. employing claim 1 to 14 either method, it is characterised in that：With silicon oxide as carrier, with copper bismuth compound as active component, by mass percentage, copper oxide is 30% ~ 60% to its composition to the catalyst, and bismuth oxide is 2% ~ 5%, and silicon oxide is surplus；The catalyst 10 ~ 40
At least more than 80%, specific surface area is 20 ~ 50 m for μm particle diameter2/ g, pore volume is 0.1 ~ 0.5 cm3·g-1 ,Pore-size distribution accounts for more than 85% between 10nm ~ 50nm, and bulk density is 1.0 ~ 1.8
g·mL-1。
16. methods according to claim 15, it is characterised in that：Copper oxide is 40% ~ 55%, and bismuth oxide is 3% ~ 4%；At least more than 85%, pore-size distribution is in 10nm ~ 50nm for 10 ~ 40 μm of particle diameters of the catalyst
Between account for 80% ~ 95%, bulk density is 1.2 ~ 1.6 gmL-1。
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| CN107335473B (en) * | 2017-09-05 | 2020-05-22 | 中国科学院成都有机化学有限公司 | Cu-Bi catalyst coated with precipitation type compound for two times and preparation method thereof |
| CN107999083A (en) * | 2017-11-22 | 2018-05-08 | 大连瑞克科技有限公司 | A kind of preparation method of synthesizing butynediol CuBiMgSi catalyst |
| CN107999083B (en) * | 2017-11-22 | 2021-06-18 | 大连瑞克科技有限公司 | Preparation method of CuBiMgSi catalyst for synthesizing butynediol |
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