CN106669698B - It is a kind of to be used to synthesize copper bismuth catalyst of 1,4- butynediols and preparation method thereof - Google Patents
It is a kind of to be used to synthesize copper bismuth catalyst of 1,4- butynediols and preparation method thereof Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
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Abstract
The present invention discloses a kind of copper bismuth catalyst for synthesizing 1,4 butynediols and preparation method thereof.For the catalyst based on the weight of catalyst, the content of copper oxide is 30wt% ~ 80wt%, and the content of bismuth oxide is the wt% of 1.0wt% ~ 10.0, and the wt% of preferably 2.5 wt%~6.5, the particle size at least more than 80% of catalyst is between 7 20um.The catalyst is prepared using multiple step coprecipitation method.The catalyst has many advantages, such as that wearability is good for synthesizing Isosorbide-5-Nitrae butynediols, and catalyst particle size is uniformly moderate, activity stability is high.
Description
Technical field
The present invention relates to a kind of copper bismuth catalysts for synthesizing Isosorbide-5-Nitrae-butynediols and preparation method thereof, relate in particular to one
Kind is combined to copper bismuth catalyst of 1,4- butynediols and preparation method thereof for formaldehyde acetylene.
Background technology
The technique of industrialized production Isosorbide-5-Nitrae-butynediols is mainly acetylene-formaldehyde process (Reppe methods), domestic manufacturing enterprise Ru Shan
Western three-dimensional, Sichuan day China, Xinjiang Meike chemical industry, state's electricity Sinopec Ningxia derived energy chemical, Xingjiang Tianye Co., Inner Mongol gouy east, four
Chuan Weinilun factories etc. use such technology.In the 1970s, develop the Reppe method techniques of improvement, using slurry bed or
Suspension bed technique is reacted and is carried out under normal pressure or lower pressure.But Reppe techniques are improved to the more demanding of catalyst, are fitted
Closing industrialized particle size should be at 1 ~ 50 μm.The particle size of catalyst is more than 50 μm, and activity will decline very much, but if
Less than 1 μm, filtering is relatively difficult.
US4110249 and US4584418 and CN1118342A is individually disclosed with DNAcarrier free malachite, carrier-free
Copper oxide/bismuth oxide catalyst, these catalyst are not wear-resisting, and metal component is easily lost in.
The copper bismuth support type that US3920759 and CN102125856A individually discloses using magnesium silicate, kaolin as carrier is urged
Agent, for the catalysis reaction of formaldehyde and acetylene reaction synthesis Isosorbide-5-Nitrae-butynediols.But such catalyst has the following disadvantages：
（1）Carrier magnesium silicate is unstable, can dissolve in the reaction system, short life；（2）Catalyst amount is more, metal copper oxide
Content is higher, easily reunites, it is impossible to give full play to the catalytic effect in each activated centre, cause the waste of copper resource.
CN201210157882.3 discloses a kind of copper bismuth catalyst and preparation method, and its step are as follows：Using organosilicon
The alcoholic solution in source is added drop-wise in the mixed liquor containing mantoquita, bismuth salt, magnesium salts and dispersant, and the pH of mixed solution is adjusted with aqueous slkali
Mixed sediment is worth to, through further aging, uses washing of the dispersant for medium progress sediment, and using inert atmosphere
It is roasted.The activity of the catalyst is higher, but cost is higher, bad mechanical strength, it is difficult to realize industrialization.
CN201210397161.X is disclosed for catalyst of Isosorbide-5-Nitrae-butynediols production and preparation method thereof, this method
Nano silicon dioxide is used as carrier, in the method for precipitation deposition, by copper and bismuth absorption on carrier.Catalysis prepared by the method
Agent has preferable activity and selectivity, but due to using urea, for precipitating reagent, reaction process is slower, can generate a large amount of ammonia
Gas causes environmental pollution, and the catalyst granules prepared is smaller, bad filtering.
CN103170342A discloses a kind of nanometer CuO-Bi for synthesizing 1,4- butynediols2O3Catalyst, feature exist
In, proper amount of surfactant and sodium hydroxide solution are separately added into copper bismuth acidic aqueous solution, at a certain temperature pyrolysis system
Standby nanocatalyst.Prepared 10 ~ 80nm of catalyst particle size.The catalyst reaction activity is higher, but due to catalyst
Particle it is small, for slurry bed or suspension bed, particle is small, sad filter.And nanometer CuO-Bi2O3Activated centre exposure is more, holds
Easy in inactivation.
CN103157500A discloses a kind of preparation method of loaded catalyst, and this method uses mesopore molecular sieve to carry
Body loads to soluble mantoquita and bismuth salt on carrier using infusion process, and the catalyst particle size of preparation is received for 10 ~ 80
Rice, the catalyst activity is higher, but catalyst granules is too small, sad filter.
CN103480382A discloses a kind of catalyst for producing Isosorbide-5-Nitrae-butynediols and preparation method thereof, and this method uses
Nano silicon dioxide after acidification is carrier, makes copper with dipping and deposition sedimentation method and bismuth is adsorbed on carrier, Ran Hougan
It is dry, roast to obtain finished catalyst.Catalyst activity prepared by this method is preferable, and intensity is higher.But catalysis prepared by the method
The particle size uniformity of agent powder is bad, and little particle is more, is unfavorable for the industrial operation of catalyst.
In conclusion the catalyst of production Isosorbide-5-Nitrae-butynediols is in the prevalence of catalyst particle size discomfort in the prior art
In, the wearability of catalyst and the technical problems such as stability is poor, active component is easily lost in.
Invention content
It is an object of the invention to above-mentioned defect in the prior art is overcome to provide a kind of synthesis 1,4- butynediols
Copper bismuth catalyst and preparation method thereof, catalyst prepared by this method has that wearability is good, and catalyst particle size is even and regular
In, the advantages that activity stability is high.
A kind of preparation method for the copper bismuth catalyst for synthesizing Isosorbide-5-Nitrae-butynediols, including following steps：
（1）Prepare the acid solution containing mantoquita and bismuth salt；
（2）Prepare precipitant solution；
（3）Bottom water is added in into reaction kettle, and adds in polyvinylpyrrolidone（PVP K-30）With N- dodecyl boric acid
Diethanol amine ester（RNB）, heat up and be heated to reaction temperature；
（4）The mode of cocurrent is taken, by step（1）Acid solution and step（2）Precipitant solution be added drop-wise to reaction
In kettle；
（5）When remaining acid solution is step（1）When preparing the 2/3 ~ 3/4 of acid solution total amount, stop reaction, carry out old
Change；
（6）After aging, continue second segment coprecipitation reaction；
（7）It treats after reaction, temperature reduces by 5~10 DEG C of progress agings；It after aging, washs, filtering；
（8）Deionized water is added in filter cake, is beaten after stirring evenly, then carries out being spray-dried obtained copper bismuth catalyst.
The method of the present invention step（1）In, mantoquita in copper sulphate, copper nitrate, copper acetate or copper chloride at least one
Kind, preferably copper nitrate.The molar concentration of mantoquita is controlled in 0.6 ~ 3.0mol/L, preferably 1.0 ~ 2.5 mol/ in acid solution
L.Bismuth salt is selected from least one of bismuth nitrate, bismuth sulfate or bismuth acetate, preferably bismuth nitrate.Bismuth salt rubs in acid solution
You are controlled in 0.01 ~ 0.05mol/L, preferably 0.02 ~ 0.04mol/L concentration.Acid solution pH value for 0 ~ 2.0, preferably 0.5 ~
1.0。
Step of the present invention（2）In, precipitating reagent is selected from sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, ammonium hydroxide, bicarbonate
At least one of sodium, preferably sodium carbonate.The molar concentration of precipitating reagent be 0.1 ~ 3.0 mol/L, preferably 0.5 ~ 2.0
mol/L。
Step of the present invention（3）In, bottom water is added in into reaction kettle, addition is 0.15 ~ 0.4 times of acid solution volume,
It is preferred that 0.2 ~ 0.3 times.The PVP K-30 amounts of addition are that its mass concentration in the water of bottom is made to be 1% ~ 5%, preferably 2% ~ 3%. RNB
Addition quality add in 0.5 ~ 5 times, preferably 1.0 ~ 3.0 times of quality for PVP K-30.Then heating is heated to reaction temperature
30 ~ 80 DEG C, optimal is 40~70 DEG C.It is stirred continuously in reaction process.
Step of the present invention（4）In, acid solution and alkaline solution are added to certain speed cocurrent in reaction kettle, are kept
The pH value control of reaction is 5.0~8.0, and optimal is 6.0~7.0, and reaction temperature is controlled at 30 ~ 80 DEG C, and optimal is 40~70 DEG C.
Step of the present invention（5）In, aging temperature is controlled at 30 ~ 80 DEG C, and optimal is 40~70 DEG C.The control of aging pH value exists
5.0~8.0, optimal is that 6.0~7.0 ageing times were controlled at 10~70 minutes, optimal 20 ~ 50 minutes.
Step of the present invention（6）In, the control of the pH value of reaction is 5.0~8.0, and optimal is 6.0~7.0, reaction temperature control
At 30 ~ 80 DEG C, optimal is 40~70 DEG C.After reaction, ageing time is 0.5~4.0 hour, and preferably 1.0~2.5 is small
When.
Step of the present invention（7）In, it is washed, is filtered using the deionized water of temperature similary with aging.
Step of the present invention（8）In, the deionized water containing potassium chloride is added in filter cake, after stirring evenly, adds in citric acid
Three ammoniums are beaten, and then carry out being spray-dried obtained copper bismuth catalyst.Potassium chloride addition be slurries in water quality 1%~
20%, preferably 5%~15%.The butt of slurry is 15%~45%, preferably 25%~35%.Triammonium citrate addition is
The 5% ~ 25% of catalyst weight, preferably 10% ~ 20%.
A kind of catalyst prepared using the above method, based on the weight of catalyst, the content of copper oxide for 30wt% ~
80wt%, preferably 40wt% ~ 70wt%, the content of bismuth oxide are the wt% of 1.0wt% ~ 10.0, the wt% of preferably 2.5 wt%~6.5,
The particle size of catalyst at least more than 80% is between 7-20um.
The present invention adds in two kinds of PVP K-30 and RNB again by two sections of coprecipitation reactions during coprecipitation reaction
With surfactant, making the catalyst prepared, not only activity is high, granularity is concentrated, but also wearability is improved, and is conducive to
The later separation of catalyst is suitble to industrialized production.Potassium chloride is introduced in the slurry of spray drying and Triammonium citrate causes
While slurries have higher solids content, it may have preferable mobility.It is preferably resistance to so as to have the catalyst powder of preparation
Performance and the distribution of particles relatively concentrated are ground, catalyst has preferable activity, selectivity and stability.
Specific embodiment
Below by the technical solution that embodiment and comparative example further illustrate the present invention, but protection scope of the present invention is not
It is limited by example.Again using pellet after the wear-resisting property of catalyst is ultrasonically treated using ultrasonication device in the present invention
The special BT-9300ST laser particle analyzers analysis in east hundred, sonication treatment time is 30 minutes, supersonic frequency 20KHZ.Catalyst
Reactivity evaluation carried out in slurry bed, using formaldehyde and acetylene reaction system, reaction temperature is 90 DEG C, and reaction pressure is
Normal pressure, acetylene flow velocity are 80mL/min, and the formaldehyde addition of catalyst amount 35mL, concentration 37wt% are 250ml.
Embodiment 1
（1）Weigh 715gCu (NO3)2.3H2O and 30g Bi (NO3)3.5H2O is put into the water containing 25g nitric acid, treats it
2000ml is settled to after dissolving.
（2）Weigh 300 grams of Na2CO3It is configured to 2000ml solution.
（3）500ml deionized waters are added in a kettle, then add in 8 grams of PVP K-30 and 16 grams of RNB,
It is stirred and heated to 50 DEG C.
（4）Acid solution and alkaline solution cocurrent are added in reaction kettle, the pH value for controlling reactant is 6.0, reaction
Temperature is 50 DEG C.
（5）Work as step（1）Acid solution 1400 ml of residue when, stop reaction, carry out aging, aging condition and reaction
Condition is identical, and ageing time is 30 minutes.
（6）After aging, continue to react, pH value in reaction 6.0, reaction temperature is 50 DEG C.When acid solution is used
Complete to stop reaction, simultaneous reactions temperature is reduced to 45 DEG C, carries out aging.
（7）After aging 1.5 hours, washed with 45 DEG C of deionized waters, in the presence of washing into cleaning solution without sodium ion,
Stop washing.
（8）Filter cake is added in 580 grams of water containing 65g potassium chloride and 31 grams of Triammonium citrates, water temperature is controlled 45
DEG C, it is beaten uniform to material, the drying of catalyst is carried out with B-290 types spray-dried instrument.Sample number into spectrum is A, sample composition
For：CuO:66.2%, Bi2O3:4.0%.Size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Embodiment 2
（1）Weigh 648gCu (NO3)2.3H2O and 31g Bi (NO3)3.5H2O is put into the water containing 25g nitric acid, treats it
2000ml is settled to after dissolving.
（2）Weigh 300 grams of Na2CO3It is configured to 2000ml solution.
（3）600ml deionized waters are added in a kettle, then add in 7 grams of PVP K-30 and 13 grams of RNB,
It is stirred and heated to 45 DEG C.
（4）Acid solution and alkaline solution cocurrent are added in reaction kettle, the pH value for controlling reactant is 6.5, reaction
Temperature is 45 DEG C.
（5）Work as step（1）Acid solution 1450 ml of residue when, stop reaction, carry out aging, aging condition and reaction
Condition is identical, and ageing time is 20 minutes.
（6）After aging, continue to react, pH value in reaction 6.5, reaction temperature is 45 DEG C.When acid solution is used
Complete to stop reaction, simultaneous reactions temperature is reduced to 40 DEG C, carries out aging.
（7）After aging 1.5 hours, washed with 45 DEG C of deionized waters, in the presence of washing into cleaning solution without sodium ion,
Stop washing.
（8）Filter cake is added in 580 grams of water containing 65g potassium chloride and 31 grams of Triammonium citrates, water temperature is controlled 45
DEG C, it is beaten uniform to material, the drying of catalyst is carried out with B-290 types spray-dried instrument.Sample number into spectrum is A, sample composition
For：CuO:60.0%, Bi2O3:4.0%.Size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Embodiment 3
（1）Weigh 956gCu (NO3)2.3H2O and 42.5g Bi (NO3)3.5H2O is put into the water containing 40g nitric acid, is treated
It is settled to 2000ml after dissolving.
（2）Weigh 320 grams of Na2CO3It is configured to 2000ml solution.
（3）600ml deionized waters are added in a kettle, then add in 20 grams of PVP K-30 and 30 grams of RNB,
It is stirred and heated to 65 DEG C.
（4）Acid solution and alkaline solution cocurrent are added in reaction kettle, the pH value for controlling reactant is 6.8, reaction
Temperature is 65 DEG C.
（5）Work as step（1）Acid solution 1480 ml of residue when, stop reaction, carry out aging, aging condition and reaction
Condition is identical, and ageing time is 25 minutes.
（6）After aging, continue to react, pH value in reaction 6.8, reaction temperature is 65 DEG C.When acid solution is used
Complete to stop reaction, simultaneous reactions temperature is reduced to 55 DEG C, carries out aging.
（7）After aging 2.0 hours, washed with 55 DEG C of deionized waters, in the presence of washing into cleaning solution without sodium ion,
Stop washing.
（8）Filter cake is added in 700 grams of water containing 75g potassium chloride and 38 grams of Triammonium citrates, water temperature is controlled 55
DEG C, it is beaten uniform to material, the drying of catalyst is carried out with B-290 types spray-dried instrument.Sample number into spectrum is A, sample composition
For：CuO:55.5%, Bi2O3:3.5%.Size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Embodiment 4
With 3 difference of embodiment in step（8）In be added without potassium chloride and citric acid tri-amonia, sample number into spectrum D, granularity
Distribution is shown in Table 1, and evaluation result is shown in Table 2.
Comparative example 1
The catalyst that there is same composition with embodiment 3 is prepared by the technical solution of CN201210397161.X embodiments 1,
Sample number into spectrum is E, and size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Comparative example 2
With 3 difference of embodiment in step（3）In be added without PVP K-30 and RNB, sample number into spectrum F, size distribution
1 is shown in Table, evaluation result is shown in Table 2.
Comparative example 3
With embodiment 3, the difference lies in should using a step co-precipitation side.Sample number into spectrum is G, and size distribution is shown in Table 1, comments
Valency the results are shown in Table 2.
The distribution of particles of 1 catalyst of table
| A | B | C | D | E | F | G | |
| Bulk density, g.mL-1 | 1.01 | 1.05 | 1.26 | 0.95 | 0.70 | 0.86 | 0.75 |
| Before supersound process, % | |||||||
| <7um | 3.2 | 2.5 | 2.3 | 3.3 | 37.6 | 2.2 | 65.4 |
| 7~20um | 87.0 | 87.5 | 85.5 | 80.8 | 23.8 | 67.6 | 24.8 |
| After supersound process, % | |||||||
| <7um | 5.5 | 4.0 | 3.2 | 5.2 | 44.6 | 5.4 | 70.8 |
| 7~20um | 89.5 | 90.3 | 89.3 | 85.9 | 38.3 | 75.8 | 25.6 |
The evaluation result of 2 catalyst of table
| Sample number into spectrum | Formaldehyde conversion, % | The selectivity of butynediols, % |
| A | 97.0 | 98.4 |
| B | 96.9 | 98.3 |
| C | 97.4 | 98.2 |
| D | 96.8 | 97.9 |
| E | 95.4 | 97.6 |
| F | 96.5 | 96.9 |
| G | 96.2 | 96.6 |
Claims (19)
1. a kind of preparation method for the copper bismuth catalyst for synthesizing Isosorbide-5-Nitrae-butynediols, it is characterised in that：Include the following steps：
（1）Prepare the acid solution containing mantoquita and bismuth salt；
（2）Prepare precipitant solution；
（3）Deionized water is added in into reaction kettle, and adds in polyvinylpyrrolidone and N- dodecyl boric acid diethanol amine esters,
Heating is heated to reaction temperature；
（4）The mode of cocurrent is taken, by step（1）Acid solution and step（2）Precipitant solution be added drop-wise in reaction kettle；
（5）When remaining acid solution is step（1）When preparing the 2/3 ~ 3/4 of acid solution total amount, stop reaction, carry out aging；
（6）After aging, continue coprecipitation reaction；
（7）It treats after reaction, temperature reduces by 5~10 DEG C of progress agings, after aging, washs, filtering；
（8）Deionized water is added in filter cake, is beaten after stirring evenly, then carries out being spray-dried obtained copper bismuth catalyst.
2. according to the method described in claim 1, it is characterized in that：Step（1）In, mantoquita is selected from copper sulphate, copper nitrate, acetic acid
At least one of copper or copper chloride, the molar concentration of mantoquita is controlled in 0.6 ~ 3.0mol/L in acid solution.
3. according to the method described in claim 2, it is characterized in that：Mantoquita is copper nitrate, and mantoquita is mole dense in acid solution
Degree control is in 1.0 ~ 2.5 mol/L.
4. according to the method described in claim 1, it is characterized in that：Step（1）In, bismuth salt be selected from bismuth nitrate, bismuth sulfate or
At least one of bismuth acetate, the molar concentration of bismuth salt is controlled in 0.01 ~ 0.05mol/L, acid solution pH value in acid solution
It is 0 ~ 2.0.
5. according to the method described in claim 4, it is characterized in that：Bismuth salt is bismuth nitrate, and bismuth salt is mole dense in acid solution
0.5 ~ 1.0, acid solution pH value is 0.02 ~ 0.04mol/L for degree control.
6. according to the method described in claim 1, it is characterized in that：Step（2）In, precipitating reagent be selected from sodium carbonate, sodium hydroxide,
At least one of potassium carbonate, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, the molar concentration of precipitating reagent is 0.1 ~ 3.0 mol/L.
7. according to the method described in claim 6, it is characterized in that：Precipitating reagent is sodium carbonate, and the molar concentration of precipitating reagent is 0.5
~2.0 mol/L。
8. according to the method described in claim 1, it is characterized in that：Step（3）In, deionized water is added in into reaction kettle, is added
Enter 0.15 ~ 0.4 times that amount is acid solution volume.
9. according to the method described in claim 1, it is characterized in that：Step（3）In, the amount of the polyvinylpyrrolidone of addition is
It is 1% ~ 5% to make its mass concentration in deionized water.
10. according to the method described in claim 1, it is characterized in that：Step（3）In, N- dodecyl boric acid diethanol amine esters
Addition quality add in 0.5 ~ 5 times of quality for polyvinylpyrrolidone.
11. according to the method described in claim 1, it is characterized in that：Step（3）Middle heating is heated to 30 ~ 80 DEG C of reaction temperature,
It is stirred continuously in reaction process.
12. according to the method described in claim 1, it is characterized in that：Step（4）In, keep the pH value control of reaction 5.0~
8.0, reaction temperature is controlled at 30 ~ 80 DEG C.
13. according to the method described in claim 1, it is characterized in that：Step（5）In, aging temperature is controlled at 30 ~ 80 DEG C, always
Change pH value control 5.0~8.0, ageing time was controlled at 10~70 minutes.
14. according to the method described in claim 1, it is characterized in that：Step（6）In, the control of the pH value of reaction 5.0~8.0,
Reaction temperature is controlled at 30 ~ 80 DEG C, and after reaction, ageing time is 0.5~4.0 hour.
15. according to the method described in claim 1, it is characterized in that：Step（7）In, using temperature similary with aging go from
Sub- water is washed, filtering.
16. according to the method described in claim 1, it is characterized in that：Step（8）In, it adds in filter cake and is gone containing potassium chloride
Ionized water after stirring evenly, adds in Triammonium citrate mashing, then carries out being spray-dried obtained copper bismuth catalyst.
17. according to the method for claim 16, it is characterised in that：Potassium chloride addition be slurries in water quality 1%~
20%, the butt of slurry is 15%~45%, and Triammonium citrate addition is the 5% ~ 25% of catalyst weight.
18. a kind of catalyst prepared using claim 1 to 17 either method, it is characterised in that：Based on the weight of catalyst,
The content of copper oxide is 30wt% ~ 80wt%, and the content of bismuth oxide is the wt% of 1.0wt% ~ 10.0, and the particle size of catalyst is at least
More than 80% between 7-20um.
19. catalyst according to claim 18, it is characterised in that：Based on the weight of catalyst, the content of copper oxide is
40wt% ~ 70wt%, the content of bismuth oxide are the wt% of 2.5 wt%~6.5.
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| CN109201056B (en) * | 2017-06-30 | 2021-07-09 | 中国石油化工股份有限公司 | Catalyst for preparing 1, 4-butanediol from dimethyl maleate |
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