CN106669698A - Copper-bismuth catalyst for synthesizing 1,4-butynediol and preparation method thereof - Google Patents
Copper-bismuth catalyst for synthesizing 1,4-butynediol 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
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- 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 invention discloses a copper-bismuth catalyst for synthesizing 1,4-butynediol and a preparation method thereof. The catalyst is prepared from the following components in percentage by weight: 30 weight percent to 80 weight percent of copper oxide and 1.0 weight percent to 10.0 weight percent of bismuth oxide; preferably, the content of the bismuth oxide is 2.5 weight percent to 6.5 weight percent; the grain size of at least not less than 80 percent of the catalyst is 7mum to 20mum. The catalyst is prepared by adopting a step-by-step co-precipitation method. The catalyst is used for synthesizing the 1,4-butynediol and has the advantages of good wearing resistance, uniform and moderate grain size of the catalyst, high activity stability and the like.
Description
Technical field
The present invention relates to a kind of copper bismuth catalyst and preparation method thereof of synthesis Isosorbide-5-Nitrae-butynediols, relate in particular to a kind of be combined to copper bismuth catalyst of Isosorbide-5-Nitrae-butynediols and preparation method thereof for formaldehyde acetylene.
Background technology
Industrialized production 1, the technique of 4- butynediols is mainly acetylene-formaldehyde process (Reppe methods), and domestic manufacturing enterprise such as Shanxi three-dimensional, Sichuan day China, Xinjiang Meike chemical industry, state's electricity Sinopec Ningxia derived energy chemical, Xingjiang Tianye Co., Inner Mongol gouy east, Sichuan Wei Nilun factories etc. adopts this kind of technology.20 century 70s, develop the Reppe method techniques of improvement, and using slurry bed or suspension bed technique, reaction is carried out under normal pressure or lower pressure.But it is higher to improve requirement of the Reppe techniques to catalyst, and suitable industrialized particle size should be at 1 ~ 50 μm.The particle size of catalyst is more than 50 μm, and activity will decline a lot, but if being less than 1 μm, filters relatively difficult.
US4110249 and US4584418 and CN1118342A are individually disclosed with DNAcarrier free malachite, and carrier-free cupric oxide/bismuth oxide catalyst, these catalyst are not wear-resisting, and metal component is easily lost in.
US3920759 and CN102125856A individually disclose the copper bismuth loaded catalyst with magnesium silicate, kaolin as carrier, for the catalytic reaction that formaldehyde and acetylene reaction synthesize Isosorbide-5-Nitrae-butynediols.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 activated centre, causes the waste of copper resource.
CN201210157882.3 discloses a kind of copper bismuth catalyst and preparation method, and its step is as follows：It is added drop-wise in the mixed liquor containing mantoquita, bismuth salt, magnesium salts 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 sediment 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 urea for precipitating reagent, 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 particle of catalyst is little, for slurry bed or suspension bed, particle is little, sad filter.And nanometer CuO-Bi2O3Activated centre exposure is more, easily inactivation.
CN103157500A discloses a kind of preparation method of loaded catalyst, the method adopts mesopore molecular sieve for carrier, soluble mantoquita and bismuth salt are loaded on carrier using infusion process, the catalyst particle size of preparation is 10 ~ 80 nanometers, 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 the technical problems such as not moderate catalyst particle size, catalyst wearability and stability are poor, active component is easily lost in.
The content of the invention
It is an object of the invention to overcome defect present in above-mentioned prior art to provide a kind of synthesis 1, copper bismuth catalyst of 4- butynediols and preparation method thereof, catalyst prepared by the method has wearability good, catalyst particle size it is uniform it is moderate, the advantages of activity stability is high.
A kind of preparation method of the copper bismuth catalyst of synthesis Isosorbide-5-Nitrae-butynediols, including following step：
（1）Prepare the acid solution containing mantoquita and bismuth salt；
（2）Prepare precipitant solution；
（3）Bottom water is added toward reactor, and adds polyvinylpyrrolidone（PVP
K-30）With N- dodecyl boric acid diethanol amine esters（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 in reactor；
（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 end, proceed second segment coprecipitation reaction；
（7）After question response terminates, 5～10 DEG C of temperature reduction carries out aging；After aging end, washing is filtered；
（8）Deionized water is added in filter cake, is beaten after stirring, then carry out being spray-dried prepared copper bismuth catalyst.
The inventive method step（1）In, at least one of the mantoquita in copper sulphate, copper nitrate, copper acetate or copper chloride, preferably copper nitrate.The molar concentration of mantoquita is controlled in 0.6 ~ 3.0mol/L, preferably 1.0 ~ 2.5 mol/L in acid solution.At least one of the bismuth salt in bismuth nitrate, bismuth sulfate or bismuth acetate, preferably bismuth nitrate.The molar concentration of bismuth salt is controlled in 0.01 ~ 0.05mol/L, preferably 0.02 ~ 0.04mol/L in acid solution.Acid solution pH value is 0 ~ 2.0, preferably 0.5 ~ 1.0.
Step of the present invention（2）In, at least one of the precipitating reagent in sodium carbonate, NaOH, potassium carbonate, potassium hydroxide, ammoniacal liquor, sodium acid carbonate, preferably sodium carbonate.The molar concentration of precipitating reagent is 0.1 ~ 3.0 mol/L, preferably 0.5 ~ 2.0 mol/L.
Step of the present invention（3）In, bottom water is added toward reactor, addition is 0.15 ~ 0.4 times, preferably 0.2 ~ 0.3 times of acid solution volume.The PVP K-30 amounts of addition are 1% ~ 5%, preferably 2% ~ 3% to make its mass concentration in the water of bottom.The addition quality of RNB is 0.5 ~ 5 times, preferably 1.0 ~ 3.0 times that PVP K-30 add quality.Then heat up and be heated to reaction temperatureDegree30 ~ 80 DEG C, optimum is 40～70 DEG C.It is stirred continuously in course of reaction.
Step of the present invention（4）In, acid solution and alkaline solution are added in reactor with certain speed cocurrent, keep the pH value control of reaction 5.0～8.0, and optimum is 6.0～7.0, and reaction temperature is controlled at 30 ~ 80 DEG C, and optimum is 40～70 DEG C.
Step of the present invention（5）In, aging temperature is controlled at 30 ~ 80 DEG C, and optimum is 40～70 DEG C.Aging pH value control is 5.0～8.0, and optimum is controlled at 10～70 minutes for 6.0～7.0 ageing times, optimum 20 ~ 50 minutes.
Step of the present invention（6）In, 5.0～8.0, optimum is 6.0～7.0, and reaction temperature is controlled at 30 ~ 80 DEG C, and optimum is 40～70 DEG C for the pH value control of reaction.After reaction terminates, ageing time is 0.5～4.0 hour, preferably 1.0～2.5 hours.
Step of the present invention（7）In, using being washed with the deionized water of aging same temperature, filter.
Step of the present invention（8）In, the deionized water containing potassium chloride is added in filter cake, after stirring, Triammonium citrate beating is added, then carry out being spray-dried prepared copper bismuth catalyst.Potassium chloride addition is 1%～20% of water quality in slurries, 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%.
Catalyst prepared by a kind of employing said method, based on the weight of catalyst, the content of cupric oxide is 30wt% ~ 80wt%, preferably 40wt% ~ 70wt%, the content of bismuth oxide is 1.0wt% ~ 10.0 wt%, preferably 2.5 wt%～6.5 wt%, the particle size at least more than 80% of catalyst is between 7-20um.
The present invention passes through two sections of coprecipitation reactions, and PVP two kinds of compound surfactants of K-30 and RNB are added during coprecipitation reaction, not only activity is high, granularity is concentrated to make the catalyst prepared, and wearability is improved, be conducive to the later separation of catalyst, be adapted to industrialized production.While introducing potassium chloride and Triammonium citrate cause slurries to have higher solids content in the slurry being spray-dried, it may have preferable mobility.So that the catalyst powder for preparing has preferable anti-wear performance and the distribution of particles relatively concentrated, catalyst has preferably activity, selectivity and stability.
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.In the present invention anti-wear performance of catalyst using ultrasonication device carry out it is ultrasonically treated after again using Dandong Bai Te BT-9300ST laser particle analyzers analyze, sonication treatment time be 30 minutes, supersonic frequency is 20KHZ
.The reactivity evaluation of catalyst is carried out in slurry bed, and 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.
Embodiment 1
（1）Weigh 715gCu (NO3)2.3H2O and 30g Bi (NO3)3.5H2O is put in the water containing 25g nitric acid, and after its dissolving 2000ml is settled to.
（2）Weigh 300 grams of Na2CO3It is configured to 2000ml solution.
（3）500ml deionized waters are added in a kettle., are subsequently adding 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 reactor, 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 is identical with reaction condition, and ageing time is 30 minutes.
（6）After aging end, proceed reaction, pH value in reaction is 6.0, reaction temperature is 50 DEG C.When acid solution is finished stopping 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, stopped 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 at 45 DEG C, is beaten to material uniformly, with B-290 types spray-dried instrument the drying of catalyst is carried out.Sample number into spectrum is A, and sample is consisted of：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 in the water containing 25g nitric acid, and after its dissolving 2000ml is settled to.
（2）Weigh 300 grams of Na2CO3It is configured to 2000ml solution.
（3）600ml deionized waters are added in a kettle., are subsequently adding 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 reactor, 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 is identical with reaction condition, and ageing time is 20 minutes.
（6）After aging end, proceed reaction, pH value in reaction is 6.5, reaction temperature is 45 DEG C.When acid solution is finished stopping 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, stopped 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 at 45 DEG C, is beaten to material uniformly, with B-290 types spray-dried instrument the drying of catalyst is carried out.Sample number into spectrum is A, and sample is consisted of：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 in the water containing 40g nitric acid, and after its dissolving 2000ml is settled to.
（2）Weigh 320 grams of Na2CO3It is configured to 2000ml solution.
（3）600ml deionized waters are added in a kettle., are subsequently adding 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 reactor, 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 is identical with reaction condition, and ageing time is 25 minutes.
（6）After aging end, proceed reaction, pH value in reaction is 6.8, reaction temperature is 65 DEG C.When acid solution is finished stopping 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, stopped 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 at 55 DEG C, is beaten to material uniformly, with B-290 types spray-dried instrument the drying of catalyst is carried out.Sample number into spectrum is A, and sample is consisted of：CuO:55.5%, Bi2O3:3.5%.Size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Embodiment 4
With the difference of embodiment 3 in step（8）In be added without potassium chloride and citric acid tri-amonia, sample number into spectrum is D, and size 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 scheme 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 the difference of embodiment 3 in step（3）In be added without PVP K-30 and RNB, sample number into spectrum is F, and size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Comparative example 3
With embodiment 3, difference is should using a step co-precipitation side.Sample number into spectrum is G, and size distribution is shown in Table 1, and evaluation result is shown in Table 2.
The distribution of particles of the catalyst of table 1
| 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 ultrasonically treated, % | |||||||
| <7um | 3.2 | 2.5 | 2.3 | 3.3 | 37.6 | 2.2 | 65.4 |
| 7~20 um | 87.0 | 87.5 | 85.5 | 80.8 | 23.8 | 67.6 | 24.8 |
| After ultrasonically treated, % | |||||||
| <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 the catalyst of table 2
| 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. it is a kind of synthesis Isosorbide-5-Nitrae-butynediols copper bismuth catalyst preparation method, it is characterised in that：Comprise the following steps：
（1）Prepare the acid solution containing mantoquita and bismuth salt；
（2）Prepare precipitant solution；
（3）Bottom water is added toward reactor, and adds polyvinylpyrrolidone and N- dodecyl boric acid diethanol amine esters, intensification 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 reactor；
（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 end, proceed coprecipitation reaction；
（7）After question response terminates, temperature reduce by 5～10 DEG C carry out it is aging, after aging end, washing, filter；
（8）Deionized water is added in filter cake, is beaten after stirring, then carry out being spray-dried prepared copper bismuth catalyst.
2. method according to claim 1, it is characterised in that：Step（1）In, at least one of the mantoquita in copper sulphate, copper nitrate, copper acetate or copper chloride, the molar concentration of mantoquita is controlled in 0.6 ~ 3.0mol/L in acid solution.
3. method according to claim 2, it is characterised in that：Mantoquita is copper nitrate, and the molar concentration of mantoquita is controlled 1.0 ~ 2.5 in acid solution
mol/L。
4. method according to claim 1, it is characterised in that：Step（1）In, at least one of the bismuth salt in bismuth nitrate, bismuth sulfate or bismuth acetate, in 0.01 ~ 0.05mol/L, acid solution pH value is 0 ~ 2.0 for the molar concentration control of bismuth salt in acid solution.
5. method according to claim 4, it is characterised in that：Bismuth salt is bismuth nitrate, and 0.5 ~ 1.0, acid solution pH value is 0.02 ~ 0.04mol/L for the molar concentration control of bismuth salt in acid solution.
6. method according to claim 1, it is characterised in that：Step（2）In, at least one of the precipitating reagent in sodium carbonate, NaOH, potassium carbonate, potassium hydroxide, ammoniacal liquor, sodium acid carbonate, the molar concentration of precipitating reagent is 0.1 ~ 3.0 mol/L.
7. method according to claim 6, it is characterised in that：Precipitating reagent is sodium carbonate, and the molar concentration of precipitating reagent is 0.5 ~ 2.0
mol/L。
8. method according to claim 1, it is characterised in that：Step（3）In, add bottom water, addition to be acid solution volume toward reactor
0.15 ~ 0.4 times.
9. method according to claim 1, it is characterised in that：Step（3）In, the amount of the polyvinylpyrrolidone of addition is to make its mass concentration in the water of bottom be 1% ~ 5%.
10. method according to claim 1, it is characterised in that：Step（3）In, the addition quality of N- dodecyl boric acid diethanol amine esters is 0.5 ~ 5 times that polyvinylpyrrolidone adds quality.
11. methods according to claim 1, it is characterised in that：Step（3）Middle intensification is heated to reaction temperatureDegree30 ~ 80 DEG C, it is stirred continuously in course of reaction.
12. methods according to claim 1, it is characterised 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. methods according to claim 1, it is characterised in that：Step（5）In, aging temperature is controlled at 30 ~ 80 DEG C, and 5.0～8.0, ageing time was controlled at 10～70 minutes for aging pH value control.
14. methods according to claim 1, it is characterised in that：Step（6）In, 5.0～8.0, reaction temperature is controlled at 30 ~ 80 DEG C for the pH value control of reaction, and after reaction terminates, ageing time is 0.5～4.0 hour.
15. methods according to claim 1, it is characterised in that：Step（7）In, using being washed with the deionized water of aging same temperature, filter.
16. methods according to claim 1, it is characterised in that：Step（8）In, the deionized water containing potassium chloride is added in filter cake, after stirring, Triammonium citrate beating is added, then carry out being spray-dried prepared copper bismuth catalyst.
17. methods according to claim 16, it is characterised in that：Potassium chloride addition is 1%～20% of water quality in slurries, and the butt of slurry is 15%～45%, and Triammonium citrate addition is the 5% ~ 25% of catalyst weight.
Catalyst prepared by a kind of 18. employing claim 1 to 17 either method, it is characterised in that：Based on the weight of catalyst, the content of cupric oxide is 30wt% ~ 80wt%, and the content of bismuth oxide is 1.0wt% ~ 10.0 wt%, and the particle size at least more than 80% of catalyst is between 7-20um.
19. catalyst according to claim 18, it is characterised in that：Based on the weight of catalyst, the content of cupric oxide is 40wt% ~ 70wt%, and the content of bismuth oxide is 2.5 wt%～6.5 wt%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107335473A (en) * | 2017-09-05 | 2017-11-10 | 中国科学院成都有机化学有限公司 | A kind of Cu Bi catalyst of the secondary cladding of sedimentation type compound and preparation method thereof |
| CN109201056A (en) * | 2017-06-30 | 2019-01-15 | 中国石油化工股份有限公司 | Dimethyl maleate prepares the catalyst of 1,4- butanediol |
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|---|---|---|---|---|
| US4107082A (en) * | 1974-02-25 | 1978-08-15 | E. I. Du Pont De Nemours And Company | Malachite preparation |
| CN102125856A (en) * | 2011-01-31 | 2011-07-20 | 华烁科技股份有限公司 | Supported catalyst for use in production of 1, 4-butynediol by Reppe method, preparation method thereof and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109201056A (en) * | 2017-06-30 | 2019-01-15 | 中国石油化工股份有限公司 | Dimethyl maleate prepares the catalyst of 1,4- butanediol |
| 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 |
| CN107335473A (en) * | 2017-09-05 | 2017-11-10 | 中国科学院成都有机化学有限公司 | A kind of Cu Bi catalyst of the secondary cladding of sedimentation type compound and preparation method thereof |
| 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 |
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