CN105709758B - A kind of copper bismuth catalyst and preparation method thereof - Google Patents
A kind of copper bismuth catalyst and preparation method thereof Download PDFInfo
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- CN105709758B CN105709758B CN201410724076.9A CN201410724076A CN105709758B CN 105709758 B CN105709758 B CN 105709758B CN 201410724076 A CN201410724076 A CN 201410724076A CN 105709758 B CN105709758 B CN 105709758B
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Abstract
The present invention discloses 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 into reactor, 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 reactor；（5）When remaining acid solution is step（1）When preparing the 1/3 ~ 1/2 of acid solution total amount, silicon source is added into remaining acid solution, continues coprecipitation reaction；（6）When the granular size 80% of thing to be precipitated is both greater than 5um, hydroxypropyl cellulose and methyl stearate sodium sulfonate of ethoxylated are added into reactor, continues to react；（7）Question response carries out aging after terminating；（8）After aging terminates, copper bismuth catalyst is made using spray drying.Catalyst prepared by this method has the advantages that wearability is good, and catalyst particle size is uniformly moderate, activity stability is high.
Description
Technical field
The present invention relates to a kind of copper bismuth catalyst for synthesizing Isosorbide-5-Nitrae-butynediols and preparation method thereof, one is related in particular to
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 a technology.In the 1970s, develop the Reppe method techniques of improvement, using slurry bed or
Suspension bed technique, react and carried out under normal pressure or lower pressure.But it is higher to improve requirement of the Reppe techniques to catalyst, fits
Closing 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
Less than 1 μm, filtering is relatively difficult.
US4110249 and US4584418 and CN1118342A is individually disclosed with DNAcarrier free malachite, carrier-free
Cupric 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, the catalytic reaction for formaldehyde and acetylene reaction synthesis Isosorbide-5-Nitrae-butynediols.But such catalyst has the following disadvantages：
（1）Carrier magnesium silicate is unstable, can be dissolved in reaction system, short life；（2）Catalyst amount is more, metal cupric oxide
Content is higher, easily reunites, it is impossible to gives 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：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 use inert atmosphere
It is calcined.The activity of the catalyst is higher, but cost is higher, bad mechanical strength, it is difficult to realizes industrialization.
CN201210397161.X discloses catalyst for Isosorbide-5-Nitrae-butynediols production and preparation method thereof, this method
Nano silicon 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, course of reaction is slower, can produce substantial amounts of ammonia
Gas, environmental pollution is caused, and the catalyst granules prepared is smaller, bad filtering.
CN103170342A discloses a kind of nanometer CuO-Bi of synthesis 1,4- butynediols2O3Catalyst, its 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, the mantoquita and bismuth salt of solubility are loaded on carrier using infusion process, 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 after acidifying is carrier, copper and bismuth is adsorbed on carrier with dipping and deposition sedimentation method, Ran Hougan
It is dry, be calcined 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 summary, the catalyst for producing Isosorbide-5-Nitrae-butynediols in the prior art is uncomfortable in the prevalence of catalyst particle size
In, the wearability of catalyst and the technical problems such as stability is 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 1,4- butynediols
Copper bismuth catalyst and preparation method thereof, catalyst prepared by this method has wearability 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）Deionized water is added into reactor, 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 to reaction
In kettle；
（5）When remaining acid solution is step（1）When preparing the 1/3 ~ 1/2 of acid solution total amount, toward remaining acid solution
Middle addition silicon source, continues coprecipitation reaction；
（6）When the granular size 80% of thing to be precipitated is both greater than 5um, hydroxypropyl cellulose and tristearin are added into reactor
Sour methyl esters sodium sulfonate of ethoxylated, continues to react；
（7）After question response terminates, slurry pH value is improved 1.0 ~ 2.0, temperature reduces by 10~20 DEG C of progress agings；
（8）After aging terminates, wash, filtering, copper bismuth catalyst is made using spray drying after mashing.
The inventive method 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 be 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, ammoniacal liquor, bicarbonate
At least one of sodium, 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, adding deionized water into reactor, volume is 100 ~ 1000 milliliters, preferably 250 ~
650 milliliters.Heating is heated to 50 ~ 80 DEG C of reaction temperature, and optimal is 60~70 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, 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 50 ~ 80 DEG C, and optimal is 60~70 DEG C.
Step of the present invention（5）In, silicon source is waterglass, Ludox, potassium silicate, at least one of tetraethyl orthosilicate, excellent
Elect Ludox or potassium silicate as.The amount of silicon source is added using its silica containing weight of institute as step（1）Aoxidized in acid solution
30%~80% meter of weight of copper, optimal is 40%~60%.The silicon source added adjusts pH value before acid solution is added
To 0.5 ~ 2.5.
Step of the present invention（6）In, the addition of hydroxypropyl cellulose is that 1wt% ~ 6wt% of copper content is aoxidized in sediment,
Preferably 2wt% ~ 4wt%, the addition quality of methyl stearate sodium sulfonate of ethoxylated add quality for hydroxypropyl cellulose
0.5 ~ 5 times, preferably 1.0 ~ 3.0 times.
Step of the present invention（7）In, after reaction terminates, ageing time is 0.5~4.0 hour, preferably 1.0~2.5 hours.
Step of the present invention（8）In, washed using the deionized water of temperature same with reaction temperature, filter, then beat
Slurry, the drying of catalyst is carried out using spray drying process.
A kind of catalyst prepared using the above method, based on the weight of catalyst, the content of cupric 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 content of silica be 15% ~ 50%, preferably 20% ~ 45%, the particle size at least more than 85% of catalyst between 10-35um,
The specific surface area of catalyst is in 20 ~ 150m2/ g, preferably 40~90 m2/g。
To continue cocurrent coprecipitated by the way that silicon source is added in acid solution in suitable coprecipitation process by the present invention
Form sediment and react, and cooled and improve pH agings, and use hydroxypropyl cellulose and methyl stearate polyoxyethylene ether sulfonic acid
The synergy of sodium, reduces rate of crystal growth, so as to overcome the catalyst particle size for using coprecipitation method to prepare
The shortcomings that uneven, the catalyst that distribution of particles is concentrated very much can be prepared, cause 85% granular size 10 ~ 35um it
Between.Not only activity is high, granularity is concentrated for the catalyst prepared, and wearability is improved, and is advantageous to the follow-up of catalyst
Separation, it is adapted to industrialized production.
Embodiment
Technical scheme is further illustrated below by embodiment and comparative example, but protection scope of the present invention is not
It is limited by example.Again using pellet after the anti-wear performance 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 20 minutes, supersonic frequency 25KHZ.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 catalyst amount 25g, concentration 37wt% formaldehyde addition are 250ml.
Embodiment 1
（1）Weigh 576gCu (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）350ml deionized waters are added in a kettle, are heated to 60 DEG C, are stirred continuously.
（4）Acid solution and alkaline solution cocurrent are added in reactor, the pH value for controlling sediment is 6.0, reaction
Temperature is 60 DEG C.
（5）Work as step（1）Acid solution 800 ml of residue when, acidified silica sol 250g is added into acid solution（With
Nitric acid adjusts the pH value of Ludox to 2.0）, continue to react.
（6）Work as step（1）Acid solution 400 ml of residue when, the catalyst granules more than 5 um has reached 81%, toward anti-
Answer in kettle while add 6.0 grams of hydroxypropyl celluloses and 8.0 grams of methyl stearate sodium sulfonate of ethoxylated, continue anti-
Should.
（7）When acid solution is finished stopping reaction, to 7.0, simultaneous reactions temperature is reduced to 45 DEG C, static for pH value regulation
Aging.
（8）After aging 2 hours, washed with 45 DEG C of deionized waters, in the presence of washing into cleaning solution without sodium ion, stopped
Only wash.The drying of catalyst is carried out after filter cake is beaten using spray drying.Sample number into spectrum is A, and sample sets turn into：CuO:
52.6%, Bi2O3:3.8%, SiO2:20.8%, the specific surface area of catalyst：60 m2/ g, size distribution are shown in Table 1, and evaluation result is shown in
Table 2.
Embodiment 2
（1）Weigh 956gCu (NO3)2.3H2O and 38.8g Bi (NO3)3.5H2O is put into the water containing 15.0g nitric acid,
2000ml is settled to after its dissolving.
（2）Weigh 300 grams of Na2CO3It is configured to 2000ml solution.
（3）400ml deionized waters are added in a kettle, are heated to 65 DEG C, are stirred continuously.
（4）Acid solution and alkaline solution cocurrent are added in reactor, the pH value for controlling sediment is 6.0, reaction
Temperature is 65 DEG C.
（5）Work as step（1）Acid solution 1000 ml of residue when, acidified silica sol 656g is added into acid solution
（The pH value of Ludox is adjusted to 2.0 with nitric acid）, continue to react.
（6）Work as step（1）Acid solution 500 ml of residue when, the catalyst granules more than 5 um has reached 80%, past
7.0 grams of hydroxypropyl celluloses and 12.0 grams of methyl stearate sodium sulfonate of ethoxylated are added in reactor simultaneously, are continued
Reaction.
（7）When acid solution is finished stopping reaction, to 7.2, simultaneous reactions temperature is reduced to 48 DEG C, static old for pH value regulation
Change.
（8）After aging 2 hours, washed with 48 DEG C of deionized waters, in the presence of washing into cleaning solution without sodium ion, stopped
Only wash.The drying of catalyst is carried out after filter cake is beaten using spray drying.Sample number into spectrum is B, and sample sets turn into：CuO:
47.6%, Bi2O3:2.90%, SiO2:31.0%.The specific surface area of catalyst：75m2/ g, size distribution are shown in Table 1, and evaluation result is shown in
Table 2.
Embodiment 3
（1）Weigh 956gCu (NO3)2.3H2O and 38.8g Bi (NO3)3.5H2O is put into the water containing 15.0g nitric acid,
2000ml is settled to after its dissolving.
（2）Weigh 80 grams of NaoH and be configured to 2000ml solution.
（3）450ml deionized waters are added in a kettle, are heated to 65 DEG C, are stirred continuously.
（4）Acid solution and alkaline solution cocurrent are added in reactor, the pH value for controlling sediment is 6.5, reaction
Temperature is 65 DEG C.
（5）Work as step（1）Acid solution 660 ml of residue when, acidified silica sol 570g is added into acid solution（With
Nitric acid adjusts the pH value of Ludox to 2.0）, continue to react.
（6）Work as step（1）Acid solution 460 ml of residue when, the catalyst granules more than 5 um has reached 82%, toward anti-
Answer in kettle while add 6.2 grams of hydroxypropyl celluloses and 11.5 grams of methyl stearate sodium sulfonate of ethoxylated, continue anti-
Should.
（7）When acid solution is finished stopping reaction, by the pH value regulation of sediment to 7.2, simultaneous reactions temperature is reduced to
50 DEG C, stop reaction, stop stirring, static aging.
（8）After aging 1.5 hours, washed with 48 DEG C of deionized waters, in the presence of washing into cleaning solution without sodium ion,
Stop washing.The drying of catalyst is carried out after filter cake is beaten using spray drying.Sample number into spectrum is C, and sample sets turn into：CuO:
50.1%, Bi2O3:3.2%, SiO2:27.0%.The specific surface area of catalyst：78 m2/ g, size distribution are shown in Table 1, and evaluation result is shown in
Table 2.
Comparative example 1
It is to omit step with the difference of embodiment 3（6）, sample number into spectrum D.Size distribution is shown in Table 1, and evaluation result is shown in
Table 2.
Comparative example 2
The catalyst that there is same composition with embodiment 3 is prepared by the technical scheme of CN201210397161.X embodiments 1,
Produce sample E.Size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Comparative example 3
It is with the difference of comparative example 1 by acidified silica sol 570g（The pH value of Ludox is adjusted to 2.0 with nitric acid）
It is added to step（1）Acid solution in, while omit step（5）, sample number into spectrum F.Size distribution is shown in Table 1, evaluation result
It is shown in Table 2.
Comparative example 4
It is step with the difference of comparative example 1（6）Aging temperature and pH value with coprecipitation reaction temperature and pH value
It is identical, sample number into spectrum G.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
The evaluation result of the catalyst of table 2
Claims (18)
- A kind of 1. preparation method for the copper bismuth catalyst for synthesizing Isosorbide-5-Nitrae-butynediols, it is characterised in that：Comprise the following steps：（1）Prepare the acid solution containing mantoquita and bismuth salt；（2）Prepare precipitant solution；（3）Deionized water is added into reactor, 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 reactor；（5）When remaining acid solution is step（1）When preparing the 1/3 ~ 1/2 of acid solution total amount, add into remaining acid solution Enter silicon source, continue coprecipitation reaction；（6）When the granular size 80% of thing to be precipitated is both greater than 5um, hydroxypropyl cellulose and stearic acid first are added into reactor Ester APEO sodium sulfonate, continue to react；（7）After question response terminates, slurry pH value is improved 1.0 ~ 2.0, temperature reduces by 10~20 DEG C of progress agings；（8）After aging terminates, wash, filtering, copper bismuth catalyst is made using spray drying after mashing.
- 2. according to the method for claim 1, it is characterised in that：Step（1）In, mantoquita is selected from copper sulphate, copper nitrate, acetic acid At least one of copper or copper chloride.
- 3. according to the method for claim 1, it is characterised in that：Step（1）In, the molar concentration control of mantoquita in acid solution System is in 0.6 ~ 3.0mol/L.
- 4. according to the method for claim 1, it is characterised in that：Step（1）In, bismuth salt be selected from bismuth nitrate, bismuth sulfate or At least one of bismuth acetate.
- 5. according to the method for claim 1, it is characterised in that：Step（1）In, the molar concentration control of bismuth salt in acid solution System is in 0.01 ~ 0.05mol/L.
- 6. according to the method for claim 1, it is characterised in that：Step（1）In, acid solution pH value is 0 ~ 2.0.
- 7. according to the method for claim 1, it is characterised in that：Step（1）In, mantoquita is copper nitrate, and mantoquita concentration is 1.0 ~ 2.5 mol/L, bismuth salt are bismuth nitrate, and bismuth salt concentration is 0.02 ~ 0.04mol/L, and acid solution pH value is 0.5 ~ 1.0.
- 8. according to the method for claim 1, it is characterised in that：Step（2）In, precipitating reagent be selected from sodium carbonate, sodium hydroxide, At least one of potassium carbonate, potassium hydroxide, ammoniacal liquor, sodium acid carbonate, the molar concentration of precipitating reagent is 0.1 ~ 3.0 mol/L.
- 9. according to the method for claim 8, it is characterised in that：Precipitating reagent is sodium carbonate, and the molar concentration of precipitating reagent is 0.5 ~2.0 mol/L。
- 10. according to the method for claim 1, it is characterised in that：Step（3）In, deionized water, body are added into reactor Product is 100 ~ 1000 milliliters, and heating is heated to 50 ~ 80 DEG C of reaction temperature.
- 11. according to the method for claim 1, it is characterised in that：Step（4）In, acid solution and alkaline solution cocurrent add Enter into reactor, keeping the pH value control of reaction, reaction temperature is controlled at 50 ~ 80 DEG C 5.0~8.0.
- 12. according to the method for claim 11, it is characterised in that：The pH value control of reaction is kept 6.0~7.0, reaction Temperature control is at 60~70 DEG C.
- 13. according to the method for claim 1, it is characterised in that：Step（5）In, silicon source is waterglass, Ludox, silicic acid At least one of potassium, tetraethyl orthosilicate, the amount of silicon source is added using its silica containing weight of institute as step（1）Acid solution 30%~80% meter of middle oxidation weight of copper, the silicon source added adjust pH value to 0.5 ~ 2.5 before acid solution is added.
- 14. according to the method for claim 13, it is characterised in that：Silicon source is Ludox or potassium silicate,The amount of silicon source is added using its silica containing weight of institute as step（1）In acid solution aoxidize weight of copper 40%~ 60% meter.
- 15. according to the method for claim 1, it is characterised in that：Step（6）In, the addition of hydroxypropyl cellulose is heavy 1wt% ~ 6wt% of copper content is aoxidized in starch, the addition quality of methyl stearate sodium sulfonate of ethoxylated is hydroxy propyl cellulose Element adds 0.5 ~ 5 times of quality.
- 16. according to the method for claim 15, it is characterised in that：Step（6）In, the addition of hydroxypropyl cellulose is heavy 2wt% ~ 4wt% of copper content is aoxidized in starch, the addition quality of methyl stearate sodium sulfonate of ethoxylated is hydroxy propyl cellulose Element adds 1.0 ~ 3.0 times of quality.
- 17. according to the method for claim 1, it is characterised in that：Step（7）In, after reaction terminates, ageing time 0.5 ~4.0 hours.
- 18. according to the method for claim 1, it is characterised in that：Step（8）In, using temperature same with reaction temperature Deionized water is washed.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5340700A (en) * | 1976-08-05 | 1978-04-13 | Du Pont | Process for preparing modified malachite |
| CN101024195A (en) * | 2007-03-23 | 2007-08-29 | 福建师范大学 | Method for preparing molecular sieve composite oxide catalyst using HZSM5 as carrier and its use |
| CN102950002A (en) * | 2012-10-18 | 2013-03-06 | 大连瑞克科技有限公司 | Catalyst for producing 1.4-butynediol and preparation method of catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2905005C (en) * | 2013-03-15 | 2021-07-27 | Basf Corporation | Novel ethynylation catalyst and method of making same |
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2014
- 2014-12-04 CN CN201410724076.9A patent/CN105709758B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5340700A (en) * | 1976-08-05 | 1978-04-13 | Du Pont | Process for preparing modified malachite |
| CN101024195A (en) * | 2007-03-23 | 2007-08-29 | 福建师范大学 | Method for preparing molecular sieve composite oxide catalyst using HZSM5 as carrier and its use |
| CN102950002A (en) * | 2012-10-18 | 2013-03-06 | 大连瑞克科技有限公司 | Catalyst for producing 1.4-butynediol and preparation method of catalyst |
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