CN106669691B - A kind of preparation method for the copper bismuth catalyst for being used to synthesize 1,4- butynediols - Google Patents
A kind of preparation method for the copper bismuth catalyst for being used to synthesize 1,4- butynediols Download PDFInfo
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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 content：The mode of cocurrent is taken, the precipitant solution of acid solution sum is added drop-wise in reaction kettle, while gas CO is passed through from reactor bottom2；When remaining acid solution is the 2/3 ~ 3/4 of acid solution total amount, stop reaction, carry out aging；After aging, 1/3 1/4 of reaction product in reaction kettle are transferred in second reaction kettle, continue to carry out dropwise reaction in second reaction kettle, the constant height for before being added dropwise of liquid level of second reaction kettle is kept simultaneously, extra reaction product is transferred in first reaction kettle, and gas CO is passed through in two reaction kettles2；It treats that after reaction, the solution in two reaction kettles is mixed, carries out aging, aging carries out being spray-dried obtained copper bismuth catalyst.Catalyst prepared by this method has many advantages, such as 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 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 overcome above-mentioned defect in the prior art, a kind of synthesis Isosorbide-5-Nitrae-butynediols is provided
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, 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, while gas CO is passed through from reactor bottom2；
（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, the 1/3-1/4 of the reaction product in reaction kettle is transferred in second reaction kettle, is continued
Dropwise reaction is carried out in second reaction kettle, while keeps the constant height for before being added dropwise of liquid level of second reaction kettle,
Extra reaction product is transferred in first reaction kettle, and gas CO is passed through in two reaction kettles2；
（7）It treats that after reaction, the solution in two reaction kettles is mixed, temperature reduces by 5~10 DEG C of progress agings, aging
After, it washs, filtering；
（8）The deionized water containing potassium nitrate and calgon is added in filter cake, after stirring evenly, is spray-dried
Copper bismuth catalyst is made.
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 step（1）The 0.15 of acid solution volume ~
0.4 times, preferably 0.2 ~ 0.3 times.Heating is heated to 30 ~ 80 DEG C of reaction temperature, and optimal is 40~70 DEG C.It is constantly stirred in reaction process
It mixes.
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.
The bottom of reaction kettle is passed through CO2, CO2It is diluted using nitrogen, CO2A concentration of 20%~60%, optimal is 30%~50%.Gas stream
Speed is 150 ~ 1000ml/min, preferably 250 ~ 800ml/min.CO2Concentration is volumetric concentration.
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 6.0~7.0, and ageing time was 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.The CO of first reaction kettle2A concentration of 20%~60%, optimal is 30%~50%.Gas stream
Speed is the reaction kettle CO of 150 ~ 1000ml/min, preferably 250 ~ 800ml/min, second2A concentration of 20%~60%, it is optimal to be
30%~50%.Gas flow rate is 20 ~ 250ml/min, preferably 50 ~ 100ml/min.CO2Concentration is volumetric concentration.
Step of the present invention（7）In, after reaction, ageing time is 0.5~4.0 hour, preferably 1.0~2.5 hours.
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 nitrate and calgon is added in filter cake, is stirred evenly
Afterwards, it carries out being spray-dried obtained copper bismuth catalyst.Potassium nitrate addition be slurries in water quality 1%~20%, preferably 5%
~15%.The butt of slurry is 15%~45%, preferably 25%~35%.Calgon addition is the 5% of catalyst weight
~ 25%, 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 is passed through carbon dioxide by two sections of coprecipitation reactions during coprecipitation reaction, makes what is prepared
Catalyst particle size is concentrated, and wearability is improved, preferable catalytic activity and stability, is conducive to follow-up point of catalyst
From suitable industrialized production.
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, are 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.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2A concentration of 40%, gas flow rate is
500ml/min。
（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, 600 mL reaction products are transferred to peristaltic pump in the second reaction kettle, are continued anti-second
Object is answered to be reacted, while the reactant total volume of the second reaction kettle of holding is 600 mL, extra reaction product is using wriggling
Pump is transferred in the first reaction kettle, pH value in reaction 6.0, and reaction temperature is 50 DEG C.
The bottom of two reaction kettles is all passed through CO2, the CO of the first reaction kettle2A concentration of 40%.Gas flow rate is 500ml/
Min, the second reaction kettle CO2A concentration of 30%, gas flow rate 80ml/min.When acid solution is finished stopping reaction, and by the
Reaction product in two reaction kettles is transferred in the first reaction kettle
（7）Temperature is reduced to 45 DEG C, carries out aging.It after aging 1.5 hours, is washed, is washed with 45 DEG C of deionized waters
Into cleaning solution without sodium ion in the presence of, stop washing.
（8）Filter cake is added in 580 grams of water containing 60g potassium nitrate and 31 grams of calgons, 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:66.0%, Bi2O3:4.0%.Size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Embodiment 2
（1）Weigh 650gCu (NO3)2•3H2O and 33g 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, are then 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.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2A concentration of 40%, gas flow rate is
500ml/min。
（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, 575 mL reaction products are transferred to peristaltic pump in the second reaction kettle, are continued anti-second
Kettle is answered to be reacted, while the reactant total volume of the second reaction kettle of holding is 575 mL, extra reaction product is using wriggling
Pump is transferred in the first reaction kettle, pH value in reaction 6.0, and reaction temperature is 50 DEG C.The bottom of two reaction kettles is all passed through CO2,
The CO of first reaction kettle2A concentration of 40%.Gas flow rate is 450ml/min, the second reaction kettle CO2A concentration of 30%, gas flow rate
For 90ml/min.When acid solution is finished stopping reaction, and the reaction product in the second reaction kettle is transferred to the first reaction kettle
In,
（7）Temperature is reduced to 40 DEG C, carries out aging.It after aging 1.5 hours, is washed, is washed with 40 DEG C of deionized waters
Into cleaning solution without sodium ion in the presence of, stop washing.
（8）Filter cake is added in 580 grams of water containing 65g potassium nitrate and 30 grams of calgons, 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:60.2%, Bi2O3:4.2%.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, are 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.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2A concentration of 40%, gas flow rate is
500ml/min。
（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, 540 mL reaction products are transferred to peristaltic pump in the second reaction kettle, are continued anti-second
Kettle is answered to be reacted, while the reactant total volume of the second reaction kettle of holding is 540 mL, extra reaction product is using wriggling
Pump is transferred in the first reaction kettle, pH value in reaction 6.8, and reaction temperature is 65 DEG C.
The bottom of two reaction kettles is all passed through CO2, the CO of the first reaction kettle2A concentration of 45%.Gas flow rate is 500ml/
Min, the second reaction kettle CO2A concentration of 40%, gas flow rate 80ml/min.When acid solution is finished stopping reaction, and by the
Reaction product in two reaction kettles is transferred in the first reaction kettle,
（7）Temperature is reduced to 60 DEG C, carries out aging.It after aging 2.0 hours, is washed, is washed with 60 DEG C of deionized waters
Into cleaning solution without sodium ion in the presence of, stop washing.
（8）Filter cake is added in 700 grams of water containing 75g potassium nitrate and 38 grams of calgons, water temperature is controlled 60
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:55.4%, Bi2O3:3.6%.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 nitrate and calgon, 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（4）（6）In be not passed through CO2, sample number into spectrum F, size distribution is shown in Table 1, comments
Valency the results are 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
The evaluation result of 2 catalyst of table
The estimation of stability result of 3 catalyst of table（Operating 200 hours）
Claims (13)
1. a kind of preparation method for the copper bismuth catalyst for synthesizing Isosorbide-5-Nitrae-butynediols, includes 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, 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,
Simultaneously gas CO is passed through from reactor bottom2；
（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, the 1/3-1/4 of the reaction product in reaction kettle is transferred in second reaction kettle, is continued
Two reaction kettles carry out dropwise reaction, while keep the constant height for before being added dropwise of liquid level of second reaction kettle, extra
Reaction product be transferred in first reaction kettle, be passed through gas CO in two reaction kettles2；
（7）It treats that after reaction, the solution in two reaction kettles is mixed, temperature reduces by 5~10 DEG C of progress agings, and aging terminates
Afterwards, it washs, filtering；
（8）The deionized water containing potassium nitrate and calgon is added in filter cake, after stirring evenly, spray drying is carried out and is made
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 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 in acid solution.
4. according to the method described in claim 1, it is characterized in that：Step（1）In, acid solution pH value is 0 ~ 2.0.
5. 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.
6. 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 amount for step（1）0.15 ~ 0.4 times of acid solution volume, heating are heated to 30 ~ 80 DEG C of reaction temperature.
7. 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, and the bottom of reaction kettle is passed through CO2, CO2It is diluted using nitrogen, CO2A concentration of 20%~
60%, gas flow rate is 100 ~ 1000ml/min.
8. according to the method described in claim 1, it is characterized in that：Step（5）In, aging temperature control is at 30 ~ 80 DEG C, aging
5.0~8.0, ageing time was controlled at 10~70 minutes for pH value control.
9. 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 control is at 30 ~ 80 DEG C, the CO of the first reaction kettle2A concentration of 20%~60%, gas flow rate is 150 ~ 1000ml/min,
Second reaction kettle CO2A concentration of 20%~60%, gas flow rate be 20 ~ 250ml/min.
10. according to the method described in claim 1, it is characterized in that：Step（7）In, after reaction, ageing time 0.5
It~4.0 hours, is washed, is filtered using the deionized water of temperature similary with aging.
11. according to the method described in claim 1, it is characterized in that：Step（8）In, it is added in filter cake and contains potassium nitrate and six
The deionized water of sodium metaphosphate after stirring evenly, carries out being spray-dried obtained copper bismuth catalyst, potassium nitrate addition is in slurries
The 1%~20% of water quality, the butt of slurry are 15%~45%, calgon addition for catalyst weight 5% ~
25%。
12. a kind of catalyst prepared by claim 1 to 11 either method, it is characterised in that：Based on the weight of catalyst, oxidation
The content of copper is 30wt% ~ 80wt%, and the content of bismuth oxide is the wt% of 1.0wt% ~ 10.0, the particle size at least 80% of catalyst with
On between 7-20um.
13. catalyst according to claim 12, it is characterised in that：The content of copper oxide be 40wt% ~ 70wt%, bismuth oxide
Content be the wt% of 1.0wt% ~ 10.0, the particle size at least more than 80% of catalyst is between 7-20um.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107082A (en) * | 1974-02-25 | 1978-08-15 | E. I. Du Pont De Nemours And Company | Malachite preparation |
| US4876231A (en) * | 1988-09-07 | 1989-10-24 | E. I. Du Pont De Nemours And Company | Process for preparing crystalline malachite |
| 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 |
| 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 |
| CN102950014A (en) * | 2012-10-18 | 2013-03-06 | 大连瑞克科技有限公司 | Catalyst for production of 1,4-butynediol and preparation method of catalyst |
-
2015
- 2015-11-09 CN CN201510750472.3A patent/CN106669691B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107082A (en) * | 1974-02-25 | 1978-08-15 | E. I. Du Pont De Nemours And Company | Malachite preparation |
| US4876231A (en) * | 1988-09-07 | 1989-10-24 | E. I. Du Pont De Nemours And Company | Process for preparing crystalline malachite |
| 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 |
| 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 |
| CN102950014A (en) * | 2012-10-18 | 2013-03-06 | 大连瑞克科技有限公司 | Catalyst for production of 1,4-butynediol and preparation method of catalyst |
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