CN106669700A - Preparation method of catalyst for producing 1,4-butynediol - Google Patents
Preparation method of catalyst for producing 1,4-butynediol Download PDFInfo
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Abstract
The invention discloses a preparation method of a catalyst for producing 1,4-butynediol. The preparation method comprises the following steps: 1, preparing acopper-bismuth mixed solution and an alkali metal salt solution; 2, adding bottom water into a reaction kettle, warming and heating to a reaction temperature, dropwise adding the copper-bismuth mixed solution and the alkali metal salt solution in parallel flow to be coprecipitated, keeping the pH value of a precipitation system be 4 to 7, wherein the use amount of the copper-bismuth mixed solution is 30% to 50% of the total use amount of the copper-bismuth mixed solution; 3, adding a silica solution into the residual copper-bismuth mixed solution and coprecipitating with the alkali metal salt solution in a parallel flow mode; 4, filtering materials, pulping the materials through the residual silica solution after the materials are washed and adding the defined amount of distilled water; 5, spray drying seriflux to obtain the catalyst for producing the 1,4-butynediol. The catalyst has the advantages of having good activity, good wear resistance and even catalyst granule and being not prone to losing in a using process.
Description
Technical field
The present invention relates to a kind of preparation method for producing Isosorbide-5-Nitrae-butynediols catalyst, belongs to technical field of chemical engineering catalysts.
Background technology
1,4- butynediols（BD）It is a kind of important organic chemical industry's intermediate, its hydrogenation products BDO（BDO）, can be used to produce gamma-butyrolacton（GBL）, tetrahydrofuran（THF）, poly- two benzene dicarboxylic acid butanediol ester（PBT）Deng.In recent years because of the demand abruptly increase of the derivatives such as PBT, China increases substantially to the demand of BDO.Industrially, the production of Isosorbide-5-Nitrae-butynediols is main adopts the formaldehyde of Coal Chemical Industry production, acetylene to be bound up, and there are abundant coal resources in China so that have advantageous condition and advantage by raw material production Isosorbide-5-Nitrae-butynediols of Coal Chemical Industry Route acetylene.
The forties in 20th century, Reppe has been invented with formaldehyde and acetylene as the technique of Material synthesis Isosorbide-5-Nitrae-butynediols.The technique adopts alkynes copper catalyst, and the operational danger of acetylene and alkynes copper is increased under reaction pressure.After the seventies, new synthesis Isosorbide-5-Nitrae-butynediols catalyst is developed again, Reppe techniques is improved.The catalyst that the technique is used is malachite, and particle is little, and activity is good, is reacted in slurry bed, improves operating pressure, reduces the danger of blast.But this catalyst is not wear-resistant, easily it is lost in.Such as patent US4110249
, US4584418 and CN1118342A.Phenomenon that is not wear-resisting for malachite catalyst, being easy to run off, the ethynylation catalyst with silica, zeolite, diatomite etc. as carrier was occurred in that later, such as patent US4288641 and US3920759, the ethynylation catalyst with molecular sieve and magnesium silicate as carrier is individually disclosed；Patent CN102125856A is prepared for formaldehyde using the kaolin for especially preparing and acetylene reaction prepares 1,4- butynediols and contains carried catalyst；But such catalyst has the following disadvantages：（1）Carrier magnesium silicate is unstable, can dissolve in reaction system, short life；（2）Catalyst amount is more, and metal oxidation copper content is higher, easily reunites, it is impossible to give full play to the catalytic effect in each activated centre, causes the waste of copper resource.
CN201210157882.3
A kind of copper bismuth catalyst and preparation method are disclosed, its step is as follows：It is added drop-wise in the mixed liquor containing mantoquita, bismuth salt, magnesium 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 into 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 following deficiency：The technical problems such as catalyst particle size is not moderate, catalyst wearability and stability is poor, the carrier complicated process of preparation relative costs height that active component is easily lost in and adopts.
The content of the invention
The purpose of the present invention is to overcome defect present in prior art, one kind is provided and synthesizes 1 in slurry bed system for formaldehyde and acetylene, the ethynylation catalyst that the active good, wearability of 4- butynediols is good, catalyst granules is uniform, not easily run off during use, and the preparation method of catalyst is simple, easy, reproducible.
The technical solution used in the present invention is：A kind of preparation method for producing Isosorbide-5-Nitrae-butynediols catalyst, it includes following preparation process：
（1）Prepare copper bismuth mixed solution and alkali metal salt soln；
（2）Bottom water, intensification is added to be heated to reaction temperature toward reactor；At the reaction temperatures, copper bismuth mixed solution and alkali metal salt soln cocurrent are added dropwise into co-precipitation, keep precipitation system pH value to be 4 ~ 7, preferably 5 ~ 6, copper bismuth solution usage used is the 30% ~ 50% of the total consumption of copper bismuth solution, preferably 35% ~ 45%；
（3）Ludox is added in remaining copper bismuth mixed solution, with alkali metal salt soln co-precipitation, step is compared（2）Deposition condition, coprecipitation reaction temperature reduce by 10 DEG C ~ 30 DEG C, preferably 15 DEG C ~ 25 DEG C, Si consumptions used be catalyst in Si total amounts 40% ~ 80%, preferably 50% ~ 65%；The rate of addition for controlling copper bismuth mixed solution is step（2）1.5 ~ 3 times；
（4）By material filtering, with the Ludox beating of remaining content after washing, by solid content 10% ~ 40%, preferably 20% ~ 30% meter, appropriate distilled water is added；
（5）Using being spray-dried, dry temperature is 100 DEG C ~ 200 DEG C to slurries, preferably 120 DEG C ~ 180 DEG C, obtains producing the catalyst of Isosorbide-5-Nitrae-butynediols.
The inventive method step（1）In, one or more of the copper in copper sulphate, copper nitrate or copper chloride, preferably copper nitrate.The molar concentration of mantoquita is controlled 0.6 ~ 3.0 in copper bismuth mixed solution
Mol/L, preferably 1.0 ~ 2.5 mol/L.One or more of bismuth in bismuth nitrate, bismuth sulfate or bismuth chloride, preferably bismuth nitrate.The molar concentration of bismuth salt is controlled in 0.01 ~ 0.05 mol/L, preferably 0.02 ~ 0.04 mol/L in copper bismuth mixed solution.
The inventive method step（1）In, one or more of the alkali metal salt in sodium carbonate, sodium acid carbonate, potassium carbonate or saleratus, preferably sodium carbonate.The molar concentration of precipitating reagent is 0.1 ~ 3.0
Mol/L, preferably 0.5 ~ 2.0 mol/L.
The inventive method step（2）In, bottom water addition is 1/6 ~ 2/3, preferably the 1/3 ~ 1/2 of reactor cumulative volume.
The inventive method step（2）In, reaction temperature is 50 DEG C ~ 80 DEG C, preferably 60 DEG C ~ 70 DEG C.
The inventive method step（2）In, the rate of addition of copper bismuth solution is that dropwise addition volume per minute accounts for the 0.1% ~ 0.5% of reactor cumulative volume, preferably 0.2% ~ 0.4%.
The inventive method step（4）In, it is described to wash to Na2O mass contents are less than 0.5%.
The catalyst of the production Isosorbide-5-Nitrae-butynediols prepared using said method, with silica as carrier, with copper bismuth compound as active component, by mass percentage, cupric oxide is 30% ~ 60% to its composition to the catalyst, and bismuth oxide is 2% ~ 5%, and silica is surplus；Between 10 ~ 40 μm, preferably more than 85% between 10 ~ 40 μm for the particle size of catalyst at least more than 80%, and bulk density is 1.0 ~ 1.8 gmL-1, preferably 1.2 ~ 1.6
g·mL-1。
Copper bismuth solution and precipitant solution are carried out coprecipitated reaction by method for preparing catalyst of the present invention first, obtain the slurries containing copper bismuth sediment, then precipitate the copper bismuth solution of introducing portion Ludox, and the wearability of the catalyst that can be caused is improved.Another part Ludox is, by the addition in the form of binding agent before it is dried, to be allowed to be more suitable for being spray-dried this dried forms.
Method for preparing catalyst of the present invention second stage it is coprecipitated during reduce reaction temperature, and improve rate of addition, both act synergistically, and can control the size of precipitation particles.Its reason is that, because rate of addition increases, the concentration of solute is improved in solution in the same time, degree of supersaturation increase, nucleus is conducive to generate, number of dies increases, but nuclei growth rate reduction and have little time to grow up so that in most of particle size integrated distribution to a narrower scope.And in the case where reaction temperature is reduced, the degree of supersaturation that can also make solute in solution becomes big, so as to produce identical effect with raising rate of addition.In addition, reduce reaction temperature and can also avoid the dissolving of little particle precipitation and be deposited in again on oarse-grained surface, it is allowed to excessively grow up.
Good catalyst activity, easily separated, catalyst granules are uniform obtained in method for preparing catalyst of the present invention, distribution is concentrated, wherein granularity accounts for more than 80% in 10 ~ 40 μm of particle, not easily runs off during catalyst use, and the preparation method of catalyst is simple, easy, reproducible.
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 is 30min, and supersonic frequency is 20KHz.Catalyst is evaluated using intermittent stirring reactor.Using formaldehyde and acetylene reaction system, reaction temperature is 90 DEG C, and reaction pressure is normal pressure, and acetylene flow velocity is 80mL/min, and catalyst amount is 35mL, and the formaldehyde addition of concentration 37wt% is 250ml.% in embodiment and comparative example if no special instructions, is mass percent.
Embodiment 1
（1）Weigh 241.6g
Cu(NO3)2.3H2O and 9.7g
Bi(NO3)3.5H2O, prepares 1000ml copper bismuth mixed solutions, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved.Prepare the Na of 1mol/L2CO3Solution for standby.
（2）The bottom water of 2L, intensification is added to be heated to 60 DEG C, take 400ml steps toward 5L reactors（1）The copper bismuth mixed solution of middle preparation and sodium carbonate liquor cocurrent are added dropwise co-precipitation, keep precipitation system pH value to be 6, and the rate of addition for controlling copper bismuth mixed solution is that dropwise addition volume per minute accounts for the 0.2% of reactor cumulative volume.
（3）The Ludox of 121.4g 30% is added in 600ml copper bismuth mixed solutions, stir, then in 40 DEG C of system temperature, pH value is under conditions of 6, with sodium carbonate liquor co-precipitation, the rate of addition for controlling copper bismuth mixed solution is that dropwise addition volume per minute accounts for the 0.4% of reactor cumulative volume.
（4）Material filtering is washed to Na2O content is less than 0.5%, then adds the Ludox beating of 80.92g 30%, based on solid content 20%, adds appropriate distilled water.
（5）Using being spray-dried, dry temperature is 130 DEG C to slurries, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Embodiment 2
（1）Weigh 241.6g
Cu(NO3)2.3H2O and 12.13g
Bi(NO3)3.5H2O, prepares 1000ml copper bismuth mixed solutions, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved.Prepare the Na of 1.5mol/L2CO3Solution for standby.
（2）The bottom water of 2.5L, intensification is added to be heated to 60 DEG C, take 350ml steps toward 5L reactors（1）The copper bismuth mixed solution of middle preparation and sodium carbonate liquor cocurrent are added dropwise co-precipitation, keep precipitation system pH value to be 6, and the rate of addition for controlling copper bismuth mixed solution is that dropwise addition volume per minute accounts for the 0.2% of reactor cumulative volume.
（3）The Ludox of 190g 30% is added in 650ml copper bismuth mixed solutions, stir, then in 40 DEG C of system temperature, pH value is under conditions of 6, with sodium carbonate liquor co-precipitation, the rate of addition for controlling copper bismuth mixed solution is that dropwise addition volume per minute accounts for the 0.4% of reactor cumulative volume.
（4）Material filtering is washed to Na2O content is less than 0.5%, then adds the Ludox beating of 190g 30%, based on solid content 20%, adds appropriate distilled water.
（5）Using being spray-dried, dry temperature is 140 DEG C to slurries, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Embodiment 3
（1）Weigh 241.6g
Cu(NO3)2.3H2O and 14.55g
Bi(NO3)3.5H2O, prepares 1000ml copper bismuth mixed solutions, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved.Prepare the Na of 1.0mol/L2CO3Solution for standby.
（2）The bottom water of 1.8L, intensification is added to be heated to 65 DEG C, take 400ml steps toward 5L reactors（1）The copper bismuth mixed solution of middle preparation and sodium carbonate liquor cocurrent are added dropwise co-precipitation, keep precipitation system pH value to be 5.5, and the rate of addition for controlling copper bismuth mixed solution is that dropwise addition volume per minute accounts for the 0.3% of reactor cumulative volume.
（3）The Ludox of 220.08g 30% is added in 600ml copper bismuth mixed solutions, stir, then in 40 DEG C of system temperature, pH value is under conditions of 5.5, with sodium carbonate liquor co-precipitation, the rate of addition for controlling copper bismuth mixed solution is that dropwise addition volume per minute accounts for the 0.6% of reactor cumulative volume.
（4）Material filtering is washed to Na2O content is less than 0.5%, then adds the Ludox beating of 146.72g 30%, based on solid content 25%, adds appropriate distilled water.
（5）Using being spray-dried, dry temperature is 120 DEG C to slurries, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Embodiment 4
（1）Weigh 241.6g
Cu(NO3)2.3H2O and 14.55g
Bi(NO3)3.5H2O, prepares 1000ml copper bismuth mixed solutions, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved.Prepare the Na of 1.5mol/L2CO3Solution for standby.
（2）The bottom water of 2.2L, intensification is added to be heated to 70 DEG C, take 450ml steps toward 5L reactors（1）The copper bismuth mixed solution of middle preparation and sodium carbonate liquor cocurrent are added dropwise co-precipitation, keep precipitation system pH value to be 6, and the rate of addition for controlling copper bismuth mixed solution is that dropwise addition volume per minute accounts for the 0.3% of reactor cumulative volume.
（3）The Ludox of 180g 30% is added in 550ml copper bismuth mixed solutions, stir, then in 55 DEG C of system temperature, pH value is under conditions of 6, with sodium carbonate liquor co-precipitation, the rate of addition for controlling copper bismuth mixed solution is that dropwise addition volume per minute accounts for the 0.8% of reactor cumulative volume.
（4）Material filtering is washed to Na2O content is less than 0.5%, then adds the Ludox beating of 120g 30%, based on solid content 30%, adds appropriate distilled water.
（5）Using being spray-dried, dry temperature is 130 DEG C to slurries, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Comparative example 1
It is step with the difference of embodiment 3（3）The Ludox of middle addition is added directly into step（1）In copper bismuth mixed solution, while omitting step（3）.
Comparative example 2
It is step with the difference of embodiment 3（3）Add after Ludox in step（2）Reaction condition under carry out.
Comparative example 3
The catalyst that there is same composition with embodiment 3 is prepared by the technical scheme of CN201210397161.X embodiments 1.
The Activity evaluation and physico-chemical property of catalyst prepared by above-mentioned comparative example and embodiment（Or size distribution）1, table 2 is shown in Table respectively.
The evaluation result of the catalyst of table 1
The physico-chemical property and distribution of particles of the catalyst of table 2
Claims (15)
1. a kind of preparation method for producing Isosorbide-5-Nitrae-butynediols catalyst, it is characterised in that：Comprise the steps：
（1）Prepare copper bismuth mixed solution and alkali metal salt soln；
（2）Bottom water, intensification is added to be heated to reaction temperature toward reactor；At the reaction temperatures, copper bismuth mixed solution and alkali metal salt soln cocurrent are added dropwise into co-precipitation, keep precipitation system pH value to be 4 ~ 7, copper bismuth solution usage used is the 30% ~ 50% of the total consumption of copper bismuth solution；
（3）Ludox is added in remaining copper bismuth mixed solution, with alkali metal salt soln co-precipitation, step is compared（2）Deposition condition, coprecipitation reaction temperature reduce by 10 DEG C ~ 30 DEG C, Si consumptions used be catalyst in Si total amounts 40% ~ 80%；The rate of addition for controlling copper bismuth mixed solution is step（2）1.5 ~ 3 times；
（4）By material filtering, with the Ludox beating of remaining content after washing, based on solid content 10% ~ 40%, appropriate distilled water is added；
（5）Using being spray-dried, dry temperature is 100 DEG C ~ 200 DEG C to slurries, obtains producing the catalyst of Isosorbide-5-Nitrae-butynediols.
2. method according to claim 1, it is characterised in that：Step（1）In, one or more of copper in copper sulphate, copper nitrate or copper chloride, the molar concentration of mantoquita is controlled in 0.6 ~ 3.0 mol/L in copper bismuth mixed solution.
3. method according to claim 2, it is characterised in that：Copper is copper nitrate, and the molar concentration of mantoquita is controlled in 1.0 ~ 2.5 mol/L in copper bismuth mixed solution.
4. method according to claim 1, it is characterised in that：Step（1）In, one or more of bismuth in bismuth nitrate, bismuth sulfate or bismuth chloride, the molar concentration of bismuth salt is controlled in 0.01 ~ 0.05 mol/L in copper bismuth mixed solution.
5. method according to claim 1, it is characterised in that：Bismuth is bismuth nitrate, and the molar concentration of bismuth salt is controlled in 0.02 ~ 0.04 mol/L in copper bismuth mixed solution.
6. method according to claim 1, it is characterised in that：Step（1）In, one or more of the alkali metal salt in sodium carbonate, sodium acid carbonate, potassium carbonate or saleratus, the molar concentration of precipitating reagent is 0.1 ~ 3.0 mol/L.
7. method according to claim 1, it is characterised in that：The alkali metal salt is sodium carbonate, and the molar concentration of sodium carbonate is 0.5 ~ 2.0 mol/L.
8. method according to claim 1, it is characterised in that：Step（2）Middle holding precipitation system pH value is 5 ~ 6, and copper bismuth solution usage used is the 35% ~ 45% of the total consumption of copper bismuth solution.
9. method according to claim 1, it is characterised in that：Step（2）In, bottom water addition is the 1/6 ~ 2/3 of reactor cumulative volume, and reaction temperature is 50 DEG C ~ 80 DEG C.
10. method according to claim 9, it is characterised in that：Bottom water addition is the 1/3 ~ 1/2 of reactor cumulative volume, and reaction temperature is 60 DEG C ~ 70 DEG C.
11. methods according to claim 1, it is characterised in that：Step（2）In, the rate of addition of copper bismuth solution is that dropwise addition volume per minute accounts for the 0.1% ~ 0.5% of reactor cumulative volume.
12. methods according to claim 1, it is characterised in that：Step（3）In, coprecipitation reaction temperature reduces by 15 DEG C ~ 25 DEG C, and Si consumptions used are 50% ~ 65% of Si total amounts in catalyst.
13. methods according to claim 1, it is characterised in that：Step（4）In, distilled water, the washing to Na are added based on solid content 20% ~ 30%2O mass contents are less than 0.5%.
Catalyst prepared by a kind of 14. employing claim 1 to 13 either method, it is characterised in that：With silica as carrier, with copper bismuth compound as active component, by mass percentage, cupric oxide is 30% ~ 60% to its composition to the catalyst, and bismuth oxide is 2% ~ 5%, and silica is surplus；Between 10 ~ 40 μm, bulk density is 1.0 ~ 1.8 gmL to the particle size of catalyst at least more than 80%-1。
15. catalyst according to claim 14, it is characterised in that：Between 10 ~ 40 μm, bulk density is 1.2 ~ 1.6 gmL to the particle size of catalyst at least more than 85%-1。
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| 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 |
| CN112717945A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for synthesizing 1, 4-butynediol and preparation method and application thereof |
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| CN112717945A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for synthesizing 1, 4-butynediol and preparation method and application thereof |
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Application publication date: 20170517 |