CN106669692A - Preparation of 1,4-butynediols catalyst and preparation method and application thereof - Google Patents

Preparation of 1,4-butynediols catalyst and preparation method and application thereof Download PDF

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CN106669692A
CN106669692A CN201510750473.8A CN201510750473A CN106669692A CN 106669692 A CN106669692 A CN 106669692A CN 201510750473 A CN201510750473 A CN 201510750473A CN 106669692 A CN106669692 A CN 106669692A
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copper
catalyst
bismuth
mol
solution
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包洪洲
张艳侠
段日
付秋红
关月明
张宝国
霍稳周
乔凯
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses preparation of a 1,4-butynediols catalyst and a preparation method and an application thereof. The catalyst takes silicon oxide as a carrier and takes a copper-bismuth compound as an active component, by mass percentage, copper oxide accounts for 30-60%, bismuth oxide accounts for 2-5%, and the balance of silicon oxide. the particle diameter with 10-40 [mu]m of the catalyst accounts for at least more than 80%, specific surface area is 20-50 m<2>/g, and pore volume is 0.1-0.5 cm<3>.g<-1>, aperture distributed between 10-50 nm accounts for more than 85%, and the bulk density is 1.0-1.8 g.mL<-1>. The catalysts is prepared by using a precipitation method. The catalyst has the advantages of good wear resistance, uniform catalyst particle, and difficult loss during a usage process.

Description

One kind production 1,4- butynediols catalyst and its preparation method and application
Technical field
The present invention relates to a kind of production Isosorbide-5-Nitrae-butynediols catalyst and its preparation method and application, belong to chemical catalyst technology Field.
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 The demand abruptly increase of the derivatives such as PBT, China increases substantially to the demand of BDO.Industrially, the production master of Isosorbide-5-Nitrae-butynediols The formaldehyde of Coal Chemical Industry production, acetylene is adopted to be bound up, China there are abundant coal resources so that with Coal Chemical Industry Route acetylene There is advantageous condition and advantage for raw material production 1,4- butynediols.
The forties in 20th century, Reppe has been invented with formaldehyde and acetylene as the technique of Material synthesis Isosorbide-5-Nitrae-butynediols.The work Skill adopts alkynes copper catalyst, and the operational danger of acetylene and alkynes copper is increased under reaction pressure.After the seventies, develop again new Type synthesizes Isosorbide-5-Nitrae-butynediols catalyst, Reppe techniques is improved.The catalyst that the technique is used be malachite, particle Little, activity is good, reacts in slurry bed, improves operating pressure, reduces the danger of blast.But this catalyst is not wear-resisting Damage, be easily lost in.Such as patent US4110249, US4584418 and CN1118342A.For malachite catalyst it is not wear-resisting, The phenomenon being easy to run off, occurred in that later the ethynylation catalyst with silica, zeolite, diatomite etc. as carrier, such as patent US4288641 and US3920759, individually discloses the ethynylation catalyst with molecular sieve and magnesium silicate as carrier；Patent CN102125856A is prepared for formaldehyde using the kaolin for especially preparing and acetylene reaction prepares 1,4- butynediols and urges containing carrier Agent；But such catalyst has the following disadvantages：（1）Carrier magnesium silicate is unstable, can dissolve in reaction system, the life-span It is short；（2）Catalyst amount is more, and metal oxidation copper content is higher, easily reunites, it is impossible to give full play to urging for each activated centre Change effect, cause 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 with aqueous slkali the pH of mixed solution is adjusted Mixed sediment is worth to, Jing is further aging, adopt dispersant carries out the washing of sediment for medium, and adopts inert atmosphere Carry out roasting.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, the method Nano silicon is adopted for carrier, the method to precipitate deposition adsorbs copper and bismuth on carrier.Catalysis prepared by the method Agent has preferable activity and selectivity, but due to adopting urea for precipitating reagent, course of reaction is slower, can produce substantial amounts of ammonia Gas, 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, its feature exists In, proper amount of surfactant and sodium hydroxide solution are separately added into copper bismuth acidic aqueous solution, pyrolysis at a certain temperature is made Standby nanocatalyst.Prepared 10 ~ 80nm of catalyst particle size.The catalyst reaction activity is higher, but due to catalyst Particle it is little, for slurry bed or suspension bed, particle is little, 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 the method adopts 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 10 ~ 80nm, The catalyst activity is higher, but catalyst granules is too little, sad filter.
CN103480382A discloses a kind of catalyst for producing Isosorbide-5-Nitrae-butynediols and preparation method thereof, and the method is adopted Nano silicon after acidifying is carrier, to impregnate and deposition sedimentation method makes copper and bismuth absorption on carrier, Ran Hougan Dry, roasting obtains finished catalyst.Preferably, intensity is higher for catalyst activity prepared by the method.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 sum, the catalyst generally existing that Isosorbide-5-Nitrae-butynediols is produced in prior art following deficiency：Catalyst Granularity is not moderate, catalyst wearability and stability is poor, active component is easily lost in and adopts carrier preparation technology are answered Dephasign is to technical problems such as expense height.
The content of the invention
The purpose of the present invention is to overcome defect present in prior art, there is provided one kind is for formaldehyde and acetylene in slurry bed system The ethynylation that the active good, wearability of middle synthesis 1,4- butynediols is good, catalyst granules is uniform, not easily run off during use is urged Agent, 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 include as Lower preparation process：
（1）Prepare copper silicon mixed solution, copper bismuth mixed solution, precipitant solution I and precipitant solution II；
（2）Bottom water, intensification is added to be heated to reaction temperature toward reactor；Reaction temperature be 50 DEG C ~ 80 DEG C, preferably 60 DEG C ~ 70 DEG C, copper silicon mixed solution and the cocurrent of precipitant solution I are added dropwise into co-precipitation, keep precipitation system pH value to be 4 ~ 7, preferably 5 ~ 6, Copper consumption used is 30% ~ 70% of the total consumption of copper in catalyst, preferably 40% ~ 60%；
（3）By material through filtering, washing, after being dried, products therefrom is sieved through 500 eye mesh screens；Collection sieves product simultaneously In being added into reactor；
（4）To step（3）In reactor add bottom water, copper bismuth mixed solution and the cocurrent of precipitant solution II are added dropwise, wherein Copper consumption used is remaining content, compares step（2）Deposition condition, coprecipitation reaction temperature reduce by 5 DEG C ~ 30 DEG C, preferably 10 DEG C ~ 20 DEG C, coprecipitation reaction pH value improves 0.2 ~ 1.5, preferably 0.5 ~ 1.2；Temperature of reaction system is improved 10 by reaction after terminating DEG C ~ 30 DEG C, preferably 15 DEG C ~ 25 DEG C carry out it is aging；
（5）By material filtering, solid content 10%-40% is pressed after washing, preferably 20% ~ 30% meter adds appropriate distilled water；
（6）Using being spray-dried, dry temperature is 100 DEG C ~ 200 DEG C to slurries, preferably 120 DEG C ~ 180 DEG C, then 350 DEG C ~ 650 DEG C of 1 ~ 5h of roasting, preferably 400 DEG C ~ 600 DEG C 2 ~ 4h of roasting, obtain 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 are excellent Elect copper nitrate as.The silicon be waterglass, Ludox, potassium silicate, the mixture of one or more in tetraethyl orthosilicate, preferably For Ludox.One or more of bismuth in bismuth nitrate, bismuth sulfate or bismuth chloride, preferably bismuth nitrate.
The inventive method step（1）In, in copper silicon mixed solution, the molar concentration of copper is controlled in 0.6 ~ 3.0 mol/L, Preferably 1.0 ~ 2.5 mol/L.In terms of silica, the molar concentration of silicon is controlled to 0.2 ~ 2.5 mol/L, and preferably 0.8 ~ 2.0 mol/L.In copper bismuth mixed solution, the molar concentration of copper is controlled in 0.6 ~ 2.5 mol/L, preferably 1.0 ~ 2.0 mol/L.Bismuth Molar concentration control in 0.015 ~ 0.045 mol/L, preferably 0.02 ~ 0.04 mol/L.
The inventive method step（1）In, precipitant solution I is selected from NaOH, sodium carbonate, potassium hydroxide, potassium carbonate, carbon One or more in potassium hydrogen phthalate, ammonium carbonate or ammoniacal liquor, the molar concentration of precipitant solution I is 1.0 ~ 8.0 mol/L, preferably 2.5~6.0 mol/L.One or more of precipitant solution II in sodium carbonate, sodium acid carbonate, potassium carbonate or saleratus, The molar concentration of precipitant solution II is 0.1 ~ 2.0 mol/L, preferably 0.5 ~ 1.5 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（3）In, it is described to wash to Na2O mass contents are less than 0.5%.
The inventive method step（4）In, bottom water addition is 1/6 ~ 2/3, preferably the 1/3 ~ 1/2 of reactor cumulative volume.
The inventive method step（4）In, ageing time is controlled in 10 ~ 70 min, preferably 20 ~ 50 min.
The inventive method step（5）In, washed using 20 DEG C ~ 30 DEG C of deionized water, wash to Na2O mass contains Amount is less than 0.5%.
Using said method prepare production Isosorbide-5-Nitrae-butynediols catalyst, the catalyst with silica as carrier, with Copper bismuth compound is active component, and by mass percentage, cupric oxide is 30% ~ 60%, preferably 40% ~ 55% to its composition, bismuth oxide For 2% ~ 5%, preferably 3% ~ 4%, silica is surplus；10 ~ 40 μm of particle diameters of the catalyst at least more than 80%, preferably More than 85%, specific surface area is 20 ~ 50 m2/ g, pore volume is 0.1 ~ 0.5 cm3·g-1, pore-size distribution is between 10nm ~ 50nm More than 85%, preferably 80% ~ 95% is accounted for, bulk density is 1.0 ~ 1.8 gmL-1, preferably 1.2 ~ 1.6 gmL-1。
Above-mentioned catalyst, for the slurry reactor that formaldehyde and acetylene synthesize Isosorbide-5-Nitrae-butynediols, formaldehyde mass percent Concentration is 10% ~ 45% aqueous solution, and catalyst is 1 with the mass ratio of formalin:20 to 1:2, acetylene partial pressure is 0.1-0.5 MPa。
Copper silicon solution and precipitant solution are carried out coprecipitated reaction by method for preparing catalyst of the present invention first, are then entered Row washing, dry, filtration, obtain copper silicon complex carrier, and this carrier is a kind of species of stable uniform, with certain catalysis While active, the wearability of catalyst is in turn ensure that.
Method for preparing catalyst of the present invention have selected precipitating reagent I in cement copper silicon carrier, and in cement copper bismuth activearm Timesharing has used precipitating reagent II, and such carrier and active component can be reacted under the conditions of each optimal so that Catalyst has suitable specific surface area, pore volume, is conducive to improving the reactivity and selectivity and stability of catalyst.
Method for preparing catalyst of the present invention improves temperature and enters after copper bismuth solution and precipitant solution II carry out coprecipitated reaction Row is aging, is conducive to the increase of active phase, improves the activity of catalyst, and in washing using normal temperature under deionization washing Wash, actually reduce the temperature of catalyst slurry liquid system so that the active component being deposited on copper silicon carrier is produced to carrier Certain to shrink, this also improves the anti-wear performance of catalyst while catalyst particle size is reduced.
Good catalyst activity, easily separated, catalyst granules are uniform obtained in method for preparing catalyst of the present invention, distribution collection In, wherein granularity accounts for more than 80% in 10-40 μm of particle, not easily runs off during catalyst use, and the preparation of catalyst Method is simple, easy, reproducible.The catalyst of the present invention has the specific surface area and pore volume being adapted to, and improves catalyst Reactivity and selectivity and stability.
Specific embodiment
Below by embodiment and comparative example technical scheme, but protection scope of the present invention are further illustrated not by real Apply the restriction of example.In the present invention anti-wear performance of catalyst using ultrasonication device carry out it is ultrasonically treated after again adopt Dandong hundred Special BT-9300ST laser particle analyzers analysis, sonication treatment time is 30min, and supersonic frequency is 20KHz.Between catalyst is adopted Stirred autoclave of having a rest is evaluated.Using formaldehyde and acetylene reaction system, reaction temperature is 90 DEG C, and reaction pressure is normal pressure, second Alkynes flow velocity is 80mL/min, and catalyst amount is 35mL, and the formaldehyde addition of concentration 37wt% is 250ml.Embodiment and compare % in example if no special instructions, is mass percent.
Embodiment 1
（1）Weigh 96.64g Cu (NO3)2.3H2The Ludox of O and 229.6g 30%, prepares 400ml copper silicon mixed solutions；Weigh 144.96g Cu(NO3)2.3H2O and 10.24g Bi (NO3)3.5H2O, prepares 600ml copper bismuth mixed solutions, adjusts molten with nitric acid The pH of liquid is 2, bismuth salt is fully dissolved；Prepare the Na of 3mol/L and 1mol/L2CO3Solution for standby.
（2）The bottom water of 2L is added toward 5L reactors, intensification is heated to 60 DEG C, by 400ml steps（1）The copper silicon of middle preparation The Na of mixed solution and 3mol/L2CO3Solution cocurrent is added dropwise co-precipitation, keeps precipitation system pH value to be 6.
（3）By material through filtering, washing to Na2O content is less than 0.5%, 4h is dried at 120 DEG C, by products therefrom Jing Cross 500 eye mesh screens to sieve, collection is sieved and product and is added into 5L reactors.
（4）To step（3）Reactor in add 2L bottoms water, by 600ml copper bismuth mixed solutions in 50 DEG C of system temperature, pH It is worth under conditions of 6.5, temperature of reaction system is improved 20 by the sodium carbonate liquor co-precipitation with 1mol/L, reaction after terminating DEG C aging 60min.
（5）By material filtering, washed with 20 ~ 30 DEG C of deionized water, washed to Na2O content is less than 0.5%, by solid Content 20% is counted, and adds appropriate distilled water.
（6）Using being spray-dried, dry temperature is 130 DEG C to slurries, then in 500 DEG C of roasting 3h, obtain producing Isosorbide-5-Nitrae- The catalyst sample of butynediols.
Embodiment 2
（1）Weigh 120.8g Cu (NO3)2.3H2The Ludox of O and 348.8g 30%, prepares 500ml copper silicon mixed solutions；Weigh 120.8g Cu(NO3)2.3H2O and 12.49g Bi (NO3)3.5H2O, prepares 500ml copper bismuth mixed solutions, uses nitre acid-conditioning solution PH be 2, bismuth salt is fully dissolved；Prepare the NaOH solution of 4mol/L and the Na of 1mol/L2CO3Solution for standby.
（2）The bottom water of 1.8L is added toward 5L reactors, intensification is heated to 65 DEG C, by 500ml steps（1）The copper of middle preparation The NaOH solution cocurrent of silicon mixed solution and 4mol/L is added dropwise co-precipitation, keeps precipitation system pH value to be 5.5.
（3）By material through filtering, washing to Na2O content is less than 0.5%, 4h is dried at 120 DEG C, by products therefrom Jing Cross 500 eye mesh screens to sieve, collection is sieved and product and is added into 5L reactors.
（4）To step（3）Reactor in add 2L bottoms water, by 500ml copper bismuth mixed solutions in 55 DEG C of system temperature, pH It is worth under conditions of 6.0, the Na with 1mol/L2CO3Temperature of reaction system is improved 20 by solution co-precipitation, reaction after terminating DEG C aging 60min.
（5）By material filtering, washed with 20 ~ 30 DEG C of deionized water, washed to Na2O content is less than 0.5%, by solid Content 25% is counted, and adds appropriate distilled water.
（6）Using being spray-dried, dry temperature is 120 DEG C to slurries, then in 450 DEG C of roasting 3h, obtain producing Isosorbide-5-Nitrae- The catalyst sample of butynediols.
Embodiment 3
（1）Weigh 144.96g Cu (NO3)2.3H2The Ludox of O and 304.7g 30%, prepares 600ml copper silicon mixed solutions；Claim Take 96.64g Cu (NO3)2.3H2O and 13.71g Bi (NO3)3.5H2O, prepares 500ml copper bismuth mixed solutions, adjusts molten with nitric acid The pH of liquid is 2, bismuth salt is fully dissolved；Prepare the ammonia spirit of 4.4mol/L and the Na of 1.5mol/L2CO3Solution for standby.
（2）The bottom water of 2.2L is added toward 5L reactors, intensification is heated to 70 DEG C, by 600ml steps（1）The copper of middle preparation The ammonia spirit cocurrent of silicon mixed solution and 4.4mol/L is added dropwise co-precipitation, keeps precipitation system pH value to be 5.5.
（3）By material through filtering, washing to Na2O content is less than 0.5%, 4h is dried at 120 DEG C, by products therefrom Jing Cross 500 eye mesh screens to sieve, collection is sieved and product and is added into 5L reactors.
（4）To step（3）Reactor in add 2L bottoms water, by 400ml copper bismuth mixed solutions in 50 DEG C of system temperature, pH It is worth under conditions of 7.0, the Na with 1.5mol/L2CO3Solution co-precipitation, reaction improves temperature of reaction system after terminating 20 DEG C of aging 60min.
（5）By material filtering, washed with 20 ~ 30 DEG C of deionized water, washed to Na2O content is less than 0.5%, by solid Content 25% is counted, and adds appropriate distilled water.
（6）Using being spray-dried, dry temperature is 130 DEG C to slurries, then in 500 DEG C of roasting 3h, obtain producing Isosorbide-5-Nitrae- The catalyst sample of butynediols.
Embodiment 4
（1）Weigh 120.8g Cu (NO3)2.3H2The Ludox of O and 273.7g 30%, prepares 500ml copper silicon mixed solutions；Weigh 96.64g Cu(NO3)2.3H2O and 12.24g Bi (NO3)3.5H2O, prepares 500ml copper bismuth mixed solutions, uses nitre acid-conditioning solution PH be 2, bismuth salt is fully dissolved；Prepare the Na of 3mol/L and 1.2mol/L2CO3Solution for standby.
（2）The bottom water of 2L is added toward 5L reactors, intensification is heated to 60 DEG C, by 500ml steps（1）The copper silicon of middle preparation The Na of mixed solution and 3mol/L2CO3Solution cocurrent is added dropwise co-precipitation, keeps precipitation system pH value to be 6.0.
（3）By material through filtering, washing to Na2O content is less than 0.5%, 4h is dried at 120 DEG C, by products therefrom Jing Cross 500 eye mesh screens to sieve, collection is sieved and product and is added into 5L reactors.
（4）To step（3）Reactor in add 2L bottoms water, by 500ml copper bismuth mixed solutions in 50 DEG C of system temperature, pH It is worth under conditions of 6.8, the Na with 1.2mol/L2CO3Solution co-precipitation, reaction improves temperature of reaction system after terminating 20 DEG C of aging 60min.
（5）By material filtering, washed with 20 ~ 30 DEG C of deionized water, washed to Na2O content is less than 0.5%, by solid Content 20% is counted, and adds appropriate distilled water.
（6）Using being spray-dried, dry temperature is 130 DEG C to slurries, then in 500 DEG C of roasting 3h, obtain producing Isosorbide-5-Nitrae- The catalyst sample of butynediols.
Comparative example 1
It is step with the difference of embodiment 1（4）Aging condition it is consistent with the reaction condition of the step.
Comparative example 2
It is step with the difference of embodiment 1（5）In, adopt and step（4）Temperature of reaction system identical deionized water is entered Row washing.
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）Point It is not shown in Table 1, table 2.
The evaluation result of the catalyst of table 1
The physico-chemical property and distribution of particles of the catalyst of table 2

Claims (18)

1. a kind of preparation method for producing Isosorbide-5-Nitrae-butynediols catalyst, it is characterised in that：Comprise the steps：
（1）Prepare copper silicon mixed solution, copper bismuth mixed solution, precipitant solution I and precipitant solution II；
（2）Bottom water, intensification is added to be heated to reaction temperature toward reactor；It it is 50 DEG C ~ 80 DEG C in reaction temperature, by the mixing of copper silicon Solution and the cocurrent of precipitant solution I are added dropwise co-precipitation, keep precipitation system pH value to be 4 ~ 7, and copper consumption used is copper in catalyst The 30% ~ 70% of total consumption；
（3）By material through filtering, washing, after being dried, products therefrom is sieved through 500 eye mesh screens；Collection sieves product simultaneously In being added into reactor；
（4）To step（3）In reactor add bottom water, copper bismuth mixed solution and the cocurrent of precipitant solution II are added dropwise, wherein Copper consumption used is remaining content, compares step（2）Deposition condition, coprecipitation reaction temperature reduce by 5 DEG C ~ 30 DEG C, co-precipitation PH value in reaction improves 0.2 ~ 1.5；Reaction terminate after by temperature of reaction system raising 10 DEG C ~ 30 DEG C carry out it is aging；
（5）By material filtering, solid content 10% ~ 40% is pressed after washing, add appropriate distilled water；
（6）Using being spray-dried, dry temperature is 100 DEG C ~ 200 DEG C to slurries, then in 350 DEG C ~ 650 DEG C 1 ~ 5h of roasting, is obtained To the catalyst of production 1,4- butynediols.
2. method according to claim 1, it is characterised in that：Step（1）In, the copper selected from copper sulphate, copper nitrate or One or more in copper chloride, the silicon be waterglass, Ludox, potassium silicate, one or more in tetraethyl orthosilicate, bismuth One or more in bismuth nitrate, bismuth sulfate or bismuth chloride.
3. method according to claim 2, it is characterised in that：The copper be copper nitrate, the silicon be Ludox, the bismuth For bismuth nitrate.
4. method according to claim 1, it is characterised in that：Step（1）In, in copper silicon mixed solution, copper it is mole dense In 0.6 ~ 3.0 mol/L, in terms of silica, the molar concentration of silicon is controlled to 0.2 ~ 2.5 mol/L for degree control, in the mixing of copper bismuth In solution, in 0.6 ~ 2.5 mol/L, the molar concentration of bismuth is controlled in 0.015 ~ 0.045 mol/L for the molar concentration control of copper.
5. method according to claim 4, it is characterised in that：In copper silicon mixed solution, the molar concentration control of copper exists 1.0 ~ 2.5 mol/L, in terms of silica, the molar concentration of silicon is controlled to 0.8 ~ 2.0 mol/L, in copper bismuth mixed solution, copper Molar concentration control in 1.0 ~ 2.0 mol/L, the molar concentration of bismuth salt is controlled in 0.02 ~ 0.04 mol/L.
6. method according to claim 1, it is characterised in that：Step（1）In, precipitant solution I selected from NaOH, One or more in sodium carbonate, potassium hydroxide, potassium carbonate, saleratus, ammonium carbonate or ammoniacal liquor, precipitant solution I mole Concentration is 2.5 ~ 6.0 mol/L.
7. method according to claim 1, it is characterised in that：Step（1）In, precipitant solution II is selected from sodium carbonate, carbon One or more in sour hydrogen sodium, potassium carbonate or saleratus, the molar concentration of precipitant solution II is 0.5 ~ 1.5 mol/L.
8. method according to claim 1, it is characterised in that：Step（2）In, reaction temperature is 60 DEG C ~ 70 DEG C, keeps heavy Shallow lake system pH is 5 ~ 6, and copper consumption used is 40% ~ 60% of the total consumption of copper in catalyst.
9. method according to claim 1, it is characterised in that：Step（2）In, bottom water addition is reactor cumulative volume 1/6~2/3。
10. method according to claim 1, it is characterised in that：Step（3）In, it is described to wash to Na2O mass contents are less than 0.5%。
11. methods according to claim 1, it is characterised in that：Step（4）In, 10 DEG C of coprecipitation reaction temperature reduction ~ 20 DEG C, coprecipitation reaction pH value improves 0.5 ~ 1.2；Temperature of reaction system is improved 15 DEG C ~ 25 DEG C and is carried out always by reaction after terminating Change.
12. methods according to claim 1, it is characterised in that：Step（4）In, bottom water addition is reactor cumulative volume 1/6 ~ 2/3.
13. methods according to claim 1, it is characterised in that：Step（4）In, ageing time is controlled in 10 ~ 70 min.
14. methods according to claim 1, it is characterised in that：Step（5）In, entered using 20 DEG C ~ 30 DEG C of deionized water Row washing, washs to Na2O mass contents are less than 0.5%.
15. methods according to claim 1, it is characterised in that：Step（6）In, slurries are using spray drying, dry temperature Spend for 120 DEG C ~ 180 DEG C, then in 400 DEG C ~ 600 DEG C 2 ~ 4h of roasting.
Catalyst prepared by a kind of 16. employing claim 1 to 15 either method, it is characterised in that：The catalyst is with silica For carrier, with copper bismuth compound as active component, by mass percentage, cupric oxide is 30% ~ 60% to its composition, and bismuth oxide is 2% ~ 5%, silica is surplus；At least more than 80%, specific surface area is 20 ~ 50 m to 10 ~ 40 μm of particle diameters of the catalyst2/ G, pore volume is 0.1 ~ 0.5 cm3·g-1, pore-size distribution accounts for more than 85% between 10nm ~ 50nm, and bulk density is 1.0 ~ 1.8 g·mL-1。
17. catalyst according to claim 16, it is characterised in that：Cupric oxide is 40% ~ 55%, and bismuth oxide is 3% ~ 4%； 10 ~ 40 μm of particle diameters of the catalyst at least more than 85%, pore-size distribution between 10nm ~ 50nm for 80% ~ 95%, Bulk density is 1.2 ~ 1.6 gmL-1。
Catalyst described in 18. claims 16 is used for the application of the slurry reactor of formaldehyde and acetylene synthesis Isosorbide-5-Nitrae-butynediols, It is characterized in that：Formaldehyde mass percent concentration is 10% ~ 45% aqueous solution, and catalyst is 1 with the mass ratio of formalin:20 To 1:2, acetylene partial pressure is 0.1-0.5 MPa.
CN201510750473.8A 2015-11-09 2015-11-09 Preparation of 1,4-butynediols catalyst and preparation method and application thereof Pending CN106669692A (en)

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