CN106669696A - Synthesized 1.4-butynediol catalyst and preparation method and application thereof - Google Patents

Synthesized 1.4-butynediol catalyst and preparation method and application thereof Download PDF

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CN106669696A
CN106669696A CN201510751280.4A CN201510751280A CN106669696A CN 106669696 A CN106669696 A CN 106669696A CN 201510751280 A CN201510751280 A CN 201510751280A CN 106669696 A CN106669696 A CN 106669696A
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copper
catalyst
bismuth
silicon
mol
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关月明
包洪洲
王永林
张艳侠
袁胜华
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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
    • B01J23/70—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
    • 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
    • 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
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • 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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Abstract

The invention discloses a synthesized 1,4-butynediol catalyst and a preparation method and application of the synthesized 1,4-butynediol catalyst. The catalyst takes silicon oxide as a carrier and copper bismuth compounds as active components, and according to mass percent, the copper oxide accounts for 30%-60%, the bismuth oxide accounts for 2%-5%, and the balance is silicon oxide; and the particle, of which the diameter is 10-40 [mu]m, of the catalyst, accounts for more than 80%, the specific surface area is 20-50 m<2>/g, the pore volume is 0.1-0.5 cm<3>*g<1>, the particle with the pore diameter distribution of 10 nm to 50 nm accounts for more than 85%, and the stacking density is 1.0-1.8 g*mL<1>. The catalyst is prepared through a coprecipitation method. The catalyst is used for synthesizing 1,4-butynediol from formaldehyde and acetylene in a slurry bed, is high in activity and wear resistance, is even in catalyst particles, and is not likely to lose in the use process, and the preparation method of the catalyst is simple and practicable, and is high in repeatability.

Description

Synthesis 1,4- Butynediols catalyst and its preparation method and application
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 derivants 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 granule 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 silicon dioxide, zeolite, kieselguhr 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 active center, 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 salt 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 precipitate 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 carbamide for precipitant, course of reaction is slower, can produce substantial amounts of ammonia, causes environmental pollution, and the catalyst granules for preparing is less, bad filtration.
CN103170342A discloses a kind of nanometer CuO-Bi of synthesis 1,4- butynediols2O3Catalyst, it is characterised in that proper amount of surfactant and sodium hydroxide solution are separately added in copper bismuth acidic aqueous solution, pyrolysis at a certain temperature prepares nanocatalyst.Prepared 10 ~ 80nm of catalyst particle size.The catalyst reaction activity is higher, but because the granule of catalyst is little, for slurry bed or suspension bed, granule is little, sad filter.And nanometer CuO-Bi2O3Active center exposure is more, easily inactivation.
CN103157500A discloses a kind of preparation method of loaded catalyst, and the method adopts mesopore molecular sieve for carrier, and the mantoquita and bismuth salt of solubility are loaded on carrier using infusion process, and the catalyst particle size of preparation is 10 ~ 80 Nm, 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 silicon mixed solution, copper bismuth mixed solution, precipitant solution I and precipitant solution II；
（2）It is 50 DEG C ~ 80 DEG C in reaction temperature, preferably 60 DEG C ~ 70 DEG C, precipitant solution I is instilled in copper silicon mixed solution, obtains copper silicon precipitate serosity；Copper consumption used is 30% ~ 70% of the total consumption of copper in catalyst, preferably 40% ~ 60%；And carry out aging；
（3）Compare step（2）Deposition condition, reduce by 5 DEG C ~ 30 DEG C, in the case of preferably 10 DEG C ~ 20 DEG C in reaction temperature, copper bismuth mixed solution is instilled in precipitant solution II, copper bismuth precipitate serosity will be obtained；Copper consumption used is remaining content；Reaction is aging after terminating；
（4）Compare step（2）Deposition condition, reduce by 10 DEG C ~ 40 DEG C, in the case of preferably 20 DEG C ~ 30 DEG C in reaction temperature, copper silicon precipitate serosity and copper bismuth precipitate serosity cocurrent are added dropwise in reactor, it is desirable value to adjust terminal pH, and is carried out 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 serosity, and preferably 120 DEG C ~ 180 DEG C, then in 350 DEG C ~ 650 DEG C 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 sulfate, copper nitrate or copper chloride, preferably copper nitrate.The silicon be waterglass, Ludox, potassium silicate, the mixture of one or more in tetraethyl orthosilicate, preferably 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 0.6 ~ 3.0 Mol/L, preferably 1.0 ~ 2.5 mol/L.In terms of silicon dioxide, the molar concentration of silicon is controlled to 0.2 ~ 2.5 mol/L, preferably 0.8 ~ 2.0 mol/L.In copper bismuth mixed solution, the molar concentration of copper is controlled 0.6 ~ 2.5 Mol/L, preferably 1.0 ~ 2.0 mol/L.The molar concentration of bismuth salt is controlled in 0.015 ~ 0.045 mol/L, and preferably 0.02 ~ 0.04 mol/L。
The inventive method step（1）In, one or more of precipitant solution I in sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, ammonium carbonate or ammonia, 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 bicarbonate, potassium carbonate or potassium bicarbonate, 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, precipitation terminal pH is controlled to 5.0 ~ 11.0, preferably 6.0 ~ 9.0, and the precipitation time is 0.2 ~ 2.0 h, preferably 0.5 ~ 1 h.
The inventive method step（2）In, aging condition is consistent with the reaction condition of the step, and ageing time is controlled 10 ~ 70 Min, preferably 20 ~ 50 min.
The inventive method step（3）In, precipitation terminal pH is controlled to 5.0 ~ 10.0, preferably 6.0 ~ 8.0；The precipitation time is 0.2 ~ 2.0h, preferably 0.5 ~ 1h.
The inventive method step（3）In, aging condition is consistent with the reaction condition of the step, and ageing time is controlled 10 ~ 70 Min, preferably 20 ~ 50 min.
The inventive method step（4）In, rate-determining steps（2）And step（3）The rate of addition of gained serosity is 1:1, endpoint pH is controlled to 5.0 ~ 8.0, preferably 6.0 ~ 7.0.
The inventive method step（4）In, aging condition is consistent with the reaction condition of the step, and ageing time is controlled 10 ~ 70 Min, preferably 20 ~ 50 min.
The inventive method step（5）In, it is described to wash to Na2O mass contents are less than 0.5%.
Using said method prepare production Isosorbide-5-Nitrae-butynediols catalyst, the catalyst with silicon oxide as carrier, with copper bismuth compound as active component, by mass percentage, copper oxide is 30% ~ 60%, preferably 40% ~ 55% to its composition, bismuth oxide is 2% ~ 5%, preferably 3% ~ 4%, and silicon oxide is surplus；10 ~ 40 μm of particle diameters of the catalyst at least more than 80%, preferably more than 85%, specific surface area be 20 ~ 50 m2/ g, pore volume is 0.1 ~ 0.5 cm3·g-1 ,Pore-size distribution accounts for more than 85%, preferably 80% ~ 95% between 10nm ~ 50nm, and bulk density is 1.0 ~ 1.8 gmL-1, preferably 1.2 ~ 1.6 g·mL-1。
Above-mentioned catalyst is used for formaldehyde and acetylene synthesizes the slurry reactor of Isosorbide-5-Nitrae-butynediols, and 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.
Method for preparing catalyst of the present invention is first with positive addition cement copper silicon mixed solution, solution ph is from low to high in precipitation process, precipitate is precipitated in the acid medium that pH value gradually increases, under these conditions, undesirable components are hardly produced, it is ensured that the homogeneity of the catalyst carrier of formation.
Method for preparing catalyst of the present invention utilizes anti-addition cement copper bismuth mixed solution, solution ph is from high to low in precipitation process, precipitate is precipitated in the alkaline medium that pH value is gradually reduced, under these conditions, the fine particle dissolving generated in colloid, and remain the granule for having generated, the catalyst granules distribution that so can be formed is concentrated.
Method for preparing catalyst of the present invention is mixed in the serosity of the serosity of cupric silicon precipitate and cupric bismuth precipitate using cocurrent process, and it is same rate of addition to control both, and operation can be made more stable, and the catalyst particle size for obtaining is more homogeneous.
Method for preparing catalyst of the present invention have selected precipitant I in cement copper silicon carrier, and used precipitant II when the copper bismuth active component of cupric silicon precipitate is precipitated, so carrier and active component can be reacted under the conditions of each optimal, so that catalyst has suitable specific surface area, pore volume, be conducive to improving the reactivity and selectivity and stability of catalyst.
SHAPE \* MERGEFORMAT 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.The anti-wear performance of catalyst is analyzed using the BT-9300ST laser particle analyzers that ultrasonication device is carried out after supersound process again using Dandong Bai Te in the present invention, and 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 96.64g Cu(NO3)2.3H2O and 229.6g 30% Ludox, 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, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved；Prepare 3 mol/L and 1 The Na of mol/L2CO3Solution for standby.
（2）By 400ml steps（1）The copper silicon mixed solution of middle preparation heats up and is heated to 60 DEG C, by the Na of 3 mol/L2CO3Solution is instilled in copper silicon mixed solution, and controlling reaction temperature is 60 DEG C, and reaction end pH is 6.After reaction terminates, reaction temperature and pH are maintained, continue to stir 30min.
（3）By step（1）The Na of 1 mol/L of middle preparation2CO3Solution is warming up to 50 DEG C, by 600ml steps（1）The copper bismuth mixed solution of middle preparation is added to Na2CO3In solution, controlling reaction temperature is 50 DEG C, and reaction end pH is 6.5, maintains reaction temperature and pH, continues to stir 30min.
（4）By step（2）Resulting copper silicon precipitate serosity and step（3）Resulting copper bismuth precipitate serosity cocurrent is added drop-wise in reactor, and controlling reaction temperature is 40 DEG C, and it is 6.5 to adjust terminal pH, maintains reaction temperature and pH, continues to stir 30min.
（5）Material filtering is washed to Na2O content is less than 0.5%, based on solid content 20%, adds appropriate distilled water.
（6）Using being spray-dried, dry temperature is 130 DEG C to serosity, then in 500 DEG C of roasting 3h, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Embodiment 2
（1）Weigh 120.8g Cu(NO3)2.3H2O and 348.8g 30% Ludox, 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, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved；Prepare the NaOH solution of 4 mol/L and the Na of 1 mol/L2CO3Solution for standby.
（2）By 500ml steps（1）The copper silicon mixed solution of middle preparation heats up and is heated to 65 DEG C, and the NaOH solution of 4 mol/L is instilled in copper silicon mixed solution, and controlling reaction temperature is 60 DEG C, and reaction end pH is 6.5.After reaction terminates, reaction temperature and pH are maintained, continue to stir 30min.
（3）By step（1）The Na of 1 mol/L of middle preparation2CO3Solution is warming up to 55 DEG C, by 500ml steps（1）The copper bismuth mixed solution of middle preparation is added to Na2CO3In solution, controlling reaction temperature is 55 DEG C, and reaction end pH is 6.0, maintains reaction temperature and pH, continues to stir 30min.
（4）By step（2）Resulting copper silicon precipitate serosity and step（3）Resulting copper bismuth precipitate serosity cocurrent is added drop-wise in reactor, and controlling reaction temperature is 45 DEG C, and it is 7.0 to adjust terminal pH, maintains reaction temperature and pH, continues to stir 30min.
（5）Material filtering is washed to Na2O content is less than 0.5%, based on solid content 25%, adds appropriate distilled water.
（6）Using being spray-dried, dry temperature is 120 DEG C to serosity, then in 500 DEG C of roasting 3h, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Embodiment 3
（1）Weigh 144.96g Cu(NO3)2.3H2O and 304.7g 30% Ludox, prepares 600ml copper silicon mixed solutions；Weigh 96.64g Cu(NO3)2.3H2O and 13.71g Bi(NO3)3.5H2O, prepares 500ml copper bismuth mixed solutions, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved；Prepare the ammonia spirit and 1.5 of 4.4 mol/L The Na of mol/L2CO3Solution for standby.
（2）By 600ml steps（1）The copper silicon mixed solution of middle preparation heats up and is heated to 70 DEG C, and the ammonia spirit of 4.4 mol/L is instilled in copper silicon mixed solution, and controlling reaction temperature is 70 DEG C, and reaction end pH is 6.5.After reaction terminates, reaction temperature and pH are maintained, continue to stir 30min.
（3）By step（1）The Na of 1.5 mol/L of middle preparation2CO3Solution is warming up to 60 DEG C, by 400ml steps（1）The copper bismuth mixed solution of middle preparation is added to Na2CO3In solution, controlling reaction temperature is 60 DEG C, and reaction end pH is 6.5, maintains reaction temperature and pH, continues to stir 40min.
（4）By step（2）Resulting copper silicon precipitate serosity and step（3）Resulting copper bismuth precipitate serosity cocurrent is added drop-wise in reactor, and controlling reaction temperature is 45 DEG C, and it is 6.5 to adjust terminal pH, maintains reaction temperature and pH, continues to stir 30min.
（5）Material filtering is washed to Na2O content is less than 0.5%, based on solid content 25%, adds appropriate distilled water.
（6）Using being spray-dried, dry temperature is 130 DEG C to serosity, then in 500 DEG C of roasting 3h, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Embodiment 4
（1）Weigh 120.8g Cu(NO3)2.3H2O and 273.7g 30% Ludox, 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, is 2 with the pH of nitre acid-conditioning solution, bismuth salt is fully dissolved；Prepare 3 mol/L and 1.2 The Na of mol/L2CO3Solution for standby
（2）By 500ml steps（1）The copper silicon mixed solution of middle preparation heats up and is heated to 60 DEG C, by the Na of 3 mol/L2CO3Solution is instilled in copper silicon mixed solution, and controlling reaction temperature is 60 DEG C, and reaction end pH is 6.0.After reaction terminates, reaction temperature and pH are maintained, continue to stir 30min.
（3）By step（1）The Na of 1.2 mol/L of middle preparation2CO3Solution is warming up to 50 DEG C, by 500ml steps（1）The copper bismuth mixed solution of middle preparation is added to Na2CO3In solution, controlling reaction temperature is 50 DEG C, and reaction end pH is 6.5, maintains reaction temperature and pH, continues to stir 40min.
（4）By step（2）Resulting copper silicon precipitate serosity and step（3）Resulting copper bismuth precipitate serosity cocurrent is added drop-wise in reactor, and controlling reaction temperature is 40 DEG C, and it is 7.0 to adjust terminal pH, maintains reaction temperature and pH, continues to stir 30min.
（5）Material filtering is washed to Na2O content is less than 0.5%, based on solid content 20%, adds appropriate distilled water.
（6）Using being spray-dried, dry temperature is 130 DEG C to serosity, then in 500 DEG C of roasting 3h, obtains producing the catalyst sample of Isosorbide-5-Nitrae-butynediols.
Comparative example 1
It is step with the difference of embodiment 1（2）In, copper silicon mixed solution and Na2CO3Solution is precipitated by the way of cocurrent Deca,
Comparative example 2
It is step with the difference of embodiment 1（3）In, also by copper bismuth mixed solution and Na2CO3Solution is precipitated by the way of cocurrent Deca.
Comparative example 3
The catalyst that there is same composition with embodiment 3 is prepared by the technical scheme of CN201210397161.X embodiments 1.
Activity rating of catalyst result and physico-chemical property prepared by above-mentioned comparative example and embodiment（Or particle 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 (20)

1. a kind of preparation method for producing Isosorbide-5-Nitrae-butynediols catalyst, it is characterised in that：Including following preparation process：
（1）Prepare copper silicon mixed solution, copper bismuth mixed solution, precipitant solution I and precipitant solution II；
（2）It is 50 DEG C ~ 80 DEG C in reaction temperature, precipitant solution I is instilled in copper silicon mixed solution, obtains copper silicon precipitate serosity；Copper consumption used is 30% ~ 70% of the total consumption of copper in catalyst；And carry out aging；
（3）Compare step（2）Deposition condition, reaction temperature reduce by 5 DEG C ~ 30 DEG C in the case of, by copper bismuth mixed solution instill precipitant solution II in, copper bismuth precipitate serosity will be obtained；Copper consumption used is remaining content；Reaction is aging after terminating；
（4）Compare step（2）Deposition condition, in the case where reaction temperature reduces by 10 DEG C ~ 40 DEG C, copper silicon precipitate serosity and copper bismuth precipitate serosity cocurrent are added dropwise in reactor, it is desirable value to adjust terminal pH, and is carried out aging；
（5）By material filtering, solid content 10% ~ 40% is pressed after washing and adds appropriate distilled water；
（6）Using being spray-dried, dry temperature is 100 DEG C ~ 200 DEG C to serosity, then in 350 DEG C ~ 650 DEG C h of roasting 1 ~ 5, 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 the copper in copper sulfate, copper nitrate or copper chloride, the silicon is waterglass, and Ludox, potassium silicate, one or more in tetraethyl orthosilicate, the bismuth is selected from one or more in bismuth nitrate, bismuth sulfate or bismuth chloride.
3. method according to claim 2, it is characterised in that：The copper is copper nitrate, and the silicon is Ludox, and the bismuth is bismuth nitrate.
4. method according to claim 1, it is characterised in that：Step（1）In, in copper silicon mixed solution, the molar concentration of copper is controlled in 0.6 ~ 3.0 mol/L, in terms of silicon dioxide, the molar concentration of silicon is controlled to 0.2 ~ 2.5 mol/L, in copper bismuth mixed solution, the molar concentration control of copper is controlled in 0.015 ~ 0.045 mol/L in 0.6 ~ 2.5 mol/L, the molar concentration of bismuth.
5. method according to claim 4, it is characterised in that：Step（1）In, in copper silicon mixed solution, the molar concentration of copper is controlled in 1.0 ~ 2.5 mol/L, in terms of silicon dioxide, the molar concentration of silicon is controlled to 0.8 ~ 2.0 mol/L, in copper bismuth mixed solution, the molar concentration control of copper is controlled in 0.02 ~ 0.04 mol/L in 1.0 ~ 2.0 mol/L, the molar concentration of bismuth.
6. method according to claim 1, it is characterised in that：Step（1）In, one or more of precipitant solution I in sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, ammonium carbonate or ammonia, the molar concentration of precipitant solution I is 2.5 ~ 6.0 mol/L.
7. method according to claim 1, it is characterised in that：One or more of precipitant solution II in sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate, 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；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, precipitation terminal pH is controlled to 5.0 ~ 11.0, and the precipitation time is 0.2 ~ 2.0 h.
10. method according to claim 9, it is characterised in that：Precipitation terminal pH is controlled to 6.0 ~ 9.0, and the precipitation time is 0.5 ~ 1 h.
11. methods according to claim 1, it is characterised in that：Step（2）In, aging condition is consistent with the reaction condition of the step, and ageing time is controlled in 10 ~ 70 min.
12. methods according to claim 1, it is characterised in that：Step（3）In, precipitation terminal pH is controlled to 5.0 ~ 10.0；The precipitation time is 0.2 ~ 2.0 h.
13. methods according to claim 1, it is characterised in that：Step（3）In, aging condition is consistent with the reaction condition of the step, and ageing time is controlled in 10 ~ 70 min.
14. methods according to claim 1, it is characterised in that：Step（4）In, rate-determining steps（2）And step（3）The rate of addition of gained serosity is identical, and endpoint pH is controlled to 5.0 ~ 8.0.
15. methods according to claim 1, it is characterised in that：Step（4）In, aging condition is consistent with the reaction condition of the step, and ageing time is controlled in 10 ~ 70 min.
16. methods according to claim 1, it is characterised in that：Step（5）In, it is described to wash to Na2O mass contents are less than 0.5%.
17. methods according to claim 1, it is characterised in that：Step（6）In, dry temperature is 120 DEG C ~ 180 DEG C, then in 400 DEG C ~ 600 DEG C 2 ~ 4h of roasting.
18. rights will remove catalyst prepared by 1 to 17 either method, it is characterised in that：With silicon oxide as carrier, with copper bismuth compound as active component, by mass percentage, copper oxide is 30% ~ 60% to its composition to the catalyst, and bismuth oxide is 2% ~ 5%, and silicon oxide is surplus；The catalyst 10 ~ 40 At least more than 80%, specific surface area is 20 ~ 50 m for μm particle diameter2/ 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。
19. methods according to claim 18, it is characterised in that：Copper oxide is 40% ~ 55%, and bismuth oxide is 3% ~ 4%；10 ~ 40 μm of particle diameters of the catalyst are at least more than 85%, and specific surface area is 20 ~ 50 m2/ g, pore volume is 0.1 ~ 0.5 cm3·g-1 ,Pore-size distribution accounts for 80% ~ 95% between 10nm ~ 50nm, and bulk density is 1.2 ~ 1.6 gmL-1。
Catalyst described in 20. claim 18 is used for formaldehyde and acetylene synthesizes the slurry reactor of Isosorbide-5-Nitrae-butynediols, it is characterised 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.
CN201510751280.4A 2015-11-09 2015-11-09 Synthesized 1.4-butynediol catalyst and preparation method and application thereof Pending CN106669696A (en)

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* Cited by examiner, † Cited by third party
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CN1118342A (en) * 1995-07-19 1996-03-13 化学工业部北京化工研究院 Unsupported catalyst for producing 1, 4-butynediol and preparation method and application thereof
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
CN102658158A (en) * 2012-05-20 2012-09-12 山西大学 Copper bismuth catalyst and preparation method thereof
CN103480382A (en) * 2013-09-18 2014-01-01 大连瑞克科技有限公司 Catalyst for preparing 1, 4-butynediol and preparation method thereof
CN103638937A (en) * 2013-12-16 2014-03-19 西安向阳航天材料股份有限公司 Ethynylation catalyst for synthesizing 1, 4-butynediol
US20140275639A1 (en) * 2013-03-15 2014-09-18 Basf Corporation Novel Ethynylation Catalyst And Method Of Making Same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1118342A (en) * 1995-07-19 1996-03-13 化学工业部北京化工研究院 Unsupported catalyst for producing 1, 4-butynediol and preparation method and application thereof
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
CN102658158A (en) * 2012-05-20 2012-09-12 山西大学 Copper bismuth catalyst and preparation method thereof
US20140275639A1 (en) * 2013-03-15 2014-09-18 Basf Corporation Novel Ethynylation Catalyst And Method Of Making Same
CN103480382A (en) * 2013-09-18 2014-01-01 大连瑞克科技有限公司 Catalyst for preparing 1, 4-butynediol and preparation method thereof
CN103638937A (en) * 2013-12-16 2014-03-19 西安向阳航天材料股份有限公司 Ethynylation catalyst for synthesizing 1, 4-butynediol

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