CN108069827A - A kind of method for preparing 1,4- butynediols coproduction propilolic alcohols - Google Patents

A kind of method for preparing 1,4- butynediols coproduction propilolic alcohols Download PDF

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CN108069827A
CN108069827A CN201610991012.4A CN201610991012A CN108069827A CN 108069827 A CN108069827 A CN 108069827A CN 201610991012 A CN201610991012 A CN 201610991012A CN 108069827 A CN108069827 A CN 108069827A
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reaction
catalyst
acid solution
method described
bismuth
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CN108069827B (en
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张艳侠
乔凯
段日
包洪洲
付秋红
王领民
霍稳周
张宝国
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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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    • 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
    • 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

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention discloses a kind of method for preparing Isosorbide-5-Nitrae butynediols, includes the following steps：Using the copper bismuth composite oxide after carbon dioxide treatment as catalyst, reaction temperature is 80 ~ 150 DEG C, preferably 90 ~ 120 DEG C, reaction pressure is 0.2 ~ 2.0MPa, and preferably 0.5 ~ 1.0 MPa, the flow of acetylene is 40 ~ 200ml/min, preferably 80 ~ 150 ml/min, formalin mass concentration is 4% ~ 25%, preferably 9% ~ 15%, and catalyst amount is 1 with the formalin mass volume ratio added in:3~1:10, preferably 1:5~1:7.This method has many advantages, such as that the yield of propilolic alcohol is high, service cycle is long.

Description

A kind of method for preparing 1,4- butynediols coproduction propilolic alcohols
Technical field
The present invention relates to a kind of methods for preparing Isosorbide-5-Nitrae-butynediols coproduction propilolic alcohol, relate in particular to a kind of for first The method that aldehyde ethinylation prepares 1,4- butynediols coproduction propilolic alcohols.
Background technology
The technique of industrialized production Isosorbide-5-Nitrae-butynediols is mainly acetylene-formaldehyde process (Reppe methods), domestic manufacturing enterprise Ru Shan Western three-dimensional, Sichuan day China, Xinjiang Meike chemical industry, state's electricity Sinopec Ningxia derived energy chemical, Xingjiang Tianye Co., Inner Mongol gouy east, four Chuan Weinilun factories etc. use such technology.In the 1970s, develop the Reppe method techniques of improvement, using slurry bed or Suspension bed technique is reacted and carried out under normal pressure or lower pressure.But Reppe techniques are improved to the more demanding of catalyst, are fitted Closing industrialized particle size should be at 1 ~ 50 μm.The particle size of catalyst is more than 50 μm, and activity will decline very much, but if Less than 1 μm, filtering is relatively difficult.Since 1,4-butanediol price constantly declined in recent years, the profit of enterprise is caused constantly to reduce, And propilolic alcohol causes it to hold at high price, so in production Isosorbide-5-Nitrae-butynediols due to the continuous increase in downstream product market While, the more propilolic alcohol of coproduction, the profit of enterprise is bigger.
US4110249 and US4584418 and CN1118342A is individually disclosed with DNAcarrier free malachite, carrier-free Copper oxide/bismuth oxide catalyst, these catalyst are not wear-resisting, and metal component is easily lost in.
The copper bismuth support type that US3920759 and CN102125856A individually discloses using magnesium silicate, kaolin as carrier is urged Agent, for the catalytic reaction of formaldehyde and acetylene reaction synthesis Isosorbide-5-Nitrae-butynediols.But such catalyst has the following disadvantages： （1）Carrier magnesium silicate is unstable, can dissolve in the reaction system, short life；（2）Catalyst amount is more, metal copper oxide Content is higher, easily reunites, it is impossible to give full play to the catalytic effect in each activated centre, cause the waste of copper resource.
CN201210157882.3 discloses a kind of copper bismuth catalyst and preparation method, and its step are as follows：Using organosilicon The alcoholic solution in source is added drop-wise in the mixed liquor containing mantoquita, bismuth salt, magnesium salts and dispersant, and the pH of mixed solution is adjusted with aqueous slkali Mixed sediment is worth to, through further aging, uses washing of the dispersant for medium progress sediment, and using inert atmosphere It is roasted.The activity of the catalyst is higher, but cost is higher, bad mechanical strength, it is difficult to realize industrialization.
CN201210397161.X is disclosed for catalyst of Isosorbide-5-Nitrae-butynediols production and preparation method thereof, this method Nano silicon dioxide is used as carrier, in the method for precipitation deposition, by copper and bismuth absorption on carrier.Catalysis prepared by the method Agent has preferable activity and selectivity, but due to using urea, for precipitating reagent, reaction process is slower, can generate substantial amounts of ammonia Gas causes environmental pollution, and the catalyst granules prepared is smaller, bad filtering.
CN103170342A discloses a kind of nanometer CuO-Bi for synthesizing 1,4- butynediols2O3Catalyst, feature exist In, proper amount of surfactant and sodium hydroxide solution are separately added into copper bismuth acidic aqueous solution, at a certain temperature pyrolysis system Standby nanocatalyst.Prepared 10 ~ 80nm of catalyst particle size.The catalyst reaction activity is higher, but due to catalyst Particle it is small, for slurry bed or suspension bed, particle is small, sad filter.And nanometer CuO-Bi2O3Activated centre exposure is more, holds Easy in inactivation.
CN103157500A discloses a kind of preparation method of loaded catalyst, and this method uses mesopore molecular sieve to carry Body loads to soluble mantoquita and bismuth salt on carrier using infusion process, and the catalyst particle size of preparation is received for 10 ~ 80 Rice, the catalyst activity is higher, but catalyst granules is too small, sad filter.
CN103480382A discloses a kind of catalyst for producing Isosorbide-5-Nitrae-butynediols and preparation method thereof, and this method uses Nano silicon dioxide after acidifying is carrier, makes copper with dipping and deposition sedimentation method and bismuth is adsorbed on carrier, Ran Hougan It is dry, roast to obtain finished catalyst.Catalyst activity prepared by this method is preferable, and intensity is higher.But catalysis prepared by the method The particle size uniformity of agent powder is bad, and little particle is more, is unfavorable for the industrial operation of catalyst.
In conclusion the catalyst for producing Isosorbide-5-Nitrae-butynediols in the prior art is uncomfortable in the prevalence of catalyst particle size In, the wearability of catalyst and the technical problems such as stability is poor, active component is easily lost in, and produce Isosorbide-5-Nitrae-butynediols Meanwhile the yield very little of propilolic alcohol.
The content of the invention
It is an object of the invention to overcome above-mentioned defect in the prior art, provide and a kind of prepare Isosorbide-5-Nitrae-butynediols The method of coproduction propilolic alcohol, this method have many advantages, such as that the yield of propilolic alcohol is high, service cycle is long.
A kind of method for preparing Isosorbide-5-Nitrae-butynediols, includes the following steps：With the copper bismuth composite oxygen after carbon dioxide treatment Compound is catalyst, and reaction temperature is 80 ~ 150 DEG C, is preferably 90 ~ 120 DEG C, and reaction pressure is 0.2 ~ 2.0MPa, preferably 0.5 ~ 1.0 MPa, the flow of acetylene is 40 ~ 200ml/min, is preferably 80 ~ 150 ml/min, formalin mass concentration is 4% ~ 25%, preferably 9% ~ 15%, catalyst amount are 1 with the formalin mass volume ratio added in:3~1:10, preferably 1:5~1: 7。
Containing mass percentage it is 0.5% ~ 3.5%, preferably 0.8 ~ 2.0% in the formalin in the above method Diethylene glycol (DEG).In alkynes aldehyde reaction, by adding in diethylene glycol (DEG) in the reaction system, the selectivity of propilolic alcohol is further improved, And the loss of metal is effectively inhibited, and the service life of catalyst can be extended, it is with good economic efficiency.
In the above method, carbon dioxide treatment step is divided into 2 stages.Processing time 1 ~ 4 at 10 ~ 45 DEG C first stage Hour, preferably 20 ~ 30 DEG C, when processing time preferably 1.5 ~ 3 is small, 1 ~ 8ml/min of flow velocity of carbon dioxide is preferably 2 ~ 4 ml/ min.Second stage is purged with nitrogen, 1 ~ 8ml/min of flow velocity of nitrogen, is preferably 2 ~ 4 ml/min, treatment temperature for 0 ~ 30 DEG C, preferably 10 ~ 20 DEG C, processing time for 1 ~ 5 it is small when, preferably 2 ~ 3 it is small when.
In the above method, the copper bismuth composite oxide catalyst by weight, the content of copper oxide for 30wt% ~ 80wt%, is preferably 40wt% ~ 70wt%, and the content of bismuth oxide is the wt% of 1.0wt% ~ 10.0, is preferably the wt% of 2.5 wt%~6.5.
In the above method, the copper bismuth composite oxide catalyst is preferably prepared with the following method.By several sections altogether Precipitation reaction, and in the different phase of coprecipitation reaction, different amounts of deionized water is added in into reaction system, to change reaction The degree of supersaturation of product makes the catalyst granules prepared larger, and is distributed and concentrates, excellent wear-resisting property.
A kind of preparation method of copper bismuth composite oxide catalyst, comprises the following steps：
（1）Prepare the acid solution containing mantoquita and bismuth salt；
（2）Prepare precipitant solution；
（3）Bottom water is added in into reaction kettle, heating is heated to reaction temperature；
（4）The mode of cocurrent is taken, by step（1）Acid solution and step（2）Precipitant solution be added drop-wise in reaction kettle, In reaction process gas CO is passed through from reactor bottom2；
（5）When remaining acid solution is step（1）When preparing the 4/5 ~ 9/10 of acid solution total amount, stop reaction, carry out aging；
（6）After aging, continue to react and continue to be passed through gas CO from reactor bottom2, when remaining acid solution is Step（1）When preparing the 1/2-3/5 of acid solution total amount, deionized water is added in reaction system, flow for acid solution and 0.5-1.5 times of alkaline solution total flow；
（7）When remaining acid solution is step（1）When preparing the 1/5-1/10 of acid solution total amount, improve to reaction system and add water Flow, flow is 2-4 times of acid solution and alkaline solution total flow；
（8）It treats after reaction, to carry out aging, after aging, wash, filtering；
（9）The deionized water containing potassium nitrate and calgon is added in filter cake, after stirring evenly, spray drying is carried out and is made Copper bismuth catalyst.
The method of the present invention step（1）In, mantoquita in copper sulphate, copper nitrate, copper acetate or copper chloride at least one Kind, it is preferably copper nitrate.The molar concentration control of mantoquita is in 0.6 ~ 3.0mol/L, preferably 1.0 ~ 2.5 mol/ in acid solution L.Bismuth salt is selected from least one of bismuth nitrate, bismuth sulfate or bismuth acetate, is preferably bismuth nitrate.Bismuth salt rubs in acid solution Your concentration is controlled in 0.01 ~ 0.05mol/L, is preferably 0.02 ~ 0.04mol/L.Acid solution pH value for 0 ~ 2.0, preferably 0.5 ~ 1.0。
Step of the present invention（2）In, precipitating reagent is selected from sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, ammonium hydroxide, bicarbonate At least one of sodium is preferably sodium carbonate.The molar concentration of precipitating reagent is 0.1 ~ 3.0 mol/L, is preferably 0.5 ~ 2.0 mol/L。
Step of the present invention（3）In, bottom water is added in into reaction kettle, addition is step（1）The 0.15 of acid solution volume ~ 0.4 times, preferably 0.2 ~ 0.3 times.Heating is heated to 30 ~ 80 DEG C of reaction temperature, and optimal is 40~70 DEG C.It is constantly stirred in reaction process It mixes.
Step of the present invention（4）In, acid solution and alkaline solution are added to certain speed cocurrent in reaction kettle, are kept The pH value control of reaction is 5.0~8.0, and optimal is 6.0~7.0, and reaction temperature is controlled at 30 ~ 80 DEG C, and optimal is 40~70 DEG C. The bottom of reaction kettle is passed through CO2, CO2It is diluted using nitrogen, CO2Concentration for 20%~60%, optimal is 30%~50%.Flow is 150 ~ 1000ml/min is preferably 600 ~ 800ml/min.CO2Concentration is volumetric concentration.
Step of the present invention（5）In, aging temperature is controlled at 30 ~ 80 DEG C, and optimal is 40~70 DEG C.The control of aging pH value exists 5.0~8.0, optimal is 6.0~7.0, and ageing time was controlled at 10~70 minutes, optimal 20 ~ 50 minutes.
Step of the present invention（6）In, the control of the pH value of reaction is 5.0~8.0, and optimal is 6.0~7.0, reaction temperature control At 30 ~ 80 DEG C, optimal is 40~70 DEG C.The CO being passed through of reaction kettle2Concentration is 20%~60%, and optimal is 30%~50%.Flow It is preferably 350 ~ 450ml/min, CO for 150 ~ 1000ml/min2Concentration is volumetric concentration.
Step of the present invention（7）In, the control of the pH value of reaction is 5.0~8.0, and optimal is 6.0~7.0, reaction temperature control At 30 ~ 80 DEG C, optimal is 40~70 DEG C.The CO of reaction kettle2Concentration is 20%~60%, and optimal is 30%~50%.Flow for 150 ~ 1000ml/min is preferably 150 ~ 250ml/min, CO2Concentration is volumetric concentration.
Step of the present invention（8）In, after reaction, when ageing time is 0.5~4.0 small, when being preferably 1.0~2.5 small. It is washed, is filtered using the deionized water of temperature similary with aging.
Step of the present invention（9）In, the deionized water containing potassium nitrate and calgon is added in filter cake, is stirred evenly Afterwards, carry out being spray-dried obtained copper bismuth catalyst.Potassium nitrate addition is 1%~20% of water quality in slurries, is preferably 5% ~15%.The butt of slurry is 15%~45%, preferably 25%~35%.Calgon addition is the 5% of catalyst weight ~ 25%, it is preferably 10% ~ 20%.
A kind of catalyst prepared using the above method, based on the weight of catalyst, the content of copper oxide for 30wt% ~ 80wt%, is preferably 40wt% ~ 70wt%, and the content of bismuth oxide is the wt% of 1.0wt% ~ 10.0, is preferably the wt% of 2.5 wt%~6.5, The particle size of catalyst at least more than 93% is between 10-30um.
Catalyst is handled before use using carbon dioxide, and the basic sites of catalyst surface is made to be inhaled by carbon dioxide Attached, during the use of catalyst, the basic sites of catalyst are constantly released with the variation of temperature, control catalysis The activity of agent improves the selectivity of propilolic alcohol, and effectively inhibits the loss of metal, and can extend catalyst uses week It is phase, with good economic efficiency.
Specific embodiment
Below by the technical solution that embodiment and comparative example further illustrate the present invention, but protection scope of the present invention is not It is limited by example.Dandong is used after the wear-resisting property of catalyst is ultrasonically treated using cell crushing instrument in the present invention again Hundred special BT-9300ST laser particle analyzers analyses, it is 3000 times to be ultrasonically treated number, and the power of Ultrasonic Cell Disruptor is 600W. The reactivity evaluation of catalyst carries out in slurry bed, and using formaldehyde and acetylene reaction system, reaction temperature is 90 DEG C, reaction Pressure is 0.75MPa, and acetylene flow velocity is 80mL/min, and the formaldehyde addition of catalyst amount 30g, concentration 15wt% are 150ml.% is mass percent unless otherwise specified for following embodiment and comparative example.
Embodiment 1
（1）Weigh 715gCu (NO3)2–3H2O and 30g Bi (NO3)3–5H2O is put into the water containing 25g nitric acid, treats its dissolving After be settled to 2000ml.
（2）Weigh 300 grams of Na2CO3It is configured to 2000ml solution.
（3）500ml deionized waters are added in a kettle, are stirred and heated to 50 DEG C.
（4）Acid solution and alkaline solution cocurrent are added in reaction kettle, the pH value for controlling reactant is 6.0, reaction Temperature is 50 DEG C.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, and gas flow rate is 500ml/min。
（5）Work as step（1）Acid solution 1700 ml of residue when, stop reaction, carry out aging, aging condition and reaction Condition is identical, and ageing time is 30 minutes.
（6）After aging, continue to react, when remaining acid solution is 1000 ml, in acid solution and alkali Property solution cocurrent while add in, 1200 ml of deionized water is equably added in into reaction kettle, the addition speed of water is 50 ml.min-1.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, and gas flow rate is 400ml/min。
（7）When remaining acid solution is 400 ml, while acid solution and alkaline solution cocurrent add in, uniformly Ground adds in 2400 ml of deionized water into reaction kettle, and the addition speed of water is 150 ml.min-1.Reaction kettle during the reaction Bottom be passed through and use N2Diluted CO2, CO2Concentration is 40%, gas flow rate 200ml/min.
（8）It treats after reaction, temperature is reduced to 45 DEG C, carries out aging.After when aging 1.5 is small, with 45 DEG C of deionizations Water is washed, and in the presence of washing into cleaning solution without sodium ion, stops washing.
（9）Filter cake is added in 580 grams of water containing 60g potassium nitrate and 31 grams of calgons, water temperature is controlled 45 DEG C, it is beaten uniform to material, the drying of catalyst is carried out with spray-dried instrument.
（10）30g catalyst is taken to be put into reactor, temperature of reactor is then risen to 25 DEG C, is passed through carbon dioxide, two The flow velocity 3ml/min of carbonoxide, is passed through time 2 h.Then reduce temperature to 20 DEG C, with nitrogen purging 2 it is small when, the stream of nitrogen Speed is 2 ml/min, when purge time is 2 small.Sample number into spectrum is A, and sample composition is：CuO:65.1%, Bi2O3:3.1%.Granularity Distribution is shown in Table 1, and evaluation result is shown in Table 2 and table 3.
Embodiment 2
（1）Weigh 650gCu (NO3)2–3H2O and 33g Bi (NO3)3–5H2O is put into the water containing 25g nitric acid, treats its dissolving After be settled to 2000ml.
（2）Weigh 300 grams of Na2CO3It is configured to 2000ml solution.
（3）600ml deionized waters are added in a kettle, are then stirred and heated to 45 DEG C.
（4）Acid solution and alkaline solution cocurrent are added in reaction kettle, the pH value for controlling reactant is 6.5, reaction Temperature is 45 DEG C.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, and gas flow rate is 500ml/min。
（5）Work as step（1）Acid solution 1600 ml of residue when, stop reaction, carry out aging, aging condition and reaction Condition is identical, and ageing time is 20 minutes.
（6）After aging, continue to react, when remaining acid solution is 1200 ml, in acid solution and alkali Property solution cocurrent while add in, 1800 ml of deionized water is equably added in into reaction kettle, the addition speed of water is 50 ml.min-1.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, and gas flow rate is 400ml/min。
（7）When remaining acid solution is 300 ml, while acid solution and alkaline solution cocurrent add in, uniformly Ground adds in 1800 ml of deionized water into reaction kettle, and the addition speed of water is 150 ml.min-1.Reaction kettle during the reaction Bottom be passed through and use N2Diluted CO2, CO2Concentration is 40%, gas flow rate 200ml/min.
（8）It treats after reaction, temperature is reduced to 40 DEG C, carries out aging.After when aging 1.5 is small, with 40 DEG C of deionizations Water is washed, and in the presence of washing into cleaning solution without sodium ion, stops washing.
（9）Filter cake is added in 580 grams of water containing 65g potassium nitrate and 30 grams of calgons, water temperature is controlled 45 DEG C, it is beaten uniform to material, the drying of catalyst is carried out with spray-dried instrument.
(10）30g catalyst is taken to be put into reactor, temperature of reactor is then risen to 25 DEG C, is passed through carbon dioxide, two The flow velocity 3ml/min of carbonoxide, be passed through the time 1.5 it is small when.Then reduce temperature to 15 DEG C, with nitrogen purging 2 it is small when, nitrogen Flow velocity is 2ml/min, when purge time is 2 small.Sample number into spectrum is B, and sample composition is：CuO:63.5%, Bi2O3:3.8%.Grain Degree distribution is shown in Table 1, and evaluation result is shown in Table 2 and table 3.
Embodiment 3
（1）Weigh 956gCu (NO3)2–3H2O and 42.5g Bi (NO3)3–5H2O is put into the water containing 40g nitric acid, treats that its is molten 2000ml is settled to after solution.
（2）Weigh 320 grams of Na2CO3It is configured to 2000ml solution.
（3）600ml deionized waters are added in a kettle, are stirred and heated to 65 DEG C.
（4）Acid solution and alkaline solution cocurrent are added in reaction kettle, the pH value for controlling reactant is 6.8, reaction Temperature is 65 DEG C.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, and gas flow rate is 500ml/min。
（5）Work as step（1）Acid solution 1800 ml of residue when, stop reaction, carry out aging, aging condition and reaction Condition is identical, and ageing time is 25 minutes.
（6）After aging, continue to react, when remaining acid solution is 1000 ml, in acid solution and alkali Property solution cocurrent while add in, 1200 ml of deionized water is equably added in into reaction kettle, the addition speed of water is 50 ml.min-1.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, and gas flow rate is 400ml/min。
（7）When remaining acid solution is 400 ml, while acid solution and alkaline solution cocurrent add in, uniformly Ground adds in 2400 ml of deionized water into reaction kettle, and the addition speed of water is 150 ml.min-1.Reaction kettle during the reaction Bottom be passed through and use N2Diluted CO2, CO2Concentration is 40%, gas flow rate 200ml/min.
（8）Temperature is reduced to 60 DEG C, carries out aging.It after when aging 2.0 is small, is washed, is washed with 60 DEG C of deionized waters Into cleaning solution without sodium ion in the presence of, stop washing.
（9）Filter cake is added in 700 grams of water containing 75g potassium nitrate and 38 grams of calgons, water temperature is controlled 60 DEG C, it is beaten uniform to material, the drying of catalyst is carried out with spray-dried instrument.
(10）30g catalyst is taken to be put into reactor, temperature of reactor is then risen to 25 DEG C, is passed through carbon dioxide gas Body, the flow velocity 3ml/min of carbon dioxide, is passed through time 2 h.Then reduce temperature to 10 DEG C, with nitrogen purging 2 it is small when, nitrogen The flow velocity of gas is 4ml/min, when purge time is 2 small.Sample number into spectrum is C, and sample composition is：CuO:61.2%, Bi2O3: 3.0%.Size distribution is shown in Table 1, and evaluation result is shown in Table 2 and table 3.
Embodiment 4
The preparation method and processing method of catalyst are shown in Table 1 with embodiment 3, sample number into spectrum D, size distribution.Catalyst is commented Valency condition：It is passed through into reactor containing the formalin 150ml that 1.0% diethylene glycol (DEG) mass concentration is 15%, is stirred continuously.So After be passed through acetylene gas, gas flow is 80 ml/min, temperature of reactor is risen to 100 DEG C, reaction pressure is controlled 0.75 MPa is reacted, reaction 6 it is small when after sampling analysis.Stability test is then proceeded by, by reaction solution all with fresh The 15% formalin 150ml containing 1.0% diethylene glycol (DEG) is cemented out, and reaction is re-started, when period of a permutation is 6 small.Reaction is total When time is 200 small.Estimation of stability the results are shown in Table 3.
Comparative example 1
With embodiment 3 the difference is that without step（10）, sample number into spectrum E, size distribution is shown in Table 1, and evaluation result is shown in Table 2 With table 3.
Comparative example 2
The catalyst that there is same composition with embodiment 3, sample are prepared by the technical solution of CN201210397161.X embodiments 1 Number is F, and size distribution is shown in Table 1, and evaluation result is shown in Table 2 and table 3.
Comparative example 3
With embodiment 3, the difference is that deionized water is no longer added in into reaction kettle during the reaction.Sample number into spectrum is G, Size distribution is shown in Table 1, and evaluation result is shown in Table 2 and table 3.
The distribution of particles of 1 catalyst of table
The evaluation result of 2 catalyst of table
The estimation of stability result of 3 catalyst of table（Operate 200 it is small when）

Claims (17)

  1. A kind of 1. method for preparing Isosorbide-5-Nitrae-butynediols, it is characterised in that：Including following content：After carbon dioxide treatment Copper bismuth composite oxide is catalyst, and reaction temperature is 80 ~ 150 DEG C, and reaction pressure is 0.2 ~ 2.0MPa, and the flow of acetylene is 40 ~ 200ml/min, formalin mass concentration are 4% ~ 25%, and catalyst amount is the same as the formalin quality volume added in Than for 1:3~1:10.
  2. 2. according to the method described in claim 1, it is characterized in that：Reaction temperature is 90 ~ 120 DEG C, reaction pressure for 0.5 ~ 1.0 MPa, the flow of acetylene is 80 ~ 150 ml/min, and formalin mass concentration is 9% ~ 15%, and catalyst amount is same to be added The formalin mass volume ratio entered is 1:5~1:7.
  3. 3. according to the method described in claim 1, it is characterized in that：It is containing mass percentage in the formalin 0.5% ~ 3.5% diethylene glycol (DEG).
  4. 4. according to the method described in claim 1, it is characterized in that：Carbon dioxide treatment step is divided into 2 stages, first stage When processing time 1 ~ 4 is small at 10 ~ 45 DEG C, 1 ~ 8ml/min of flow velocity of carbon dioxide, second stage is purged with nitrogen, nitrogen 1 ~ 8ml/min of flow velocity of gas, treatment temperature are 0 ~ 30 DEG C, when processing time is 1 ~ 5 small.
  5. 5. according to the method described in claim 4, it is characterized in that：Processing time 1.5 ~ 3 at 20 ~ 30 DEG C first stage is small When, the flow velocity of carbon dioxide is 2 ~ 4 ml/min, and the flow velocity of nitrogen is 2 ~ 4 ml/min, and treatment temperature is 10 ~ 20 DEG C, during processing Between for 2 ~ 3 it is small when.
  6. 6. according to the method described in claim 1, it is characterized in that：The copper bismuth composite oxide catalyst by weight, The content of copper oxide is 30wt% ~ 80wt%, and the content of bismuth oxide is the wt% of 1.0wt% ~ 10.0.
  7. 7. according to the method described in claim 1, it is characterized in that：The copper bismuth composite oxide catalyst uses such as lower section It is prepared by method：
    （1）Prepare the acid solution containing mantoquita and bismuth salt；
    （2）Prepare precipitant solution；
    （3）Bottom water is added in into reaction kettle, heating is heated to reaction temperature；
    （4）The mode of cocurrent is taken, by step（1）Acid solution and step（2）Precipitant solution be added drop-wise in reaction kettle, In reaction process gas CO is passed through from reactor bottom2；
    （5）When remaining acid solution is step（1）When preparing the 4/5 ~ 9/10 of acid solution total amount, stop reaction, carry out aging；
    （6）After aging, continue to react and continue to be passed through gas CO from reactor bottom2, when remaining acid solution is step Suddenly（1）When preparing the 1/2-3/5 of acid solution total amount, deionized water is added in reaction system, flow is acid solution and alkali 0.5-1.5 times of property solution total flow；
    （7）When remaining acid solution is step（1）When preparing the 1/5-1/10 of acid solution total amount, improve to reaction system and add water Flow, flow is 2-4 times of acid solution and alkaline solution total flow；
    （8）It treats after reaction, to carry out aging, after aging, wash, filtering；
    （9）The deionized water containing potassium nitrate and calgon is added in filter cake, after stirring evenly, spray drying is carried out and is made Copper bismuth catalyst.
  8. 8. according to the method described in claim 7, it is characterized in that：Step（1）In, mantoquita is selected from copper sulphate, copper nitrate, acetic acid At least one of copper or copper chloride, the molar concentration of mantoquita is controlled in 0.6 ~ 3.0mol/L in acid solution, and bismuth salt is selected from At least one of bismuth nitrate, bismuth sulfate or bismuth acetate, in acid solution the molar concentration control of bismuth salt 0.01 ~ 0.05mol/L, acid solution pH value are 0 ~ 2.0.
  9. 9. according to the method described in claim 7, it is characterized in that：Step（2）In, precipitating reagent is selected from sodium carbonate, hydroxide At least one of sodium, potassium carbonate, potassium hydroxide, ammonium hydroxide, sodium acid carbonate, the molar concentration of precipitating reagent is 0.1 ~ 3.0 mol/L.
  10. 10. according to the method described in claim 7, it is characterized in that：Step（3）In, bottom water, addition are added in into reaction kettle For step（1）0.15 ~ 0.4 times of acid solution volume, heating are heated to 30 ~ 80 DEG C of reaction temperature.
  11. 11. according to the method described in claim 7, it is characterized in that：Step（4）In, acid solution and alkaline solution cocurrent add Enter into reaction kettle, keep the pH value control of reaction 5.0~8.0, reaction temperature control is at 30 ~ 80 DEG C, the bottom of reaction kettle It is passed through CO2, CO2It is diluted using nitrogen, CO2Volumetric concentration for 20%~60%, flow is 150 ~ 1000ml/min.
  12. 12. according to the method described in claim 7, it is characterized in that：Step（5）In, aging temperature is controlled at 30 ~ 80 DEG C, always Change pH value control 5.0~8.0, ageing time was controlled at 10~70 minutes.
  13. 13. according to the method described in claim 7, it is characterized in that：Step（6）In, the control of the pH value of reaction 5.0~8.0, Reaction temperature control is at 30 ~ 80 DEG C, the CO being passed through of reaction kettle2Volumetric concentration is 20%~60%, and flow is 150 ~ 1000ml/ min。
  14. 14. according to the method described in claim 7, it is characterized in that：Step（8）In, after reaction, ageing time 0.5 ~4.0 it is small when.
  15. 15. according to the method described in claim 7, it is characterized in that：Step（9）In, it is added in filter cake and contains potassium nitrate and six The deionized water of sodium metaphosphate after stirring evenly, carries out being spray-dried obtained copper bismuth catalyst.
  16. 16. according to the method for claim 15, it is characterised in that：Potassium nitrate addition be slurries in water quality 1%~ 20%, the butt of slurry is 15%~45%, and calgon addition is the 5% ~ 25% of catalyst weight.
  17. 17. according to the method described in claim 7, it is characterized in that：The catalyst of preparation, based on the weight of catalyst, oxidation The content of copper is 30wt% ~ 80wt%, and the content of bismuth oxide is the wt% of 1.0wt% ~ 10.0, the particle size at least 93% of catalyst with On between 10-30um.
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