CN108069827B - Method for preparing 1, 4-butynediol and co-producing propiolic alcohol - Google Patents

Method for preparing 1, 4-butynediol and co-producing propiolic alcohol Download PDF

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CN108069827B
CN108069827B CN201610991012.4A CN201610991012A CN108069827B CN 108069827 B CN108069827 B CN 108069827B CN 201610991012 A CN201610991012 A CN 201610991012A CN 108069827 B CN108069827 B CN 108069827B
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reaction
catalyst
flow rate
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copper
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CN108069827A (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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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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Abstract

The invention discloses a method for preparing 1, 4-butynediol, which comprises the following steps: the method comprises the steps of taking a copper bismuth composite oxide treated by carbon dioxide as a catalyst, wherein the reaction temperature is 80-150 ℃, the preferable temperature is 90-120 ℃, the reaction pressure is 0.2-2.0 MPa, the preferable pressure is 0.5-1.0 MPa, the flow rate of acetylene is 40-200 ml/min, the preferable flow rate is 80-150 ml/min, the mass concentration of a formaldehyde aqueous solution is 4-25%, the preferable flow rate is 9-15%, and the mass-volume ratio of the catalyst to the added formaldehyde aqueous solution is 1: 3-1: 10, and the preferable flow rate is 1: 5-1: 7. The method has the advantages of high yield of the propiolic alcohol, long running period and the like.

Description

Method for preparing 1, 4-butynediol and co-producing propiolic alcohol
Technical Field
The invention relates to a method for preparing 1, 4-butynediol and coproducing propargyl alcohol, in particular to a method for preparing 1, 4-butynediol and coproducing propargyl alcohol by ethynylation of formaldehyde.
Background
The process for industrially producing the 1, 4-butynediol is mainly an acetylenic aldehyde method (Reppe method), and domestic production enterprises such as Shanxi three-dimensional, Sichuan Tianhua, Xinjiang Meike chemical industry, China electric China petrochemical Ningxia energy chemical industry, Xinjiang Tianye, inner Mongolian Guyidong, Sichuan Weini wheel factories and the like all adopt the technology. In the 70's of the 20 th century, a modified Reppe process was developed, which employs a slurry bed or suspension bed technique, and the reaction was carried out under normal or low pressure. However, the improved Reppe process has higher requirements on the catalyst, and the particle size suitable for industrialization is 1-50 μm. The catalyst has a particle size of more than 50 μm, and the activity is considerably lowered, but if it is less than 1 μm, the filtration is difficult. The profit of enterprises is reduced continuously due to the continuous reduction of the price of the 1, 4-butanediol in recent years, and the price of the propiolic alcohol is high due to the continuous increase of the downstream product market, so that the more the propiolic alcohol is co-produced while the 1, 4-butynediol is produced, the greater the profit of the enterprises is.
US4110249 and US4584418 and CN1118342A disclose unsupported malachite, unsupported copper/bismuth oxide catalysts, respectively, which are not attrition resistant and are prone to metal component loss.
US3920759 and CN102125856A disclose a copper bismuth supported catalyst using magnesium silicate and kaolin as carriers, respectively, for the catalytic reaction of synthesizing 1, 4-butynediol by the reaction of formaldehyde and acetylene. However, the catalyst has the following defects: (1) the carrier magnesium silicate is unstable and can be dissolved in a reaction system, so that the service life is short; (2) the catalyst has more dosage and higher content of metal copper oxide, is easy to agglomerate, cannot fully exert the catalytic effect of each active center, and causes the waste of copper resources.
CN201210157882.3 discloses a copper bismuth catalyst and a preparation method thereof, the steps of which are as follows: dripping alcohol solution of organic silicon source into mixed solution containing copper salt, bismuth salt, magnesium salt and dispersant, regulating pH value of the mixed solution with alkali solution to obtain mixed precipitate, further aging, washing the precipitate with dispersant as medium, and roasting in inert atmosphere. The catalyst has high activity, but has high cost and poor mechanical strength, and is difficult to realize industrialization.
CN20121039739X discloses a catalyst for the production of 1, 4-butynediol and a preparation method thereof, wherein nano-silica is adopted as a carrier, and copper and bismuth are adsorbed on the carrier by a precipitation deposition method. The catalyst prepared by the method has better activity and selectivity, but because urea is used as a precipitator, the reaction process is slow, a large amount of ammonia gas can be generated, the environmental pollution is caused, and the prepared catalyst has small particles and is not easy to filter.
CN103170342A discloses a nano CuO-Bi for synthesizing 1, 4-butynediol2O3The catalyst is characterized in that a proper amount of surfactant and sodium hydroxide solution are respectively added into the copper bismuth acidic aqueous solution, and the nano catalyst is prepared by pyrolysis at a certain temperature. The particle size of the prepared catalyst is 10-80 nm. The catalyst has high reaction activity, but is used for slurry bed or suspension bed due to small particles, and the particles are small and difficult to filter. And nano CuO-Bi2O3The active center is exposed much and is easily inactivated.
CN103157500A discloses a preparation method of a supported catalyst, which adopts a mesoporous molecular sieve as a carrier, and utilizes an impregnation method to load soluble copper salt and bismuth salt on the carrier, wherein the size of the prepared catalyst particles is 10-80 nanometers, and the catalyst has higher activity, but the catalyst particles are too small to be filtered.
CN103480382A discloses a catalyst for producing 1, 4-butynediol and a preparation method thereof, wherein the method adopts acidified nano-silica as a carrier, copper and bismuth are adsorbed on the carrier by impregnation and deposition precipitation methods, and then the finished product of the catalyst is obtained by drying and roasting. The catalyst prepared by the method has good activity and high strength. However, the catalyst powder prepared by the method has poor uniformity of particle size and more small particles, and is not beneficial to the industrial operation of the catalyst.
In conclusion, the catalyst for producing 1, 4-butynediol in the prior art generally has the technical problems of non-moderate catalyst particle size, poor wear resistance and stability of the catalyst, easy loss of active components and the like, and the yield of the propiolic alcohol is very small while the 1, 4-butynediol is produced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for preparing 1, 4-butynediol and coproducing propiolic alcohol, which has the advantages of high yield of propiolic alcohol, long running period and the like.
A process for preparing 1, 4-butynediol comprising the steps of: the method comprises the steps of taking a copper bismuth composite oxide treated by carbon dioxide as a catalyst, wherein the reaction temperature is 80-150 ℃, the preferable temperature is 90-120 ℃, the reaction pressure is 0.2-2.0 MPa, the preferable pressure is 0.5-1.0 MPa, the flow rate of acetylene is 40-200 ml/min, the preferable flow rate is 80-150 ml/min, the mass concentration of a formaldehyde aqueous solution is 4-25%, the preferable flow rate is 9-15%, and the mass-volume ratio of the catalyst to the added formaldehyde aqueous solution is 1: 3-1: 10, and the preferable flow rate is 1: 5-1: 7.
In the method, the formaldehyde aqueous solution contains 0.5-3.5 wt% of diglycol, preferably 0.8-2.0 wt%. In the alkyne hydroformylation reaction, the diethylene glycol is added into the reaction system, so that the selectivity of the propiolic alcohol is further improved, the loss of metal is effectively inhibited, the service life of the catalyst can be prolonged, and the catalyst has good economic benefit.
In the above method, the carbon dioxide treatment step is divided into 2 stages. In the first stage, the treatment time is 1-4 hours, preferably 20-30 ℃, at 10-45 ℃, the treatment time is preferably 1.5-3 hours, and the flow rate of carbon dioxide is 1-8 ml/min, preferably 2-4 ml/min. And in the second stage, nitrogen is used for purging, the flow rate of the nitrogen is 1-8 ml/min, preferably 2-4 ml/min, the treatment temperature is 0-30 ℃, preferably 10-20 ℃, and the treatment time is 1-5 hours, preferably 2-3 hours.
In the method, the copper oxide content of the copper bismuth composite oxide catalyst is 30wt% -80 wt%, preferably 40wt% -70 wt%, and the bismuth oxide content is 1.0wt% -10.0 wt%, preferably 2.5 wt% -6.5 wt%.
In the above method, the copper bismuth composite oxide catalyst is preferably prepared by the following method. Through several stages of coprecipitation reactions, different amounts of deionized water are added into a reaction system at different stages of the coprecipitation reaction to change the supersaturation degree of a reaction product, so that the prepared catalyst particles are large, centralized in distribution and excellent in wear resistance.
A preparation method of a copper-bismuth composite oxide catalyst comprises the following steps:
(1) preparing an acidic solution containing copper salt and bismuth salt;
(2) preparing a precipitant solution;
(3) adding bottom water into the reaction kettle, and heating to a reaction temperature;
(4) dropwise adding the acidic solution obtained in the step (1) and the precipitant solution obtained in the step (2) into a reaction kettle in a parallel flow mode, and introducing CO gas from the bottom of the reaction kettle in the reaction process2；
(5) When the residual acidic solution is 4/5-9/10 of the total amount of the acidic solution prepared in the step (1), stopping the reaction, and aging;
(6) after the aging is finished, the reaction is continued and gas CO is continuously introduced from the bottom of the reaction kettle2When the residual acid solution is 1/2-3/5 of the total amount of the acid solution prepared in the step (1), adding deionized water into the reaction system, wherein the flow rate of the deionized water is 0.5-1.5 times of the total flow rate of the acid solution and the alkaline solution;
(7) when the residual acid solution is 1/5-1/10 of the total amount of the acid solution prepared in the step (1), the flow rate of adding water into the reaction system is increased, and the flow rate is 2-4 times of the total flow rate of the acid solution and the alkaline solution;
(8) after the reaction is finished, aging, and after the aging is finished, washing and filtering;
(9) and adding deionized water containing potassium nitrate and sodium hexametaphosphate into the filter cake, uniformly stirring, and performing spray drying to obtain the copper bismuth catalyst.
In step (1) of the method of the present invention, the copper salt is at least one selected from copper sulfate, copper nitrate, copper acetate and copper chloride, and is preferably copper nitrate. The molar concentration of the copper salt in the acidic solution is controlled to be 0.6-3.0 mol/L, preferably 1.0-2.5 mol/L. The bismuth salt is at least one selected from bismuth nitrate, bismuth sulfate and bismuth acetate, and is preferably bismuth nitrate. The molar concentration of the bismuth salt in the acid solution is controlled to be 0.01-0.05 mol/L, preferably 0.02-0.04 mol/L. The pH of the acidic solution is 0 to 2.0, preferably 0.5 to 1.0.
In step (2) of the present invention, the precipitant is at least one selected from sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, ammonia water and sodium bicarbonate, and preferably sodium carbonate. The molar concentration of the precipitant is 0.1-3.0 mol/L, preferably 0.5-2.0 mol/L.
In the step (3), bottom water is added into the reaction kettle, and the adding amount is 0.15-0.4 time, preferably 0.2-0.3 time of the volume of the acid solution in the step (1). Heating to the reaction temperature of 30-80 ℃, and optimally 40-70 ℃. Stirring is continuously carried out in the reaction process.
In the step (4), an acidic solution and an alkaline solution are added into a reaction kettle in a parallel flow mode at a certain speed, the pH value of the reaction is kept to be controlled to be 5.0-8.0, the optimal pH value is 6.0-7.0, the reaction temperature is controlled to be 30-80 ℃, and the optimal pH value is 40-70 ℃. Introducing CO into the bottom of the reaction kettle2，CO2Diluting with nitrogen, CO2The concentration of (A) is 20-60%, preferably 30-50%. The flow rate is 150 to 1000ml/min, preferably 600 to 800 ml/min. CO 22The concentrations are volume concentrations.
In the step (5), the aging temperature is controlled to be 30-80 ℃, and the optimal temperature is 40-70 ℃. The aging pH value is controlled to be 5.0-8.0, the optimal value is 6.0-7.0, and the aging time is controlled to be 10-70 minutes, and the optimal value is 20-50 minutes.
In the step (6), the pH value of the reaction is controlled to be 5.0-8.0, the optimal pH value is 6.0-7.0, the reaction temperature is controlled to be 30-80 ℃, and the optimal pH value is 40-70 ℃. CO introduced into the reactor2The concentration is 20-60%, optimally 30-50%. The flow rate is 150-1000 ml/min, preferably 350-450 ml/min, CO2The concentrations are volume concentrations.
In the step (7), the pH value of the reaction is controlled to be 5.0-8.0, the optimal pH value is 6.0-7.0, the reaction temperature is controlled to be 30-80 ℃, and the optimal pH value is 40-70 ℃. CO of reaction kettle2The concentration is 20-60%, optimally 30-50%. The flow rate is 150-1000 ml/min, preferably 150-250 ml/min, CO2The concentrations are volume concentrations.
In the step (8), after the reaction is finished, the aging time is 0.5 to 4.0 hours, preferably 1.0 to 2.5 hours. And washing with deionized water at the same temperature as the aged deionized water, and filtering.
In the step (9), deionized water containing potassium nitrate and sodium hexametaphosphate is added into the filter cake, and after the deionized water is uniformly stirred, the mixture is subjected to spray drying to obtain the copper bismuth catalyst. The adding amount of potassium nitrate is 1-20% of the mass of water in the slurry, preferably 5-15%. The dry basis of the slurry is 15 to 45 percent, preferably 25 to 35 percent. The adding amount of the sodium hexametaphosphate is 5-25% of the weight of the catalyst, and preferably 10-20%.
According to the weight of the catalyst, the content of copper oxide is 30wt% -80 wt%, preferably 40wt% -70 wt%, the content of bismuth oxide is 1.0wt% -10.0 wt%, preferably 2.5 wt% -6.5 wt%, and the particle size of the catalyst is at least 93% and is between 10-30 mu m.
The catalyst is treated by carbon dioxide before use, so that the alkaline site on the surface of the catalyst is adsorbed by the carbon dioxide, and is released continuously along with the change of temperature in the use process of the catalyst, so that the activity of the catalyst is controlled, the selectivity of the propiolic alcohol is improved, the loss of metal is effectively inhibited, the service life of the catalyst can be prolonged, and the catalyst has good economic benefit.
Detailed Description
The technical solutions of the present invention are further illustrated by the following examples and comparative examples, but the scope of the present invention is not limited by the examples. The wear resistance of the catalyst is subjected to ultrasonic treatment by a cell disruptor and then analyzed by a BT-9300ST laser particle size analyzer in Dandongboet, the ultrasonic treatment frequency is 3000 times, and the power of the ultrasonic disruptor is 600W. The evaluation of the reactivity of the catalyst is carried out on a slurry bed, a formaldehyde and acetylene reaction system is adopted, the reaction temperature is 90 ℃, the reaction pressure is 0.75MPa, the acetylene flow rate is 80mL/min, the catalyst dosage is 30g, and the formaldehyde addition with the concentration of 15 wt% is 150 mL. The following examples and comparative examples are all% by mass unless otherwise specified.
Example 1
(1) Weighing 715gCu (NO)3)23H2O and 30g Bi (NO)3)35H2O is put into water containing 25g of nitric acid, and the volume is adjusted to 2000ml after the O is dissolved.
(2) Weighing 300 g of Na2CO32000ml of solution was prepared.
(3) 500ml of deionized water was added to the reaction kettle, stirred and heated to 50 ℃.
(4) And (3) adding the acidic solution and the alkaline solution into the reaction kettle in a concurrent flow manner, controlling the pH value of the reactants to be 6.0, and controlling the reaction temperature to be 50 ℃. N is introduced into the bottom of the reaction kettle in the reaction process2Diluted CO2，CO2The concentration was 40% and the gas flow rate was 500 ml/min.
(5) When 1700 ml of the acid solution in the step (1) is remained, stopping the reaction, and carrying out aging under the same aging conditions as the reaction conditions for 30 minutes.
(6) After the aging is finished, the reaction is continued, when the residual acid solution is 1000ml, 1200 ml of deionized water is uniformly added into the reaction kettle while the acid solution and the alkaline solution are added in a concurrent flow manner, and the adding speed of the water is 50 ml.min-1. N is introduced into the bottom of the reaction kettle in the reaction process2Diluted CO2，CO2The concentration was 40% and the gas flow rate was 400 ml/min.
(7) When the residual acid solution is 400ml, 2400 ml of deionized water is uniformly added into the reaction kettle while the acid solution and the alkaline solution are added in a concurrent flow manner, and the adding speed of the water is 150 ml.min-1. N is introduced into the bottom of the reaction kettle in the reaction process2Diluted CO2，CO2The concentration was 40% and the gas flow rate was 200 ml/min.
(8) After the reaction is finished, the temperature is reduced to 45 ℃ for aging. After aging for 1.5 hours, washing with deionized water at 45 ℃, and stopping washing until no sodium ions exist in the washing liquid.
(9) The filter cake was added to 580 g of water containing 60g of potassium nitrate and 31 g of sodium hexametaphosphate, the water temperature was controlled at 45 ℃, the slurry was stirred until the material was uniform, and the catalyst was dried by a spray dryer.
(10) 30g of catalyst is taken and put into a reactor, then the temperature of the reactor is raised to 25 ℃, carbon dioxide is introduced, the flow rate of the carbon dioxide is 3ml/min, and the introduction time is 2 hours. Then the temperature is reduced to 20 ℃, and the nitrogen is used for purging for 2 hours, the flow rate of the nitrogen is 2ml/min, and the purging is carried outThe time is 2 hours. Sample number is a, sample composition is: 65.1% of CuO and Bi2O33.1 percent. The particle size distribution is shown in Table 1, and the evaluation results are shown in tables 2 and 3.
Example 2
(1) Weighing 650gCu (NO)3)23H2O and 33g Bi (NO)3)35H2O is put into water containing 25g of nitric acid, and the volume is adjusted to 2000ml after the O is dissolved.
(2) Weighing 300 g of Na2CO32000ml of solution was prepared.
(3) 600ml of deionized water was added to the reaction kettle, which was then stirred and heated to 45 ℃.
(4) And (3) adding the acidic solution and the alkaline solution into the reaction kettle in a concurrent flow manner, controlling the pH value of the reactant to be 6.5, and controlling the reaction temperature to be 45 ℃. N is introduced into the bottom of the reaction kettle in the reaction process2Diluted CO2，CO2The concentration was 40% and the gas flow rate was 500 ml/min.
(5) When 1600 ml of the acid solution in the step (1) is remained, stopping the reaction, and carrying out aging under the same aging condition and reaction condition for 20 minutes.
(6) After the aging is finished, the reaction is continued, when the residual acid solution is 1200 ml, 1800 ml of deionized water is uniformly added into the reaction kettle while the acid solution and the alkaline solution are added in a concurrent flow manner, and the adding speed of the water is 50 ml.min-1. N is introduced into the bottom of the reaction kettle in the reaction process2Diluted CO2，CO2The concentration was 40% and the gas flow rate was 400 ml/min.
(7) When the residual acid solution is 300 ml, 1800 ml of deionized water is uniformly added into the reaction kettle while the acid solution and the alkaline solution are added in a concurrent flow manner, and the adding speed of the water is 150 ml.min-1. N is introduced into the bottom of the reaction kettle in the reaction process2Diluted CO2，CO2The concentration was 40% and the gas flow rate was 200 ml/min.
(8) After the reaction is finished, the temperature is reduced to 40 ℃ for aging. And after aging for 1.5 hours, washing with deionized water at 40 ℃, and stopping washing until no sodium ions exist in the washing liquid.
(9) The filter cake was added to 580 g of water containing 65g of potassium nitrate and 30g of sodium hexametaphosphate, the water temperature was controlled at 45 ℃, the slurry was stirred until the material was uniform, and the catalyst was dried by a spray dryer.
(10) 30g of catalyst is taken and put into a reactor, then the temperature of the reactor is raised to 25 ℃, carbon dioxide is introduced, the flow rate of the carbon dioxide is 3ml/min, and the introduction time is 1.5 hours. The temperature was then lowered to 15 ℃ and purged with nitrogen at a flow rate of 2ml/min for 2 hours. Sample number B, sample composition: 63.5% of CuO and Bi2O33.8 percent. The particle size distribution is shown in Table 1, and the evaluation results are shown in tables 2 and 3.
Example 3
(1) 956gCu (NO) was weighed3)23H2O and 42.5g Bi (NO)3)35H2O is put into water containing 40g of nitric acid, and the volume is adjusted to 2000ml after the O is dissolved.
(2) 320 g of Na are weighed2CO32000ml of solution was prepared.
(3) 600ml of deionized water was added to the reaction kettle, stirred and heated to 65 ℃.
(4) And (3) adding the acidic solution and the alkaline solution into the reaction kettle in a concurrent flow manner, controlling the pH value of the reactants to be 6.8 and controlling the reaction temperature to be 65 ℃. N is introduced into the bottom of the reaction kettle in the reaction process2Diluted CO2，CO2The concentration was 40% and the gas flow rate was 500 ml/min.
(5) When 1800 ml of the acid solution in the step (1) is remained, stopping the reaction, and aging for 25 minutes under the same aging condition and reaction condition.
(6) After the aging is finished, the reaction is continued, when the residual acid solution is 1000ml, 1200 ml of deionized water is uniformly added into the reaction kettle while the acid solution and the alkaline solution are added in a concurrent flow manner, and the adding speed of the water is 50 ml.min-1. N is introduced into the bottom of the reaction kettle in the reaction process2Diluted CO2，CO2The concentration was 40% and the gas flow rate was 400 ml/min.
(7) When the residual acid solution is 400ml, 2400 ml of deionized water is uniformly added into the reaction kettle while the acid solution and the alkaline solution are added in a concurrent flow manner, and the adding speed of the water is 150 ml.min-1. N is introduced into the bottom of the reaction kettle in the reaction process2Diluted CO2，CO2The concentration was 40% and the gas flow rate was 200 ml/min.
(8) The temperature is reduced to 60 ℃ and aging is carried out. And after aging for 2.0 hours, washing with deionized water at 60 ℃, and stopping washing until no sodium ions exist in the washing liquid.
(9) The filter cake was added to 700 g of water containing 75g of potassium nitrate and 38 g of sodium hexametaphosphate, the water temperature was controlled at 60 ℃, the slurry was stirred until the material was uniform, and the catalyst was dried by a spray dryer.
(10) 30g of catalyst is taken and put into a reactor, then the temperature of the reactor is raised to 25 ℃, carbon dioxide gas is introduced, the flow rate of the carbon dioxide is 3ml/min, and the introduction time is 2 hours. The temperature was then lowered to 10 ℃ and purged with nitrogen at a flow rate of 4ml/min for 2 hours. Sample number is C, sample composition is: 61.2% of CuO and Bi2O33.0 percent. The particle size distribution is shown in Table 1, and the evaluation results are shown in tables 2 and 3.
Example 4
The preparation and treatment of the catalyst were as in example 3, sample number D, and particle size distribution is shown in Table 1. Evaluation conditions of the catalyst: 150ml of a 15% formaldehyde solution containing 1.0% diethylene glycol by mass was introduced into the reactor, and the mixture was stirred. Then acetylene gas is introduced, the gas flow is 80ml/min, the temperature of the reactor is raised to 100 ℃, the reaction pressure is controlled to be 0.75MPa, the reaction is carried out, and the sampling analysis is carried out after the reaction is carried out for 6 hours. Then, the stability test was continued, and the reaction solution was completely replaced with 150ml of a fresh 15% formaldehyde solution containing 1.0% diethylene glycol, and the reaction was resumed for 6 hours. The total reaction time was 200 hours. The stability evaluation results are shown in Table 3.
Comparative example 1
The difference from example 3 is that step (10) was not included, sample No. E, particle size distribution is shown in Table 1, and evaluation results are shown in tables 2 and 3.
Comparative example 2
A catalyst having the same composition as in example 3 was prepared according to the technical scheme of cn201210397351. x example 1, with sample number F, particle size distribution as shown in table 1, and evaluation results as shown in tables 2 and 3.
Comparative example 3
The same as example 3, except that deionized water was not added to the reaction vessel during the reaction. The sample number is G, the particle size distribution is shown in Table 1, and the evaluation results are shown in tables 2 and 3.
TABLE 1 particle distribution of the catalyst
Figure 133023DEST_PATH_IMAGE002
TABLE 2 evaluation results of catalysts
Figure 508247DEST_PATH_IMAGE004
TABLE 3 evaluation results of catalyst stability (200 hours of operation)
Figure 330709DEST_PATH_IMAGE006

Claims (13)

1. A process for preparing 1, 4-butynediol, characterized by: the method comprises the following steps: the method comprises the following steps of taking a copper-bismuth composite oxide treated by carbon dioxide as a catalyst, controlling the reaction temperature to be 80-150 ℃, the reaction pressure to be 0.2-2.0 MPa, the flow rate of acetylene to be 40-200 mL/min, the mass concentration of a formaldehyde aqueous solution to be 4-25%, and the mass-volume ratio of the catalyst to the added formaldehyde aqueous solution in g/mL to be 1: 3-1: 10; the copper bismuth composite oxide catalyst is prepared by the following method:
(1) preparing an acidic solution containing copper salt and bismuth salt;
(2) preparing a precipitant solution;
(3) adding deionized water into the reaction kettle, and heating to a reaction temperature;
(4) dropwise adding the acidic solution obtained in the step (1) and the precipitant solution obtained in the step (2) into a reaction kettle in a parallel flow mode, and introducing CO gas from the bottom of the reaction kettle in the reaction process2；
(5) When the residual acidic solution is 4/5-9/10 of the total volume of the acidic solution prepared in the step (1), stopping the reaction, and aging;
(6) after the aging is finished, the reaction is continued and gas CO is continuously introduced from the bottom of the reaction kettle2When the residual acid solution is 1/2-3/5 of the total volume of the acid solution prepared in the step (1), adding deionized water into the reaction system, wherein the flow rate of the deionized water is 0.5-1.5 times of the total volume flow rate of the acid solution and the precipitator solution;
(7) when the residual acid solution is 1/5-1/10 of the total amount of the acid solution prepared in the step (1), increasing the flow of water added into the reaction system, wherein the flow is 2-4 times of the total flow of the acid solution and the precipitant solution;
(8) after the reaction is finished, aging, and after the aging is finished, washing and filtering;
(9) adding deionized water containing potassium nitrate and sodium hexametaphosphate into the filter cake, uniformly stirring, and performing spray drying to obtain the copper bismuth catalyst;
wherein the aqueous formaldehyde solution contains 0.5-3.5 wt% of diethylene glycol.
2. The method of claim 1, wherein: the reaction temperature is 90-120 ℃, the reaction pressure is 0.5-1.0 MPa, the flow rate of acetylene is 80-150 mL/min, the mass concentration of the formaldehyde aqueous solution is 9-15%, and the mass volume ratio of the dosage of the catalyst to the mass volume ratio of the added formaldehyde aqueous solution is 1: 5-1: 7 in terms of g/mL.
3. The method of claim 1, wherein: the carbon dioxide treatment step is divided into 2 stages, the first stage is carried out at 10-45 ℃ for 1-4 hours, the flow rate of carbon dioxide is 1-8 mL/min, the second stage is carried out by purging with nitrogen, the flow rate of nitrogen is 1-8 mL/min, the treatment temperature is 0-30 ℃, and the treatment time is 1-5 hours.
4. The method of claim 3, wherein: in the first stage, the treatment time is 1.5-3 hours at 20-30 ℃, the flow rate of carbon dioxide is 2-4 mL/min, the flow rate of nitrogen is 2-4 mL/min, the treatment temperature is 10-20 ℃, and the treatment time is 2-3 hours.
5. The method of claim 1, wherein: the copper-bismuth composite oxide catalyst comprises, by weight, 30-80 wt% of copper oxide and 1.0-10.0 wt% of bismuth oxide.
6. The method of claim 1, wherein: in the step (1), the copper salt is at least one selected from copper sulfate, copper nitrate, copper acetate or copper chloride, the molar concentration of the copper salt in the acidic solution is controlled to be 0.6-3.0 mol/L, the bismuth salt is at least one selected from bismuth nitrate, bismuth sulfate or bismuth acetate, the molar concentration of the bismuth salt in the acidic solution is controlled to be 0.01-0.05 mol/L, and the pH value of the acidic solution is 0-2.0.
7. The method of claim 1, wherein: in the step (2), the precipitator is at least one selected from sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, ammonia water and sodium bicarbonate, and the molar concentration of the precipitator is 0.1-3.0 mol/L.
8. The method of claim 1, wherein: in the step (3), adding bottom water into the reaction kettle, wherein the adding amount is 0.15-0.4 times of the volume of the acid solution in the step (1), and heating to the reaction temperature of 30-80 ℃.
9. The method of claim 1, wherein: in the step (4), the acidic solution and the precipitator solution are added into the reaction kettle in parallel flowKeeping the pH value of the reaction at 5.0-8.0, controlling the reaction temperature at 30-80 ℃, and introducing CO into the bottom of the reaction kettle2，CO2Diluting with nitrogen, CO2The volume concentration of the water is 20-60%, and the flow rate is 150-1000 mL/min.
10. The method of claim 1, wherein: in the step (5), the aging temperature is controlled to be 30-80 ℃, the aging pH value is controlled to be 5.0-8.0, and the aging time is controlled to be 10-70 minutes.
11. The method of claim 1, wherein: in the step (6), the pH value of the reaction is controlled to be 5.0-8.0, the reaction temperature is controlled to be 30-80 ℃, and CO introduced into the reaction kettle2The volume concentration is 20-60%, and the flow rate is 150-1000 ml/min.
12. The method of claim 1, wherein: in the step (8), after the reaction is finished, the aging time is 0.5-4.0 hours.
13. The method of claim 1, wherein: according to the weight of the catalyst, the content of copper oxide is 30-80 wt%, the content of bismuth oxide is 1.0-10.0 wt%, and the particle size of the catalyst is at least 93% and is 10-30 mu m.
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