CN108069825A - A kind of method for improving formaldehyde and acetylene reaction and preparing 1,4- butynediols catalyst service life - Google Patents

A kind of method for improving formaldehyde and acetylene reaction and preparing 1,4- butynediols catalyst service life Download PDF

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CN108069825A
CN108069825A CN201610990986.0A CN201610990986A CN108069825A CN 108069825 A CN108069825 A CN 108069825A CN 201610990986 A CN201610990986 A CN 201610990986A CN 108069825 A CN108069825 A CN 108069825A
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catalyst
reactor
temperature
cleaned
reaction
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CN108069825B (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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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

Abstract

The present invention discloses a kind of method for improving formaldehyde and acetylene reaction and preparing Isosorbide-5-Nitrae butynediols catalyst service life, includes the following steps：（1）It is online to carry out catalyst sampling and be simultaneously dried, it is roasted after dry, the loss of weight 10% ~ 50% before catalyst is compared to roasting, when optimal 20% ~ 40%, is shut down；（2）Catalyst in reaction unit after shutting down is cleaned, removes the impurity and organic matter for being covered in catalyst surface；（3）Remove copper sulfide, the phosphorized copper deposited in catalyst；（4）To step（3）Treated catalyst continues formaldehyde after being cleaned using deionized water and acetylene reaction prepares the reaction of 1,4 butynediols.This method can be obviously prolonged the service life of catalyst.

Description

A kind of raising formaldehyde and acetylene reaction prepare 1,4- butynediols catalyst service life Method
Technical field
The present invention relates to a kind of method for improving formaldehyde and acetylene reaction and preparing Isosorbide-5-Nitrae-butynediols catalyst service life, specifically Ground is said, is related to a kind of method for improving slurry bed formaldehyde and acetylene reaction and preparing Isosorbide-5-Nitrae-butynediols catalyst service life.
Background technology
Reppe methods trickle bed, suspension bed and slurry bed etc. may be employed using formaldehyde and acetylene synthesis 1,4- butynediols Technique.Since slurry bed process has many advantages, such as that synthesising reacting speed is fast, pressure is low, safe operation, catalyst change are convenient, mesh One of preceding main method for having become synthesis 1,4- butynediols.
Slurry bed process synthesis 1,4- butynediols uses copper bismuth catalyst mostly.Main Components oxidation in such catalyst Copper, with formaldehyde and acetylene reaction generation alkynes copper complex, PARA FORMALDEHYDE PRILLS(91,95) and acetylene synthesis Isosorbide-5-Nitrae-butynediols catalytic action, and its In the main function of bismuth oxide component be then to inhibit the acetylene polymerization side reaction that generates in reaction process.Above-mentioned catalyst is in life Due to being influenced be subject to impurity, operating condition and by-product acetylene polymer in raw material during production, catalytic performance can be gradual It reduces.For the production for keeping high catalytic activity and stablizing, it is necessary to the catalyst often more renewed, the use of general catalyst Cycle is 3 months.Annual production capacity is 100,000 tons of 1,4-butanediol device, and changing agent every time needs 20 tons of copper bismuth catalysts, together When to generate 50 ~ 100 tons of dead catalyst, so not only increase the cost of acetylene-formaldehyde process production 1,4-butanediol, and generate Useless agent can not handle, threaten to the Environmental security of surrounding.There are many factor of catalyst inactivation, including in catalyst Malicious, sintering and heat inactivation, coking and blocking etc..For the catalytic reaction for synthesizing Isosorbide-5-Nitrae-butynediols, due to acetylene gas and Containing excessive impurity and fluctuation of service factor catalyst inactivation is caused to be most important reason in formaldehyde raw material.
Many experts and scholars are finding practicable recovery method, to solve the problem of outlet of useless alkynes copper catalyst. Such as smelting, the metallic copper and bismuth in catalyst are mainly recycled, but this method danger is larger, and Technical comparing is answered Miscellaneous, practical application difficulty is larger.In another example acid hydrolyzation, is that strong acid and alkynes copper compound is utilized to act on after generating salt, then makes again Standby new catalyst, but this method removal process is long, consumes substantial amounts of strong acid, and recovery cost is very high.
United States Patent (USP) US4,311,611 disclose a kind of method of oxidizing process recycling catalyst, which is that one kind contains There is the oxide of the metals such as iron, antimony, copper, cobalt, nickel, magnesium, be mainly used in the techniques such as the oxidation, ammoxidation and oxidative dehydrogenation of hydrocarbon. This method is to utilize H2O2It as oxidant, is acted on dead catalyst, then using filter, dry, calcining, makes useless urge Agent is regenerated.But the copper scrap bismuth catalyst of the present invention containing explosive alkynes copper compound is not provided in this patent again Generation method.
CN95116599.2 is disclosed a kind of synthesizes Isosorbide-5-Nitrae-butynediols with urging for slurry-bed reaction by formaldehyde and acetylene The renovation process of agent is that dead catalyst and strong oxidizer are carried out oxidation reaction in the liquid phase, is then separated, dried After obtain regenerated catalyst, this method solve processing easily decompose, explosion alkynes copper catalyst safety problem, processing procedure Simply, conveniently, product recovery rate it is high, the catalyst for regenerating gained has the catalytic performance identical with raw catalyst, reduces silt The production cost of bed process synthesis Isosorbide-5-Nitrae-butynediols is starched, reduces the pollution to environment.But such method easily generates chloroethene Alkynes, there is the danger of explosion.
CN95116600.X is disclosed a kind of synthesizes Isosorbide-5-Nitrae-butynediols with urging for slurry-bed reaction by formaldehyde and acetylene The renovation process of agent, dead catalyst and formalin are reacted, and then carry out separation of solid and liquid, the solids that will be obtained Matter is washed to remove water-solubility impurity, dry, and black powder solid is obtained after being roasted in air or oxygen, be copper and The oxide of bismuth that is to say to obtain the regenerated catalyst for being used to synthesize Isosorbide-5-Nitrae-butynediols.Copper oxide prepared by such method It can assemble with bismuth oxide catalyst, the stability of regenerated catalyst is not good enough.
The content of the invention
The purpose of the present invention is exactly to overcome above-mentioned defect in the prior art, is proposed a kind of anti-for slurry bed The application method of Isosorbide-5-Nitrae-butynediols should be synthesized by formaldehyde and acetylene, this method can be obviously prolonged the service life of catalyst.
A kind of method for improving formaldehyde and acetylene reaction and preparing Isosorbide-5-Nitrae-butynediols catalyst service life, including walking as follows Suddenly：
（1）It is online to carry out catalyst sampling and be simultaneously dried, roasted after dry, before catalyst is compared to roasting loss of weight 10% ~ 50%, when optimal 20% ~ 40%, shut down；
（2）Catalyst in reaction unit after shutting down is cleaned, remove be covered in catalyst surface impurity and Organic matter；
（3）Remove copper sulfide, the phosphorized copper deposited in catalyst；
（4）To step（3）Treated continues formaldehyde and acetylene reaction system after catalyst cleaned using deionized water The reaction of standby 1,4- butynediols.
The above method, step（1）The weight composition of the catalyst of middle taking-up is as follows：CuO contents are 38% ~ 78%, Bi2O3Contain It measures as 2.3% ~ 4.8%, remaining is organic matter and impurity.The catalyst taken out is 1 ~ 10 gram, and optimal 2 ~ 8 grams, drying temperature is 40 ~ 80 DEG C, the time for 1 ~ 3 it is small when, calcination temperature be 650 ~ 900 DEG C, optimal 750 ~ 850 DEG C, roasting time for 1 ~ 4 it is small when； Line carries out the time of catalyst sampling as reaction unit operating 20 ~ 70 days, preferably 30 ~ 60 days.
In the above method, step（2）The method that middle catalyst is cleaned includes to remove being covered in catalyst surface Impurity and water-soluble organic matter either method, cleaning carried out online preferably in reactor.It is gone it is preferred that using first Ionized water is cleaned, and is then cleaned using the aqueous solution containing surfactant；Finally using alkaline solution to catalysis Agent is cleaned.
Described to be cleaned with deionized water in the above method, the volume of deionized water used is catalyst volume 10 ~ 30 times, divide 2-4 times and cleaned, each flushing water stops 10 ~ 50 minutes in the reactor, optimal 20 ~ 30 minutes.
In the above method, aqueous solution of the described use containing surfactant is cleaned, the surfactant by Ether, alcohol composition.Described ether can be ether, propylene-glycol ethyl ether, dipropylene glycol methyl ether, propylene glycol monomethyl ether, in butyl glycol ether One or more；Described alcohol can be the one or more in methanol, ethyl alcohol, ethylene glycol, isopropanol.Ether and alcohol mass ratio For 1:1~8:2；Mass content is 2% ~ 30%, optimal 5% ~ 15% to surfactant in water, and wash temperature is optimal at 30 ~ 70 DEG C 40 ~ 60 DEG C, the described aqueous solution used containing surfactant adds in volume as 5 ~ 30 times of catalyst volume, optimal 10 ~ 20 times, divide 2-4 addition, each flushing water stops 10 ~ 50 minutes in the reactor, optimal 20 ~ 30 minutes.
In the above method, described alkaline solution can be one in sodium methoxide, sodium carbonate, sodium pyrophosphate, sodium ethoxide etc. Kind is several, preferably sodium carbonate and sodium pyrophosphate.The mass concentration of alkaline solution is 0.1% ~ 1.0%, optimal 0.3 ~ 0.5%.It is used Volume be 10 ~ 15 times of catalyst volume, divide 1-2 times and be rinsed.The temperature of lye be 80 ~ 100 DEG C, optimal 90 ~ 95 ℃.It rinses and stops 10 ~ 50 minutes, preferably 20 ~ 40 minutes every time.
In the above method, step（3）In, remove the copper sulfide that deposits and phosphorized copper in catalyst may be employed it is any existing Technology.Catalyst is covered it is preferred that being passed through a certain amount of water into reactor, temperature of reactor is raised simultaneously, works as temperature of reactor When rising to certain temperature, air or the air Mixture containing hydrogen are passed through into reactor, sulphur on a catalyst will be deposited Change the sulphur in cuprous and copper phosphide and phosphorus removes；
Above-mentioned preferred embodiment detailed process is as follows：The temperature of reactor is increased to 80 ~ 100 DEG C, optimal 90 ~ 95 DEG C.Toward reaction Be passed through air in device, the flow velocity of air is 1 ~ 10L/min, optimal 2 ~ 5L/min, be passed through the time for 1 ~ 5 it is small when, it is optimal 2 ~ 3 it is small when Or the mixed gas of air and hydrogen is passed through into reactor, the temperature of reactor is room temperature, hydrogen and air Mixture Flow velocity is 1 ~ 10L/min, and the volumetric concentration of optimal 2 ~ 5L/min, wherein hydrogen in gaseous mixture is 1% ~ 8%, optimal 2% ~ 4%, is led to The angle of incidence for 1 ~ 5 it is small when, it is optimal 2 ~ 3 it is small when.
The above method, step（4）In, the volume of the deionized water used is optimal for 10 ~ 30 times of caltalyst accumulated amount It 15 ~ 20 times, rinses several times, rinses stop 10 ~ 50 minutes, optimal 20 ~ 30 minutes every time.The temperature of deionized water used is 80 ~ 100 DEG C, optimal 90 ~ 95 DEG C.
The above method, step（4）Continue formaldehyde after being cleaned using deionized water and acetylene reaction prepares 1,4- The reaction condition of butynediols is as follows：It is 10% ~ 45% aqueous solution and acetylene for raw material using formaldehyde mass percent concentration, catalysis The mass ratio of agent and formalin is 1:20 to 1:2, acetylene partial pressure is 0.1-0.5MPa.
Formaldehyde and acetylene reaction prepare the copper bismuth catalyst of Isosorbide-5-Nitrae-butynediols, and surface can cover largely during the reaction Organic matter, handled when surface covering reaches 20% ~ 40% or so, can be prolonged by this catalyst occupation mode online The service life of long catalyst reduces the generation of dead catalyst.
Catalyst by will be covered in the organic matter of catalyst surface by the present invention by surfactant and lye online Effectively removing, then catalyst deposits catalyst surface in air atmosphere or in the mixed atmosphere of hydrogen and air Cuprous sulfide and copper phosphide in sulphur and phosphorus removed in a manner of hydrogen sulfide and hydrogen phosphide, make catalyst activity obtain it is extensive It is multiple.The effective service life for extending catalyst, extension cycle are up to 30%.
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.The elemental analysis of catalyst is analyzed using X-ray fluorescence spectra.The reactivity of catalyst is evaluated in mould Intend carrying out in slurry bed, using formaldehyde and acetylene reaction system, reaction temperature is 90 DEG C, and reaction pressure is normal pressure, acetylene flow velocity For 60mL/min, the formaldehyde addition of catalyst amount 50mL, concentration 37wt% are 250ml.Following embodiments and comparative example The mark terminated reaction time is reduced to formaldehyde conversion for the activity of catalyst and is reduced to 35%, that is, stops reaction.
Embodiment 1
（1）800 grams of catalyst are loaded in 10L reaction kettles, after reacting 30 days, 8 grams of catalyst is taken out from reaction kettle, are placed on 40 When drying 2 is small in the baking oven of degree, then in 800 degree of burning kiln roasting, calcination loss of weight is measured as 20%.By urging after burning Agent send XRF analysis.Sample is A.
（2）Temperature of reactor is down to room temperature, and is passed through 16L deionized waters, is passed through at twice, is passed through 8L every time.Every time Deionized water stops 25 minutes in a kettle.This process blender is constantly stirred.
（3）Cleaning finishes, and the deionized water 12L containing 400 grams of 800 grams of propylene-glycol ethyl ether and isopropanol is passed into instead It answers in kettle, is passed through in three times, each 4L, the temperature of reactor is maintained at 45 degree, water and surfactant each residence time For 25 minutes.
（4）After the above-mentioned water containing surfactant is excluded, by the sodium carbonate liquor 10L that mass percentage is 0.4% It is passed into reaction kettle, is passed through at twice, and keep the temperature of lye the temperature of reactor is 45 degree for 95 degree.Each stops It is 20 minutes to stay the time.
（5）After lye is excluded, deionized water will be slowly passed through in reaction kettle, when catalyst surface is covered by deionized water Afterwards, slowly heating response device, while be stirred using blender to catalyst, when the temperature of reactor reaches 95 degree, from Reactor bottom is passed through air, flow velocity 3L/min.Keep 2 it is small when.
（6）12L deionized waters are passed through into reaction kettle, divides 3 times and is passed through, are passed through 4L every time, the temperature of water is 90 degree, is stopped It is discharged after 25 minutes.A small amount of catalyst is then taken out, 800 degree of roastings is carried out, and send XRF analysis.It the results are shown in Table 1.Continue The activity rating of catalyst, evaluating data are shown in Table 2.
Embodiment 2
(1) 820 grams of catalyst are loaded in 10L reaction kettles, after reacting 60 days, 10 grams of catalyst are taken out from reaction kettle, it is placed on When drying 1 is small in 50 degree of baking oven, then in 850 degree of burning kiln roasting, calcination loss of weight is measured as 35%.After burning Catalyst send XRF analysis.Sample is B.
(2) temperature of reactor is down to room temperature, and is passed through 18L deionized waters, be passed through at twice, be passed through 9L every time.Every time Deionized water stops 25 minutes in a kettle.This process blender is constantly stirred.
(3) cleaning finishes, and the deionized water 12L containing 405 grams of 810 grams of ether and isopropanol is passed into reaction kettle, It is passed through in three times, each 4L, the temperature of reactor is maintained at 45 degree, and water and surfactant each residence time are 25 points Clock.
(4) after the above-mentioned water containing surfactant is excluded, by the sodium carbonate liquor 11L that mass percentage is 0.4% It is passed into reaction kettle, is passed through at twice, and keep the temperature of lye the temperature of reactor is 45 degree for 95 degree.Each stops It is 25 minutes to stay the time.
(5) deionized water will be slowly passed through in reaction kettle, after catalyst surface is covered by deionized water, slowly heating is anti- Device is answered, while catalyst is stirred using blender, when the temperature of reactor reaches 95 degree, is passed through from reactor bottom Air, flow velocity 3L/min.Keep 2.5 it is small when.
(6) stop being passed through air, 12L deionized waters are passed through into reaction kettle, divides 3 times and is passed through, be passed through 4L, the temperature of water every time It spends for 90 degree, is discharged after stopping 25 minutes.After cleaning, a small amount of catalyst is taken out, 850 degree of roastings is carried out, and send XRF points Analysis.It the results are shown in Table 1.Activity rating data are shown in Table 2.
Embodiment 3
（1）800 grams of catalyst are loaded in 10L reaction kettles, after reacting 28 days, 8 grams of catalyst is taken out from reaction kettle, are placed on 45 When drying 1 is small in the baking oven of degree, then in 800 degree of burning kiln roasting, calcination loss of weight is measured as 24%.By urging after burning Agent send XRF analysis.Sample is C.
（2）Temperature of reactor is down to room temperature, and is passed through 16L deionized waters, is passed through at twice,
It is passed through 8L every time.Each deionized water stops 25 minutes in a kettle.This process blender is constantly stirred.
（3）Cleaning finishes, and the deionized water 12L containing 400 grams of 800 grams of propylene-glycol ethyl ether and isopropanol is passed into reaction It in kettle, is passed through in three times, each 4L, the temperature of reactor is maintained at 45 degree, and water and surfactant each residence time be 25 minutes.
（4）After the above-mentioned water containing surfactant is excluded, by the sodium carbonate liquor 10L that mass percentage is 0.4% It is passed into reaction kettle, is passed through at twice, and keep the temperature of lye the temperature of reactor is 45 degree for 95 degree.Each stops It is 20 minutes to stay the time.
（5）Deionized water will be slowly passed through in reaction kettle, after catalyst surface is covered by deionized water, from reactor bottom Portion is passed through the mixed gas of hydrogen and air, and the flow velocity of mixed gas is 3L/min, and wherein the volumetric concentration of hydrogen is 4%, is kept 2 it is small when.
（6）Stopping is passed through hydrogen and air Mixture, and deionized water is discharged.12L deionized waters are passed through into reaction kettle, Divide 3 times and be passed through, be passed through 4L every time, the temperature of water is 90 degree, is discharged after stopping 25 minutes.After cleaning, a small amount of catalysis is taken out Agent carries out 800 degree of roastings, and send XRF analysis.It the results are shown in Table 1.Activity rating data are shown in Table 2.
Comparative example 1
Catalyst negates the catalyst for answering 30 days and reacting 60 days without regeneration treatment.Reaction 30 days and reaction 60 days are urged Agent passes through 50 degree of oven drying, and XRF analysis are sent after then being burned at 800 degree.Number is D, the results are shown in Table 1.Activity rating It the results are shown in Table 2.
Comparative example 2
By the of embodiment 1（3）(4）Step is saved, remaining is same as Example 1.Catalyst number is E, and Activity evaluation is shown in Table 2.
Comparative example 3
By the of embodiment 1（5）Step is saved, remaining is same as Example 1.Catalyst number is F, and Activity evaluation is shown in Table 2.
Comparative example 4
According to the method that CN95116600.X is disclosed, 60.266 grams of the catalyst answered 30 days is negated, is added in stirring and condensation In 1000 milliliters of glass there-necked flasks of device, and 36.27% 600 grams of formalin is added in, when 100 DEG C of reactions 6 are small, isolated Solid is washed, drying, at 450~500 DEG C roast 2 it is small when after, obtain black solid catalyst.By urging after regeneration Agent carries out corresponding active appraisal experiment.2 are the results are shown in Table after evaluating 5 days.Front and rear catalyst will be regenerated simultaneously and is placed on burns In burning stove after 820 degree of burning disposals, XRF analysis are sent, number G, the result is shown in tables 1.The activity rating data of catalyst are shown in Table 2。
The physicochemical property of 1 catalyst of table
The activity rating data of 2 catalyst of table

Claims (16)

  1. A kind of 1. method for improving formaldehyde and acetylene reaction and preparing Isosorbide-5-Nitrae-butynediols catalyst service life, it is characterised in that： Include the following steps：
    （1）It is online to carry out catalyst sampling and be simultaneously dried, roasted after dry, before catalyst is compared to roasting loss of weight 10% ~ 50%, it shuts down；
    （2）Catalyst in reaction unit after shutting down is cleaned, remove be covered in catalyst surface impurity and Organic matter；
    （3）Remove copper sulfide, the phosphorized copper deposited in catalyst；
    （4）To step（3）Treated continues formaldehyde and acetylene reaction system after catalyst cleaned using deionized water The reaction of standby 1,4- butynediols.
  2. 2. according to the method described in claim 1, it is characterized in that：Step（1）The weight composition of the catalyst of middle taking-up is as follows： CuO contents are 38% ~ 78%, Bi2O3Content is 2.3% ~ 4.8%, remaining is organic matter and impurity.
  3. 3. according to the method described in claim 1, it is characterized in that：Step（1）Middle taken out catalyst is 1 ~ 10 gram, dry Temperature is 40 ~ 80 DEG C, and calcination temperature is 650 ~ 900 DEG C, when roasting time is 1 ~ 4 small；The online time for carrying out catalyst sampling It is operated 20 ~ 70 days for reaction unit.
  4. 4. according to the method described in claim 1, it is characterized in that：Step（2）The method that middle catalyst is cleaned includes energy Enough either method for removing the impurity and organic matter that are covered in catalyst surface, clean and are carried out online in reactor.
  5. 5. according to the method described in claim 3, it is characterized in that：Step（2）In cleaned first using deionized water, so It is cleaned afterwards using the aqueous solution containing surfactant；Finally catalyst is cleaned using alkaline solution.
  6. 6. according to the method described in claim 5, it is characterized in that：Described to be cleaned with deionized water, the used deionization The volume of water is 10 ~ 30 times of catalyst volume, divides 2-4 times and is cleaned, each flushing water stops 10 ~ 50 points in the reactor Clock.
  7. 7. according to the method described in claim 5, it is characterized in that：Aqueous solution of the described use containing surfactant carries out Cleaning, the surfactant are made of ether, alcohol.
  8. 8. according to the method described in claim 7, it is characterized in that：Described ether be ether, propylene-glycol ethyl ether, dipropylene glycol first Ether, propylene glycol monomethyl ether, the one or more in butyl glycol ether；Described alcohol is methanol, in ethyl alcohol, ethylene glycol, isopropanol One or more, ether and alcohol mass ratio are 1:1~4:1.
  9. 9. according to the method described in claim 7, it is characterized in that：Wash temperature is 30 ~ 70 DEG C, and the use contains surface The aqueous solution of activating agent adds in 5 ~ 30 times that volume is catalyst volume, divides 2-4 addition, and each flushing water stops in the reactor It stays 10 ~ 50 minutes.
  10. 10. according to the method described in claim 5, it is characterized in that：Described alkaline solution is sodium methoxide, sodium carbonate, burnt phosphorus One or more of sour sodium, sodium ethoxide etc., the mass concentration of alkaline solution is 0.1% ~ 1.0%, and volume used is catalysis 10 ~ 15 times of agent volume, divide 1-2 times and are rinsed, and the temperature of lye is 80 ~ 100 DEG C, rinses stop 10 ~ 50 minutes every time.
  11. 11. according to the method described in claim 1, it is characterized in that：Step（3）In, remove the copper sulfide deposited in catalyst Any prior art is used with phosphorized copper.
  12. 12. according to the method for claim 11, it is characterised in that：It is passed through water into reactor to cover catalyst, simultaneously Temperature of reactor is raised, when temperature of reactor rises to certain temperature, air or the air containing hydrogen are passed through into reactor Gaseous mixture removes the sulphur in the cuprous sulfide and copper phosphide of deposition on a catalyst and phosphorus.
  13. 13. according to the method for claim 12, it is characterised in that：The temperature of reactor is increased to 80 ~ 100 DEG C, toward instead Answer and air be passed through in device, the flow velocity of air is 1 ~ 10L/min, be passed through the time for 1 ~ 5 it is small when.
  14. 14. according to the method for claim 12, it is characterised in that：The gaseous mixture of air and hydrogen is passed through into reactor Body, the temperature of reactor are room temperature, and the flow velocity of hydrogen and air Mixture is 1 ~ 10L/min, and wherein hydrogen is in gaseous mixture Volumetric concentration be 1% ~ 8%, be passed through the time for 1 ~ 5 it is small when.
  15. 15. according to the method described in claim 1, it is characterized in that：, step（4）In, the volume of the deionized water used for 10 ~ 30 times of caltalyst accumulated amount, are rinsed several times, rinse stop 10 ~ 50 minutes every time, the temperature of deionized water used is 80~100℃。
  16. 16. according to the method described in claim 1, it is characterized in that：Step（4）Continue after being cleaned using deionized water into The reaction condition that row formaldehyde and acetylene reaction prepare 1,4- butynediols is as follows：Using formaldehyde mass percent concentration as 10% ~ 45% Aqueous solution and acetylene be raw material, the mass ratio of catalyst and formalin is 1:20 to 1:2, acetylene partial pressure is 0.1- 0.5MPa。
CN201610990986.0A 2016-11-11 2016-11-11 Method for prolonging service cycle of catalyst for preparing 1, 4-butynediol through reaction of formaldehyde and acetylene Active CN108069825B (en)

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CN1130102A (en) * 1995-10-27 1996-09-04 化学工业部北京化工研究院 Catalyst regenerating method for synthesizing 1,4-butynediol from formaldehyde and acetylene by slurry-bed reaction
CN1132114A (en) * 1995-10-27 1996-10-02 化学工业部北京化工研究院 Regenerating method of catalyst for 1,4-butine-glycol synthetized by formaldehyde and acetylene reacted in slurry bed
WO2010119448A1 (en) * 2009-04-17 2010-10-21 Hindustan Organic Chemicals Limited An 'in-situ' prepared, improved catalyst for low pressure continuous butynediol synthesis
CN105413711A (en) * 2015-11-20 2016-03-23 苏英慧 Regeneration preparing method for supported copper-bismuth catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1130102A (en) * 1995-10-27 1996-09-04 化学工业部北京化工研究院 Catalyst regenerating method for synthesizing 1,4-butynediol from formaldehyde and acetylene by slurry-bed reaction
CN1132114A (en) * 1995-10-27 1996-10-02 化学工业部北京化工研究院 Regenerating method of catalyst for 1,4-butine-glycol synthetized by formaldehyde and acetylene reacted in slurry bed
WO2010119448A1 (en) * 2009-04-17 2010-10-21 Hindustan Organic Chemicals Limited An 'in-situ' prepared, improved catalyst for low pressure continuous butynediol synthesis
CN105413711A (en) * 2015-11-20 2016-03-23 苏英慧 Regeneration preparing method for supported copper-bismuth catalyst

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