CN108069825B - Method for prolonging service cycle of catalyst for preparing 1, 4-butynediol through reaction of formaldehyde and acetylene - Google Patents
Method for prolonging service cycle of catalyst for preparing 1, 4-butynediol through reaction of formaldehyde and acetylene Download PDFInfo
- Publication number
- CN108069825B CN108069825B CN201610990986.0A CN201610990986A CN108069825B CN 108069825 B CN108069825 B CN 108069825B CN 201610990986 A CN201610990986 A CN 201610990986A CN 108069825 B CN108069825 B CN 108069825B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reactor
- temperature
- cleaning
- acetylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- 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 invention discloses a method for prolonging the service life of a catalyst for preparing 1, 4-butynediol by reacting formaldehyde and acetylene, which comprises the following steps: (1) sampling and drying the catalyst on line, roasting the catalyst after drying, and stopping operation when the weight of the catalyst is reduced by 10-50% compared with that before roasting, and the optimal weight is 20-40%; (2) cleaning the catalyst in the reaction device after the operation is stopped, and removing impurities and organic matters covering the surface of the catalyst; (3) removing copper sulfide and copper phosphide deposited in the catalyst; (4) and (4) cleaning the catalyst treated in the step (3) by using deionized water, and then continuously carrying out a reaction for preparing 1, 4-butynediol by reacting formaldehyde and acetylene. The method can obviously prolong the service life of the catalyst.
Description
Technical Field
The invention relates to a method for prolonging the service life of a catalyst for preparing 1, 4-butynediol through the reaction of formaldehyde and acetylene, in particular to a method for prolonging the service life of a catalyst for preparing 1, 4-butynediol through the reaction of formaldehyde and acetylene in a slurry bed.
Background
The 1, 4-butynediol is synthesized by formaldehyde and acetylene by adopting a process of a trickle bed, a suspension bed, a slurry bed and the like. The slurry bed process has the advantages of high synthesis reaction speed, low pressure, safe operation, convenient catalyst replacement and the like, and is one of the main methods for synthesizing the 1, 4-butynediol at present.
The slurry bed process for the synthesis of 1, 4-butynediol mostly uses a copper bismuth catalyst. The main component of the catalyst is copper oxide which reacts with formaldehyde and acetylene to generate an acetylene copper complex which plays a catalytic role in synthesizing 1, 4-butynediol from formaldehyde and acetylene, and the main function of the bismuth oxide component is to inhibit the acetylene polymerization side reaction generated in the reaction process. The catalyst has gradually reduced catalytic performance during the production process due to the influence of impurities in the raw materials, operating conditions and by-product acetylene polymers. In order to maintain high catalytic activity and stable production, the catalyst must be frequently replaced with a new one, and the service life of the catalyst is generally 3 months. The annual production capacity of the 1, 4-butanediol device is 10 ten thousand tons, 20 tons of copper bismuth catalysts are needed for changing the catalysts every time, and 50-100 tons of waste catalysts are generated, so that the cost of producing the 1, 4-butanediol by the alkynal method is increased, and the generated waste agents cannot be treated, thereby threatening the safety of the surrounding environment. The factors for catalyst deactivation are many, including catalyst poisoning, sintering and thermal deactivation, coking and plugging, etc. The catalyst deactivation due to the excessive impurities in the acetylene gas and formaldehyde starting materials and the operational instability factors is the most significant cause for the catalytic reaction for the synthesis of 1, 4-butynediol.
Many experts and scholars are seeking a feasible recovery method to solve the problem of the waste copper acetylide catalyst. For example, the smelting method is mainly used for recovering the metal copper and bismuth in the catalyst, but the method has higher danger, more complex technology and higher difficulty in practical application. For example, the acid hydrolysis method is to produce a salt by the action of a strong acid and a copper acetylide compound and then prepare a new catalyst again, but the method has a long recovery process, consumes a large amount of the strong acid and has high recovery cost.
U.S. Pat. No. 4, 4,311,611 discloses a method for recovering catalyst by oxidation, the catalyst is a metal containing iron, antimony, copper, cobalt, nickel, magnesium, etcThe oxide of (2) is mainly used for the processes of oxidation, ammoxidation, oxidative dehydrogenation and the like of hydrocarbons. This method utilizes H2O2As oxidant, the catalyst reacts with waste catalyst, and then the waste catalyst is regenerated through the steps of filtering, drying, calcining and the like. However, the patent does not disclose the regeneration method of the waste copper bismuth catalyst containing the explosive copper acetylide compound according to the present invention.
CN95116599.2 discloses a regeneration method of a catalyst for synthesizing 1, 4-butynediol from formaldehyde and acetylene in slurry bed reaction, which comprises the steps of carrying out oxidation reaction on a waste catalyst and a strong oxidant in a liquid phase, then separating and drying to obtain a regenerated catalyst. However, this method is liable to produce chloroethyne, and there is a risk of explosion.
CN95116600.X discloses a regeneration method of catalyst for synthesizing 1, 4-butynediol from formaldehyde and acetylene in slurry bed reaction, which comprises reacting waste catalyst with formaldehyde solution, then carrying out solid-liquid separation, washing the obtained solid matter with water to remove water-soluble impurities, drying, and calcining in air or oxygen to obtain black powder solid, i.e. oxides of copper and bismuth, i.e. regenerated catalyst for synthesizing 1, 4-butynediol. The copper oxide and bismuth oxide catalysts prepared by the method can aggregate, and the stability of the regenerated catalysts is poor.
Disclosure of Invention
The object of the present invention is to overcome the above-mentioned drawbacks of the prior art by providing a process for the synthesis of 1, 4-butynediol from formaldehyde and acetylene in a slurry bed reaction, which process allows a significant extension of the catalyst life.
A method for improving the service cycle of a catalyst for preparing 1, 4-butynediol by reacting formaldehyde and acetylene comprises the following steps:
(1) sampling and drying the catalyst on line, roasting the catalyst after drying, and stopping operation when the weight of the catalyst is reduced by 10-50% compared with that before roasting, and the optimal weight is 20-40%;
(2) cleaning the catalyst in the reaction device after the operation is stopped, and removing impurities and organic matters covering the surface of the catalyst;
(3) removing copper sulfide and copper phosphide deposited in the catalyst;
(4) and (4) cleaning the catalyst treated in the step (3) by using deionized water, and then continuously carrying out a reaction for preparing 1, 4-butynediol by reacting formaldehyde and acetylene.
In the method, the weight composition of the catalyst taken out in the step (1) is as follows: the CuO content is 38% -78%, and Bi2O3The content is 2.3% -4.8%, and the balance is organic matters and impurities. The weight of the taken catalyst is 1-10 g, preferably 2-8 g, the drying temperature is 40-80 ℃, the time is 1-3 hours, the roasting temperature is 650-900 ℃, preferably 750-850 ℃, and the roasting time is 1-4 hours; the time for sampling the catalyst on line is 20 to 70 days, preferably 30 to 60 days, of the operation of the reaction device.
Among the above methods, the method for washing the catalyst in the step (2) includes any method capable of removing impurities and water-soluble organic substances covering the surface of the catalyst, and the washing is preferably carried out in-line in the reactor. Preferably, deionized water is firstly adopted for cleaning, and then aqueous solution containing surfactant is adopted for cleaning; finally, the catalyst is cleaned by alkaline solution.
In the method, the deionized water is used for cleaning, the volume of the used deionized water is 10-30 times of the volume of the catalyst, the cleaning is carried out for 2-4 times, and each time of washing water stays in the reactor for 10-50 minutes, and the optimal time is 20-30 minutes.
In the method, the cleaning is carried out by adopting an aqueous solution containing a surfactant, and the surfactant consists of ether and alcohol. The ether can be one or more of diethyl ether, propylene glycol diethyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether and ethylene glycol butyl ether; the alcohol may be one or more of methanol, ethanol, ethylene glycol and isopropanol. The mass ratio of the ether to the alcohol is 1: 1-8: 2; the mass content of the surfactant in water is 2-30%, optimally 5-15%, the washing temperature is 30-70 ℃, optimally 40-60 ℃, the adding volume of the water solution containing the surfactant is 5-30 times, optimally 10-20 times of the volume of the catalyst, the water solution is added for 2-4 times, and each time of washing water stays in the reactor for 10-50 minutes, optimally 20-30 minutes.
In the above method, the alkaline solution may be one or more of sodium methoxide, sodium carbonate, sodium pyrophosphate, sodium ethoxide, etc., and sodium carbonate and sodium pyrophosphate are preferred. The mass concentration of the alkaline solution is 0.1-1.0%, and the optimal mass concentration is 0.3-0.5%. The volume of the catalyst is 10-15 times of the volume of the catalyst, and the catalyst is washed for 1-2 times. The temperature of the alkali liquor is 80-100 ℃, and the optimal temperature is 90-95 ℃. Each time of washing is kept for 10-50 minutes, preferably 20-40 minutes.
In the above method, in the step (3), any one of the prior arts can be used for removing the copper sulfide and the copper phosphide deposited in the catalyst. Preferably, a certain amount of water is introduced into the reactor to cover the catalyst, the temperature of the reactor is raised, and when the temperature of the reactor is raised to a certain temperature, air or air mixed gas containing hydrogen is introduced into the reactor to remove sulfur and phosphorus in the cuprous sulfide and cuprous phosphide deposited on the catalyst;
the preferred scheme comprises the following specific processes: the temperature of the reactor is raised to 80-100 ℃, preferably 90-95 ℃. Introducing air into the reactor, wherein the flow rate of the air is 1-10L/min, optimally 2-5L/min, the introduction time is 1-5 hours, optimally 2-3 hours or introducing mixed gas of the air and the hydrogen into the reactor, the temperature of the reactor is room temperature, the flow rate of the mixed gas of the hydrogen and the air is 1-10L/min, optimally 2-5L/min, wherein the volume concentration of the hydrogen in the mixed gas is 1-8%, optimally 2-4%, the introduction time is 1-5 hours, and optimally 2-3 hours.
According to the method, in the step (4), the volume of the deionized water is 10-30 times, optimally 15-20 times of that of the catalyst, washing is carried out for multiple times, and each washing is kept for 10-50 minutes, optimally 20-30 minutes. The temperature of the used deionized water is 80-100 ℃, and the optimal temperature is 90-95 ℃.
In the method, deionized water is adopted in the step (4) for cleaning, and then formaldehyde and acetylene are continuously reacted to prepare the 1, 4-butynediol under the following reaction conditions: the method comprises the steps of taking an aqueous solution with formaldehyde mass percentage concentration of 10-45% and acetylene as raw materials, wherein the mass ratio of a catalyst to the formaldehyde solution is 1: 20-1: 2, and the acetylene partial pressure is 0.1-0.5 MPa.
The copper bismuth catalyst for preparing 1, 4-butynediol by reacting formaldehyde and acetylene has the advantages that a large amount of organic matters can be covered on the surface in the reaction process, and the surface covering matter can reach about 20-40% for online treatment, so that the use period of the catalyst can be prolonged and the generation of waste catalysts can be reduced.
The organic matter covered on the surface of the catalyst is effectively removed by the catalyst through a surfactant and alkali liquor on line, and then the catalyst removes sulfur and phosphorus in cuprous sulfide and cuprous phosphide deposited on the surface of the catalyst in the air atmosphere or the mixed atmosphere of hydrogen and air in a hydrogen sulfide and phosphine mode, so that the activity of the catalyst is recovered. The service life of the catalyst is effectively prolonged, and the cycle is prolonged to 30 percent.
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 elemental analysis of the catalyst was carried out by X-ray fluorescence spectroscopy. The evaluation of the reactivity of the catalyst is carried out on a simulated slurry bed, a formaldehyde and acetylene reaction system is adopted, the reaction temperature is 90 ℃, the reaction pressure is normal pressure, the acetylene flow rate is 60mL/min, the catalyst dosage is 50mL, and the formaldehyde addition with the concentration of 37 wt% is 250 mL. The end of the reaction cycle in the following examples and comparative examples was marked by the fact that the activity of the catalyst was reduced to 35% and the reaction was stopped.
Example 1
(1) 800 g of catalyst was charged in a 10L reactor, and after 30 days of reaction, 8 g of catalyst was taken out from the reactor, dried in a 40 ℃ oven for 2 hours, and then calcined in an 800 ℃ incinerator, and the ignition loss was measured to be 20%. The calcined catalyst was sent for XRF analysis. Sample is a.
(2) The reactor temperature was reduced to room temperature and 16L of deionized water was passed in, two times with 8L each. Deionized water was allowed to remain in the autoclave for 25 minutes each time. The stirrer is continuously stirring in the process.
(3) After the washing, 12L of deionized water containing 800 g of propylene glycol ethyl ether and 400 g of isopropanol was introduced into the reactor in three 4L portions, the temperature of the reactor was maintained at 45 ℃ and the residence time of water and surfactant was 25 minutes each time.
(4) After the water containing the surfactant is removed, 10L of sodium carbonate solution with the mass percentage of 0.4 percent is introduced into the reaction kettle for twice, and the temperature of the alkali liquor is kept at 95 ℃ and the temperature of the reactor is kept at 45 ℃. The residence time for each was 20 minutes.
(5) And (3) removing the alkali liquor, slowly introducing deionized water into the reaction kettle, slowly heating the reactor after the surface of the catalyst is covered by the deionized water, simultaneously stirring the catalyst by adopting a stirrer, and introducing air from the bottom of the reactor when the temperature of the reactor reaches 95 ℃, wherein the flow rate is 3L/min. The holding time was 2 hours.
(6) And (3) introducing 12L of deionized water into the reaction kettle, introducing 4L of deionized water into the reaction kettle for 3 times, keeping the temperature of the water at 90 ℃, and discharging the water after the water stays for 25 minutes. A small amount of catalyst was then removed, calcined at 800 degrees and sent for XRF analysis. The results are shown in Table 1. The activity evaluation of the catalyst was continued, and the evaluation data are shown in Table 2.
Example 2
(1) 820 g of catalyst was charged into a 10L reactor, and after 60 days of reaction, 10 g of the catalyst was taken out of the reactor, dried in an oven at 50 ℃ for 1 hour, and then calcined in an incinerator at 850 ℃ to find that the loss on ignition was 35%. The calcined catalyst was sent for XRF analysis. Sample B.
(2) The reactor temperature was reduced to room temperature and 18L of deionized water was passed in, twice for 9L each. Deionized water was allowed to remain in the autoclave for 25 minutes each time. The stirrer is continuously stirring in the process.
(3) After washing, 12L of deionized water containing 810 g of diethyl ether and 405 g of isopropanol was introduced into the reactor in three 4L portions, the reactor temperature was maintained at 45 ℃ and the residence time of water and surfactant was 25 minutes each.
(4) After the water containing the surfactant is removed, 11L of sodium carbonate solution with the mass percentage of 0.4 percent is introduced into the reaction kettle for twice, and the temperature of the alkali liquor is kept at 95 ℃ and the temperature of the reactor is kept at 45 ℃. The residence time was 25 minutes each time.
(5) And slowly introducing deionized water into the reaction kettle, slowly heating the reactor after the surface of the catalyst is covered by the deionized water, simultaneously stirring the catalyst by adopting a stirrer, and introducing air from the bottom of the reactor when the temperature of the reactor reaches 95 ℃, wherein the flow rate is 3L/min. The holding time was 2.5 hours.
(6) Stopping introducing air, introducing 12L of deionized water into the reaction kettle for 3 times, introducing 4L of water each time, keeping the temperature of the water at 90 ℃, and discharging after the water stays for 25 minutes. After the completion of the washing, a small amount of the catalyst was taken out, calcined at 850 ℃ and subjected to XRF analysis. The results are shown in Table 1. The activity evaluation data are shown in Table 2.
Example 3
(1) 800 g of catalyst was charged in a 10L reactor, and after 28 days of reaction, 8 g of catalyst was taken out of the reactor, dried in a 45 ℃ oven for 1 hour, and then calcined in an 800 ℃ incinerator, and the ignition loss was found to be 24%. The calcined catalyst was sent for XRF analysis. The sample is C.
(2) The temperature of the reactor is reduced to room temperature, 16L of deionized water is introduced, the introduction is carried out twice,
8L of the solution was introduced each time. Deionized water was allowed to remain in the autoclave for 25 minutes each time. The stirrer is continuously stirring in the process.
(3) After the washing, 12L of deionized water containing 800 g of propylene glycol ethyl ether and 400 g of isopropanol was introduced into the reactor in three 4L portions, the temperature of the reactor was maintained at 45 ℃ and the residence time of water and surfactant was 25 minutes each time.
(4) After the water containing the surfactant is removed, 10L of sodium carbonate solution with the mass percentage of 0.4 percent is introduced into the reaction kettle for twice, and the temperature of the alkali liquor is kept at 95 ℃ and the temperature of the reactor is kept at 45 ℃. The residence time for each was 20 minutes.
(5) And slowly introducing deionized water into the reaction kettle, and introducing mixed gas of hydrogen and air from the bottom of the reactor when the surface of the catalyst is covered by the deionized water, wherein the flow rate of the mixed gas is 3L/min, the volume concentration of the hydrogen is 4%, and the mixed gas is kept for 2 hours.
(6) Stopping introducing the mixed gas of hydrogen and air, and discharging the deionized water. And (3) introducing 12L of deionized water into the reaction kettle, introducing 4L of deionized water into the reaction kettle for 3 times, keeping the temperature of the water at 90 ℃, and discharging the water after the water stays for 25 minutes. After the completion of the washing, a small amount of the catalyst was taken out, calcined at 800 ℃ and subjected to XRF analysis. The results are shown in Table 1. The activity evaluation data are shown in Table 2.
Comparative example 1
The catalyst is not regenerated, and the catalyst which reacts for 30 days and 60 days is taken. The catalyst reacted for 30 days and 60 days was oven dried at 50 degrees and then incinerated at 800 degrees before being sent for XRF analysis. Numbered D, the results are shown in Table 1. The results of the activity evaluation are shown in Table 2.
Comparative example 2
The steps (3) and (4) of example 1 are omitted, and the process is otherwise the same as example 1. The catalyst number is E, and the activity evaluation results are shown in Table 2.
Comparative example 3
The step (5) of example 1 was omitted, and the same procedure as in example 1 was repeated. The catalyst was numbered F, and the activity evaluation results are shown in Table 2.
Comparative example 4
According to the method disclosed in CN95116600.X, 60.266 g of catalyst after 30 days of reaction is taken and added into a 1000 ml glass three-necked bottle with a stirrer and a condenser, 600 g of 36.27% formaldehyde solution is added, the mixture reacts for 6 hours at 100 ℃, solid is separated out and washed by water, dried and roasted for 2 hours at 450-500 ℃, and then the black solid catalyst is obtained. The regenerated catalyst was subjected to the corresponding activity evaluation test. The results after 5 days of evaluation are shown in Table 2. Meanwhile, the catalyst before and after regeneration was incinerated at 820 ℃ in an incinerator and then analyzed by XRF, the number of which is G, and the results are shown in Table 1. The activity evaluation data of the catalyst are shown in Table 2.
TABLE 1 physicochemical Properties of the catalyst
Table 2 evaluation data of catalyst activity
Claims (14)
1. A method for improving the service cycle of a catalyst for preparing 1, 4-butynediol by reacting formaldehyde and acetylene is characterized by comprising the following steps: the method comprises the following steps:
(1) sampling and drying the catalyst on line, roasting the catalyst after drying, and stopping operation when the weight of the catalyst is reduced by 10-50% compared with that before roasting;
(2) cleaning the catalyst in the reaction device after the operation is stopped, and removing impurities and organic matters covering the surface of the catalyst;
(3) removing copper sulfide and copper phosphide deposited in the catalyst;
(4) washing the catalyst treated in the step (3) by using deionized water, and then continuously carrying out a reaction for preparing 1, 4-butynediol by reacting formaldehyde and acetylene;
wherein, in the step (3), the specific process for removing the copper sulfide and the copper phosphide deposited in the catalyst is as follows: and introducing water into the reactor to cover the catalyst, raising the temperature of the reactor, and introducing air or air mixed gas containing hydrogen into the reactor when the temperature of the reactor is raised to a certain temperature to remove sulfur and phosphorus in the copper sulfide and the copper phosphide deposited on the catalyst.
2. The method of claim 1, wherein: the weight composition of the catalyst taken out in the step (1) is as follows: CuO content38 to 78 percent of Bi2O3The content is 2.3% -4.8%, and the balance is organic matters and impurities.
3. The method of claim 1, wherein: 1-10 g of catalyst taken out in the step (1), drying temperature of 40-80 ℃, roasting temperature of 650-900 ℃ and roasting time of 1-4 hours; the time for sampling the catalyst on line is 20 to 70 days for the operation of the reaction device.
4. The method of claim 1, wherein: the method for cleaning the catalyst in the step (2) includes any method capable of removing impurities and organic substances coated on the surface of the catalyst, and the cleaning is performed in-line in the reactor.
5. The method of claim 3, wherein: in the step (2), firstly, deionized water is adopted for cleaning, and then, an aqueous solution containing a surfactant is adopted for cleaning; finally, the catalyst is cleaned by alkaline solution.
6. The method of claim 5, wherein: and cleaning with deionized water, wherein the volume of the deionized water is 10-30 times of that of the catalyst, the cleaning is carried out for 2-4 times, and each time of cleaning water stays in the reactor for 10-50 minutes.
7. The method of claim 5, wherein: the cleaning is carried out by adopting an aqueous solution containing a surfactant, and the surfactant consists of ether and alcohol.
8. The method of claim 7, wherein: the ether is one or more of ethyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether and ethylene glycol butyl ether; the alcohol is one or more of methanol, ethanol, glycol and isopropanol, and the mass ratio of ether to alcohol is 1: 1-4: 1.
9. The method of claim 7, wherein: the washing temperature is 30-70 ℃, the adding volume of the water solution containing the surfactant is 5-30 times of the volume of the catalyst, the water solution is added in 2-4 times, and each time of washing water stays in the reactor for 10-50 minutes.
10. The method of claim 5, wherein: the alkaline solution is one or more of sodium methoxide, sodium carbonate, sodium pyrophosphate and sodium ethoxide, the mass concentration of the alkaline solution is 0.1-1.0%, the volume of the alkaline solution is 10-15 times of the volume of the catalyst, the alkaline solution is washed for 1-2 times, the temperature of the alkaline solution is 80-100 ℃, and the alkaline solution stays for 10-50 minutes in each washing.
11. The method of claim 1, wherein: and raising the temperature of the reactor to 80-100 ℃, and introducing air into the reactor at the flow rate of 1-10L/min for 1-5 hours.
12. The method of claim 1, wherein: and introducing mixed gas of air and hydrogen into the reactor, wherein the temperature of the reactor is room temperature, the flow rate of the mixed gas of the hydrogen and the air is 1-10L/min, the volume concentration of the hydrogen in the mixed gas is 1-8%, and the introduction time is 1-5 hours.
13. The method of claim 1, wherein: in the step (4), the volume of the deionized water is 10-30 times of that of the catalyst, the washing is carried out for multiple times, the washing time is 10-50 minutes each time, and the temperature of the deionized water is 80-100 ℃.
14. The method of claim 1, wherein: and (4) washing with deionized water, and then continuing to perform a reaction between formaldehyde and acetylene to prepare the 1, 4-butynediol under the following reaction conditions: the method comprises the steps of taking an aqueous solution with formaldehyde mass percentage concentration of 10-45% and acetylene as raw materials, wherein the mass ratio of a catalyst to the formaldehyde solution is 1: 20-1: 2, and the acetylene partial pressure is 0.1-0.5 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610990986.0A CN108069825B (en) | 2016-11-11 | 2016-11-11 | Method for prolonging service cycle of catalyst for preparing 1, 4-butynediol through reaction of formaldehyde and acetylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610990986.0A CN108069825B (en) | 2016-11-11 | 2016-11-11 | Method for prolonging service cycle of catalyst for preparing 1, 4-butynediol through reaction of formaldehyde and acetylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108069825A CN108069825A (en) | 2018-05-25 |
| CN108069825B true CN108069825B (en) | 2020-11-10 |
Family
ID=62154681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610990986.0A Active CN108069825B (en) | 2016-11-11 | 2016-11-11 | Method for prolonging service cycle of catalyst for preparing 1, 4-butynediol through reaction of formaldehyde and acetylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108069825B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115945228A (en) * | 2022-12-12 | 2023-04-11 | 巴斯夫公司 | Regeneration method for preparing 1,4-butynediol catalyst through alkyne hydroformylation reaction |
Citations (4)
| 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 | Regeneration method of catalyst for synthesizing 1, 4-butynediol from formaldehyde and acetylene in slurry bed reaction |
| CN1132114A (en) * | 1995-10-27 | 1996-10-02 | 化学工业部北京化工研究院 | Regeneration method of catalyst for synthesizing 1, 4-butynediol from formaldehyde and acetylene in slurry bed reaction |
| 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 |
-
2016
- 2016-11-11 CN CN201610990986.0A patent/CN108069825B/en active Active
Patent Citations (4)
| 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 | Regeneration method of catalyst for synthesizing 1, 4-butynediol from formaldehyde and acetylene in slurry bed reaction |
| CN1132114A (en) * | 1995-10-27 | 1996-10-02 | 化学工业部北京化工研究院 | Regeneration method of catalyst for synthesizing 1, 4-butynediol from formaldehyde and acetylene in slurry bed reaction |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108069825A (en) | 2018-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2866207C (en) | Method for preparing solid nitrosyl ruthenium nitrate by using waste catalyst containing ruthenium | |
| CN105195140B (en) | Palladium/alkali metal compound supported catalyst and preparation method and application thereof | |
| JPH10204006A (en) | Production of trifluoromethane iodide | |
| CN109647387A (en) | The method and catalyst of the cracking recycling diphenol of catalytic hydrogenation containing phenolic tar | |
| CN108435171B (en) | Preparation method of bimetallic Pt-Bi catalyst and method for preparing DHA (docosahexaenoic acid) by selectively catalyzing and oxidizing glycerol | |
| CN112341312A (en) | Method for preparing cyclohexanol and derivative thereof by selective hydrogenolysis of lignin | |
| JP2001129405A (en) | Iron oxide-based catalyst for decomposing organic waste, its manufacturing method and treating method of organic waste | |
| CN108069825B (en) | Method for prolonging service cycle of catalyst for preparing 1, 4-butynediol through reaction of formaldehyde and acetylene | |
| CN110105173A (en) | A kind of purification process of efficient HPPO technique recycling design | |
| CN118742390A (en) | Regeneration method for preparing 1, 4-butanediol catalyst by alkyne hydroformylation reaction | |
| CN107011150B (en) | Method for preparing gluconic acid/gluconate and hydrogen by catalytic dehydrogenation of glucose under mild condition | |
| JPH0617160A (en) | Method for recovering rhenium from used catalyst | |
| CN108069827B (en) | Method for preparing 1, 4-butynediol and co-producing propiolic alcohol | |
| US5674796A (en) | Processes of regenerating Ni catalysts and of preparing Ni catalysts | |
| CN103657683A (en) | Regeneration method of Pt/C catalyst | |
| CN112774670A (en) | Application of rhodium monatomic catalyst in reaction for preparing m-chloroaniline through selective hydrogenation of m-chloronitrobenzene | |
| CN103506126B (en) | A kind of preparation method of copper radical synthesizing methanol catalyst | |
| CN105688908B (en) | The catalyst and preparation method thereof of prepared by dimethyl oxalate plus hydrogen methyl glycollate and ethylene glycol | |
| JPH10165818A (en) | Decomposition catalyst for nitrous oxide and removing method of nitrous oxide | |
| CN109824634A (en) | A kind of method that furfural direct oxidation esterification prepares methylfuroate | |
| CN105801455A (en) | Method for oxidatively synthesizing p-carboxybenzene sulfonamide through oxygen | |
| CN101817727A (en) | Treatment method of front cut fractions during production process of o-phenyl phenol | |
| US4038376A (en) | Process for the recovery of selenium from urethanes containing selenium or compounds thereof | |
| CN114950449B (en) | Heterogeneous catalyst and preparation method and application thereof | |
| CN114920787B (en) | Preparation method of fructose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |