CN1132114A - Regenerating method of catalyst for 1,4-butine-glycol synthetized by formaldehyde and acetylene reacted in slurry bed - Google Patents
Regenerating method of catalyst for 1,4-butine-glycol synthetized by formaldehyde and acetylene reacted in slurry bed Download PDFInfo
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- CN1132114A CN1132114A CN 95116599 CN95116599A CN1132114A CN 1132114 A CN1132114 A CN 1132114A CN 95116599 CN95116599 CN 95116599 CN 95116599 A CN95116599 A CN 95116599A CN 1132114 A CN1132114 A CN 1132114A
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Abstract
A process for regenerating catalyst used to synthesize 1,4-butynediol from formaldehyde and acetylene on slurry bed includes oxidation of waste catalyst with strong oxidant in liquid, separation and drying, and features high safety and recovery rate, simple process and the same catalytic activity of regenerated catalyst as the original.
Description
The present invention relates to a kind of renovation process of catalyst, more particularly, relate to a kind of slurry-bed reaction that is used for and synthesize 1 by formaldehyde and acetylene, the 4-butynediols renovation process of catalyst.
Utilize formaldehyde and acetylene to synthesize 1, the 4-butynediols can adopt technologies such as Reppe method trickle bed, suspension bed and slurry bed.Advantages such as synthesising reacting speed is fast, pressure is low because slurry bed technology has, handling safety, catalyst replacing convenience have become at present and have synthesized 1, one of main method of 4-butynediols.
The slurry bed method synthesizes 1, and the 4-butynediols uses the copper bismuth catalyst mostly.Main component cupric oxide in this type of catalyst, generate the alkynes copper complex with formaldehyde and acetylene reaction, PARA FORMALDEHYDE PRILLS(91,95) and acetylene synthesize 1, and the 4-butynediols plays catalytic action, and the main effect of bismuth oxide component wherein then is the acetylene polymerization side reaction that produces in the inhibitory reaction process.Owing to be subjected to the influence of impurity in the raw material, operating condition and accessory substance acetylene polymer, its catalytic performance can reduce above-mentioned catalyst gradually in process of production.In order to keep high catalytic activity and stable production, must regularly replace or add at any time catalyst, therefore can produce a large amount of dead catalyst, contain a large amount of very unsettled in this dead catalyst, the alkynes copper compound of decomposition explosion takes place in chance heat, friction or bump, brings very big difficulty to handling and recycle catalyst.
The dead catalyst that normally will contain alkynes copper takes underground buried method to handle, and this kind method has not only caused the waste of a large amount of non-ferrous metal copper and bismuth, and can cause more serious pollution to environment.
Many experts and scholars are seeking practicable recovery method, solve the problem of outlet of useless alkynes copper catalyst.For example smelting method, mainly be metallic copper and the bismuth that reclaims in the catalyst, but this method danger is bigger, and the technology more complicated, and the practical application difficulty is bigger.Acid hydrolyzation for example is after utilizing strong acid and the effect of alkynes copper compound to generate salt, prepare new catalyst more again, but this method removal process to be long again, consume a large amount of strong acid, and recovery cost is very high.Up to now, also do not see having with this dead catalyst regeneration, the technology of reusing.
U.S. Pat 4,311,611 have announced that a kind of oxidizing process reclaims the method for catalyst, this catalyst is a kind of oxide that contains metals such as iron, antimony, copper, cobalt, nickel, magnesium, is mainly used on the technologies such as oxidation, ammoxidation and oxidative dehydrogenation of hydrocarbon.This method is to utilize H
2O
2As oxidant, with the dead catalyst effect, and then after filtration, steps such as drying, calcining, make dead catalyst obtain regeneration.But do not provide the renovation process that contains the copper scrap bismuth catalyst of explosive alkynes copper compound of the present invention in this patent.
Purpose of the present invention is exactly the defective that exists in the above-mentioned prior art in order to overcome, and proposes a kind of slurry-bed reaction that is used for and synthesizes 1 by formaldehyde and acetylene, the 4-butynediols renovation process of catalyst.
The inventor has proposed a kind of slurry-bed reaction that is used for and has synthesized 1, the renovation process of 4-butynediols copper scrap bismuth catalyst by formaldehyde and acetylene through research for many years.
The objective of the invention is to realize according to following flow process:
Dead catalyst and strong oxidizer are carried out oxidation reaction in liquid phase, carry out Separation of Solid and Liquid then, the solid matter that obtains is washed to remove water-solubility impurity, obtain the black powder solid after the drying, it promptly is the oxide of copper and bismuth, that is to say that being used for of obtaining regenerating is synthetic 1, the catalyst of 4-butynediols.
Be used for slurry-bed reaction and synthesize 1 by formaldehyde and acetylene, 4-butynediols catalyst for reaction is the mixture of cupric oxide and bismuth oxide, and the weight ratio between copper and the bismuth is 100: 1～100: 40, and general carrier-free exists.After being used for slurry-bed reaction, cupric oxide in the catalyst and formaldehyde and acetylene reaction generate the alkynes copper complex, and to synthesizing 1, the 4-butynediols has reacted catalytic action.In said method, alkynes copper complex in the decaying catalyst and strong oxidizer reaction generate cupric oxide, make catalyst obtain regeneration.
Oxidation reaction is the key of whole regenerative process, and its quality directly influences the performance of catalyst, and it mainly is performance, oxidant consumption, reaction temperature and the influence in reaction time of oxidant.
Above-mentioned dead catalyst is synthetic 1 by formaldehyde and acetylene, and the 4-butynediols is used for the catalyst of inactivation behind the slurry-bed reaction.
Above-mentioned strong oxidizer can be selected from hydrogen peroxide, perchloric acid, perchlorate, chloric acid, chlorate, hypochlorous acid, a kind of in the hypochlorite or their mixture; Be preferably hypochlorite; The best is hypochlorous sodium salt.Wherein the ratio of dead catalyst and clorox (in Cl) weight of material is within 1: 0.5～1: 5.0 scope; 1: 2.0～1: 4.5 comparatively suitable; 1: 3.0～1: 4.0 is best.
Above-mentioned hypochlorous sodium salt is 1～13.5% the aqueous solution, wherein adds a certain amount of NaOH, makes solution be alkalescence, helps oxidation reaction, and the addition of NaOH is 0.1～20% of a solution, is preferably 1～15%, is preferably 2～3%.
Above-mentioned oxidation reaction is carried out in two steps, and first step reaction temperature is 30 ℃～90 ℃, in 10～50 minutes reaction time, is preferably 20～30 minutes; The second step reaction temperature is 100 ℃～108 ℃, and the reaction time is 20～60 minutes, is preferably 30～40 minutes.Wherein first step reaction temperature is controlled by the speed of dropping oxidizing agent.
The present invention has the following advantages:
(1) in the present invention because oxidation reaction is to carry out in liquid phase, so solved the safety problem of handling easily the alkynes copper catalyst that decomposes, explodes;
(2) strong oxidizer used in the present invention is simple and easy to, the product recovery rate height, and processing procedure is simple, convenient.
(3) the regenerate catalyst of gained of the present invention has the catalytic performance identical with raw catalyst, and it is synthetic 1 to have reduced the slurry bed method, and the production cost of 4-butynediols has reduced the pollution to environment.
Embodiment:
Example 1: with dead catalyst 55.0 grams of cupric 42.16% and bismuth 5.85%, put into one 3000 milliliters beaker, under condition of stirring, in beaker, drip 2280.0 grams and (contain [Cl] 12.41%, NaOH2.64%) liquor natrii hypochloritis, in temperature is under 50～70 ℃, adds in 20 minutes; Under agitation boiled 30 minutes in 100～108 ℃, tell solid after the cooling and wash, obtain black solid catalyst (oxidation state) 31.9337 grams after the oven dry, wherein copper 70.986%, and bismuth 9.9% is 97.83% in the metal rate of recovery.
Example 2: in 500 milliliters of glass there-necked flasks that have stirring and condenser, dead catalyst 10.0 grams that add cupric 42.3% and bismuth 6.3%, (contain [Cl] 12.41%, liquor natrii hypochloritis NaOH2.64%) added in 20 minutes to drip 400.0 grams at 50～60 ℃; Under agitation continue to react 30 minutes in 107 ℃, the copper complex formazan content of alkynes is 0 in the assaying reaction product, and the copper loss mistake is 0.41% in the solution.Under similarity condition, the temperature in the time of only will feeding in raw material changes 90～95 ℃ into, and the copper loss mistake is 0.27% in the solution.
Example 3: the condition identical with example 2, only changing charge ratio (alkynes copper/[Cl]) is 1: 2.48 and 1: 4.96, and the former has alkynes copper to exist and acid non-soluble substance, and the copper loss mistake is 0.68% in the solution, and the latter does not have existence of alkynes copper and acid non-soluble substance, and the copper loss mistake is 0.34% in the solution.
Example 4: the condition identical with example 2, charge ratio (alkynes copper/[Cl]) is 1: 4.96, changes clorox concentration, and clorox [Cl] is respectively 12.41% and 5.76%, the no alkynes copper in reaction back exists and acid non-soluble substance, and copper loss is lost and is respectively 0.34% and 0.48% in the solution.
Example 5: the condition identical with example 2, charge ratio (alkynes copper/[Cl]) is 1: 4.96, the content that changes NaOH among the liquor natrii hypochloritis is respectively 0.28%, 0.78% and 3.84%, the no alkynes copper in reaction back exists and acid non-soluble substance, and copper loss is lost and is respectively 0.48%, 0.34% and 0.12% in the solution.
Example 6: the regenerated catalyst of example 1 gained is used for formaldehyde and acetylene synthetic 1, the slurry-bed reaction of 4-butynediols, reaction condition is: under 90 ℃, normal pressure, reacted 7 hours, raw material formalin/catalyst is 9: 1 (weight ratio), and the concentration of formalin is 35.84wt%.Reaction result is: the conversion ratio of formaldehyde: 88.52%, and space-time yield 14.42g/g.d, selectivity 97.42%.
Example 7: it is synthetic 1 that raw catelyst is used for formaldehyde and acetylene, and the slurry-bed reaction of 4-butynediols, reaction condition are with example 6, and reaction result is: the conversion ratio of formaldehyde: 90.0%, and space-time yield 14.22g/g.d, selectivity 96.60%.
By the test data of example 6 and example 7 more as can be seen, it is synthetic 1 to utilize the catalyst of regeneration to be used for formaldehyde and acetylene, the slurry-bed reaction of 4-butynediols can obtain the reaction result identical with raw catelyst.
Claims (10)
1, a kind of slurry-bed reaction synthesizes 1, and the renovation process of the catalyst that the 4-butynediols is used is characterized in that, it comprises following step:
(1) dead catalyst and strong oxidizer are carried out oxidation reaction in liquid phase;
(2) mixture that reaction is obtained carries out Separation of Solid and Liquid, obtains solids;
(3) solids of step (2) gained is washed, being used for of obtaining after the drying regenerating is synthetic 1, the catalyst of 4-butynediols.
2, method according to claim 1 is characterized in that, described strong oxidizer can be selected from hydrogen peroxide, perchloric acid, perchlorate, chloric acid, chlorate, hypochlorous acid, a kind of in the hypochlorite or their mixture.
3, method according to claim 1 is characterized in that, described oxidation reaction is carried out in two steps, and first step reaction temperature is 30 ℃～90 ℃, and the reaction time is 10～50 minutes; The second step reaction temperature is 100 ℃～108 ℃, and the reaction time is 20～60 minutes.
4, method according to claim 1 is characterized in that, described strong oxidizer is hypochlorous sodium salt.
5, method according to claim 4 is characterized in that, described hypochlorous sodium salt is 1～13.5% the aqueous solution, wherein contains 0.1～20% NaOH.
6, method according to claim 4 is characterized in that, contains 1～15% NaOH in the aqueous solution of described hypochlorous sodium salt.
7, method according to claim 4 is characterized in that, contains 2～3% NaOH in the aqueous solution of described hypochlorous sodium salt.
According to the described method of one of claim 4～7, it is characterized in that 8, the ratio of described dead catalyst and clorox [Cl] weight of material is 1: 0.5～1: 5.0.
9,, it is characterized in that the ratio of described dead catalyst and clorox [Cl] weight of material is 1: 2.0～1: 4.5 according to the described method of one of claim 4～7.
10,, it is characterized in that the ratio of described dead catalyst and clorox [Cl] weight of material is 1: 3.0～1: 4.0 according to the described method of one of claim 4～7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95116599A CN1048919C (en) | 1995-10-27 | 1995-10-27 | Regenerating method of catalyst for 1,4-butine-glycol synthetized by formaldehyde and acetylene reacted in slurry bed |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95116599A CN1048919C (en) | 1995-10-27 | 1995-10-27 | Regenerating method of catalyst for 1,4-butine-glycol synthetized by formaldehyde and acetylene reacted in slurry bed |
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| CN1132114A true CN1132114A (en) | 1996-10-02 |
| CN1048919C CN1048919C (en) | 2000-02-02 |
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| CN95116599A Expired - Fee Related CN1048919C (en) | 1995-10-27 | 1995-10-27 | Regenerating method of catalyst for 1,4-butine-glycol synthetized by formaldehyde and acetylene reacted in slurry bed |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413711A (en) * | 2015-11-20 | 2016-03-23 | 苏英慧 | Regeneration preparing method for supported copper-bismuth catalyst |
| CN108069825A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of method for improving formaldehyde and acetylene reaction and preparing 1,4- butynediols catalyst service life |
| CN111229785A (en) * | 2020-03-04 | 2020-06-05 | 河南理工大学 | Method for treating industrial catalytic waste of copper acetylide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5945422B2 (en) * | 1978-12-05 | 1984-11-06 | 日東化学工業株式会社 | Method for regenerating antimony-containing oxide catalyst |
| JPS63137755A (en) * | 1986-11-28 | 1988-06-09 | Nippon Shokubai Kagaku Kogyo Co Ltd | Reactivation of catalyst |
| CN1051683A (en) * | 1989-11-16 | 1991-05-29 | 甘肃省刘家峡化肥厂 | The recovery method of waste copper-series catylist |
| DE4200006A1 (en) * | 1992-01-02 | 1993-07-08 | Tech Hochschule C Schorlemmer | Activating molybdenum-contg. mixed oxide catalyst for propene ammoxidation - by treating with readily-dispersed bismuth-III cpd. at 300-600 deg.C |
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1995
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413711A (en) * | 2015-11-20 | 2016-03-23 | 苏英慧 | Regeneration preparing method for supported copper-bismuth catalyst |
| CN108069825A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of method for improving formaldehyde and acetylene reaction and preparing 1,4- butynediols catalyst service life |
| CN108069825B (en) * | 2016-11-11 | 2020-11-10 | 中国石油化工股份有限公司抚顺石油化工研究院 | Method for prolonging service cycle of catalyst for preparing 1, 4-butynediol through reaction of formaldehyde and acetylene |
| CN111229785A (en) * | 2020-03-04 | 2020-06-05 | 河南理工大学 | Method for treating industrial catalytic waste of copper acetylide |
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