CN105413711A - Regeneration preparing method for supported copper-bismuth catalyst - Google Patents
Regeneration preparing method for supported copper-bismuth catalyst Download PDFInfo
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- CN105413711A CN105413711A CN201510805047.XA CN201510805047A CN105413711A CN 105413711 A CN105413711 A CN 105413711A CN 201510805047 A CN201510805047 A CN 201510805047A CN 105413711 A CN105413711 A CN 105413711A
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Abstract
The invention relates to a regeneration preparing method for a supported copper-bismuth catalyst generated in a reaction of synthesizing acetylene and formaldehyde into 1,4-butynediol. The steps of water seal suction filtration and two-time liquid-phase oxidation are adopted. The regeneration preparing method concretely includes the steps that a filter cake is added into a stirrer, an oxidizing agent is added into the stirrer and stirred, a copper ion protective agent is added then, and the stirred materials are heated, stirred, cooled, filtered in a suction mode, washed and dried to obtain a regenerated copper-bismuth catalyst. As the waste copper-bismuth catalyst, the oxidizing agent and the copper ion protective agent react at different temperatures, high polymer impurities such as formaldehyde and polyyne compounds in the waste copper-bismuth catalyst are removed, and finally the catalyst can be regenerated and used. The regeneration preparing method is low in energy consumption, small in pollution coefficient and high in safety and has high economic value.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of by acetylene-formaldehyde synthesis 1, the regenerative preparation of the discarded copper bismuth catalyst generated in the reaction of 4 butynediols, be specifically related to a kind of regenerative preparation being synthesized the carried copper bismuth catalyst generated in the reaction of Isosorbide-5-Nitrae butynediols by acetylene-formaldehyde.
Background technology
Current alkynes aldehyde method is the main technique of producing BDO, and the production capacity of the method accounts for 46.3% of world's aggregated capacity, in the highest flight.Useless alkynes aldehyde reaction catalyst in alkynes aldehyde method real estate technique and copper bismuth catalyst will be discharged as refuse, the main component of discarded copper bismuth catalyst is metallic copper bismuth and remaining formaldehyde, carbene compounds etc., the processing method of current copper scrap bismuth catalyst is generally sell to waste metal returned enterprise outward, carries out the recovery of copper.This kind of method very easily causes the discarded of bismuth metal and environmental pollution.Therefore the recovery of copper bismuth catalyst and regeneration issues seem particularly important.
Copper bismuth catalyst is along with the increase in reaction time, 1, the conversion ratio of 4 butynediols can progressively decline, main cause is that deviation appears in the control of reacting phase related parameter (formaldehyde and acetylene amount than do not mate, reaction temperature, pH value and purity acetylene) for a long time, catalyst surface is caused to cover number of polymers, the specific area of loaded catalyst is reduced greatly, impact reflection effect and product yield on the one hand, reduce by 1,4 butynediols reaction yields, reduce service life and the filter effect of filter plant on the other hand.General by LOI(loss on ignition) value carrys out quantitative measurment catalyst surface overlie polymer, can meet need of production according to actual conditions LOI value general control being less than 60%.If LOI value is greater than 65% needs carry out regeneration process in time.Mainly through supplementary raw catelyst and replacing spent catalyst.
A set of catalyst regeneration special purpose device of the renovation process of present waste and old copper bismuth catalyst mainly Ai Si Man exploitation.The principle of the method is by discarded copper bismuth catalyst by 700 ~ 800 DEG C of incinerator high temperature incinerations, then through stages such as washing, enrichments, finally the copper bismuth catalyst of removing high polymer impurity is turned back to BYD reaction system and recycles.This kind of method is with simple to operation, but power consumption is higher, pollutes larger.Meanwhile, material the most dangerous in catalyst regeneration process is the acetylene copper that possible remain, and dry acetylene copper is to warm and impact extremely responsive, and friction can be ignited, and safety coefficient is low.The method is comparatively large to the destructiveness of catalyst support structures in addition, greatly can reduce the activity of catalyst.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency of the prior art and provide a kind of power consumption low, polluting little, the regenerative preparation of the carried copper bismuth catalyst that safety coefficient is high.
The object of the present invention is achieved like this:
A regenerative preparation for carried copper bismuth catalyst, is characterized in that: comprise the following steps:
Step 1), to produce: discarded copper bismuth catalyst is added water-stop, preserve 1-6 days, take the filter cake that suction filtration is crossed, filter cake refers to that liquid is by after filter, being retained in the solid matter contained by the stoste on filter, is the solid matter after the mixture of discarded copper bismuth catalyst and water filters;
Step 2), carry out liquid phase oxidation first: the filter cake obtained in step 1) is added in agitator, then in agitator, add the hydrogen peroxide that percentage by weight is 30%, stir, add the copper ion protective agent sodium acetate solid that percentage by weight is 0.2% again, heating makes stirring temperature of charge to 30-40 DEG C, stir 30-50min, cooling, suction filtration, washing leaching cake, drying, obtain dried filter cake;
Step 3), second time carry out liquid phase oxidation: by step 2) carry out second time oxidation through the dried filter cake of washing; add the hydrogen peroxide that percentage by weight is 10%; stir; add the copper ion protective agent sodium acetate solid that percentage by weight is 0.2% again; heating makes stirring temperature of charge to 90-100 DEG C; stir 30-50min, cooling, suction filtration, washing leaching cake, drying, dried filter cake is the copper bismuth catalyst of regeneration.
The present invention has following good effect:
1, water seal preserving type and liquid phase oxidation process are taked to discarded discarded copper bismuth catalyst, avoid the danger of acetylene copper blast, improve security.
2, the heating-up temperature required for this technique is lower, consume energy low, pollute little, technological operation is easy.
3, adopt liquid phase oxidation that catalyst activity can be made to remain on about 85%-90%, improve salvage value, economic benefit is obvious.
Detailed description of the invention
The present invention is set forth further below in conjunction with specific embodiment:
The regenerative preparation of embodiment 1. 1 kinds of carried copper bismuth catalysts, is characterized in that: comprise the following steps:
Step 1), to produce: discarded copper bismuth catalyst is added water-stop, preserve 1-6 days, take the filter cake that suction filtration is crossed, filter cake refers to that liquid is by after filter, being retained in the solid matter contained by the stoste on filter, is the solid matter after the mixture of discarded copper bismuth catalyst and water filters;
Step 2), carry out liquid phase oxidation first: the filter cake obtained in step 1) is added in agitator, then in agitator, add the oxidant that percentage by weight is 30%, stir, add the copper ion protective agent that percentage by weight is 0.2% again, copper ion protective agent is sodium acetate solid, and heating makes stirring temperature of charge to 30-40 DEG C, stirs 30-50min, cooling, suction filtration, washing leaching cake, drying, obtain dried filter cake;
Step 3), second time carry out liquid phase oxidation: by step 2) carry out second time oxidation through the dried filter cake of washing; add the hydrogen peroxide that percentage by weight is 10%; stir; add the copper ion protective agent that percentage by weight is 0.2% again; copper ion protective agent is sodium acetate solid, and heating makes stirring temperature of charge to 90-100 DEG C, stirs 30-50min; cooling, suction filtration, washing leaching cake, drying, dried filter cake is the copper bismuth catalyst of regeneration.
Described take the filter cake that suction filtration crosses and refer to that liquid is by after filter, is retained in the solid matter contained by the stoste on filter, is the solid matter after the mixture of discarded copper bismuth catalyst and water filters.
Claims (1)
1. a regenerative preparation for carried copper bismuth catalyst, is characterized in that: comprise the following steps:
Step 1), to produce: discarded copper bismuth catalyst is added water-stop, preserve 1-6 days, take the filter cake that suction filtration is crossed, filter cake refers to that liquid is by after filter, being retained in the solid matter contained by the stoste on filter, is the solid matter after the mixture of discarded copper bismuth catalyst and water filters;
Step 2), carry out liquid phase oxidation first: the filter cake obtained in step 1) is added in agitator, then in agitator, add the hydrogen peroxide that percentage by weight is 30%, stir, add the copper ion protective agent sodium acetate solid that percentage by weight is 0.2% again, heating makes stirring temperature of charge to 30-40 DEG C, stir 30-50min, cooling, suction filtration, washing leaching cake, drying, obtain dried filter cake;
Step 3), second time carry out liquid phase oxidation: by step 2) carry out second time oxidation through the dried filter cake of washing; add the hydrogen peroxide that percentage by weight is 10%; stir; add the copper ion protective agent sodium acetate solid that percentage by weight is 0.2% again; heating makes stirring temperature of charge to 90-100 DEG C; stir 30-50min, cooling, suction filtration, washing leaching cake, drying, dried filter cake is the copper bismuth catalyst of regeneration.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510805047.XA CN105413711A (en) | 2015-11-20 | 2015-11-20 | Regeneration preparing method for supported copper-bismuth catalyst |
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| CN201510805047.XA CN105413711A (en) | 2015-11-20 | 2015-11-20 | Regeneration preparing method for supported copper-bismuth catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108067240A (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 renovation process for preparing 1,4- butynediols dead 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 |
| CN111589836A (en) * | 2019-09-16 | 2020-08-28 | 徐光耀 | Method for treating waste containing acetylides |
| CN113209980A (en) * | 2021-04-25 | 2021-08-06 | 西安航天源动力工程有限公司 | Regeneration method of waste copper bismuth catalyst |
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| CN1118342A (en) * | 1995-07-19 | 1996-03-13 | 化学工业部北京化工研究院 | Unsupported catalyst for producing 1, 4-butynediol and preparation method and application thereof |
| 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 |
| CN102658158A (en) * | 2012-05-20 | 2012-09-12 | 山西大学 | Copper bismuth catalyst and preparation method thereof |
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| CN1118342A (en) * | 1995-07-19 | 1996-03-13 | 化学工业部北京化工研究院 | Unsupported catalyst for producing 1, 4-butynediol and preparation method and application thereof |
| 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 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108067240A (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 renovation process for preparing 1,4- butynediols dead 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 |
| CN111589836A (en) * | 2019-09-16 | 2020-08-28 | 徐光耀 | Method for treating waste containing acetylides |
| CN111229785A (en) * | 2020-03-04 | 2020-06-05 | 河南理工大学 | Method for treating industrial catalytic waste of copper acetylide |
| CN113209980A (en) * | 2021-04-25 | 2021-08-06 | 西安航天源动力工程有限公司 | Regeneration method of waste copper bismuth catalyst |
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