CN111589836B - Method for treating waste containing acetylides - Google Patents
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- CN111589836B CN111589836B CN201910870435.4A CN201910870435A CN111589836B CN 111589836 B CN111589836 B CN 111589836B CN 201910870435 A CN201910870435 A CN 201910870435A CN 111589836 B CN111589836 B CN 111589836B
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- 239000002699 waste material Substances 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000000476 acetylides Chemical class 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims description 141
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- 239000000741 silica gel Substances 0.000 claims description 40
- 229910002027 silica gel Inorganic materials 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 32
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- NPKGQBIUYHHPOT-UHFFFAOYSA-N [Cu+2].[C-]#[C-] Chemical compound [Cu+2].[C-]#[C-] NPKGQBIUYHHPOT-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 9
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- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- SLERPCVQDVNSAK-UHFFFAOYSA-N silver;ethyne Chemical compound [Ag+].[C-]#C SLERPCVQDVNSAK-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
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- 238000000354 decomposition reaction Methods 0.000 description 21
- 238000011084 recovery Methods 0.000 description 21
- 239000003381 stabilizer Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000004880 explosion Methods 0.000 description 17
- WTFDOFUQLJOTJQ-UHFFFAOYSA-N [Ag].C#C Chemical compound [Ag].C#C WTFDOFUQLJOTJQ-UHFFFAOYSA-N 0.000 description 12
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 11
- 238000011069 regeneration method Methods 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- -1 acetylene cadmium Chemical compound 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002360 explosive Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- BBGINXZYXBFSEW-UHFFFAOYSA-N [Cu].C#C Chemical compound [Cu].C#C BBGINXZYXBFSEW-UHFFFAOYSA-N 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000003915 air pollution Methods 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
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- 238000003786 synthesis reaction Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 239000007791 liquid phase Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- RWVDMVCOVCFEJM-UHFFFAOYSA-N [Hg].C#C Chemical compound [Hg].C#C RWVDMVCOVCFEJM-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005474 detonation Methods 0.000 description 2
- KZXVOMYVNQPCKX-UHFFFAOYSA-N ethyne;mercury(1+) Chemical compound [Hg+].[C-]#C KZXVOMYVNQPCKX-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- NNTGAOLTGGLLPE-UHFFFAOYSA-N [Zn+2].[C-]#[C-] Chemical compound [Zn+2].[C-]#[C-] NNTGAOLTGGLLPE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- DIWKDXFZXXCDLF-UHFFFAOYSA-N chloroethyne Chemical compound ClC#C DIWKDXFZXXCDLF-UHFFFAOYSA-N 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the field of waste treatment, and particularly relates to a method for treating waste containing acetylides.
Description
Technical Field
The invention relates to the field of waste treatment, in particular to a method for treating waste containing acetylide.
Background
Acetylides are used as important active ingredients of organic synthesis reactions, and are often used for industrial production, and common acetylides include acetylide copper, acetylene mercury, acetylene silver, acetylene cadmium and the like. Among them, copper acetylide is used as a catalytic active component for the production and synthesis of 1, 4-butynediol in large quantities, and cadmium acetylide and mercury acetylide are also used for the synthesis of alcohols, the ethynylation reaction and the like. With the increase of the reaction time, the surface of the catalyst is gradually covered by the polymer, the pore channels of the catalyst are blocked by impurities, the metal components gradually run off, and the catalytic performance is lost. At this time, the catalyst needs to be replaced, and the replaced waste catalyst is generally delivered to a hazardous waste plant for incineration disposal. Due to the explosive nature of acetylides, there is no specific regeneration or treatment method in China for a while. The waste catalyst can only be mixed with other waste catalysts in batches for disposal, but secondary pollution and resource waste are often caused; silver acetylene is often used as an intermediate product for silver extraction and also as one of the photosensitive initiators for weapons and ammunition. Along with long-time storage or failure caused by other reasons, the explosive can only be detonated for treatment, and accidental casualties are easy to cause due to improper operation, so that financial resources are wasted, and the explosive is dangerous.
The international existing acetylene compound regeneration method mainly utilizes a set of special catalyst regeneration device developed by the Ismann company. The principle of the method is that the waste catalyst is placed in an incinerator to be incinerated at the temperature of 200-600 ℃ under the controlled atmosphere, and then the catalyst with high polymer impurities removed is returned to a BYD reaction system for recycling after the stages of washing, thickening and the like are carried out. The inventor of the proposal realizes uncontrollable decomposition reaction of the acetylide and tries to reduce the possibility of explosion by controlling the temperature of the atmosphere in the furnace, but does not radically change the decomposition speed of the acetylide and improve the stability of the decomposition; so that the possibility of explosion still remains. In addition, the property difference of the waste catalyst is large, and the disposal quantity of the waste catalyst of several tons/h is difficult to control by using the method. In addition, the materials are usually contaminated with organic matters, and are heated by atmosphere, so that all the organic matters are difficult to degrade at the furnace temperature of less than 600 ℃, and organic gas is likely to leak to cause secondary pollution.
The invention is also applied to the treatment of the compound waste catalyst containing the acetylene copper in China, for example, the waste catalyst and a strong oxidant are subjected to oxidation or reduction reaction in a liquid phase, and then are separated and dried to obtain a regenerated catalyst. Although the regeneration of the catalyst is theoretically possible, it also brings about a new problem that the process requires a large amount of an oxidizing agent or a reducing agent to be consumed, is expensive, and also generates waste water and explosive chloroethyne.
The recovery of waste materials such as acetylene silver, acetylene mercury and the like in China is not patented, and only a part of patents assume that silver in a silver material is dissolved and converted into acetylene silver, and then the acetylene silver is reduced by using dimethylhydrazine to obtain silver, but the dimethylhydrazine involved in the method has carcinogenicity and higher cost.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for treating waste containing acetylides, which is aimed at solving the problems of difficult control of decomposition rate, poor treatment, new environmental protection problem or waste regeneration, high energy consumption, high cost, pollution and potential safety hazard, and extending the applicability of the treated target, and is also applicable to non-catalyst waste containing acetylides.
The technical scheme adopted by the invention for solving the technical problems is as follows: provides a method for treating waste containing acetylides,
adding a porous structure substance and water to stir the waste for 3-5h until the materials are fully mixed, wherein the dosage of the porous structure substance is 90% -120% of the acetylene compounds in the waste, and the liquid-solid ratio is (2-3): 1, and controlling the pH value to be 5-7;
dehydrating the waste material and the porous structure material to a moisture content of less than 66%;
when the waste is the waste catalyst, sampling and detecting the comprehensive performance ratio of the regenerated catalyst:
the comprehensive performance ratio of the regenerated catalyst is more than 90 percent, and the waste catalyst is placed into an incinerator for roasting and sorting at the temperature of 300-850 ℃ so as to return to production;
the comprehensive performance ratio of the regenerated catalyst is less than 90 percent, and the waste catalyst is placed into an incinerator and is roasted and degraded at the temperature of 1500 ℃ under 300 ℃ to obtain metal;
when the waste is non-catalyst waste, the waste is treated by the same process with the catalyst waste containing acetylide with the inactivation ratio of less than 90 percent;
wherein the comprehensive performance ratio refers to the productivity mass ratio of each kilogram of the regenerated catalyst to each kilogram of the new catalyst before deactivation in unit time under the same production working condition.
Further, the porous structure substance is one or more of silica gel, alumina gel, diatomite or other porous structure substances.
Further, the stirring speed is 900-.
Further, the dehydration is carried out by distillation, adsorption or extrusion singly or in combination.
Further, the dehydration is carried out by adopting a combination of distillation and adsorption modes.
Further, when the catalytic efficiency of the waste catalyst is more than 90% of that before deactivation, the liquid-solid mass ratio is 3: 1.
Further, when the catalytic efficiency of the waste catalyst is more than 90% of that before deactivation, the liquid-solid mass ratio is 2: 1.
Further, the incinerator is a reverberatory furnace, a cupola furnace or other similar furnace types.
Has the advantages that: the invention provides a method for treating waste containing acetylides, which comprises the steps of adding a substance with a porous structure as a stabilizer in the treatment process of the waste containing acetylides, adding water, stirring the liquid phase until the liquid phase is fully mixed, controlling the liquid-solid ratio and the pH value to achieve a better passivation effect, dehydrating, and respectively baking at different temperatures according to the types and properties of the waste to treat and recycle the waste.
Detailed Description
The present invention provides a method for treating waste containing acetylides, and the present invention is further described in detail below in order to make the objects, technical schemes and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
According to the method for treating the waste containing the acetylide provided by the preferred embodiment of the invention, firstly, a porous structure substance and water are added to stir the waste for 3-5 hours until the waste is fully mixed, and the stirring rotating speed is preferably 900-; wherein the dosage of the porous structure substance is 90-120% of the acetylene substance in the waste, preferably 100%, and the liquid-solid mass ratio is (2-3): 1, and controlling the pH value to be 5-7, wherein the acetylide passivation effect is good in the pH value range, the pH value can be adjusted through caustic soda or other alkaline substance solutions when the pH value is lower, and can be adjusted through adding an acetic acid solution when the pH value is higher so as to achieve the pH value with a better passivation effect.
Then, the spent catalyst and the porous structural substance are dehydrated to a moisture content of less than 66%, and the subsequent calcination temperature can reach the set temperature due to the moisture content of less than 66%. The invention adopts single or combined distillation, adsorption or extrusion modes to dehydrate, preferably adopts a combination of distillation and adsorption modes to dehydrate, and the water content after dehydration can be detected by weighing to determine whether the water content meets the requirement.
As the acetylide-containing waste typically comprises acetylide-containing spent catalyst and acetylide-containing non-catalyst waste. The waste catalyst containing acetylide can be regenerated for improving economic value. However, if the catalyst can be regenerated, the comprehensive performance ratio of the regenerated catalyst needs to be sampled and detected for judgment.
Therefore, if the waste material is a waste catalyst, the waste catalyst is sampled and regenerated, and the comprehensive performance ratio of the regenerated catalyst is detected. Because acetylides are mostly used as catalysts for organic synthesis, after the catalysts are used for a period of time, polymer and impurity ions can cover the inner and outer surfaces of the catalysts to hinder the reaction; improper operating conditions can reduce the concentration of metal ions in the acetylide; the catalyst can be abraded and other factors in the using process, so that the catalyst is partially or completely inactivated, the catalysis efficiency is low, the production cannot be met, and the catalyst needs to be replaced, so that the waste catalyst is generated. However, the waste catalyst has different catalytic effects after regeneration due to the difference of factors such as the use time, conditions and the like, and in order to better treat and utilize the waste catalyst, the waste catalyst is sampled and subjected to a catalytic test, when the productivity of the regenerated catalyst per kilogram of unit time is not less than 90% of that of the new catalyst, the regenerated catalyst is regarded as the waste catalyst with better comprehensive performance, otherwise, the regenerated catalyst is regarded as the waste catalyst with poorer comprehensive performance, and the performance is distinguished and then the waste catalyst is recycled in the following different modes.
And finally, when the comprehensive performance ratio of the regenerated catalyst is more than 90%, placing the waste catalyst into an incinerator for roasting and sorting at the temperature of 850 ℃ under 300-. In the process, the waste catalyst not only contains the acetylide, but also contains other organic matters and compounds, and the temperatures required for decomposing the substances are different, so the furnace temperature range is wide, and the temperature can be selected according to the specifically related organic matters. After organic matters and carbon are removed by roasting at a proper temperature, the regenerated acetylide catalyst, the porous structure substance and the metal-containing residue can be obtained, wherein the metal-containing residue can be sold as a secondary resource.
Or the comprehensive performance of the regenerated catalyst accounts for less than 90% of that of the catalyst before deactivation, and the waste catalyst is placed into an incinerator and subjected to 300-1500 ℃ baking degradation to obtain metal; wherein the combination of the performance refers to the productivity per unit time of 1 kg of the regenerated catalyst and the recycling amount of the spent catalyst. The temperature of the waste catalyst containing the copper acetylide which is usually treated is 1500 ℃ below 1000 ℃, and carbon-carbon bonds can be broken generally above 1000 ℃, so that the organic matter can be fully degraded by baking at 1500 ℃ below 1000 ℃, and the alloy, the porous structure substance and the residue containing the metal can be obtained, wherein the residue containing the metal can be sold as a secondary resource.
The acetylene compound-containing non-catalyst waste is treated by the same process as the acetylene compound-containing catalyst waste with the comprehensive performance of less than 90 percent.
Because the acetylene compounds are decomposed to generate a strongly exothermic chain reaction and further explode, the generation of the ton-shift chain reaction needs to be fundamentally hindered to fundamentally solve the problem of violent decomposition reaction, and a porous structure substance is added as a stabilizer in the reaction process, which is mainly considered from the following factors:
1. the porous structure substance has a higher specific surface area, so that active free radicals and active molecules of acetylide can be adsorbed, collision is reduced, the chain reaction rate is influenced, the sensitivity is reduced, and the acetylene compound is passivated;
2. after the porous structure substance absorbs water, the effective energy of detonation of the acetylide is reduced;
3. the porous structure substance belongs to an inert material, does not burn, is provided with holes inside, and can effectively block part of microscopic explosion in the holes, weaken the conduction of explosion shock waves and prevent detonation explosion.
In conclusion, through multiple influences and comprehensive action, the original explosion reaction of the acetylide during heating decomposition is changed into mild decomposition reaction, and the aim of safely treating and recycling the waste catalyst is fulfilled.
Further, the porous structure substance is one or more of silica gel, alumina gel, diatomite or other porous structure substances. Silica gel is preferred.
Further, in the present embodiment, the incinerator is a reverberatory furnace or a cupola furnace.
The preparation method is simple and convenient, has high stability, is easy for industrial production and is convenient for popularization and application. According to experimental tests, the scheme of the invention is adopted to recover the waste containing the acetylide, the regeneration recovery rate of the waste with good performance reaches 75-85%, the recovery rate of the waste catalyst metal with poor performance reaches more than 92%, and the recovery rates of the two porous structure substances subjected to roasting treatment reach more than 95%.
The invention is illustrated in detail below with specific examples:
the method can realize catalytic recovery of acetylene metal complexes such as copper acetylide, silver acetylide, zinc acetylide, cadmium acetylide, mercury acetylide, palladium acetylide and the like in the waste materials, and the waste catalysts of the copper acetylide and the silver acetylide are selected for exemplification in consideration of both the actual dosage and the stability in the use process because the explosiveness of the silver acetylide and the copper acetylide is strong and the use range of the copper acetylide is wide, of course, the non-catalysts containing the acetylide can be treated by the scheme of the following embodiments 5 to 7, and the detailed description is not repeated in the following embodiments.
It should be noted that, in the production and synthesis process of 1, 4-butynediol, the catalyst which is put in at the beginning is a copper bismuth catalyst, and copper bismuth exists in the catalyst in the form of oxide, when the reaction is activated, copper oxide is converted into copper acetylide, and copper acetylide is also a component with catalytic activity. Although there is a significant portion of explosive copper acetylides present with catalyst failure, the presence of this portion is a danger for disposal of the spent copper bismuth catalyst.
Example 1
Taking 1000g of waste copper bismuth catalyst containing 6.35% of copper, adding 60 g of stabilizer silica gel and water, controlling the solid-to-liquid ratio to be 3:1, stirring for 4h at normal temperature, and controlling the rotating speed to be 950r/min to fully mix the waste copper bismuth catalyst and the waste copper bismuth catalyst. During the stirring process, the pH value is controlled to be 7.
And (3) dehydrating the stabilized waste catalyst and silica gel in a distillation and adsorption mode, wherein the water content of the dehydrated waste catalyst is 65%, and the wastewater returns to a BYD sewage plant.
And (3) putting the dehydrated waste catalyst and silica gel into an incinerator, controlling the furnace temperature to be 650 ℃, and removing organic matters and carbon.
Adopting gravity separation to obtain 66.8g of regenerated catalyst, with a recovery rate of 80%; 58.2g of stabilizer, 97% recovery, the remaining poor performance residue generally contains metal and can be sold as a secondary resource.
The embodiment is an optimal scheme for treating the waste catalyst containing the copper acetylide, the explosive decomposition temperature of the copper acetylide is about 105-110 ℃, but in the operation process of the embodiment, the copper acetylide is passivated by controlling silica gel and PH value, so that the decomposition reaction is mild and controllable, the reaction temperature fluctuation is 650-680 ℃ under the condition, the reaction temperature fluctuation is small, the explosion sound is avoided, and the air pollution is avoided; the waste catalyst containing acetylide with good performance is efficiently utilized, a small amount of silica gel is consumed, the higher regeneration rate of the catalyst is realized, the industrial cyclic utilization is realized, and the rest residues are sold as secondary resources, so that the cost is saved and a certain economic benefit is brought.
Example 2
Taking 1000g of waste copper bismuth catalyst containing 6.35% of copper, adding 48 g of stabilizer silica gel and water, controlling the solid-to-liquid ratio to be 3:1, stirring for 4h at normal temperature, and controlling the rotating speed to be 950r/min to fully mix the waste copper bismuth catalyst and the waste copper bismuth catalyst. During the stirring process, the pH value is controlled to be 7.
And (3) dehydrating the stabilized waste catalyst and silica gel in a distillation and adsorption mode, wherein the water content of the dehydrated waste catalyst is 65%, and the wastewater returns to a BYD sewage plant.
And (3) putting the dehydrated waste catalyst and silica gel into an incinerator, controlling the furnace temperature to be 650 ℃, and removing organic matters and carbon.
Sorting to obtain 62.6g of regenerated catalyst, and the recovery rate is 75%; 39.36g of stabilizer, the recovery rate is more than 82%, and the residue with poor performance generally contains metal and can be sold as a secondary resource.
The explosion decomposition temperature of the acetylene copper is about 105-110 ℃, and because the dosage of the silica gel in the embodiment is only 80% of the mass of the acetylene copper in the waste catalyst, in the operation process of the embodiment, even if the acetylene copper is passivated by controlling the silica gel and the pH value, the decomposition reaction is burnt and locally detonated, the smoke and dust amount of the flue gas is increased, the reaction temperature fluctuation is 650-1020 ℃ under the condition, the slight explosion sound is generated, and the recovery rates of the catalyst and the stabilizer are reduced.
Example 3
Taking 1000g of waste copper bismuth catalyst containing 6% of acetylene copper, wherein the copper content is 6.35%, adding 60 g of stabilizer silica gel and water, and controlling the solid-to-liquid ratio to be 3:1, stirring for 4 hours at normal temperature, and controlling the rotating speed at 950r/min to fully mix the two. The pH value is controlled to be 5.5 during the stirring process.
And (3) dehydrating the stabilized waste catalyst and silica gel in a distillation and adsorption mode, wherein the water content of the dehydrated waste catalyst is 65%, and the wastewater returns to a BYD sewage plant.
And (3) putting the dehydrated waste catalyst and silica gel into an incinerator, controlling the furnace temperature to be 650 ℃, and removing organic matters and carbon.
Adopting gravity separation to obtain 66g of regenerated catalyst, and having a recovery rate of 79%; 58.2g of stabilizer, 97% recovery, the remaining poor performance residue generally contains metal and can be sold as a secondary resource.
The explosive decomposition temperature of the copper acetylide is about 105-110 ℃, but in the operation process of the embodiment, the pH value is reduced to 5.5 by controlling the silica gel and the pH value compared with that of the embodiment 1, the copper acetylide is passivated, so that the decomposition reaction is mild and controllable, the reaction temperature fluctuation is 650-720 ℃ under the condition, the temperature fluctuation range is larger, but the explosion sound is avoided, and the air pollution is avoided; the waste catalyst containing acetylide with good performance is efficiently utilized, a small amount of silica gel is consumed, the higher regeneration rate of the catalyst is realized, the industrial cyclic utilization is realized, and the rest residues are sold as secondary resources, so that the cost is saved and a certain economic benefit is brought.
Example 4
Taking 1000g of waste copper bismuth catalyst containing 6.35% of copper, adding 72 g of stabilizer silica gel and water, controlling the solid-to-liquid ratio to be 3:1, stirring for 4h at normal temperature, and controlling the rotating speed to be 950r/min to fully mix the two. During the stirring process, the pH value is controlled to be 7.
And (3) dehydrating the stabilized waste catalyst and silica gel in a distillation and adsorption mode, wherein the water content of the dehydrated waste catalyst is 65%, and the wastewater returns to a BYD sewage plant.
And (3) putting the dehydrated waste catalyst and silica gel into an incinerator, controlling the furnace temperature to be 650 ℃, and removing organic matters and carbon.
Sorting to obtain 66.9g of regenerated catalyst with a recovery rate of 80.1%; 74.1g of stabilizer, 95% recovery, and the remaining poor performance residue, which generally contains metal, can be sold as a secondary resource.
The explosion decomposition temperature of the copper acetylide is about 105-110 ℃, and the mass of the copper acetylide in the waste catalyst is 120 percent, so that the decomposition reaction is mild and controllable by passivating the copper acetylide through controlling silica gel and PH value in the operation process, the reaction temperature is well maintained at 600-650 ℃ under the condition, the temperature fluctuation range is in the middle, no explosion sound exists, and no air pollution is caused; the waste catalyst containing acetylide with good performance is efficiently utilized, a small amount of silica gel is consumed, the higher regeneration rate of the catalyst is realized, the industrial cyclic utilization is realized, and the rest residues are sold as secondary resources, so that the cost is saved and a certain economic benefit is brought.
Example 5
Taking 1000g of waste catalyst containing copper 6.35% of acetylized copper, adding 60 g of stabilizer silica gel and water, controlling the solid-to-liquid ratio to be 2:1, stirring for 4h at normal temperature, and controlling the rotating speed to be 1000r/min to fully mix the two. During the stirring process, the pH value is controlled to be 7.
And (3) dehydrating the stabilized waste catalyst and silica gel in a distillation and adsorption mode, wherein the water content of the dehydrated waste catalyst is 51%, and the wastewater returns to a BYD sewage plant.
And (3) putting the dehydrated waste catalyst and silica gel into an incinerator, controlling the furnace temperature to 1200 ℃, removing organic matters and carbon, and refining metals.
Copper and bismuth are liquid metals, and the stabilizing agent is separated in the form of slag. Obtaining 65g of alloy, wherein the recovery rate is more than 96%; 58.8g of stabilizing agent, the recovery rate is more than 98 percent, and the rest residues are sold as general secondary resources.
Because the explosion decomposition temperature of the copper acetylide is about 105-110 ℃, the copper acetylide is passivated by controlling silica gel and PH value in the operation process of the embodiment, so that the decomposition reaction is mild and controllable, the reaction temperature fluctuation is 1200-1250 ℃ under the condition, no explosion sound exists, and no air pollution is caused; and the waste catalyst containing acetylide with good performance is efficiently utilized, most metals are recycled by losing a small amount of silica gel, industrial recycling is realized, and the rest residues are sold as secondary resources, so that the cost is saved and certain economic benefit is brought.
Example 6
Taking 1000g of acetylene silver-containing waste, wherein the silver content is 75%, adding 600 g of stabilizer silica gel and 4000g of water, stirring for 5h at normal temperature, and controlling the rotating speed at 1000r/min to fully mix the acetylene silver-containing waste and the water. The pH was controlled at 6.7 during the stirring.
And (3) dehydrating the stabilized waste catalyst and silica gel in a distillation and adsorption mode, wherein the water content of the dehydrated waste catalyst and silica gel is 57%, and the wastewater is recycled.
And (3) putting the dehydrated waste catalyst and silica gel into an incinerator, supporting combustion by natural gas, controlling the temperature of the incinerator to be 350 ℃, and removing organic matters and acidic substances.
732.8g of silver is obtained by adopting gravity separation, and the recovery rate is more than 97.77%; 594g of stabilizing agent, the recovery rate is more than 99%, 23.14g of smoke dust, and the smoke dust and the stabilizing agent are recycled.
The embodiment is an optimal scheme for treating the waste catalyst containing the acetylene silver, because the explosion decomposition temperature of the acetylene silver is about 140 ℃ and 150 ℃, the embodiment passivates the acetylene copper by controlling silica gel and PH value in the operation process, so that the decomposition reaction is mild and controllable, the reaction temperature fluctuation is 350-400 ℃ under the condition, no explosion sound exists, and no air pollution is caused; the waste catalyst containing acetylide with good performance is efficiently utilized, a small amount of silica gel is consumed, so that high metal content is realized, industrial recycling is realized, and the rest residues are sold as secondary resources, so that the cost is saved and a certain economic benefit is brought.
Example 7
Taking 1000g of acetylene silver-containing waste, wherein the silver content is 75%, adding 600 g of stabilizer silica gel and 4000g of water, stirring for 5h at normal temperature, and controlling the rotating speed at 1000r/min to fully mix the acetylene silver-containing waste and the water. The pH value is controlled to be 5.2 during the stirring process.
And (3) dehydrating the stabilized waste catalyst and silica gel in a distillation and adsorption mode, wherein the water content of the dehydrated waste catalyst and silica gel is 57%, and the wastewater is recycled.
And (3) putting the dehydrated waste catalyst and silica gel into an incinerator, supporting combustion by natural gas, controlling the temperature of the incinerator to be 350 ℃, and removing organic matters and acidic substances.
Adopting gravity separation to obtain 735g of silver, wherein the recovery rate is more than 98%; 594g of stabilizing agent, the recovery rate is more than 99%, the smoke dust is 20.94g, and the smoke dust and the stabilizing agent are recycled.
Because the explosion decomposition temperature of the acetylene silver is about 140-; the waste catalyst containing acetylide with good performance is efficiently utilized, a small amount of silica gel is consumed, so that high metal content is realized, industrial recycling is realized, and the rest residues are sold as secondary resources, so that the cost is saved and a certain economic benefit is brought.
In the above embodiments, it can be seen that the severity of the decomposition reaction of the acetylide can be effectively deactivated by adding the porous substance and adjusting the PH, and the replaced waste catalyst can be efficiently utilized without causing other pollution. The rule can be obtained from the experiment, the usage of the porous structure substance is within 90-120%, the higher the usage is, the better the passivation effect is, the reaction temperature can be reduced, but the recovery rate of the catalyst and the porous structure substance is slightly reduced, and the furnace temperature is also reduced; for the waste catalyst containing the copper acetylide, the PH value is neutral, and the passivation effect is better; for the waste catalyst containing acetylene silver, the PH value is weak and acidic, and the passivation effect is better.
It should be understood that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same, and those skilled in the art can modify the technical solutions described in the above embodiments, or make equivalent substitutions for some technical features; and all such modifications and alterations are intended to fall within the scope of the appended claims.
Claims (7)
1. A method for treating waste containing acetylides, which is characterized by comprising the following steps:
adding a porous structure substance and water to stir the waste for 3-5h until the materials are fully mixed, wherein the dosage of the porous structure substance is 90% -120% of the acetylene compounds in the waste, and the liquid-solid ratio is (2-3): 1, controlling the pH value to be 5-7, wherein when the waste material comprises copper acetylide, the adjusted pH value is neutral, when the waste material comprises silver acetylide, the pH value is weak acidity, and the porous structure substance is one or more of silica gel, alumina gel, diatomite or other porous structure substances;
dehydrating the waste material and the porous structure material to a moisture content of less than 66%;
when the waste is the waste catalyst, sampling and detecting the comprehensive performance ratio of the regenerated catalyst:
the comprehensive performance ratio of the regenerated catalyst is more than 90 percent, and the waste catalyst is placed into an incinerator for roasting and sorting at the temperature of 300-850 ℃ so as to return to production;
wherein the roasting sorting comprises:
roasting the dehydrated mixture according to the roasting temperature corresponding to the acetylide in the waste, wherein the mixture is obtained by adding the porous structure substance and water to the waste and fully mixing;
performing gravity separation on the roasted substances to obtain a regenerated catalyst, a porous structure substance and residues corresponding to the waste;
the comprehensive performance ratio of the regenerated catalyst is less than 90 percent, and the waste catalyst is placed into an incinerator and is roasted and degraded at the temperature of 1500 ℃ under 300 ℃ to obtain metal;
when the waste is non-catalyst waste, the waste is treated by the same process as the waste catalyst with the comprehensive performance ratio of less than 90 percent;
wherein the comprehensive performance ratio refers to the productivity mass ratio of each kilogram of the regenerated catalyst to each kilogram of the new catalyst before deactivation in unit time under the same production working condition.
2. The method as claimed in claim 1, wherein the stirring speed is 900-1000 r/min.
3. The acetylide-containing waste treatment process of claim 1, wherein the dehydration is carried out by distillation, adsorption or extrusion, singly or in combination.
4. The method of claim 3, wherein the dehydration is performed by a combination of distillation and adsorption.
5. The method of claim 1, wherein the ratio of the total performance of the regenerated catalyst is greater than 90% and the ratio of the liquid to the solid is 3: 1.
6. The method of claim 1, wherein the liquid-to-solid mass ratio is 2:1 when the regenerated catalyst combination property ratio is less than 90% or the waste is a non-catalyst waste.
7. The method of any one of claims 1 to 6, wherein the incinerator is a reverberatory furnace, cupola furnace or similar type furnace.
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