CN111229785A - Method for treating industrial catalytic waste of copper acetylide - Google Patents
Method for treating industrial catalytic waste of copper acetylide Download PDFInfo
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- CN111229785A CN111229785A CN202010142812.5A CN202010142812A CN111229785A CN 111229785 A CN111229785 A CN 111229785A CN 202010142812 A CN202010142812 A CN 202010142812A CN 111229785 A CN111229785 A CN 111229785A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Abstract
A method for treating industrial catalytic waste acetylene copper is characterized by comprising the following steps: the method comprises the following steps: a. putting the industrial catalytic waste acetylene copper ore pulp into a container, adding distilled water with the mass 1-1.5 times of that of the acetylene copper ore pulp, and uniformly stirring; b. adding hydrogen peroxide with the mass of 0.15-0.5 times that of the acetylene copper ore pulp into the container, and uniformly stirring; c. adding the diluted acid solution with the concentration of 15-30% into a container, stirring and reacting for 5 hours at normal temperature, and collecting reaction gas by using a gas bag; d. after the reaction is finished, adding an alkali solution to adjust the pH value of the reaction solution to 11-12, centrifuging the residue after the reaction, and washing for three times to obtain a centrifugate which can be continuously recycled; e. drying at 60 deg.C to obtain residue sample, and observing whether deflagration phenomenon occurs in a muffle furnace at 150 deg.C.
Description
Technical Field
The invention relates to the field of treatment, utilization and recovery of industrial catalytic waste copper acetylide, in particular to an explosion-proof safety technology of the industrial catalytic waste copper acetylide.
Background
With the rapid development of the world economy and the high-speed promotion of industrialization, the demand of the current society for the production of polymer synthesis chemical industry is more and more important, acetylene is widely applied as a basic raw material for organic synthesis in the production of polymer synthesis chemical industry, and mainly used as a main important raw material for synthetic rubber, synthetic organic solvents, synthetic resins and synthetic fibers. Several dozens of important high molecular monomers can be synthesized by acetylene through cyclopolymerization, chain polymerization or addition reaction, and finally many synthetic high molecular products are prepared. However, in a considerable part of the process flow, some copper (or copper scrap) or copper salt catalyst and the like react with acetylene to generate acetylene derivatives (such as copper acetylide) with explosive properties.
Copper acetylide is a metal acetylene derivative and has extremely strong explosive capacity. Since acetylene has active hydrogen atoms, it can react with metal or metal salt to form M2C2Or MHC2Acetylene type compounds, so that under neutral or basic conditions (i.e. relatively favouring the ionization of hydrogen atoms), acetylene can form Cu with copper salts2C2And CuC2These copper acetylide compounds are abbreviated as "copper acetylides". The generation and explosion performance of the copper acetylide are influenced by the conditions of water vapor, acidity, acetylene pressure, temperature, ammonia and the like, and the copper acetylide containing water under different conditions is decomposed before 130 ℃ and then exploded no matter how heated. (study on influence of Maoxinyuzueli on generation and explosion performance of acetylene copper [ J ]]Fire science 1986.12.31).
Explosion of copper acetylideNo gas is generated during explosion. The anion of the compound acting as the oxidant Cu in the decomposition reaction2C2(s) → 2 Cu(s) + 2C(s). The moist copper acetylide is relatively stable and can be handled safely. The dried copper acetylide is extremely sensitive and can be detonated by friction. Copper acetylides can form inside copper tubes or high copper content alloy tubes, which can lead to a violent explosion sound. This is believed to be the cause of the explosion of acetylene plants, resulting in such plants abandoning copper as a material in the structure. Copper catalysts used in petrochemical industry also pose risks under certain conditions. In 2016, 8, 9 days, a storage tank containing spent copper acetylide catalyst and Butynediol (BYD) was accidentally exploded in a Butanediol (BDO) plant located in the northwest of China, causing one person to die. (inversion of an acquired amplification used by reaction of a missing repair filler acetate and butyl diol [ J]. Journal of LossPrevention in the Process Industries,2019-09-29.)。
Nowadays, chemical manufacturing plays a very important place in industrial production, but the recycling of chemical waste gas is also important. With the continuous expansion of the scale of chemical enterprises, the chemical safety also becomes a major problem in the current society. At present, most enterprises do much work on recycling acetylene gas at the beginning of recycling acetylene tail gas, and like a method and a system for concentrating and recycling the acetylene tail gas, which are provided by CN106422669A and CN206138959U, the acetylene gas is well recycled, but acetylene copper waste cannot be well treated; the recovery and regeneration of the acetylide catalyst also suggests a method like CN1129608 for the regeneration of catalysts containing acetylides, in particular copper acetylides. Although the method well recovers the acetylene catalyst to recycle the acetylene catalyst, the potential safety hazard of waste cannot be treated when the method is applied to enterprise waste treatment.
Disclosure of Invention
The invention aims to provide a method for treating industrial catalytic waste copper acetylide aiming at the defects in the prior art.
The process of the invention utilizes diluted industrial catalytic wasteAdding a certain amount of hydrogen peroxide and acid into the waste copper acetylide, stirring to fully react, and generating CO after reaction2And a small amount of CO gas, adding strong base into the reaction solid waste liquid, then centrifugally washing, recycling the supernatant, and greatly reducing the harmfulness of the waste gas and residues. The process is simple and effective in solving the explosion-proof problem of the dry industrial waste pulp of the copper acetylide, simultaneously realizes the closed cycle of the alkali-containing solution, realizes the recycling of wastes, reduces the discharge of alkali-containing waste liquid, and effectively avoids the pollution and the damage to the environment in the recovery process of the waste pulp.
The technical measures of the invention are as follows:
the method for treating the industrial catalytic waste acetylene copper ore pulp comprises the following steps:
a. putting the industrial catalytic waste acetylene copper ore pulp into a container, adding distilled water with the mass 1-1.5 times of that of the acetylene copper ore pulp, and uniformly stirring;
b. adding hydrogen peroxide with the mass of 0.15-0.5 times that of the acetylene copper ore pulp into the container, and uniformly stirring;
c. adding the diluted acid solution with the concentration of 15-30% into a container, stirring and reacting for 5 hours at normal temperature, and collecting reaction gas by using a gas bag;
d. after the reaction is finished, adding an alkali solution to adjust the pH value of the reaction solution to 11-12, centrifuging the residue after the reaction, and washing for three times to obtain a centrifugate which can be continuously recycled;
e. drying at 60 deg.C to obtain residue sample, and observing whether deflagration phenomenon occurs in a muffle furnace at 150 deg.C.
Furthermore, the raw material used for preparing the acid solution in the step c of the invention is taken from sulfuric acid or nitric acid; the raw material for preparing the alkali solution in the step d is taken from sodium hydroxide or potassium hydroxide.
The adding amount of the hydrogen peroxide in the step b can be obtained by a calculation method, namely after the acetylene copper ore pulp is calcined at 800 ℃, the content of the copper oxide is 25 percent, and the required amount of the hydrogen peroxide is 0.2669g according to calculation.
The invention has the following beneficial effects:
the process is simple and effectively solves the problems of difficulty and environmental pollution brought to enterprises by industrial catalytic waste acetylene copper ore pulp, also improves the safety coefficient of the enterprises and ensures the life safety of enterprise workers; meanwhile, the closed circulation of the alkali-containing solution is realized, and the discharge of the alkali-containing solution is reduced. The invention effectively avoids the influence of industrial waste acetylene copper ore pulp on the environment and enterprises.
Drawings
FIG. 1 is a process diagram for treating and recovering acetylene copper.
Figure 2 is a DSC (differential scanning calorimetry) test of a sulfuric acid treated copper acetylene pulp.
Detailed Description
The invention will be further described with reference to the following examples:
copper acetylide adopted in the following examples is industrial catalytic waste, sodium hydroxide adopted for preparing a sodium hydroxide solution is a product of a continental chemical reagent plant in Tianjin, sulfuric acid is sulfuric acid with the concentration of 98% produced by double chemical industry limited company in Nicotai, the nitric acid is nitric acid with the concentration of 65% -68% produced by double chemical industry limited company in Nicotai, and the diluted acid is V acid V distilled water.
The following examples are all treated with sulfuric acid, dilute sulfuric acid as VH2SO4：VH2ODiluting for later use by 1: 3.
Example 1
A. Weighing 10g of acetylene copper ore pulp, placing the pulp in a container, adding 10g of distilled water, and uniformly stirring. 2ml of hydrogen peroxide was added thereto and stirred uniformly, and 2ml of prepared dilute sulfuric acid (S2) was rapidly added to the vessel, stirred in an oil bath and reacted at room temperature for 5 hours. The reaction gas was collected with a gas bag. After the reaction is finished, adjusting the pH value to 11-12 by NaOH, then centrifuging the residue after the reaction, washing for three times, and drying at 60 ℃ to obtain a residue sample M2.
B. Weighing 10g of acetylene copper ore pulp, placing the pulp in a container, adding 10g of distilled water, and uniformly stirring. 2ml of hydrogen peroxide was added thereto and stirred uniformly, and 4ml of prepared dilute sulfuric acid (S4) was rapidly added to the vessel, stirred in an oil bath and reacted at room temperature for 5 hours. The reaction gas was collected with a gas bag. After the reaction is finished, adjusting the pH value to 11-12 by NaOH, then centrifuging the residue after the reaction, washing for three times, and drying at 60 ℃ to obtain a residue sample M4.
C. Weighing 10g of acetylene copper ore pulp, placing the pulp in a container, adding 10g of distilled water, and uniformly stirring. 2ml of hydrogen peroxide was added thereto and stirred uniformly, and 6ml of prepared dilute sulfuric acid (S6) was quickly added to the vessel, stirred in an oil bath and reacted at room temperature for 5 hours. The reaction gas was collected with a gas bag. After the reaction is finished, adjusting the pH value to 11-12 by NaOH, then centrifuging the residue after the reaction, washing for three times, and drying at 60 ℃ to obtain a residue sample M6.
D. Weighing 10g of acetylene copper ore pulp, placing the pulp in a container, adding 10g of distilled water, and uniformly stirring. 2ml of hydrogen peroxide was added thereto and stirred uniformly, and 8ml of prepared dilute sulfuric acid (S8) was quickly added to the vessel, stirred in an oil bath and reacted at room temperature for 5 hours. The reaction gas was collected with a gas bag. After the reaction is finished, adjusting the pH value to 11-12 by NaOH, then centrifuging the residue after the reaction, washing for three times, and drying at 60 ℃ to obtain a residue sample M8.
And (3) placing the M sample in a cupel, and observing whether the deflagration phenomenon exists or not in a muffle furnace at 150 ℃.
It can be seen from the experiment that more than 2ml of V is addedH2SO4：VH2ODilute sulfuric acid and hydrogen peroxide in the ratio of 1:3 can ensure that the copper acetylide does not explode at the temperature of 150 ℃.
The following examples were all treated with nitric acid, diluted nitric acid as VHNO 3: VH2O =1:2 for dilution.
Example 2
A. Weighing 10g of acetylene copper ore pulp, placing the pulp in a container, adding 10g of distilled water, and uniformly stirring. 2ml of hydrogen peroxide was added thereto and stirred uniformly, and 5ml of prepared dilute nitric acid (S5) was added to the vessel and stirred in an oil bath and reacted at room temperature for 5 hours. The reaction gas was collected with a gas bag. After the reaction is finished, adjusting the pH value to 11-12 by NaOH/KOH, centrifuging the residue after the reaction, washing for three times, and drying at 60 ℃ to obtain a residue sample M5.
B. Weighing 10g of acetylene copper ore pulp, placing the pulp in a container, adding 10g of distilled water, and uniformly stirring. 2ml of hydrogen peroxide was added thereto and stirred uniformly, and 10ml of the prepared dilute nitric acid (S10) was added to the vessel and stirred in an oil bath and reacted at room temperature for 5 hours. The reaction gas was collected with a gas bag. After the reaction is finished, adjusting the pH value to 11-12 by NaOH/KOH, centrifuging the residue after the reaction, washing for three times, and drying at 60 ℃ to obtain a residue sample M10.
C. Weighing 10g of acetylene copper ore pulp, placing the pulp in a container, adding 10g of distilled water, and uniformly stirring. 2ml of hydrogen peroxide was added thereto and stirred uniformly, and 15ml of prepared dilute nitric acid (S15) was added to the vessel and stirred in an oil bath and reacted at room temperature for 5 hours. The reaction gas was collected with a gas bag. After the reaction is finished, adjusting the pH value to 11-12 by NaOH/KOH, centrifuging the residue after the reaction, washing for three times, and drying at 60 ℃ to obtain a residue sample M15.
D. Weighing 10g of acetylene copper ore pulp, placing the pulp in a container, adding 10g of distilled water, and uniformly stirring. 2ml of hydrogen peroxide was added thereto and stirred uniformly, and 20ml of prepared dilute nitric acid (S20) was added to the vessel and stirred in an oil bath and reacted at room temperature for 5 hours. The reaction gas was collected with a gas bag. After the reaction is finished, adjusting the pH value to 11-12 by NaOH/KOH, centrifuging the residue after the reaction, washing for three times, and drying at 60 ℃ to obtain a residue sample M20.
And (3) placing the M sample in a cupel, and observing whether the deflagration phenomenon exists or not in a muffle furnace at 150 ℃.
From the experiment it can be seen that 5ml of V was addedHNO3：VH2OAfter reaction of dilute nitric acid of =1:2, explosion phenomenon occurs in a muffle furnace at 150 ℃, and 10ml of V is addedHNO3：VH2ODilute nitric acid solution with the ratio of 1:2 or more can ensure that the copper acetylide does not explode at the temperature of 150 ℃.
It can be seen from the experiment that more than 10ml of V is addedHNO3：VH2ODilute nitric acid and hydrogen peroxide in the ratio of 1:2 can ensure that the copper acetylide does not explode at the temperature of 150 ℃.
Table 1 shows the XRF (X-ray fluorescence spectrometer) test results of copper acetylide and copper acetylide after calcination at 800 ℃.
As can be seen from the results in Table 1, Cu is removed by high temperature calcination when XRF test is performed on the copper acetylide as it is2C2800 and Cu2C2The contents of the components are basically the same, and Cu2C2In-800, since Na element remains in the alkali treatment, other components and Cu2C2There is a slight difference.
As shown in FIG. 2, which is a Differential Scanning Calorimetry (DSC) test of a sample selected from 2ml and 8ml of sulfuric acid with 2ml of hydrogen peroxide added, was raised from room temperature to 500 ℃ at a ramp rate of 10 ℃/min under a nitrogen atmosphere. From the results in the figure, it can be seen that at 40 ℃ to 176 ℃, copper acetylide is mainly an endothermic reaction, and the process is mainly that the adsorbed water in the copper acetylide is desorbed in the heating process, so that an endothermic process is generated. With further increase in temperature, copper acetylide undergoes decomposition reaction, releasing a large amount of heat. Thus, an exothermic peak of higher intensity appears in the DSC curve. As the temperature continued to rise, the organic substances such as carbon contained in the copper acetylide started to decompose and release heat, and thus the DSC continued to release heat in the range of 176 ℃ to 550 ℃.
It can be seen from the figure that the exothermic amount of acetylene copper pulp is greatly reduced after the dilute sulfuric acid and the hydrogen peroxide are added for reaction, so that the treated acetylene pulp does not explode at 150 ℃.
Claims (2)
1. A method for treating industrial catalytic waste acetylene copper is characterized by comprising the following steps: the method comprises the following steps:
a. putting the industrial catalytic waste acetylene copper ore pulp into a container, adding distilled water with the mass 1-1.5 times of that of the acetylene copper ore pulp, and uniformly stirring;
b. adding hydrogen peroxide with the mass of 0.15-0.5 times that of the acetylene copper ore pulp into the container, and uniformly stirring;
c. adding the diluted acid solution with the concentration of 15-30% into a container, stirring and reacting for 5 hours at normal temperature, and collecting reaction gas by using a gas bag;
d. after the reaction is finished, adding an alkali solution to adjust the pH value of the reaction solution to 11-12, centrifuging the residue after the reaction, and washing for three times to obtain a centrifugate which can be continuously recycled;
e. drying at 60 deg.C to obtain residue sample, and observing whether deflagration phenomenon occurs in a muffle furnace at 150 deg.C.
2. The method of claim 1, further comprising: the raw material for preparing the acid solution in the step c is taken from sulfuric acid or nitric acid; the raw material for preparing the alkali solution in the step d is taken from sodium hydroxide or potassium hydroxide.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4536491A (en) * | 1984-06-04 | 1985-08-20 | E. I. Dupont De Nemours And Company | Agglomerates of malachite crystals and method for their preparation |
| CN1132114A (en) * | 1995-10-27 | 1996-10-02 | 化学工业部北京化工研究院 | Regenerating method of catalyst for 1,4-butine-glycol synthetized by formaldehyde and acetylene reacted in slurry bed |
| CN105413711A (en) * | 2015-11-20 | 2016-03-23 | 苏英慧 | Regeneration preparing method for supported copper-bismuth catalyst |
| CN109622039A (en) * | 2018-12-26 | 2019-04-16 | 杭州更蓝生物科技有限公司 | A method of preparing 1,4- butynediols |
-
2020
- 2020-03-04 CN CN202010142812.5A patent/CN111229785A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4536491A (en) * | 1984-06-04 | 1985-08-20 | E. I. Dupont De Nemours And Company | Agglomerates of malachite crystals and method for their preparation |
| CN85104324A (en) * | 1984-06-04 | 1986-12-03 | 纳幕尔·杜邦公司 | Malachite crystalline caking and its preparation method |
| CN1132114A (en) * | 1995-10-27 | 1996-10-02 | 化学工业部北京化工研究院 | Regenerating method of catalyst for 1,4-butine-glycol synthetized by formaldehyde and acetylene reacted in slurry bed |
| CN105413711A (en) * | 2015-11-20 | 2016-03-23 | 苏英慧 | Regeneration preparing method for supported copper-bismuth catalyst |
| CN109622039A (en) * | 2018-12-26 | 2019-04-16 | 杭州更蓝生物科技有限公司 | A method of preparing 1,4- butynediols |
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Application publication date: 20200605 |