CN113262786B - Heterogeneous nano copper catalyst and preparation method and application thereof - Google Patents

Heterogeneous nano copper catalyst and preparation method and application thereof Download PDF

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CN113262786B
CN113262786B CN202110643918.8A CN202110643918A CN113262786B CN 113262786 B CN113262786 B CN 113262786B CN 202110643918 A CN202110643918 A CN 202110643918A CN 113262786 B CN113262786 B CN 113262786B
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copper
complex
wastewater
pcb
catalyst
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CN113262786A (en
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朝飞
李晓怡
梁广锋
郎睿
吴传德
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Guangdong University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The application belongs to the technical field of printed circuit board recovery, and particularly relates to a heterogeneous nano copper catalyst and a preparation method and application thereof. The application provides a heterogeneous nano-copper catalyst, including: mixing the complex copper wastewater with an adsorption carrier, and then removing a solvent of the complex copper wastewater to obtain a mixture; and calcining the mixture under the condition of protective gas to prepare the heterogeneous nano copper catalyst. This application utilizes the more active carbon adsorption PCB complex waste water of defect position to be difficult to the copper complex who gets rid of, through getting rid of behind the solvent in the complex waste water, turns into heterogeneous copper catalyst with the active carbon after adsorbing the copper complex under the high temperature calcination condition. The method greatly reduces the high cost required in the traditional method for treating the PCB complexing wastewater, solves the problems of copper recovery and ammonia nitrogen treatment in the PCB complexing wastewater, prepares products with high added values while treating the waste liquid, changes waste into valuable, saves resources, reduces the cost and creates income for enterprises.

Description

Heterogeneous nano copper catalyst and preparation method and application thereof
Technical Field
The application belongs to the technical field of printed circuit board recovery, and particularly relates to a heterogeneous nano copper catalyst and a preparation method and application thereof.
Background
With the advent of the information age, the electronic industry and the information industry have gradually developed, the related electronic industry has become one of the important post industries in China, and the printed circuit board (pcb) industry related to the related electronic industry has also been rapidly developed. According to the survey results of the China society for printed Circuit industry (CPCA), the annual output of PCBs reaches 1.98 hundred million m in 2011 of China with more than 2000 PCB professional manufacturers in China at present 2 The production value of the PCB industry is increased from 79.6 hundred million estimated in 2004 to 327 hundred million estimated in 2018, the production value is estimated to reach 406 hundred million in 2023, China becomes a large country for producing printed circuit boards, and a series of industry chains with the printed circuit boards as cores are formed.
The PCB production process reaches 20 times, most processes generate waste liquid, and etching waste liquid is the main waste liquid in the production process. Copper in copper etching waste liquidThe content of (A) is 110-160 g/L, which exceeds 11 ten thousand times of the national emission standard; the ammonia nitrogen content of the alkaline etching waste liquid is 90-120 g/L and exceeds 3600 times of the national secondary waste liquid discharge standard. And if the waste liquid is not treated, serious waste is caused, the environment is polluted, and the concept of sustainable development is not met. The existence form of copper in the copper etching waste water is mainly complex copper, the complexing agent of the copper etching waste water comprises ammonia, EDTA (ethylene diamine tetraacetic acid), citric acid, tartaric acid and the like, and the stability constant of the complex formed by the copper and the complexing agent is less than that of Cu (OH) 2 If the ordinary precipitation method (such as precipitation of copper by adding alkali) is adopted, the treatment effect is poor, and the copper ions in the effluent hardly reach the standard (0.5mg/L), the complex copper can be released in the ionic state only after the complex copper is broken, and then the copper in the waste liquid can be removed by coagulating precipitation. Common methods of breaking collaterals include: na (Na) 2 S method, heavy metal trapping agent method, oxidant complex breaking method, iron salt shielding method and biochemical method. Although the complex breaking method is more, the complex breaking method inevitably needs to add additional reagents into the complex waste water, the price of part of the reagents is high, and the part of the reagents is easy to cause secondary pollution, so that the problem undoubtedly increases the waste liquid treatment cost. In order to realize the recycling of resources, the most reasonable mode is to change the complexing wastewater into a product with an additional value for recycling or selling.
In conclusion, the prior printed circuit board waste liquid treatment process has the technical problems that the complex copper is difficult to recover and the ammonia nitrogen treatment does not reach the standard.
Disclosure of Invention
In view of this, the application provides a heterogeneous nano copper catalyst, a preparation method and an application thereof, which effectively solve the technical problems that complex copper is difficult to recover and ammonia nitrogen treatment does not reach the standard in the existing process of treating waste liquid of a printed circuit board.
The present application provides in a first aspect a heterogeneous nanocopper catalyst, comprising:
step 1, mixing the complex copper wastewater with an adsorption carrier, and then adjusting the pH value of the complex copper wastewater to 6-7 to obtain a mixed solution;
step 2, removing the solvent of the mixed solution, and drying to obtain a mixture;
and 3, calcining the mixture under the condition of protective gas to obtain the heterogeneous nano copper catalyst.
Specifically, the complex copper wastewater is prepared without preparation, and is derived from complex copper wastewater generated in the working procedures of copper deposition, countercurrent cleaning and the like in the PCB double-sided board manufacturing process.
In another embodiment, the adsorbent support is selected from one or more of activated carbon, metal hydroxides, molecular sieves, and ionic liquids.
In another embodiment, the adsorbent support is selected from activated carbon.
Specifically, the heterogeneous nano-copper catalyst is a copper complex (EDTA-Cu and [ Cu- (NH)) which is difficult to remove by adsorbing PCB (printed Circuit Board) complex wastewater by using activated carbon with more defect sites 3 ) 4 ] 2+ Etc.), the copper complex adsorbed by the activated carbon is converted into a heterogeneous copper catalyst under a high-temperature calcination condition by removing the solvent in the complex wastewater, and is applied to an organic reaction.
In another embodiment, the metal hydroxide is selected from Al (OH) 3 、Mg(OH) 2 、Fe(OH) 3 And hydrotalcite; the molecular sieve is selected from one or more of MCM-41, ZSM-5, SAPO-34 and SBA-15; the ionic liquid is selected from one or more of imidazole type ionic liquid, pyridine type ionic liquid, tetramethylguanidine type ionic liquid and choline chloride type ionic liquid.
In another embodiment, the metal hydroxide is selected from Al (OH) 3 Or/and Mg (OH) 2 (ii) a The molecular sieve is selected from MCM-41; the ionic liquid is selected from imidazole type ionic liquids.
In another embodiment, the copper complex wastewater and the adsorption carrier in the step 1 are stirred and mixed for 1-5 h until the metal complex of the copper complex wastewater is fully adsorbed on the adsorption carrier.
In another embodiment, the complexed copper wastewater is derived from wastewater generated in PCB production; the copper content of the complex copper wastewater is not lower than 20 mg/L; the pH value of the complex copper wastewater is less than or equal to 5.
In another embodiment, the source of complexing copper wastewater is with wastewater produced in PCB production; the copper content of the complex copper wastewater is 80 mg/L; the pH value of the complex copper wastewater is less than 5.
In another embodiment, the amount of the activated carbon is 0.5-8.0 g/L.
Specifically, the dosage of the activated carbon is 0.5-8.0g/L, the copper content of the complex copper wastewater is 80mg/L, and the copper loading range of the prepared heterogeneous nano copper catalyst is 1-16 wt%.
In another embodiment, the calcining temperature is 500-800 ℃; the calcination time is 1-4 h; the heating rate of the calcination is 7 ℃/min.
Specifically, the calcining temperature is 800 ℃; the calcination time is 2 h; the heating rate of the calcination is 7 ℃/min.
Specifically, the ligand framework in the copper complex wastewater is pyrolyzed through calcination, and the carbon-fixed heterogeneous nano-copper solid particle catalyst with a certain arrangement sequence is obtained.
Specifically, in the step 1, the pH value of the mixed solution is adjusted to 6-7 by adding strong base; the strong base is conventional hydroxide, such as sodium hydroxide solution and the like.
In another embodiment, step 2 further comprises condensing, refluxing and collecting the solvent of the mixed solution; and removing the solvent of the mixed solution by heating and evaporating, and then collecting the solvent of the mixed solution by condensing and refluxing.
Specifically, the heating and evaporating temperature is 60-100 ℃.
Specifically, the solvent evaporated and removed in step 2 of the present application is collected by condensation and reflux, and can be used for preparing electroplating solution for recycling.
In another embodiment, step 2 further comprises drying the mixture for calcination; the drying temperature is 40-100 ℃, and the drying time is 1-5 h.
In another embodiment, the drying temperature is 50 ℃ and the drying time is 2 h.
In another embodiment, the protective gas in step 3 is nitrogen, and the purity thereof is 99.99% or more.
The second aspect of the present application provides a preparation method of the heterogeneous nano copper catalyst, comprising:
step 1, mixing the complex copper wastewater with an adsorption carrier, and then adjusting the pH value of the complex copper wastewater to 6-7 to obtain a mixed solution;
step 2, removing the solvent of the mixed solution, and drying to obtain a mixture;
and 3, calcining the mixture under the condition of protective gas to prepare the heterogeneous nano copper catalyst.
The third aspect of the application discloses the application of the heterogeneous nano-copper catalyst in organic matter synthesis.
In another embodiment, the heterogeneous nano copper catalyst can participate in a Cham-Lam reaction, an Ullmann reaction and the like, is used for realizing C-X bond coupling and the reaction of synthesizing a drug intermediate and a pesticide, and can also be applied to a copper-catalyzed coupling reaction and a reduction reaction.
When the heterogeneous nano-copper catalyst is obtained, the metal copper and ammonia nitrogen in the PCB complex copper wastewater can be fully recycled, the copper complex in the PCB complex copper wastewater is adsorbed by using a cheap and easily-obtained adsorption carrier (such as activated carbon) as a carrier, and copper ions are agglomerated at high temperature, so that the nano-copper catalyst with high added value is prepared, and the cost for treating the wastewater is greatly saved; the difficulty of copper complex wastewater generated when the PCB industry processes the PCB is reduced to a certain extent; the complex copper wastewater is processed into a heterogeneous nano copper catalyst with high added value to be sold, and the solvent water of the complex copper wastewater is evaporated and reused, so that waste is changed into valuable, and the environmental protection pressure of enterprises is relieved; the copper nano catalyst has the advantages of adjustable loading capacity, simple operation, short steps and manpower and material resource saving.
To sum up, but metal copper and ammonia nitrogen in this application recycle PCB complex waste water have solved the problem of the complex copper that exists in the PCB production process that is difficult to retrieve on the one hand, and on the other hand solves and handles this process ammonia nitrogen and administers the problem not up to standard.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is a reaction schematic diagram of step 1 in the preparation method of the heterogeneous nano-copper catalyst provided in the present application;
fig. 2 is a reaction schematic diagram of step 2 in the preparation method of the heterogeneous nano-copper catalyst provided in the present application;
FIG. 3 is an XRD characterization of the 5.0 wt% PCB-Cu-C catalyst prepared in example 2 of the present application;
FIG. 4 is a transmission electron microscope image of a 1.0 wt% PCB-Cu-C catalyst prepared in example 1 of the present application under different magnification conditions;
FIG. 5 is a transmission electron microscope image of a 1.0 wt% PCB-Cu-C catalyst prepared in example 1 of the present application under different magnification conditions;
FIG. 6 is a reaction scheme of 4-methoxy diphenyl sulfide 1a provided in the examples herein.
Detailed Description
The application provides a heterogeneous nano copper catalyst and a preparation method and application thereof, which are used for solving the technical defects that complex copper is difficult to recover and ammonia nitrogen treatment does not reach the standard in the process of treating waste liquid of a printed circuit board in the prior art.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Wherein, the reagents or raw materials used in the following examples are all commercially available or self-made.
The method of the following embodiment comprises:
(1) introducing the PCB complex copper wastewater into a stirring evaporation tank, adding active carbon (the adding amount of the active carbon is changed according to the requirement of obtaining heterogeneous nano copper catalysts with different mass ratios), adjusting the pH value of the complex copper wastewater to be 6-7, stirring for 3h at normal temperature (the stirring time needs to be increased when the treatment amount of the complex copper wastewater is increased), and fully adsorbing the metal complex on the active carbon, wherein the metal complex is shown in figure 1;
heating and stirring after normal temperature stirring operation to remove the solvent (the solvent of the complex copper wastewater is mainly water), condensing, refluxing and collecting the evaporated solvent, wherein the evaporated solvent can be used for preparing electroplating solution, and then obtaining a mixture (activated carbon adsorbed with complex copper) which is further dried;
(2) and (3) placing the dried mixture in an inert gas atmosphere, calcining at 500-800 ℃, and pyrolyzing the ligand framework in the complexing wastewater to obtain the heterogeneous nano-copper catalyst (the nano-copper solid particles with a certain arrangement order and fixed by carbon), as shown in fig. 2.
The preparation method of the PCB complexing wastewater used in the following examples comprises the following steps:
taking PCB complexing wastewater generated by PCB enterprises to put in a beaker, dripping 2mol/LNaOH solution into the beaker, and adjusting the pH value of the solution to be about 6 to obtain solution, namely the PCB complexing wastewater; wherein the copper content of the PCB complexing wastewater obtained by pre-preparation is 80 mg/L.
The heterogeneous nano copper catalyst is referred to as a PCB-Cu-C catalyst for short.
Example 1
The embodiment of the application provides a preparation method of a 1.0 wt% PCB-Cu-C catalyst, which specifically comprises the following steps:
adding 20mL of PCB complexing wastewater (the copper content is 80mg/L) and 160mg of activated carbon into a 50mL beaker, magnetically stirring at normal temperature for 30min, heating to 100 ℃, and removing the solvent water under the condition of magnetic stirring. After the solvent is evaporated to dryness, the catalyst is transferred into a forced air drier and dried for 2h at 50 ℃. Then taking out the dried catalyst, moving the catalyst to a tubular furnace, and reacting the catalyst in N 2 Calcining in an atmosphere under the following conditions: the initial temperature is 30 ℃, the heating rate is 7 ℃/min, the temperature is increased to 800 ℃, and the temperature is reduced after 2 hours of heat preservation at 800 ℃. After calcination, a black solid powder 1 is obtained52mg, and the PCB-Cu-C catalyst with the mass percent of the metal copper of 1.0 wt% is prepared.
Example 2
The embodiment of the application provides a preparation method of a 5.0 wt% PCB-Cu-C catalyst, which specifically comprises the following steps:
200mL of the complex wastewater (the copper content is 80mg/L) and 320mg of the active carbon are added into a 500mL beaker, the mixture is magnetically stirred at normal temperature for 30min and then heated to 100 ℃, and the solvent water is removed under the condition of magnetic stirring. After the solvent is evaporated to dryness, the catalyst is transferred into a forced air drier and dried for 2h at 50 ℃. Then taking out the dried catalyst, transferring the catalyst to a tubular furnace, and reacting the catalyst in N 2 Calcining under the atmosphere, wherein the calcining conditions are as follows: the initial temperature is 30 ℃, the heating rate is 7 ℃/min, the temperature is increased to 800 ℃, and the temperature is kept at 800 ℃ for 2h and then is reduced. The black solid powder of 369mg was obtained after calcination, and a PCB-Cu-C catalyst having a metallic copper mass percentage of 5.0 wt% was prepared.
Example 3
The embodiment of the application provides a preparation method of a 10.0 wt% PCB-Cu-C catalyst, which specifically comprises the following steps:
200mL of LPCB complex wastewater (the copper content is 80mg/L) and 160mg of activated carbon are added into a 500mL beaker, the temperature is raised to 100 ℃ after magnetic stirring is carried out for 30min at normal temperature, and the solvent water is removed under the condition of magnetic stirring. After the solvent is evaporated to dryness, the catalyst is transferred into a forced air drier and dried for 2h at 50 ℃. Then taking out the dried catalyst, moving the catalyst to a tubular furnace, and reacting the catalyst in N 2 Calcining in an atmosphere under the following conditions: the initial temperature is 30 ℃, the heating rate is 7 ℃/min, the temperature is increased to 800 ℃, and the temperature is kept at 800 ℃ for 2h and then is reduced. After calcination, 187mg of black solid powder was obtained, and a PCB-Cu-C catalyst having a metallic copper content of 10.0 wt% was prepared.
Example 4
The embodiment of the application is to carry out XRD representation, electron microscope observation and functional verification on the prepared PCB-Cu-C catalyst, and comprises the following steps:
1. XRD characterization was performed on the PCB-Cu-C catalyst prepared in example 2, and the results are shown in FIG. 3. from FIG. 3, it can be seen that the PCB-Cu-C catalyst prepared in the present application contains copper.
2. The results of electron microscope observation of the PCB-Cu-C catalyst prepared in example 1 are shown in fig. 4 to 5, and it can be seen from fig. 4 to 5 that the metal complex in the PCB-Cu-C catalyst prepared in the present application is sufficiently adsorbed on the activated carbon.
3. A functional verification test was performed on the PCB-Cu-C catalyst prepared in example 3, including:
according to the reaction scheme of FIG. 6, a 50mL round-bottomed flask was taken, and 0.028mg (0.2mmol) of 4-methoxythiophenol, 0.024mg (0.2mmol) of phenylboronic acid, 0.048mg (0.4mmol) of potassium tert-butoxide, 44mg of 10 wt% PCB-Cu-C catalyst and 2mL of DMF were added as solvents, respectively. The product was obtained in 78.12% yield by moving the round bottom flask to a magnetic stirrer and reacting at 80 ℃ for 12h, and the 1HNMR analysis of the product proved to be the target product 4-methoxy diphenyl sulfide 1a, and the 1HNMR data of the target product 4-methoxy diphenyl sulfide 1a is as follows:
1HNMR(400MHz,CDCl 3 )δ7.42(d,J＝8.8Hz,2H,Ar-H),7.22(d,J＝7.4Hz,2H,Ar-H),7.15(dd,J＝16.0,7.5Hz,3H,Ar-H),6.90(d,J＝8.8Hz,2H,Ar-H),3.82(s,3H,OCH 3 )；13C NMR(100MHz,CDCl 3 )δ135.35,128.91,128.21,125.75,114.98,77.32,77.00,76.68,55.36,29.69。
therefore, the PCB-Cu-C catalyst prepared by the embodiment of the application can participate in copper catalytic reaction.
The foregoing is only a preferred embodiment of the present application and it should be noted that, as will be apparent to those skilled in the art, numerous modifications and adaptations can be made without departing from the principles of the present application and such modifications and adaptations are intended to be considered within the scope of the present application.

Claims (4)

1. A preparation method of a heterogeneous nano copper catalyst is characterized by comprising the following steps:
step 1, mixing complex copper wastewater with an adsorption carrier, and then adjusting the pH value of the complex copper wastewater to 6-7 to obtain a mixed solution;
step 2, removing the solvent of the mixed solution, and drying to obtain a mixture;
step 3, calcining the mixture under the condition of protective gas to prepare a heterogeneous nano copper catalyst;
the protective gas is nitrogen;
the calcining temperature is 500-800 ℃; the calcination time is 1-4 h;
the adsorption carrier is selected from activated carbon;
the complex copper wastewater is derived from wastewater generated by treating printed circuit board waste liquid.
2. The method for preparing the heterogeneous nano-copper catalyst according to claim 1, wherein the copper content of the copper complex wastewater is not less than 20 mg/L; the pH value of the complex copper wastewater is less than or equal to 5.
3. The preparation method of the heterogeneous nano-copper catalyst according to claim 1, wherein the amount of the activated carbon is 0.5-8.0 g/L.
4. The method for preparing the heterogeneous nano-copper catalyst according to claim 1, further comprising the step of collecting the solvent of the mixed solution by condensing and refluxing in step 2: and removing the solvent of the mixed solution by heating and evaporating, and then collecting the solvent of the mixed solution by condensing and refluxing.
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JPS5222361A (en) * 1975-08-14 1977-02-19 Mitsui Toatsu Chem Inc Wet catalyst oxidation treting process
WO2009071997A2 (en) * 2007-12-06 2009-06-11 Centre National De La Recherche Scientifique (C.N.R.S.) Iron and copper catalytic systems for cross-coupling reactions
CN101564673B (en) * 2009-05-27 2011-05-04 北京化工大学 Liquid absorbent for absorbing copper ions
CN105567980B (en) * 2016-02-02 2017-04-26 长沙汇聚环境技术有限公司 Method for recovering copper from brown oxidation wastewater of printed circuit board
CN105906154B (en) * 2016-06-14 2019-04-16 同济大学 A kind of method of the recycling treatment recycling of board wastewater
CN110152663A (en) * 2018-02-11 2019-08-23 中国科学院大连化学物理研究所 It is a kind of for the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and its preparation and application
CN109731577B (en) * 2018-12-11 2022-01-11 温州大学 Copper element doped carbon material, application and reaction method for preparing primary aromatic amine through coupling reaction of halogenated aromatic compound and ammonia water
CN112316896B (en) * 2020-10-12 2022-10-14 昆明理工大学 Resource utilization method of waste copper adsorbent

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