CN115178300A - Hydrogenation catalyst regeneration wastewater treatment method - Google Patents
Hydrogenation catalyst regeneration wastewater treatment method Download PDFInfo
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- CN115178300A CN115178300A CN202210826038.9A CN202210826038A CN115178300A CN 115178300 A CN115178300 A CN 115178300A CN 202210826038 A CN202210826038 A CN 202210826038A CN 115178300 A CN115178300 A CN 115178300A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 45
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 15
- 230000008929 regeneration Effects 0.000 title claims description 8
- 238000011069 regeneration method Methods 0.000 title claims description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000012065 filter cake Substances 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 34
- 238000001914 filtration Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 15
- BPPZXJZYCOETDA-UHFFFAOYSA-N 1-benzylpiperidin-4-ol Chemical compound C1CC(O)CCN1CC1=CC=CC=C1 BPPZXJZYCOETDA-UHFFFAOYSA-N 0.000 claims description 10
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- CQNGAZMLFIMLQN-UHFFFAOYSA-N 2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-trien-17-amine Chemical compound O1CCOCCOCCOCCOC2=CC(N)=CC=C21 CQNGAZMLFIMLQN-UHFFFAOYSA-N 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000413 hydrolysate Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 7
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 6
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- -1 firstly Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000003983 crown ethers Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000012372 quality testing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a method for treating regenerated wastewater of a hydrogenation catalyst, which belongs to the technical field of wastewater treatment and comprises the following steps: adding the filtered hydrogenation catalyst into an alcohol washing kettle; adding an ethanol solution into the alcohol washing kettle, stirring and filtering to obtain a filtrate, namely primary wastewater, and transferring a filter cake into an ultrasonic cleaning machine; adding an ethanol solution into an ultrasonic cleaning machine, cleaning, filtering, wherein the filtrate is secondary wastewater, and transferring a filter cake to a washing kettle; adding water into a washing kettle, stirring and filtering, wherein the filtrate is tertiary wastewater, drying a filter cake to obtain a regenerated hydrogenation catalyst, converging primary wastewater, secondary wastewater and tertiary wastewater into a wastewater treatment tank, adding modified titanium dioxide, treating under the irradiation of an LED ultraviolet lamp, filtering, carrying out next-step treatment on the filter cake, and normally discharging the filtrate.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for treating regenerated wastewater of a hydrogenation catalyst.
Background
The palladium-carbon catalyst is a catalyst commonly used for hydrogenation reaction in the chemical field, and the palladium-carbon hydrogenation has the characteristics of high hydrogenation reducibility, good selectivity, stable performance, small feed ratio in use and the like, however, in the use process of the palladium-carbon catalyst, micropores are blocked by organic matters, active component palladium is covered by the organic matters, palladium crystal grains grow up to reduce the dispersion degree of the palladium crystal grains, the palladium falls off and other factors, so that the activity of the catalyst is reduced, even the catalyst is completely inactivated.
O-phenylenediamine is a white crystalline solid and is prepared by reducing o-nitroaniline, a catalytic hydrogenation reduction process is mostly adopted in the existing manufacturing process, a palladium-carbon catalyst is used as a hydrogenation catalyst, the existing palladium-carbon catalyst is regenerated, generally used palladium-carbon catalyst is cleaned, metal particles are usually separated from a catalyst carrier under the action of flushing pressure and the like in the cleaning process and enter a cleaning agent, and further wastewater containing the metal particles is generated and does not meet the discharge standard, so that the technical problem to be solved at present is provided.
Disclosure of Invention
In order to solve the technical problems mentioned in the background technology, the invention provides a method for treating hydrogenation catalyst regeneration wastewater.
The purpose of the invention can be realized by the following technical scheme:
a method for treating regenerated wastewater of a hydrogenation catalyst comprises the following steps:
firstly, taking out a hydrogenation catalyst from a catalyst filter in a final-stage kettle of a four-stage serial hydrogenation kettle for performing o-phenylenediamine hydrogenation reaction, and transferring the hydrogenation catalyst to an alcohol washing kettle;
secondly, adding an ethanol solution with the mass fraction of 20-50% into an alcohol washing kettle, stirring for 20-30min at the temperature of 30-45 ℃ and the rotating speed of 500-800r/min, filtering, wherein the filtrate is first-stage wastewater, and transferring a filter cake into an ultrasonic cleaning machine;
thirdly, adding an ethanol solution with the mass fraction of 10-32% into an ultrasonic cleaning machine, cleaning for 20-30min at the frequency of 35-42kHz, filtering, wherein the filtrate is secondary wastewater, and transferring a filter cake to a water washing kettle;
and fourthly, adding water into a washing kettle, stirring for 20-40min at the temperature of 40-50 ℃ and the rotating speed of 500-1000r/min, filtering to obtain a filtrate, namely three-level wastewater, drying a filter cake at the temperature of 40-60 ℃ to obtain a regenerated hydrogenation catalyst, converging the primary wastewater, the secondary wastewater and the three-level wastewater into a wastewater treatment pool, adding modified titanium dioxide into the wastewater treatment pool, treating for 4-6h under the irradiation of an LED ultraviolet lamp, filtering, carrying out next-step treatment on the filter cake, and normally discharging the filtrate.
Further, the modified titanium dioxide is prepared by the following steps:
s1, mixing absolute ethyl alcohol, deionized water and a coupling agent KH-560 according to a mass ratio of 75-80:8-10:20, uniformly mixing, hydrolyzing at room temperature for 0.5h to obtain a hydrolysate, ultrasonically treating the nano titanium dioxide in absolute ethyl alcohol, adding the hydrolysate, heating to 75-80 ℃, stirring for reaction for 2h, performing suction filtration after the reaction is finished, washing a filter cake for 3 times by using absolute ethyl alcohol, and drying to obtain epoxidized nano titanium dioxide; the mass ratio of the nano titanium dioxide, the absolute ethyl alcohol and the hydrolysate is 10:100:35-40;
s2, mixing the epoxidized nano titanium dioxide, 4 '-aminobenzo-15-crown-5-ether, N-benzyl-4-piperidinol and DMF, controlling the temperature to be 50-60 ℃, stirring for reaction for 10min, then adding potassium hydroxide, heating to 137-145 ℃, stirring for reaction for 3-5h, filtering after the reaction is finished, washing and drying a filter cake to obtain modified titanium dioxide, wherein the dosage ratio of the epoxidized nano titanium dioxide, the 4' -aminobenzo-15-crown-5-ether, the N-benzyl-4-piperidinol, the DMF and the potassium hydroxide is 10g:0.4g:0.4-0.6g:50-60mL:0.8-1.2g.
Furthermore, the using amount of the modified titanium dioxide is 1-2% of the mass of the first-level wastewater, the second-level wastewater and the third-level wastewater.
Further, the wavelength of the LED ultraviolet lamp is 380-450nm.
The invention has the beneficial effects that:
in order to solve the problem that the existing hydrogenation catalyst generates metal particles to fall off to pollute a water source in the cleaning and recycling process, modified titanium dioxide is added into the regeneration wastewater of the hydrogenation catalyst, the modified titanium dioxide has the photocatalytic degradation characteristic of nano titanium dioxide and also has the complexing action of an organic adsorbent on the metal particles, firstly, silane coupling agent KH-560 is utilized to carry out surface treatment on the nano titanium dioxide to ensure that the surface of the nano titanium dioxide contains epoxy groups, then, under the alkaline condition, the terminal amino group of 4' -aminobenzo-15-crown-5-ether, the alcoholic hydroxyl group of N-benzyl-4-piperidinol and the epoxy groups are subjected to ring-opening reaction to obtain modified silicon dioxide, and the crown ether structure and the N-benzyl-4-piperidinol structure on the surface of the modified silicon dioxide can form the complexing action with heavy metal particles (particularly palladium ions), so as to purify the heavy metal pollutants in the wastewater, and effectively reduce the content of the pollutants in the regeneration catalyst wastewater by combining the photocatalytic action of the nano titanium dioxide under the irradiation of an ultraviolet lamp.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 invention.
Example 1
A modified titanium dioxide is prepared by the following steps:
s1, mixing absolute ethyl alcohol, deionized water and a coupling agent KH-560 according to a mass ratio of 75:8:20, uniformly mixing, hydrolyzing at room temperature for 0.5h to obtain hydrolysate, ultrasonically treating 10g of nano titanium dioxide in 100mL of absolute ethyl alcohol, adding 35mL of hydrolysate, heating to 75 ℃, stirring for reacting for 2h, after the reaction is finished, performing suction filtration, washing a filter cake for 3 times by using absolute ethyl alcohol, and drying to obtain epoxidized nano titanium dioxide;
s2, mixing 10g of epoxidized nano titanium dioxide, 0.4g of 4' -aminobenzo-15-crown-5-ether, 0.4g N-benzyl-4-piperidinol and 50mL of DMF, controlling the temperature to be 50 ℃, stirring for reaction for 10min, then adding 0.8g of potassium hydroxide, then heating to 137 ℃, stirring for reaction for 3h, filtering after the reaction is finished, washing and drying a filter cake, and obtaining the modified titanium dioxide.
Example 2
A modified titanium dioxide is prepared by the following steps:
s1, mixing absolute ethyl alcohol, deionized water and a coupling agent KH-560 according to a mass ratio of 78:9:20, uniformly mixing, hydrolyzing at room temperature for 0.5h to obtain hydrolysate, ultrasonically treating 10g of nano titanium dioxide in 100mL of absolute ethyl alcohol, adding 38mL of hydrolysate, heating to 78 ℃, stirring for reacting for 2h, after the reaction is finished, performing suction filtration, washing a filter cake for 3 times by using absolute ethyl alcohol, and drying to obtain epoxidized nano titanium dioxide;
s2, mixing 10g of epoxidized nano titanium dioxide, 0.4g of 4' -aminobenzo-15-crown-5-ether, 0.5g N-benzyl-4-piperidinol and 55mL of DMF, controlling the temperature to be 55 ℃, stirring for reaction for 10min, then adding 1.0g of potassium hydroxide, then heating to 143 ℃, stirring for reaction for 4h, filtering after the reaction is finished, washing and drying filter cakes, and obtaining the modified titanium dioxide.
Example 3
A modified titanium dioxide is prepared by the following steps:
s1, mixing absolute ethyl alcohol, deionized water and a coupling agent KH-560 according to a mass ratio of 80:10:20, uniformly mixing, hydrolyzing at room temperature for 0.5h to obtain hydrolysate, ultrasonically treating 10g of nano titanium dioxide in 100mL of absolute ethyl alcohol, adding 40mL of hydrolysate, heating to 80 ℃, stirring for reacting for 2h, after the reaction is finished, performing suction filtration, washing a filter cake for 3 times by using absolute ethyl alcohol, and drying to obtain epoxidized nano titanium dioxide;
s2, mixing 10g of epoxidized nano titanium dioxide, 0.4g of 4' -aminobenzo-15-crown-5-ether, 0.6g N-benzyl-4-piperidinol and 60mL of DMF, controlling the temperature to be 60 ℃, stirring for reaction for 10min, then adding 1.2g of potassium hydroxide, heating to 145 ℃, stirring for reaction for 5h, filtering after the reaction is finished, washing and drying filter cakes, and obtaining the modified titanium dioxide.
Comparative example 1
The 4' -aminobenzo-15-crown-5-ether in example 1 was removed, and the remaining raw materials and preparation were the same as in example 1.
Comparative example 2
The N-benzyl-4-piperidinol in example 2 was removed, and the remaining starting materials and preparation were the same as in example 2.
Example 4
A method for treating regenerated wastewater of a hydrogenation catalyst comprises the following steps:
firstly, taking out a hydrogenation catalyst from a catalyst filter in a final-stage kettle of a four-stage serial hydrogenation kettle for performing o-phenylenediamine hydrogenation reaction, and transferring the hydrogenation catalyst to an alcohol washing kettle;
secondly, adding an ethanol solution with the mass fraction of 50% into an alcohol washing kettle, stirring for 30min at the temperature of 45 ℃ and the rotating speed of 800r/min, filtering to obtain a filtrate, namely first-stage wastewater, and transferring a filter cake into an ultrasonic cleaning machine;
thirdly, adding an ethanol solution with the mass fraction of 32% into an ultrasonic cleaning machine, cleaning for 30min at the frequency of 42kHz, filtering, wherein the filtrate is secondary wastewater, and transferring a filter cake to a washing kettle;
and fourthly, adding water into the washing kettle, stirring for 40min at the temperature of 50 ℃ and the rotating speed of 1000r/min, filtering to obtain a filtrate, drying a filter cake at the temperature of 60 ℃ to obtain a regenerated hydrogenation catalyst, converging the primary wastewater, the secondary wastewater and the tertiary wastewater into a wastewater treatment tank, adding the modified titanium dioxide of the embodiment 1 into the wastewater treatment tank, treating for 6h under the irradiation of an LED ultraviolet lamp, filtering, carrying out the next step of treatment on the filter cake, and normally discharging the filtrate.
Wherein the dosage of the modified titanium dioxide is 2 percent of the mass of the primary wastewater, the secondary wastewater and the tertiary wastewater, and the wavelength of the LED ultraviolet lamp is 450nm.
Example 5
A method for treating hydrogenation catalyst regeneration wastewater comprises the following steps:
firstly, taking out a hydrogenation catalyst from a catalyst filter in a final-stage kettle of a four-stage serial hydrogenation kettle for performing o-phenylenediamine hydrogenation reaction, and transferring the hydrogenation catalyst to an alcohol washing kettle;
secondly, adding an ethanol solution with the mass fraction of 20% into an alcohol washing kettle, stirring for 20min at the temperature of 30 ℃ and the rotating speed of 500r/min, filtering, wherein the filtrate is first-grade wastewater, and transferring a filter cake into an ultrasonic cleaner;
thirdly, adding an ethanol solution with the mass fraction of 10% into an ultrasonic cleaning machine, cleaning for 20min at the frequency of 35kHz, filtering, wherein the filtrate is secondary wastewater, and transferring a filter cake to a washing kettle;
and fourthly, adding water into a washing kettle, stirring for 20min at the temperature of 40 ℃ and the rotating speed of 500r/min, filtering to obtain a filtrate, drying a filter cake at the temperature of 40 ℃ to obtain a regenerated hydrogenation catalyst, converging the primary wastewater, the secondary wastewater and the tertiary wastewater into a wastewater treatment tank, adding the modified titanium dioxide of the embodiment 2 into the wastewater treatment tank, treating for 4h under the irradiation of an LED ultraviolet lamp, filtering, carrying out next-step treatment on the filter cake, and normally discharging the filtrate.
Wherein the dosage of the modified titanium dioxide is 1 percent of the mass of the primary wastewater, the secondary wastewater and the tertiary wastewater, and the wavelength of the LED ultraviolet lamp is 380nm.
Example 6
A method for treating regenerated wastewater of a hydrogenation catalyst comprises the following steps:
firstly, taking out a hydrogenation catalyst from a catalyst filter in a final-stage kettle of a four-stage serial hydrogenation kettle for performing o-phenylenediamine hydrogenation reaction, and transferring the hydrogenation catalyst to an alcohol washing kettle;
secondly, adding an ethanol solution with the mass fraction of 30% into an alcohol washing kettle, stirring for 25min at the temperature of 40 ℃ and the rotating speed of 600r/min, filtering to obtain a filtrate, namely first-stage wastewater, and transferring a filter cake into an ultrasonic cleaning machine;
thirdly, adding an ethanol solution with the mass fraction of 15% into an ultrasonic cleaning machine, cleaning for 25min at the frequency of 38kHz, filtering, wherein the filtrate is secondary wastewater, and transferring a filter cake to a washing kettle;
and fourthly, adding water into a washing kettle, stirring for 30min at the temperature of 45 ℃ and at the rotating speed of 800r/min, filtering to obtain filtrate, namely tertiary wastewater, drying a filter cake at the temperature of 50 ℃ to obtain a regenerated hydrogenation catalyst, converging the primary wastewater, the secondary wastewater and the tertiary wastewater into a wastewater treatment tank, adding the modified titanium dioxide obtained in the embodiment 3 into the wastewater treatment tank, treating for 5h under the irradiation of an LED ultraviolet lamp, filtering, carrying out next-step treatment on the filter cake, and normally discharging the filtrate.
Wherein the dosage of the modified titanium dioxide is 1.5 percent of the mass of the primary wastewater, the secondary wastewater and the tertiary wastewater, and the wavelength of the LED ultraviolet lamp is 400nm.
Comparative example 3
The modified titanium dioxide in the example 4 is replaced by the nano titanium dioxide, and the rest of the raw materials and the preparation process are the same as the example 4.
Comparative example 4
The modified titanium dioxide of example 5 was substituted for the material of comparative example 1, and the remaining raw materials and preparation process were the same as those of example 5.
Comparative example 5
The modified titanium dioxide of example 6 was replaced with the material of comparative example 2, and the other raw materials and the preparation process were the same as in example 6.
The effluent filtrates of examples 4 to 6 and comparative examples 3 to 5 were subjected to water quality testing, and the results are shown in Table 1:
TABLE 1
| Item | Total Palladium (μ g/L) | COD cr |
| Example 4 | Not detected out | 5.3 |
| Example 5 | Not detected out | 5.1 |
| Example 6 | Not detected out | 4.8 |
| Comparative example 3 | 0.05 | 5.3 |
| Comparative example 4 | 0.03 | 5.5 |
| Comparative example 5 | 0.01 | 5.7 |
As can be seen from Table 1, the filtrates from examples 4 to 6 discharged lower palladium content and COD than those from comparative examples 3 to 5 cr Lower, meets the relevant requirements of Integrated wastewater discharge Standard (GB 8978-1996), and can be directly discharged.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. A method for treating regenerated wastewater of hydrogenation catalyst is characterized by comprising the following steps:
firstly, adding a filtered hydrogenation catalyst into an alcohol washing kettle;
secondly, adding an ethanol solution with the mass fraction of 20-50% into an alcohol washing kettle, stirring for 20-30min at the temperature of 30-45 ℃, filtering to obtain a filtrate, namely first-stage wastewater, and transferring a filter cake into an ultrasonic cleaning machine;
thirdly, adding an ethanol solution with the mass fraction of 10-32% into an ultrasonic cleaning machine, cleaning for 20-30min at the frequency of 35-42kHz, filtering, wherein the filtrate is secondary wastewater, and transferring a filter cake to a water washing kettle;
and fourthly, adding water into the washing kettle, stirring for 20-40min at the temperature of 40-50 ℃, filtering to obtain a filtrate which is tertiary wastewater, drying a filter cake at the temperature of 40-60 ℃ to obtain a regenerated hydrogenation catalyst, converging the primary wastewater, the secondary wastewater and the tertiary wastewater into a wastewater treatment tank, adding modified titanium dioxide into the wastewater treatment tank, treating for 4-6h under the irradiation of an LED ultraviolet lamp, filtering, carrying out next-step treatment on the filter cake, and normally discharging the filtrate.
2. The method for treating the regeneration wastewater of the hydrogenation catalyst as recited in claim 1, wherein the modified titanium dioxide is prepared by the steps of:
s1, mixing absolute ethyl alcohol, deionized water and a coupling agent KH-560 according to a mass ratio of 75-80:8-10:20, uniformly mixing, hydrolyzing at room temperature for 0.5h to obtain a hydrolysate, ultrasonically treating the nano titanium dioxide in absolute ethyl alcohol, adding the hydrolysate, heating to 75-80 ℃, stirring for reacting for 2h, performing suction filtration, washing and drying a filter cake to obtain epoxidized nano titanium dioxide;
s2, mixing the epoxidized nano titanium dioxide, 4' -aminobenzo-15-crown-5-ether, N-benzyl-4-piperidinol and DMF, stirring at 50-60 ℃, adding potassium hydroxide after reaction, heating to 137-145 ℃, stirring for reaction for 3-5h, filtering, washing a filter cake, and drying to obtain the modified titanium dioxide.
3. The method for treating the regenerated wastewater of the hydrogenation catalyst according to claim 2, wherein the mass ratio of the nano titanium dioxide, the absolute ethyl alcohol and the hydrolysate in the step S1 is 10:100:35-40.
4. The method for treating regenerated wastewater of hydrogenation catalyst as claimed in claim 2, wherein the dosage ratio of the nano-titania, 4' -aminobenzo-15-crown-5-ether, N-benzyl-4-piperidinol, DMF and potassium hydroxide in step S2 is 10g:0.4g:0.4-0.6g:50-60mL:0.8-1.2g.
5. The method for treating regenerated wastewater of hydrogenation catalyst as claimed in claim 1, wherein the amount of the modified titanium dioxide is 1-2% of the mass of the primary wastewater, the secondary wastewater and the tertiary wastewater.
6. The method for treating the regeneration wastewater of the hydrogenation catalyst according to claim 1, wherein the wavelength of the LED ultraviolet lamp is 380-450nm.
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