WO2022099455A1 - Preparation method for cuo/humic acid composite material - Google Patents
Preparation method for cuo/humic acid composite material Download PDFInfo
- Publication number
- WO2022099455A1 WO2022099455A1 PCT/CN2020/127798 CN2020127798W WO2022099455A1 WO 2022099455 A1 WO2022099455 A1 WO 2022099455A1 CN 2020127798 W CN2020127798 W CN 2020127798W WO 2022099455 A1 WO2022099455 A1 WO 2022099455A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solid particles
- humic acid
- beaker
- preparation
- parts
- Prior art date
Links
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000004021 humic acid Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 239000012498 ultrapure water Substances 0.000 claims abstract description 6
- 239000004809 Teflon Substances 0.000 claims abstract description 4
- 229920006362 Teflon® Polymers 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 14
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 6
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000006228 supernatant Substances 0.000 abstract description 5
- 238000003760 magnetic stirring Methods 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000004506 ultrasonic cleaning Methods 0.000 abstract 2
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000011068 loading method Methods 0.000 abstract 1
- 238000000520 microinjection Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
Definitions
- the invention relates to a preparation method of a CuO/humic acid composite material.
- methylene blue (MB) is easy to form a monovalent "cationic" quaternary ammonium salt ion group in aqueous solution. It has deep chromaticity, stable chemical properties, and is difficult to degrade by natural biochemistry. , causing serious harm to the natural environment and people's lives.
- the treatment methods of methylene blue wastewater mainly include catalytic oxidation method, biological oxidation method, chemical oxidation method and adsorption method.
- the adsorption method has the characteristics of small equipment investment, simple operation and low production cost. more extensive research and application.
- Humic acid (HA) contains a variety of active groups such as carboxyl, phenolic, alcoholic, quinone, carbonyl and amine groups, and has good physical and chemical properties such as adsorption and coordination. It is used to modify the composition of metal oxides. Composite materials are widely studied and applied in the environmental field.
- the preparation methods of synthetic nano-copper oxide include solid-phase method, sol-gel method, liquid-phase method, microemulsion method, chemical precipitation method, electrochemical method and hydrothermal method.
- the hydrothermal method refers to a method in which the solubility of some hydroxides in water is greater than that of the corresponding oxides in water under high temperature and high pressure, so the hydroxides are dissolved in water and the oxides are precipitated. Hydrothermal synthesis of nano-copper oxide has the characteristics of low production cost, good dispersibility and controllable crystal form.
- the purpose of the present invention is to provide a preparation method of CuO/humic acid composite material.
- a preparation method of CuO/humic acid composite material comprising the following steps: adding 50-60 parts of distilled water, 8-12 parts of concentrated ammonia water and 10-20 parts of humic acid in sequence to a beaker, magnetic stirring for 25-35 minutes, under stirring conditions Then, pump 90-100 parts of copper acetate solution with a concentration of 18g/L into the beaker with a micro-syringe pump at a speed of 8mL/min, stir magnetically for 2-3h, and form a suspension in the beaker; Put it into a Teflon hydrothermal reactor, put it into a constant temperature drying box at 165-175°C for 13-15h, transfer the cooled suspension to a centrifuge cup, centrifuge it at 3500r/min for 12-15min, take it out, remove the supernatant, Then add high-purity water, ultrasonically clean the solid particles for 4-6 times, and then centrifuge to obtain solid particles, add ethanol, ultrasonically clean the solid particles, and place the obtained solid
- the preparation method it is placed in a constant temperature drying box at 170° C. for 14 hours.
- centrifuge at 3500 r/min for 14 min and then take out.
- the obtained solid particles are placed in a drying oven at 45° C. for drying for 12 hours.
- the method is simple, fast and easy to operate, and the prepared CuO/humic acid composite material has good adsorption performance for methylene blue and excellent cyclic regeneration performance. Potential application prospects.
- a preparation method of CuO/humic acid composite material comprising the following steps: adding 55 parts of distilled water, 10 parts of concentrated ammonia water and 15 parts of humic acid in sequence to a beaker, stirring magnetically for 30 minutes, and using a micro-syringe pump to add 8 mL of humic acid under stirring conditions.
- a preparation method of CuO/humic acid composite material comprising the following steps: adding 50 parts of distilled water, 8 parts of concentrated ammonia water and 10 parts of humic acid in sequence to a beaker, stirring magnetically for 25 minutes, and using a micro-syringe pump to add 8 mL of humic acid under stirring conditions.
- a preparation method of CuO/humic acid composite material comprising the following steps: adding 60 parts of distilled water, 12 parts of concentrated ammonia water and 20 parts of humic acid in sequence to a beaker, stirring magnetically for 35 minutes, and under stirring conditions, using a micro-syringe pump to add 8 mL 100 parts of copper acetate solution with a concentration of 18g/L were pumped into the beaker at a speed of A constant temperature drying box was kept for 15 hours, the cooled suspension was transferred to a centrifuge cup, centrifuged at 3500 r/min for 15 minutes, taken out, the supernatant was removed, then high-purity water was added, and the solid particles were ultrasonically cleaned for 6 times, and then the solid particles were obtained by centrifugation. Ethanol was added, the solid particles were ultrasonically cleaned, and the obtained solid particles were placed in a dry oven at 46° C. to dry for 13 hours, and then cooled to obtain; each raw material was in parts by weight.
- the method is simple, fast and easy to operate, and the prepared CuO/humic acid composite material has good adsorption performance for methylene blue and excellent cyclic regeneration performance. Potential application prospects.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
Disclosed is a preparation method for a CuO/humic acid composite material. The steps comprise: sequentially adding distilled water, stronger ammonia water and humic acid in a beaker, and performing magnetic stirring for 25-35 min; in a stirring condition, pumping a copper acetate solution into the beaker by using a micro-injection pump, and performing magnetic stirring for 2-3 h to form a suspension in the beaker; loading the suspension into a Teflon hydrothermal reactor, and placing the reactor into 165-175°C of a constant temperature drying oven for heat preservation for 13-15 h; transferring the cooled suspension to a centrifugal cup, taking out same after centrifugation, and removing a supernatant liquid; then adding high purity water, performing ultrasonic cleaning on solid particles, and then performing centrifugation operation to obtain the solid particles; adding ethyl alcohol, performing ultrasonic cleaning on the solid particles, drying, and cooling. The CuO/humic acid composite material prepared by means of the method has good adsorption property for methylene blue and good recycling and regeneration property, and has good potential application prospects.
Description
本发明涉及一种CuO/腐植酸复合材料的制备方法。The invention relates to a preparation method of a CuO/humic acid composite material.
随着纺织印染需求的增大，世界每年所需染料量超过100万吨，其中偶氮染料用量占2/3以上，在染料生产及印染过程中产生大量了染料废水，其中大部分为含氮染料废水。亚甲基蓝(MB)作为典型的水溶性偶氮染料代表物，在水溶液中易形成一价“阳离子型”季铵盐离子基团，色度深、化学性质稳定，自然生化难以降解，如果排放处理不当，给自然环境和人们生活造成严重的危害。目前，亚甲基蓝废水的处理方法主要有催化氧化法、生物氧化法、化学氧化法和吸附法等，其中吸附法处理具有设备投资小、操作简便、生产成本低等特性，在处理含亚甲基蓝废水方面有着较广泛地研究与应用。With the increasing demand for textile printing and dyeing, the world needs more than 1 million tons of dyes every year, of which the amount of azo dyes accounts for more than 2/3. In the process of dye production and printing and dyeing, a large amount of dye wastewater is generated, most of which are nitrogen-containing. Dye Wastewater. As a typical representative of water-soluble azo dyes, methylene blue (MB) is easy to form a monovalent "cationic" quaternary ammonium salt ion group in aqueous solution. It has deep chromaticity, stable chemical properties, and is difficult to degrade by natural biochemistry. , causing serious harm to the natural environment and people's lives. At present, the treatment methods of methylene blue wastewater mainly include catalytic oxidation method, biological oxidation method, chemical oxidation method and adsorption method. Among them, the adsorption method has the characteristics of small equipment investment, simple operation and low production cost. more extensive research and application.
腐植酸(HA)因含有羧基、酚羟基、醇羟基、醌基、羰基和胺基等多种活性基团，具有良好的吸附和配位等物理、化学特性，用来改性金属氧化物构成复合材料，在环境领域方面被广泛研究与应用。目前，合成纳米氧化铜的制备方法有固相法、溶胶凝胶法、液相法、微乳液法、化学沉淀法、电化学法和水热法等。其中水热法是指在高温高压下一些氢氧化物在水中的溶解度大于对应的氧化物在水中的溶解度，于是氢氧化物溶于水中同时析出氧化物的方法。水热法合成纳米氧化铜具有生产成本低、分散性好、晶型可控制等特性。Humic acid (HA) contains a variety of active groups such as carboxyl, phenolic, alcoholic, quinone, carbonyl and amine groups, and has good physical and chemical properties such as adsorption and coordination. It is used to modify the composition of metal oxides. Composite materials are widely studied and applied in the environmental field. At present, the preparation methods of synthetic nano-copper oxide include solid-phase method, sol-gel method, liquid-phase method, microemulsion method, chemical precipitation method, electrochemical method and hydrothermal method. The hydrothermal method refers to a method in which the solubility of some hydroxides in water is greater than that of the corresponding oxides in water under high temperature and high pressure, so the hydroxides are dissolved in water and the oxides are precipitated. Hydrothermal synthesis of nano-copper oxide has the characteristics of low production cost, good dispersibility and controllable crystal form.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种CuO/腐植酸复合材料的制备方法。The purpose of the present invention is to provide a preparation method of CuO/humic acid composite material.
本发明通过下面技术方案实现：The present invention is achieved through the following technical solutions:
一种CuO/腐植酸复合材料的制备方法，包括如下步骤：在烧杯中依次加入50-60份蒸馏水、8-12份浓氨水和10-20份腐植酸，磁力搅拌25-35min，在搅拌条件下，用微量注射泵以8mL/min的速度将90-100份浓度为18g/L的乙酸铜溶液泵入烧杯中，磁力搅拌2-3h，在烧杯中形成悬浊液；将悬浊液装入Teflon水热反应釜中，放入165-175℃恒温干燥箱保温13-15h，将冷却后的悬浮液转移至离心杯中，以3500r/min离心12-15min后取出，去除上层清液，然后加入高纯水，超声清洗固体颗粒4-6次，然后离心操作得固体颗粒，加入乙醇，超声清洗固体颗粒，将得到的固体颗粒放置于干烘箱44-46℃干燥11-13h，冷却即得；各原料均为重量份。A preparation method of CuO/humic acid composite material, comprising the following steps: adding 50-60 parts of distilled water, 8-12 parts of concentrated ammonia water and 10-20 parts of humic acid in sequence to a beaker, magnetic stirring for 25-35 minutes, under stirring conditions Then, pump 90-100 parts of copper acetate solution with a concentration of 18g/L into the beaker with a micro-syringe pump at a speed of 8mL/min, stir magnetically for 2-3h, and form a suspension in the beaker; Put it into a Teflon hydrothermal reactor, put it into a constant temperature drying box at 165-175°C for 13-15h, transfer the cooled suspension to a centrifuge cup, centrifuge it at 3500r/min for 12-15min, take it out, remove the supernatant, Then add high-purity water, ultrasonically clean the solid particles for 4-6 times, and then centrifuge to obtain solid particles, add ethanol, ultrasonically clean the solid particles, and place the obtained solid particles in a drying oven at 44-46 °C for 11-13 hours, and cool to obtain; All raw materials are in parts by weight.
优选地，所述的制备方法中，放入170℃恒温干燥箱保温14h。Preferably, in the preparation method, it is placed in a constant temperature drying box at 170° C. for 14 hours.
优选地，所述的制备方法中，以3500r/min离心14min后取出。Preferably, in the preparation method, centrifuge at 3500 r/min for 14 min and then take out.
优选地，所述的制备方法中，将得到的固体颗粒放置于干烘箱45℃干燥12h。Preferably, in the preparation method, the obtained solid particles are placed in a drying oven at 45° C. for drying for 12 hours.
本发明技术效果：Technical effect of the present invention:
该方法简便、快捷、易操作，制备的CuO/腐植酸复合材料对亚甲基蓝具有良好的吸附性能，及优良的循环再生性能，该复合材料是一种高效脱除亚甲基蓝的吸附材料，具有较好的潜在应用前景。The method is simple, fast and easy to operate, and the prepared CuO/humic acid composite material has good adsorption performance for methylene blue and excellent cyclic regeneration performance. Potential application prospects.
下面结合实施例具体介绍本发明的实质性内容。The substantive content of the present invention will be specifically described below with reference to the embodiments.
实施例1Example 1
一种CuO/腐植酸复合材料的制备方法，包括如下步骤：在烧杯中依次加入55份蒸馏水、10份浓氨水和15份腐植酸，磁力搅拌30min，在搅拌条件下，用微量注射泵以8mL/min的速度将95份浓度为18g/L的乙酸铜溶液泵入烧杯中，磁力搅拌2.5h，在烧杯中形成悬浊液；将悬浊液装入Teflon水热反应釜中，放入170℃恒温干燥箱保温14h，将冷却后的悬浮液转移至离心杯中，以3500r/min离心14min后取出，去除上层清液，然后加入高纯水，超声清洗固体颗粒5次，然后离心操作得固体颗粒，加入乙醇，超声清洗固体颗粒，将得到的固体颗粒放置于干烘箱45℃干燥12h，冷却即得；各原料均为重量份。A preparation method of CuO/humic acid composite material, comprising the following steps: adding 55 parts of distilled water, 10 parts of concentrated ammonia water and 15 parts of humic acid in sequence to a beaker, stirring magnetically for 30 minutes, and using a micro-syringe pump to add 8 mL of humic acid under stirring conditions. At the speed of /min, 95 parts of copper acetate solution with a concentration of 18g/L were pumped into the beaker, magnetically stirred for 2.5h, and a suspension was formed in the beaker; The temperature was kept in a constant temperature drying box for 14 hours, the cooled suspension was transferred to a centrifuge cup, centrifuged at 3500 r/min for 14 minutes, taken out, the supernatant was removed, high-purity water was added, and the solid particles were ultrasonically cleaned for 5 times, and then the solid particles were obtained by centrifugation. , adding ethanol, ultrasonically cleaning the solid particles, placing the obtained solid particles in a dry oven at 45° C. to dry for 12 hours, and cooling to obtain; each raw material is in parts by weight.
实施例2Example 2
一种CuO/腐植酸复合材料的制备方法，包括如下步骤：在烧杯中依次加入50份蒸馏水、8份浓氨水和10份腐植酸，磁力搅拌25min，在搅拌条件下，用微量注射泵以8mL/min的速度将90份浓度为18g/L的乙酸铜溶液泵入烧杯中，磁力搅拌2h，在烧杯中形成悬浊液；将悬浊液装入Teflon水热反应釜中，放入165℃恒温干燥箱保温13h，将冷却后的悬浮液转移至离心杯中，以3500r/min离心12min后取出，去除上层清液，然后加入高纯水，超声清洗固体颗粒4次，然后离心操作得固体颗粒，加入乙醇，超声清洗固体颗粒，将得到的固体颗粒放置于干烘箱44℃干燥11h，冷却即得；各原料均为重量份。A preparation method of CuO/humic acid composite material, comprising the following steps: adding 50 parts of distilled water, 8 parts of concentrated ammonia water and 10 parts of humic acid in sequence to a beaker, stirring magnetically for 25 minutes, and using a micro-syringe pump to add 8 mL of humic acid under stirring conditions. Pump 90 parts of copper acetate solution with a concentration of 18g/L into the beaker at the speed of /min, stir magnetically for 2h, and form a suspension in the beaker; put the suspension into the Teflon hydrothermal reaction kettle, put it into 165 ℃ The constant temperature drying box was kept for 13 hours, the cooled suspension was transferred to a centrifuge cup, centrifuged at 3500 r/min for 12 minutes, taken out, the supernatant was removed, then high-purity water was added, and the solid particles were ultrasonically cleaned for 4 times, and then the solid particles were obtained by centrifugation. Ethanol was added, the solid particles were ultrasonically cleaned, and the obtained solid particles were placed in a dry oven at 44° C. to dry for 11 hours, and then cooled to obtain; each raw material was in parts by weight.
实施例3Example 3
一种CuO/腐植酸复合材料的制备方法，包括如下步骤：在烧杯中依次加入60份蒸馏水、12份浓氨水和20份腐植酸，磁力搅拌35min，在搅拌条件下，用微量注射泵以8mL/min的速度将100份浓度为18g/L的乙酸铜溶液泵入烧杯中，磁力搅拌3h，在烧杯中形成悬浊液；将悬浊液装入Teflon水热反应釜中，放入175℃恒温干燥箱保温15h，将冷却后的悬浮液转移至离心杯中，以3500r/min离心15min后取出，去除上层清液，然后加入高纯水，超声清洗固体颗粒6次，然后离心操作得固体颗粒，加入乙醇，超声清洗固体颗粒，将得到的固体颗粒放置于干烘箱46℃干燥13h，冷却即得；各原料均为重量份。A preparation method of CuO/humic acid composite material, comprising the following steps: adding 60 parts of distilled water, 12 parts of concentrated ammonia water and 20 parts of humic acid in sequence to a beaker, stirring magnetically for 35 minutes, and under stirring conditions, using a micro-syringe pump to add 8 mL 100 parts of copper acetate solution with a concentration of 18g/L were pumped into the beaker at a speed of A constant temperature drying box was kept for 15 hours, the cooled suspension was transferred to a centrifuge cup, centrifuged at 3500 r/min for 15 minutes, taken out, the supernatant was removed, then high-purity water was added, and the solid particles were ultrasonically cleaned for 6 times, and then the solid particles were obtained by centrifugation. Ethanol was added, the solid particles were ultrasonically cleaned, and the obtained solid particles were placed in a dry oven at 46° C. to dry for 13 hours, and then cooled to obtain; each raw material was in parts by weight.
该方法简便、快捷、易操作，制备的CuO/腐植酸复合材料对亚甲基蓝具有良好的吸附性能，及优良的循环再生性能，该复合材料是一种高效脱除亚甲基蓝的吸附材料，具有较好的潜在应用前景。The method is simple, fast and easy to operate, and the prepared CuO/humic acid composite material has good adsorption performance for methylene blue and excellent cyclic regeneration performance. Potential application prospects.
Claims (4)
- 一种CuO/腐植酸复合材料的制备方法，其特征在于包括如下步骤：在烧杯中依次加入50-60份蒸馏水、8-12份浓氨水和10-20份腐植酸，磁力搅拌25-35min，在搅拌条件下，用微量注射泵以8mL/min的速度将90-100份浓度为18g/L的乙酸铜溶液泵入烧杯中，磁力搅拌2-3h，在烧杯中形成悬浊液；将悬浊液装入Teflon水热反应釜中，放入165-175℃恒温干燥箱保温13-15h，将冷却后的悬浮液转移至离心杯中，以3500r/min离心12-15min后取出，去除上层清液，然后加入高纯水，超声清洗固体颗粒4-6次，然后离心操作得固体颗粒，加入乙醇，超声清洗固体颗粒，将得到的固体颗粒放置于干烘箱44-46℃干燥11-13h，冷却即得；各原料均为重量份。A preparation method of CuO/humic acid composite material, which is characterized by comprising the steps of: adding 50-60 parts of distilled water, 8-12 parts of concentrated ammonia water and 10-20 parts of humic acid in sequence to a beaker, stirring magnetically for 25-35 minutes, Under stirring conditions, pump 90-100 parts of copper acetate solution with a concentration of 18g/L into a beaker with a micro-syringe pump at a speed of 8mL/min, stir magnetically for 2-3h, and form a suspension in the beaker; The turbid liquid was placed in a Teflon hydrothermal reaction kettle, placed in a constant temperature drying box at 165-175°C for 13-15 hours, and the cooled suspension was transferred to a centrifuge cup, centrifuged at 3500r/min for 12-15min, taken out, and the upper layer was removed. Then add high-purity water, ultrasonically clean the solid particles for 4-6 times, and then centrifuge to obtain solid particles, add ethanol, ultrasonically clean the solid particles, and place the obtained solid particles in a drying oven at 44-46 °C for 11-13 hours, and cool. That is, each raw material is in parts by weight.
- 根据权利要求1所述的制备方法，其特征在于：放入170℃恒温干燥箱保温14h。The preparation method according to claim 1, characterized in that: putting it into a constant temperature drying box at 170°C for 14 hours.
- 根据权利要求1所述的制备方法，其特征在于：以3500r/min离心14min后取出。The preparation method according to claim 1, characterized in that: take out after centrifugation at 3500r/min for 14min.
- 根据权利要求1所述的制备方法，其特征在于：将得到的固体颗粒放置于干烘箱45℃干燥12h。The preparation method according to claim 1, wherein the obtained solid particles are placed in a drying oven at 45°C for drying for 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2020/127798 WO2022099455A1 (en) | 2020-11-10 | 2020-11-10 | Preparation method for cuo/humic acid composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2020/127798 WO2022099455A1 (en) | 2020-11-10 | 2020-11-10 | Preparation method for cuo/humic acid composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022099455A1 true WO2022099455A1 (en) | 2022-05-19 |
Family
ID=81600745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2020/127798 WO2022099455A1 (en) | 2020-11-10 | 2020-11-10 | Preparation method for cuo/humic acid composite material |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2022099455A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058257A (en) * | 2013-01-04 | 2013-04-24 | 南京大学 | CuO ball, preparation method and use thereof, as well as visible light catalyst |
| CN105347382A (en) * | 2015-12-10 | 2016-02-24 | 济南大学 | Method for preparing garland-shaped nanometer copper oxide material |
| CN105731517A (en) * | 2016-01-15 | 2016-07-06 | 电子科技大学 | Flower-shaped copper oxide nanostructure material and preparation method thereof |
| CN106935826A (en) * | 2017-03-23 | 2017-07-07 | 江西理工大学 | The lithium ion battery preparation method of nano cupric oxide graphene composite material |
-
2020
- 2020-11-10 WO PCT/CN2020/127798 patent/WO2022099455A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058257A (en) * | 2013-01-04 | 2013-04-24 | 南京大学 | CuO ball, preparation method and use thereof, as well as visible light catalyst |
| CN105347382A (en) * | 2015-12-10 | 2016-02-24 | 济南大学 | Method for preparing garland-shaped nanometer copper oxide material |
| CN105731517A (en) * | 2016-01-15 | 2016-07-06 | 电子科技大学 | Flower-shaped copper oxide nanostructure material and preparation method thereof |
| CN106935826A (en) * | 2017-03-23 | 2017-07-07 | 江西理工大学 | The lithium ion battery preparation method of nano cupric oxide graphene composite material |
Non-Patent Citations (1)
| Title |
|---|
| LIU ZHIXIONG, ZHANG JIALI;HONG XUYAN;TIAN GUIYING;TANG ZHIHAO;HU MINGYU: "Preparation of CuO-Humic Acid Composite and Its Adsorption Properties", CHEMICAL INDUSTRY AND ENGINEERING PROGRESS, vol. 37, no. 10, 5 October 2018 (2018-10-05), pages 4060 - 4067, XP055931854, ISSN: 1000-6613, DOI: 10.16085/j.issn.1000-6613.2018-0092 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109193063B (en) | Method for reprocessing positive active material of waste lithium ion battery | |
| CN107349787B (en) | Preparation method of forward osmosis membrane added with aminated graphene quantum dots, prepared forward osmosis membrane and application of forward osmosis membrane | |
| CN106629660A (en) | Preparation method of N, P co-doping carbon quantum dots, and product and application thereof | |
| CN102071267B (en) | Method for coproducing xylose, white carbon black and active carbon from rice hulls | |
| CN107879335B (en) | Preparation method of nitrogen-doped graphene quantum dot material | |
| CN104229787B (en) | The method that native graphite pretreatment is improved preparing graphene by using supercritical fluid productivity | |
| TW201132594A (en) | Method for recycling solvent of Lyocell fibers | |
| CN102964878B (en) | Preparation method of rare earth oxide/hollow glass bead composite material | |
| CN106831894B (en) | A kind of method of deacetylation Coupling Adsorption separation D-Glucosamine Hydrochloride | |
| CN102329212A (en) | Refining method for long-chain binary acid | |
| WO2022099455A1 (en) | Preparation method for cuo/humic acid composite material | |
| KR101899015B1 (en) | Process for the production of l-carnitine tartrate | |
| CN101544944B (en) | Novel method for accelerating aging and impurity removal of white spirit by immobilized enzyme | |
| CN109133144A (en) | A kind of preparation method of monodisperse ultra-small grain size ceria nano-crystalline | |
| CN107739825A (en) | It is a kind of to utilize the method that vanadium product is prepared containing vanadium leachate | |
| CN110105196A (en) | The recovery method of terephthalic acid (TPA) | |
| CN110002498A (en) | A kind of porous nano V2O5Preparation method | |
| CN104789541A (en) | Simple method for extracting lysozyme from egg white | |
| CN113800744A (en) | Conditioning agent for blue algae dehydration of filter press and application thereof | |
| CN102070552A (en) | Method for preparing 3-amino-5-nitro-2,1-benzisothiazole and diazonium salt thereof | |
| CN111186848A (en) | Process and device for refining byproduct ammonium sulfate in isophthalonitrile production | |
| TW202142758A (en) | Auxiliary for dyeing, manufacturing method thereof and dyeing process using the same capable of increasing the dyeing rate of the fabric during the dyeing process and reducing the dye residual rate in the subsequent produced wastewater | |
| CN105776307B (en) | The pre-treating method that a kind of rare earth oxide isolates and purifies | |
| TWI811017B (en) | Purification method of bio-indigo dye | |
| CN115960474B (en) | Preparation method of high-solid-content liquid brilliant blue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20961014 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205N DATED 04.07.23) |