CN112058081A - Method for removing hexachlorobenzene generated in spice extraction process - Google Patents
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol
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Abstract
The invention relates to the technical field of chemical industry, in particular to a method for removing hexachlorobenzene generated in the extraction process of spices; the absorption liquid is prepared from gamma-type aluminum oxide, iron powder, sodium carbonate and paraffin oil, and under the alkaline action of the sodium carbonate and the coordination action of a hydrogen donor of the paraffin oil, the gamma-type aluminum oxide and the iron powder are mutually cooperated, so that hexachlorobenzene in the spice mother liquid can be effectively and efficiently removed; moreover, the catalyst prepared by the method has larger volume, and the space diversity of a three-dimensional topological structure formed by the catalyst is more complex, so that the specific surface area of the catalyst is remarkably increased, and the contact area of the catalyst and hexachlorobenzene is effectively increased; the solvent is matched with absorption liquid, so that the removal capacity of the p-hexachlorobenzene can be improved to the ground; the hexachlorobenzene can be efficiently dechlorinated; moreover, the purity and the chroma of the spice mother liquor treated by the method are greatly improved.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for removing hexachlorobenzene generated in the extraction process of spices.
Background
The perfume is also called as a fragrant raw material, is a substance which can be smelled to smell or smells to produce fragrance, and is used for preparing essence. Most of the perfumes cannot be used alone except for individual species. The perfume is divided into natural perfume and artificial perfume, wherein the natural perfume comprises animal natural perfume and plant natural perfume; artificial flavors include both isolated flavors and synthetic flavors.
In the existing perfume extraction process, in a working section for extracting a mother liquor, chloroform is adopted by soybeans as an extracting agent to recover residual maltol in the mother liquor, and extracted materials are easy to form trace hexachlorobenzene in a perfume sublimation product, in the existing process, the hexachlorobenzene is removed by an irradiation method and a photocatalytic oxidation method, but the method only can play a role in removing the hexachlorobenzene to a certain extent, namely the efficiency of removing the hexachlorobenzene is relatively low (the removal efficiency of the irradiation method is about 80 percent, and the removal efficiency of the photocatalytic oxidation method is about 85 percent).
Therefore, it is an urgent technical problem to be solved by those skilled in the art to provide a method for efficiently removing hexachlorobenzene generated in the perfume extraction process.
Disclosure of Invention
In view of the problems, the invention provides a method for removing hexachlorobenzene generated in the process of extracting perfume, which not only has higher dechlorination efficiency to hexachlorobenzene, but also has very high removal rate to hexachlorobenzene. In addition, the purity and the chroma of the spice mother liquor treated by the method are improved to a great extent, and the quality of the spice mother liquor is ensured.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for removing hexachlorobenzene generated in a perfume extraction process comprises the following steps:
firstly, preparing a catalyst;
accurately weighing a proper amount of sodium phosphotungstate, lanthanum nitrate and nano metal nickel, respectively pretreating the sodium phosphotungstate, lanthanum nitrate and nano metal nickel, soaking the pretreated sodium phosphotungstate, lanthanum nitrate and nano metal nickel in a mixed solution consisting of inorganic acid liquid and absolute ethyl alcohol, and uniformly mixing and stirring the inorganic acid liquid and the absolute ethyl alcohol to form a stable dispersion phase; then, regulating the pH value of the mixed component to 2.0-3.5 by using a hydrochloric acid solution with the concentration of 0.3-0.5 mol/L to obtain a mixed component; then placing the obtained mixed components in a microwave reactor, carrying out microwave heating for 10-18 h at the temperature of 60-80 ℃, taking out the mixed components from the microwave reactor, and aging the mixed components in a constant-temperature drying oven for 3-5 h; filtering out the solid mixture in the mixed components after the aging is finished, and washing the solid mixture to be neutral by using distilled water; finally, placing the washed solid mixture in a muffle furnace for roasting, taking the solid mixture out of the muffle furnace after roasting is finished, and cooling the solid mixture to room temperature under natural conditions to obtain a finished catalyst;
secondly, filling a catalyst;
the method comprises the following steps of filling catalysts diluted by activated carbon particles into a fixed bed catalytic distillation tower from top to bottom in six sections, wherein the mass percentage of the catalysts filled in each section from top to bottom is 10-15%, 2-5%, 16-20%, 35-40%, 55-60% and 75-81% in sequence;
thirdly, pretreating the catalyst;
introducing nitrogen from the bottom of the fixed bed catalytic distillation tower to replace air in the tower, continuously introducing the nitrogen for more than 3 hours, then switching the nitrogen into pure hydrogen, simultaneously heating the fixed bed catalytic distillation tower, so that the temperatures of the sections from top to bottom are 185-215 ℃, 195-225 ℃, 245-265 ℃, 280-295 ℃, 295-315 ℃ and 310-325 ℃, the heating rates are 3-5 ℃/min, and keeping the constant temperature at the temperature for 3-5 hours after the temperature is raised to the target temperature; after the catalyst is activated, sequentially reducing the temperature of each section of the fixed bed catalytic distillation tower from top to bottom to 135-148 ℃, 178-190 ℃, 210-220 ℃, 255-265 ℃, 280-290 ℃ and 230-245 ℃, and keeping each section of the fixed bed catalytic distillation tower under the temperature condition;
catalyzing and removing tetrachlorobenzene;
extracting mother liquor generated in a spice extraction section by using chloroform as an extracting agent to recover residual maltol in the mother liquor, introducing the extracted mother liquor containing trace hexachlorobenzene into a reaction kettle containing absorption liquid, and continuously introducing nitrogen into the reaction kettle for 5-10 min; then closing the intake valve; then heating and stirring the materials, wherein the stirring speed is about 120-150 r/min; about 20-30 min after heating; the temperature of the material is raised to a set value of 230-250 ℃; after reacting for 3-6 h, turning off a heating power supply; reducing the temperature of the reaction kettle to about 50-60 ℃; heating the temperature of residual liquid in the reaction kettle to 230-240 ℃, introducing the residual liquid from the bottom of the fixed bed catalytic distillation tower, introducing mixed gas of hydrogen chloride and hydrogen from each gas supplementing port, discharging dichlorobenzene serving as a reaction product from the second section of the fixed bed catalytic distillation tower, and discharging chlorobenzene from the first section; and the hydrogen chloride is discharged from the top of the tower and recycled, and finally the hexachlorobenzene is efficiently removed.
Furthermore, the mass ratio of the sodium phosphotungstate to the lanthanum nitrate to the nano metal nickel is 1.0-1.5: 2.0-3.0: 9.0-10.0.
Further, the pretreatment specifically comprises the following steps: and (2) ultrasonically cleaning sodium phosphotungstate, lanthanum nitrate and nano metal nickel for 20-30 min at the frequency of 28-35 kHz respectively, then washing the sodium phosphotungstate, lanthanum nitrate and nano metal nickel for 2-3 times by using distilled water, and finally drying the sodium phosphotungstate, lanthanum nitrate and nano metal nickel in a constant-temperature drying box.
Furthermore, the inorganic acid is a sulfuric acid solution with a concentration of 0.3-0.5 mol/L, and the mass ratio of the inorganic acid solution to the absolute ethyl alcohol in the mixed solution is 2.5-3.6: 1.0.
Furthermore, when the solid mixture is roasted, the roasting temperature of the muffle furnace is set to be 450-560 ℃, and the roasting time is 3-5 h.
Further, in the catalyst packing step, the second to fifth stages of the fixed-bed catalytic distillation column are each provided with an air replenishment port.
Furthermore, the mixed gas consists of hydrogen and hydrogen chloride gas, and the volume concentration of the hydrogen is 25-35%.
Furthermore, the absorption liquid is formed by ultrasonically mixing aluminum oxide, iron powder, sodium carbonate and paraffin oil according to the mass ratio of 1.0-1.6: 0.3-0.5: 10-13: 85-100; and the alumina is gamma-type alumina.
By adopting the technical scheme, the invention has the beneficial effects that:
the method comprises the steps of firstly absorbing and removing the spice mother liquor containing the hexachlorobenzene by using absorption liquid, wherein the absorption liquid is prepared from gamma-type aluminum oxide, iron powder, sodium carbonate and paraffin oil, and under the alkaline action of the sodium carbonate and the coordination action of a hydrogen donor of the paraffin oil, the gamma-type aluminum oxide and the iron powder are mutually cooperated, so that the hexachlorobenzene in the spice mother liquor can be effectively and efficiently removed. Thereby realizing the preliminary removal of the hexachlorobenzene.
In addition, sodium phosphotungstate, lanthanum nitrate and nano metal nickel are used as main raw materials for preparing the catalyst, the prepared catalyst is larger in volume, and the space diversity of a three-dimensional topological structure formed by the catalyst is more complex, so that the specific surface area of the catalyst is remarkably increased, and the contact area of the catalyst and hexachlorobenzene is effectively increased. In addition, the nanometer metal nickel and the lanthanum nitrate can be effectively attached to the surface and the inner wall of the sodium phosphotungstate, so that the space contact area between the lanthanum nitrate and the metal nickel and the hexachlorobenzene is effectively increased, and the nanometer metal nickel is favorably and fully removed. The method is matched with absorption liquid, so that the removal capacity of the p-hexachlorobenzene can be improved to the great extent. Can also carry out efficient dechlorination treatment on hexachlorobenzene. Through detection, the fragrance mother liquor is treated by the method, the dechlorination efficiency of the hexachlorobenzene is 95.6-97.8%, and the removal rate of the hexachlorobenzene is 99.2-99.7%. Moreover, the purity and the chroma of the spice mother liquor treated by the method are greatly improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1:
a method for removing hexachlorobenzene generated in a perfume extraction process comprises the following steps:
firstly, preparing a catalyst;
accurately weighing a proper amount of sodium phosphotungstate, lanthanum nitrate and nano metal nickel, respectively pretreating the sodium phosphotungstate, lanthanum nitrate and nano metal nickel, soaking the pretreated sodium phosphotungstate, lanthanum nitrate and nano metal nickel in a mixed solution consisting of inorganic acid liquid and absolute ethyl alcohol, and uniformly mixing and stirring the inorganic acid liquid and the absolute ethyl alcohol to form a stable dispersion phase; then regulating the pH value of the mixed component to 2.0 by using hydrochloric acid solution with the concentration of 0.3mol/L to obtain a mixed component; then placing the obtained mixed components in a microwave reactor, carrying out microwave heating for 10h at the temperature of 60 ℃, taking out the mixed components from the microwave reactor, and aging the mixed components in a constant-temperature drying oven for 3 h; filtering out the solid mixture in the mixed components after the aging is finished, and washing the solid mixture to be neutral by using distilled water; finally, placing the washed solid mixture in a muffle furnace for roasting, taking the solid mixture out of the muffle furnace after roasting is finished, and cooling the solid mixture to room temperature under natural conditions to obtain a finished catalyst;
secondly, filling a catalyst;
the method comprises the following steps of filling catalysts diluted by activated carbon particles into six sections from top to bottom in a fixed bed catalytic distillation tower, wherein the mass percentage of the catalysts filled in each section from top to bottom is 10%, 2%, 16%, 35%, 55% and 75% in sequence;
thirdly, pretreating the catalyst;
introducing nitrogen from the bottom of the fixed bed catalytic distillation tower to replace air in the tower, continuously introducing the nitrogen for more than 3 hours, then switching the nitrogen into pure hydrogen, simultaneously heating the fixed bed catalytic distillation tower to enable the temperatures of the sections from top to bottom to be 185 ℃, 195 ℃, 245 ℃, 280 ℃, 295 ℃ and 310 ℃, wherein the heating rates are 3 ℃/min, and keeping the constant temperature for 3 hours at the temperature after the temperature is raised to the target temperature; after the catalyst activation is finished, sequentially reducing the temperature of each section of the fixed bed catalytic distillation tower from top to bottom to 135 ℃, 178 ℃, 210 ℃, 255 ℃, 280 ℃ and 230 ℃, and keeping each section of the fixed bed catalytic distillation tower under the temperature condition;
catalyzing and removing tetrachlorobenzene;
extracting mother liquor generated in a spice extraction section by using chloroform as an extracting agent to recover residual maltol in the mother liquor, introducing the extracted mother liquor containing trace hexachlorobenzene into a reaction kettle containing absorption liquid, and continuously introducing nitrogen into the reaction kettle for 5 min; then closing the intake valve; then heating and stirring the materials, wherein the stirring speed is about 120 r/min; about 20min after the start of heating; the temperature of the material rises to a set value of 230 ℃; after reacting for 3h, turning off the heating power supply; reducing the temperature of the reaction vessel to about 50 ℃; heating the residual liquid in the reaction kettle to 230 ℃, introducing the residual liquid from the bottom of the fixed bed catalytic distillation tower, introducing a mixed gas of hydrogen chloride and hydrogen from each gas supplementing port, discharging dichlorobenzene serving as a reaction product from the second section of the fixed bed catalytic distillation tower, and discharging chlorobenzene from the first section; and the hydrogen chloride is discharged from the top of the tower and recycled, and finally the hexachlorobenzene is efficiently removed.
The mass ratio of the sodium phosphotungstate to the lanthanum nitrate to the nano metal nickel is 1.0:2.0: 9.0.
The pretreatment comprises the following specific operations: and (2) ultrasonically cleaning sodium phosphotungstate, lanthanum nitrate and nano metal nickel for 20min at the frequency of 28kHz respectively, then washing the sodium phosphotungstate, lanthanum nitrate and nano metal nickel for 2 times by using distilled water, and finally placing the sodium phosphotungstate, lanthanum nitrate and nano metal nickel in a constant-temperature drying box for drying.
The inorganic acid is sulfuric acid solution with the concentration of 0.3mol/L, and the mass ratio of the inorganic acid solution to the absolute ethyl alcohol in the mixed solution is 2.5: 1.0.
When the solid mixture is roasted, the roasting temperature of a muffle furnace is set to be 450 ℃, and the roasting time is 3 hours.
In the catalyst filling step, the second to fifth sections of the fixed bed catalytic distillation column are provided with air make-up ports.
The mixed gas consists of hydrogen and hydrogen chloride gas, and the volume concentration of the hydrogen is 25%.
The absorption liquid is formed by ultrasonically mixing aluminum oxide, iron powder, sodium carbonate and paraffin oil according to the mass ratio of 1.0:0.3:10: 85; and the alumina is gamma-type alumina.
Example 2:
a method for removing hexachlorobenzene generated in a perfume extraction process comprises the following steps:
firstly, preparing a catalyst;
accurately weighing a proper amount of sodium phosphotungstate, lanthanum nitrate and nano metal nickel, respectively pretreating the sodium phosphotungstate, lanthanum nitrate and nano metal nickel, soaking the pretreated sodium phosphotungstate, lanthanum nitrate and nano metal nickel in a mixed solution consisting of inorganic acid liquid and absolute ethyl alcohol, and uniformly mixing and stirring the inorganic acid liquid and the absolute ethyl alcohol to form a stable dispersion phase; then regulating the pH value of the mixed component to 3.0 by using hydrochloric acid solution with the concentration of 0.4mol/L to obtain a mixed component; then placing the obtained mixed components in a microwave reactor, carrying out microwave heating for 15h at the temperature of 70 ℃, taking out the mixed components from the microwave reactor, and aging the mixed components in a constant-temperature drying oven for 4 h; filtering out the solid mixture in the mixed components after the aging is finished, and washing the solid mixture to be neutral by using distilled water; finally, placing the washed solid mixture in a muffle furnace for roasting, taking the solid mixture out of the muffle furnace after roasting is finished, and cooling the solid mixture to room temperature under natural conditions to obtain a finished catalyst;
secondly, filling a catalyst;
the method comprises the following steps of filling catalysts diluted by activated carbon particles into six sections from top to bottom in a fixed bed catalytic distillation tower, wherein the mass percentage of the catalysts filled in the sections from top to bottom is 13%, 3%, 18%, 38%, 58% and 80% in sequence;
thirdly, pretreating the catalyst;
introducing nitrogen from the bottom of the fixed bed catalytic distillation tower to replace air in the tower, continuously introducing the nitrogen for more than 3 hours, then switching the nitrogen into pure hydrogen, simultaneously heating the fixed bed catalytic distillation tower to make the temperatures of all sections from top to bottom be 195 ℃, 210 ℃, 255 ℃, 290 ℃, 205 ℃ and 315 ℃ in sequence, wherein the heating rates are all 4 ℃/min, and keeping the constant temperature for 4 hours at the temperature after the temperature is raised to the target temperature; after the catalyst is activated, the temperature of each section of the fixed bed catalytic distillation tower is reduced to 140 ℃, 185 ℃, 215 ℃, 260 ℃, 285 ℃ and 2340 ℃ from top to bottom in sequence, and each section of the fixed bed catalytic distillation tower is kept under the temperature condition;
catalyzing and removing tetrachlorobenzene;
extracting mother liquor generated in a spice extraction section by using chloroform as an extracting agent to recover residual maltol in the mother liquor, introducing the extracted mother liquor containing trace hexachlorobenzene into a reaction kettle containing absorption liquid, and continuously introducing nitrogen into the reaction kettle for 8 min; then closing the intake valve; then heating and stirring the materials, wherein the stirring speed is about 150 r/min; about 25min after the start of heating; the temperature of the material rises to the set value of 240 ℃; after 5h of reaction, the heating power supply is turned off; reducing the temperature of the reaction vessel to about 55 ℃; heating the residual liquid in the reaction kettle to 235 ℃, introducing gas from the bottom of the fixed bed catalytic distillation tower, introducing mixed gas of hydrogen chloride and hydrogen from each gas supplementing port, discharging dichlorobenzene serving as a reaction product from the second section of the fixed bed catalytic distillation tower, and discharging chlorobenzene from the first section; and the hydrogen chloride is discharged from the top of the tower and recycled, and finally the hexachlorobenzene is efficiently removed.
The mass ratio of the sodium phosphotungstate to the lanthanum nitrate to the nano metal nickel is 1.3:2.5: 9.5.
The pretreatment comprises the following specific operations: respectively ultrasonically cleaning sodium phosphotungstate, lanthanum nitrate and nano metal nickel for 25min at the frequency of 30kHz, then washing the sodium phosphotungstate, lanthanum nitrate and nano metal nickel for 2 times by using distilled water, and finally placing the sodium phosphotungstate, lanthanum nitrate and nano metal nickel in a constant-temperature drying box for drying.
The inorganic acid is sulfuric acid solution with the concentration of 0.4mol/L, and the mass ratio of the inorganic acid solution to the absolute ethyl alcohol in the mixed solution is 3.0: 1.0.
When the solid mixture is roasted, the roasting temperature of a muffle furnace is set to be 500 ℃, and the roasting time is 4 hours.
In the catalyst filling step, the second to fifth sections of the fixed bed catalytic distillation column are provided with air make-up ports.
The mixed gas consists of hydrogen and hydrogen chloride gas, and the volume concentration of the hydrogen is 30%.
The absorption liquid is formed by ultrasonically mixing aluminum oxide, iron powder, sodium carbonate and paraffin oil according to the mass ratio of 1.4:0.4:12: 90; and the alumina is gamma-type alumina.
Example 3:
a method for removing hexachlorobenzene generated in a perfume extraction process comprises the following steps:
firstly, preparing a catalyst;
accurately weighing a proper amount of sodium phosphotungstate, lanthanum nitrate and nano metal nickel, respectively pretreating the sodium phosphotungstate, lanthanum nitrate and nano metal nickel, soaking the pretreated sodium phosphotungstate, lanthanum nitrate and nano metal nickel in a mixed solution consisting of inorganic acid liquid and absolute ethyl alcohol, and uniformly mixing and stirring the inorganic acid liquid and the absolute ethyl alcohol to form a stable dispersion phase; then regulating the pH value of the mixed component to 3.5 by using hydrochloric acid solution with the concentration of 0.5mol/L to obtain a mixed component; then placing the obtained mixed components in a microwave reactor, carrying out microwave heating for 18h at the temperature of 80 ℃, taking out the mixed components from the microwave reactor, and aging the mixed components in a constant-temperature drying oven for 5 h; filtering out the solid mixture in the mixed components after the aging is finished, and washing the solid mixture to be neutral by using distilled water; finally, placing the washed solid mixture in a muffle furnace for roasting, taking the solid mixture out of the muffle furnace after roasting is finished, and cooling the solid mixture to room temperature under natural conditions to obtain a finished catalyst;
secondly, filling a catalyst;
the method comprises the following steps of filling catalysts diluted by activated carbon particles into six sections from top to bottom in a fixed bed catalytic distillation tower, wherein the mass percentage of the catalysts filled in each section from top to bottom is 15%, 5%, 20%, 40%, 60% and 81% in sequence;
thirdly, pretreating the catalyst;
introducing nitrogen from the bottom of the fixed bed catalytic distillation tower to replace air in the tower, continuously introducing the nitrogen for more than 3 hours, then switching the nitrogen into pure hydrogen, simultaneously heating the fixed bed catalytic distillation tower, so that the temperatures of the sections from top to bottom are 215 ℃, 225 ℃, 265 ℃, 295 ℃, 315 ℃ and 325 ℃, the heating rates are 5 ℃/min, and keeping the constant temperature for 5 hours at the temperature after the temperature is raised to the target temperature; after the catalyst activation is finished, sequentially reducing the temperature of each section of the fixed bed catalytic distillation tower from top to bottom to 148 ℃, 190 ℃, 220 ℃, 265 ℃, 290 ℃ and 245 ℃, and keeping each section of the fixed bed catalytic distillation tower under the temperature condition;
catalyzing and removing tetrachlorobenzene;
extracting mother liquor generated in a spice extraction section by using chloroform as an extracting agent to recover residual maltol in the mother liquor, then introducing the extracted mother liquor containing trace hexachlorobenzene into a reaction kettle containing absorption liquid, and continuously introducing nitrogen into the reaction kettle for 10 min; then closing the intake valve; then heating and stirring the materials, wherein the stirring speed is about 150 r/min; about 30min after the start of heating; the temperature of the material is raised to a set value of 250 ℃; after reacting for 6h, turning off the heating power supply; reducing the temperature of the reaction vessel to about 60 ℃; heating the residual liquid in the reaction kettle to 240 ℃, introducing the residual liquid from the bottom of the fixed bed catalytic distillation tower, introducing mixed gas of hydrogen chloride and hydrogen from each gas supplementing port, discharging dichlorobenzene serving as a reaction product from the second section of the fixed bed catalytic distillation tower, and discharging chlorobenzene from the first section; and the hydrogen chloride is discharged from the top of the tower and recycled, and finally the hexachlorobenzene is efficiently removed.
The mass ratio of the sodium phosphotungstate to the lanthanum nitrate to the nano metal nickel is 1.5:3.0: 10.0.
The pretreatment comprises the following specific operations: respectively ultrasonically cleaning sodium phosphotungstate, lanthanum nitrate and nano metal nickel for 30min at the frequency of 35kHz, then washing the sodium phosphotungstate, lanthanum nitrate and nano metal nickel for 3 times by using distilled water, and finally placing the sodium phosphotungstate, lanthanum nitrate and nano metal nickel in a constant-temperature drying box for drying.
The inorganic acid is sulfuric acid solution with the concentration of 0.5mol/L, and the mass ratio of the inorganic acid solution to the absolute ethyl alcohol in the mixed solution is 3.6: 1.0.
When the solid mixture is roasted, the roasting temperature of a muffle furnace is set to be 560 ℃, and the roasting time is 5 hours.
In the catalyst filling step, the second to fifth sections of the fixed bed catalytic distillation column are provided with air make-up ports.
The mixed gas consists of hydrogen and hydrogen chloride gas, and the volume concentration of the hydrogen is 35%.
The absorption liquid is formed by ultrasonically mixing aluminum oxide, iron powder, sodium carbonate and paraffin oil according to the mass ratio of 1.6:0.5:13: 100; and the alumina is gamma-type alumina.
And (3) experimental verification:
the fragrance liquor was subjected to the hexachlorobenzene removal test (noted as examples 1-3) by the method provided in examples 1-3 of the present invention, and the results are reported in the following table:
note: comparative example a dechlorination and removal experiment of hexachlorobenzene was carried out using photocatalytic oxidation on an amount of fragrance mother liquor equal to that used in examples 1-3.
The data in the above table show that the treatment of the fragrance liquor by the present invention results in a dechlorination efficiency of 95.6-97.8% for hexachlorobenzene and a removal rate of 99.2-99.7% for hexachlorobenzene. Moreover, the purity and the chroma of the spice mother liquor treated by the method are greatly improved. Compared with the traditional method (a photocatalytic oxidation method), the method provided by the invention has wider market prospect and is more suitable for popularization.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for removing hexachlorobenzene generated in a perfume extraction process is characterized by comprising the following steps:
firstly, preparing a catalyst;
accurately weighing a proper amount of sodium phosphotungstate, lanthanum nitrate and nano metal nickel, respectively pretreating the sodium phosphotungstate, lanthanum nitrate and nano metal nickel, soaking the pretreated sodium phosphotungstate, lanthanum nitrate and nano metal nickel in a mixed solution consisting of inorganic acid liquid and absolute ethyl alcohol, and uniformly mixing and stirring the inorganic acid liquid and the absolute ethyl alcohol to form a stable dispersion phase; then, regulating the pH value of the mixed component to 2.0-3.5 by using a hydrochloric acid solution with the concentration of 0.3-0.5 mol/L to obtain a mixed component; then placing the obtained mixed components in a microwave reactor, carrying out microwave heating for 10-18 h at the temperature of 60-80 ℃, taking out the mixed components from the microwave reactor, and aging the mixed components in a constant-temperature drying oven for 3-5 h; filtering out the solid mixture in the mixed components after the aging is finished, and washing the solid mixture to be neutral by using distilled water; finally, placing the washed solid mixture in a muffle furnace for roasting, taking the solid mixture out of the muffle furnace after roasting is finished, and cooling the solid mixture to room temperature under natural conditions to obtain a finished catalyst;
secondly, filling a catalyst;
the method comprises the following steps of filling catalysts diluted by activated carbon particles into a fixed bed catalytic distillation tower from top to bottom in six sections, wherein the mass percentage of the catalysts filled in each section from top to bottom is 10-15%, 2-5%, 16-20%, 35-40%, 55-60% and 75-81% in sequence;
thirdly, pretreating the catalyst;
introducing nitrogen from the bottom of the fixed bed catalytic distillation tower to replace air in the tower, continuously introducing the nitrogen for more than 3 hours, then switching the nitrogen into pure hydrogen, simultaneously heating the fixed bed catalytic distillation tower, so that the temperatures of the sections from top to bottom are 185-215 ℃, 195-225 ℃, 245-265 ℃, 280-295 ℃, 295-315 ℃ and 310-325 ℃, the heating rates are 3-5 ℃/min, and keeping the constant temperature at the temperature for 3-5 hours after the temperature is raised to the target temperature; after the catalyst is activated, sequentially reducing the temperature of each section of the fixed bed catalytic distillation tower from top to bottom to 135-148 ℃, 178-190 ℃, 210-220 ℃, 255-265 ℃, 280-290 ℃ and 230-245 ℃, and keeping each section of the fixed bed catalytic distillation tower under the temperature condition;
catalyzing and removing tetrachlorobenzene;
extracting mother liquor generated in a spice extraction section by using chloroform as an extracting agent to recover residual maltol in the mother liquor, introducing the extracted mother liquor containing trace hexachlorobenzene into a reaction kettle containing absorption liquid, and continuously introducing nitrogen into the reaction kettle for 5-10 min; then closing the intake valve; then heating and stirring the materials, wherein the stirring speed is about 120-150 r/min; about 20-30 min after heating; the temperature of the material is raised to a set value of 230-250 ℃; after reacting for 3-6 h, turning off a heating power supply; reducing the temperature of the reaction kettle to about 50-60 ℃; heating the temperature of residual liquid in the reaction kettle to 230-240 ℃, introducing the residual liquid from the bottom of the fixed bed catalytic distillation tower, introducing mixed gas of hydrogen chloride and hydrogen from each gas supplementing port, discharging dichlorobenzene serving as a reaction product from the second section of the fixed bed catalytic distillation tower, and discharging chlorobenzene from the first section; and the hydrogen chloride is discharged from the top of the tower and recycled, and finally the hexachlorobenzene is efficiently removed.
2. The method of claim 1, wherein the solvent is selected from the group consisting of: the mass ratio of the sodium phosphotungstate to the lanthanum nitrate to the nano metal nickel is 1.0-1.5: 2.0-3.0: 9.0-10.0.
3. The method for removing hexachlorobenzene generated in the perfume extraction process according to claim 1, wherein the pretreatment comprises the following specific operations: and (2) ultrasonically cleaning sodium phosphotungstate, lanthanum nitrate and nano metal nickel for 20-30 min at the frequency of 28-35 kHz respectively, then washing the sodium phosphotungstate, lanthanum nitrate and nano metal nickel for 2-3 times by using distilled water, and finally drying the sodium phosphotungstate, lanthanum nitrate and nano metal nickel in a constant-temperature drying box.
4. The method of claim 1, wherein the solvent is selected from the group consisting of: the inorganic acid is sulfuric acid solution with the concentration of 0.3-0.5 mol/L, and the mass ratio of the inorganic acid solution to the absolute ethyl alcohol in the mixed solution is 2.5-3.6: 1.0.
5. The method of claim 1, wherein the solvent is selected from the group consisting of: when the solid mixture is roasted, the roasting temperature of the muffle furnace is set to be 450-560 ℃, and the roasting time is 3-5 h.
6. The method of claim 1, wherein the solvent is selected from the group consisting of: in the catalyst filling step, the second to fifth sections of the fixed bed catalytic distillation column are provided with air make-up ports.
7. The method of claim 1, wherein the solvent is selected from the group consisting of: the mixed gas consists of hydrogen and hydrogen chloride gas, and the volume concentration of the hydrogen is 25-35%.
8. The method of claim 1, wherein the solvent is selected from the group consisting of: the absorption liquid is formed by ultrasonically mixing aluminum oxide, iron powder, sodium carbonate and paraffin oil according to the mass ratio of 1.0-1.6: 0.3-0.5: 10-13: 85-100; and the alumina is gamma-type alumina.
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