CN110981733A - Novel deacidification process for isooctyl nitrate crude product - Google Patents
Novel deacidification process for isooctyl nitrate crude product Download PDFInfo
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Abstract
The invention discloses a novel deacidification process for a isooctyl nitrate crude product, which comprises the following steps: (1) sequentially adding sodium pyrophosphate and methanol into the aqueous solution of polyacrylamide, stirring the solution for more than 5min, then heating to 50-60 ℃, and keeping the temperature for 60-80 min; (2) cooling to 45-48 ℃ and keeping the temperature constant, adding ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene into the solution in the process of keeping the temperature constant, stirring the solution for 30-40 min, and cooling to normal temperature in air; (3) filtering the mixture, washing a solid phase with acetone for 2-3 times, and drying to obtain a deacidification treatment agent; (4) mixing the isooctyl nitrate crude product with a deacidification treatment agent, controlling the temperature of the mixture below 20 ℃, preserving the temperature for more than 10 hours, filtering, standing and separating liquid of a liquid phase, and removing the water phase to obtain a deacidified isooctyl nitrate fine product. The method realizes the deacidification process of the isooctyl nitrate crude product prepared by the mixed acid method at the temperature of below 20 ℃, avoids the safety risk of high-temperature isooctyl nitrate purification, and has obvious deacidification effect.
Description
Technical Field
The invention belongs to the technical field of production of petrochemical nitrate, and particularly relates to a novel deacidification process for a crude isooctyl nitrate product.
Background
Isooctyl nitrate (EHN) is an important liquid energetic material, which is prepared by a nitration process and is an O-nitro compound. The substance is a common cetane number improver, can effectively improve the combustion performance of diesel oil and reduce ignition energy, and is widely applied in the petrochemical industry, while EHN is used as a liquid propellant assistant in the aerospace field and is widely applied in the rocket propulsion technology.
In the production of isooctyl nitrate, a mixed acid method is generally adopted, i.e. isooctyl alcohol is added into mixed acid of concentrated sulfuric acid and concentrated nitric acid to react at low temperature, liquid separation is carried out after the reaction is finished, an organic phase is washed by alkali, washed by water, dried and purified to obtain the isooctyl nitrate product. The acid value is an important index for measuring the quality of the isooctyl nitrate product. According to the existing production process of isooctyl nitrate, alkali washing is needed to remove free inorganic strong acid contained in the crude product of isooctyl nitrate, and the alkali used as a deacidification agent is sodium bicarbonate, sodium carbonate and ammonia water generally. The Chinese patent application No. 200610045162.2 discloses a method for neutralizing acid by ammonia water, which needs to be heated to 58-60 ℃, has high energy consumption, and has potential danger when heated to isooctyl nitrate. The acid value of sodium bicarbonate and sodium carbonate aqueous solution is difficult to reach below 3mg/KOH/100ml, and the acid value of the isooctyl nitrate product which is not preserved is easy to rebound.
Disclosure of Invention
The invention provides a novel deacidification process for a isooctyl nitrate crude product, which does not solve the defects in the prior art and comprises the following steps:
(1) preparing an aqueous solution of polyacrylamide, sequentially adding sodium pyrophosphate and methanol into the aqueous solution of polyacrylamide, stirring the solution for more than 5min, and then heating to 50-60 ℃ and keeping the temperature for 60-80 min;
(2) after the constant temperature is finished, cooling the solution in air to 45-48 ℃ and keeping the temperature constant, adding ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene into the solution again in the constant temperature process, stirring the solution for 30-40 min after the addition is finished, and cooling the mixture in air to the normal temperature;
(3) filtering the mixture, washing a solid phase with acetone for 2-3 times, and drying to obtain a deacidification treatment agent;
(4) mixing the isooctyl nitrate crude product mixed with acid and water with the deacidification treatment agent, controlling the temperature of the mixture below 20 ℃, preserving the temperature for more than 10 hours, stirring the mixture in the heat preservation process, filtering the mixture after the heat preservation is finished, standing and separating a liquid phase, and removing a water phase to obtain a deacidified isooctyl nitrate fine product.
Further, the preparation method of the ZnO powder comprises the following steps:
1) preparing an aqueous solution of zinc nitrate, adding polyethylene glycol 1000 into the aqueous solution of zinc nitrate, and stirring for more than 5min to obtain a mixed solution;
2) stirring the mixed solution, adding ammonia water into the mixed solution, then quickly pouring the mixed solution into a sealed container, sealing the container, heating to 180-190 ℃, preserving the temperature for more than 10 hours, and magnetically stirring the solution in the heat preservation process;
3) after stirring, cooling the sealed container in air to normal temperature, then taking out the mixed solution, filtering, washing the solid phase with deionized water, drying, calcining for 1-2 h at 400-450 ℃, and cooling in air to obtain a solid phase A;
4) preparing an oxalic acid solution, soaking the solid phase A in the oxalic acid solution for 1-2 min, then filtering, ultrasonically cleaning the solid phase A2-3 times by using deionized water, soaking the cleaned solid phase A in a sodium hydroxide aqueous solution again to obtain a mixture, placing the mixture in a sealed container, sealing the container, heating to 120-140 ℃, preserving heat for 1-2 h, cooling to normal temperature after heat preservation, taking out the mixture for solid-liquid separation, washing the solid phase with the deionized water for more than 3 times, and drying to obtain ZnO powder.
Further, the concentration of polyacrylamide in the polyacrylamide water solution is 30-38 g/500mL, and the balance is water; the mass ratio of the added sodium pyrophosphate to the polyacrylamide in the polyacrylamide aqueous solution is polyacrylamide: sodium pyrophosphate: methanol =10:1 to 3:0.3 to 0.9.
Further, in the step (2), the mass ratio of the added amounts of ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene to the mass of polyacrylamide in the solution is polyacrylamide to ZnO powder to sodium carbonate to dimethyl sulfoxide to hydrogen peroxide to methyl ketene =10: 18-25: 3-5: 0.2-0.5: 1-2: 0.1-0.3, and the hydrogen peroxide is an aqueous solution with the mass percentage of hydrogen peroxide of 20-30%.
Further, in the step (4), the mixing weight ratio of the isooctyl nitrate crude product to the deacidification treatment agent is 10-30 g of deacidification treatment agent/1 kg of isooctyl nitrate crude product.
Further, in the aqueous solution of zinc nitrate, the concentration of zinc nitrate is 0.8-1.2 g/100mL, and the balance is water; the ratio of the added mass of the polyethylene glycol 1000 to the mass of the zinc nitrate in the solution is zinc nitrate: polyethylene glycol 1000=1: 0.1-0.4.
Further, the mass percentage of the solute in the ammonia water is 20%, the adding weight of the ammonia water is 8-10 times of the weight of the zinc nitrate in the solution, the mass percentage of the solute in the oxalic acid solution is 3-5%, and the balance is water; the mass percentage of solute in the sodium hydroxide aqueous solution is 1% -5%, and the balance is water.
Therefore, the beneficial effects of the invention are as follows: the method realizes the deacidification process of the isooctyl nitrate crude product prepared by the mixed acid method at the temperature of below 20 ℃, avoids the safety risk of high-temperature isooctyl nitrate purification, has obvious deacidification effect and obviously reduces the acidity value of the isooctyl nitrate refined product.
Detailed Description
The following is a detailed description with reference to examples:
example 1
A novel deacidification process for a crude isooctyl nitrate product comprises the following steps:
(1) preparing a polyacrylamide aqueous solution with the polyacrylamide concentration of 30g/500mL, and sequentially adding sodium pyrophosphate and methanol into the polyacrylamide aqueous solution, wherein the mass ratio of the sodium pyrophosphate to the methanol to the polyacrylamide in the polyacrylamide aqueous solution is as follows: sodium pyrophosphate: stirring the solution for 5min with methanol =10:1:0.3, then heating to 50-60 ℃, and keeping the temperature for 60 min;
(2) after the constant temperature is finished, cooling the solution in air to 45-48 ℃ and keeping the temperature constant, adding ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene into the solution again in the constant temperature process, wherein the mass ratio of the added ZnO powder, the sodium carbonate, the dimethyl sulfoxide, the hydrogen peroxide to the polyacrylamide in the solution is that the ZnO powder, the sodium carbonate, the dimethyl sulfoxide and the hydrogen peroxide (20 mass percent of aqueous solution of hydrogen peroxide) and the methyl ketene =10:18:3:0.2:1: 0.1; stirring the solution for 30min after the addition is finished, and cooling the mixture to normal temperature in air;
(3) filtering the mixture, washing the solid phase with acetone for 3 times, and drying to obtain deacidification treatment agent;
(4) mixing the isooctyl nitrate crude product (acidity of 593mgKOH/g and water content of 4530ppm) mixed with acid and water and the deacidification treatment agent according to the weight ratio of 10g of deacidification treatment agent to 1kg of isooctyl nitrate crude product, controlling the temperature of the mixture below 20 ℃ and keeping the temperature for 10 hours, stirring the mixture in the heat preservation process, filtering the mixture after the heat preservation is finished, standing and separating a liquid phase, and removing a water phase to obtain a deacidified isooctyl nitrate fine product.
The preparation method of the ZnO powder described in this example is:
1) preparing a zinc nitrate aqueous solution with the concentration of 0.8g/100mL, adding polyethylene glycol 1000 into the zinc nitrate aqueous solution, wherein the ratio of the adding mass of the polyethylene glycol 1000 to the mass of the zinc nitrate in the solution is zinc nitrate: stirring polyethylene glycol 1000=1:0.1 for 5min to obtain a mixed solution;
2) stirring the mixed solution, adding ammonia water (the mass percentage of solute is 20%) into the mixed solution, wherein the adding weight of the ammonia water is 8 times of the weight of zinc nitrate in the solution, then quickly pouring the mixed solution into a sealed container, sealing the container, heating to 180-190 ℃, preserving heat for 10 hours, and magnetically stirring the solution in the heat preservation process;
3) after stirring, cooling the sealed container in air to normal temperature, then taking out the mixed solution, filtering, washing the solid phase with deionized water, drying, calcining for 2h at 400 ℃, and cooling in air to obtain a solid phase A;
4) preparing an oxalic acid aqueous solution with solute mass percentage of 3%, soaking the solid phase A in the oxalic acid aqueous solution for 1min, wherein the mass of the oxalic acid aqueous solution is 10 times of that of the solid phase A soaked in the oxalic acid aqueous solution, then filtering, ultrasonically cleaning the solid phase A3 times by using deionized water, soaking the cleaned solid phase A in a sodium hydroxide aqueous solution with solute mass percentage of 3% again to obtain a mixture, placing the mixture in a sealed container, sealing the container, heating to 120-140 ℃, preserving heat for 1h, cooling to normal temperature after heat preservation, taking out the mixture for solid-liquid separation, washing the solid phase by using the deionized water for 3 times, and drying to obtain ZnO powder.
Example 2
A novel deacidification process for a crude isooctyl nitrate product comprises the following steps:
(1) preparing a polyacrylamide aqueous solution with the polyacrylamide concentration of 33g/500mL, and sequentially adding sodium pyrophosphate and methanol into the polyacrylamide aqueous solution, wherein the mass ratio of the sodium pyrophosphate to the methanol to the polyacrylamide in the polyacrylamide aqueous solution is as follows: sodium pyrophosphate: stirring the solution for 5min with methanol =10:2:0.5, then heating to 50-60 ℃, and keeping the temperature for 60 min;
(2) after the constant temperature is finished, cooling the solution in air to 45-48 ℃ and keeping the temperature constant, adding ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene into the solution again in the constant temperature process, wherein the mass ratio of the added ZnO powder, the sodium carbonate, the dimethyl sulfoxide, the hydrogen peroxide to the polyacrylamide in the solution is that the ZnO powder, the sodium carbonate, the dimethyl sulfoxide and the hydrogen peroxide (20 mass percent of aqueous solution of hydrogen peroxide) and the methyl ketene =10:20:4:0.3:1.3: 0.2; stirring the solution for 30min after the addition is finished, and cooling the mixture to normal temperature in air;
(3) filtering the mixture, washing the solid phase with acetone for 3 times, and drying to obtain deacidification treatment agent;
(4) mixing the isooctyl nitrate crude product (acidity of 593mgKOH/g and water content of 4530ppm) mixed with acid and water and the deacidification treatment agent according to the weight ratio of 20g of deacidification treatment agent to 1kg of isooctyl nitrate crude product, controlling the temperature of the mixture below 20 ℃, preserving the temperature for 10 hours, stirring the mixture in the heat preservation process, filtering the mixture after the heat preservation is finished, standing and separating a liquid phase, and removing a water phase to obtain a deacidified isooctyl nitrate fine product.
The preparation method of the ZnO powder described in this example is:
1) preparing a zinc nitrate aqueous solution with the concentration of 1.0g/100mL, adding polyethylene glycol 1000 into the zinc nitrate aqueous solution, wherein the ratio of the adding mass of the polyethylene glycol 1000 to the mass of the zinc nitrate in the solution is zinc nitrate: stirring polyethylene glycol 1000=1:0.2 for 5min to obtain a mixed solution;
2) stirring the mixed solution, adding ammonia water (the mass percentage of solute is 20%) into the mixed solution, wherein the adding weight of the ammonia water is 8 times of the weight of zinc nitrate in the solution, then quickly pouring the mixed solution into a sealed container, sealing the container, heating to 180-190 ℃, preserving heat for 10 hours, and magnetically stirring the solution in the heat preservation process;
3) after stirring, cooling the sealed container in air to normal temperature, then taking out the mixed solution, filtering, washing the solid phase with deionized water, drying, calcining for 2h at the temperature of 420 ℃, and cooling in air to obtain a solid phase A;
4) preparing an oxalic acid aqueous solution with solute mass percentage of 3%, soaking the solid phase A in the oxalic acid aqueous solution for 1min, wherein the mass of the oxalic acid aqueous solution is 10 times of that of the solid phase A soaked in the oxalic acid aqueous solution, then filtering, ultrasonically cleaning the solid phase A3 times by using deionized water, soaking the cleaned solid phase A in a sodium hydroxide aqueous solution with solute mass percentage of 3% again to obtain a mixture, placing the mixture in a sealed container, sealing the container, heating to 120-140 ℃, preserving heat for 1h, cooling to normal temperature after heat preservation, taking out the mixture for solid-liquid separation, washing the solid phase by using the deionized water for 3 times, and drying to obtain ZnO powder.
Example 3
A novel deacidification process for a crude isooctyl nitrate product comprises the following steps:
(1) preparing a polyacrylamide aqueous solution with the polyacrylamide concentration of 36g/500mL, and sequentially adding sodium pyrophosphate and methanol into the polyacrylamide aqueous solution, wherein the mass ratio of the sodium pyrophosphate to the methanol to the polyacrylamide in the polyacrylamide aqueous solution is as follows: sodium pyrophosphate: stirring the solution for 5min with methanol =10:2:0.7, then heating to 50-60 ℃, and keeping the temperature for 60 min;
(2) after the constant temperature is finished, cooling the solution in air to 45-48 ℃ and keeping the temperature constant, adding ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene into the solution again in the constant temperature process, wherein the mass ratio of the added ZnO powder, the sodium carbonate, the dimethyl sulfoxide, the hydrogen peroxide to the polyacrylamide in the solution is that the ZnO powder, the sodium carbonate, the dimethyl sulfoxide and the hydrogen peroxide (20 mass percent of aqueous solution of hydrogen peroxide) and the methyl ketene =10:22:4:0.4:1.8: 0.2; stirring the solution for 30min after the addition is finished, and cooling the mixture to normal temperature in air;
(3) filtering the mixture, washing the solid phase with acetone for 3 times, and drying to obtain deacidification treatment agent;
(4) mixing the isooctyl nitrate crude product (acidity of 593mgKOH/g and water content of 4530ppm) mixed with acid and water and the deacidification treatment agent according to the weight ratio of 20g of deacidification treatment agent to 1kg of isooctyl nitrate crude product, controlling the temperature of the mixture below 20 ℃, preserving the temperature for 10 hours, stirring the mixture in the heat preservation process, filtering the mixture after the heat preservation is finished, standing and separating a liquid phase, and removing a water phase to obtain a deacidified isooctyl nitrate fine product.
The preparation method of the ZnO powder described in this example is:
1) preparing a zinc nitrate aqueous solution with the concentration of 1.1g/100mL, adding polyethylene glycol 1000 into the zinc nitrate aqueous solution, wherein the ratio of the adding mass of the polyethylene glycol 1000 to the mass of the zinc nitrate in the solution is zinc nitrate: stirring polyethylene glycol 1000=1:0.3 for 5min to obtain a mixed solution;
2) stirring the mixed solution, adding ammonia water (the mass percentage of solute is 20%) into the mixed solution, wherein the adding weight of the ammonia water is 8 times of the weight of zinc nitrate in the solution, then quickly pouring the mixed solution into a sealed container, sealing the container, heating to 180-190 ℃, preserving heat for 10 hours, and magnetically stirring the solution in the heat preservation process;
3) after stirring, cooling the sealed container in air to normal temperature, then taking out the mixed solution, filtering, washing the solid phase with deionized water, drying, calcining for 1h at the temperature of 440 ℃, and cooling in air to obtain a solid phase A;
4) preparing an oxalic acid aqueous solution with solute mass percentage of 3%, soaking the solid phase A in the oxalic acid aqueous solution for 1min, wherein the mass of the oxalic acid aqueous solution is 10 times of that of the solid phase A soaked in the oxalic acid aqueous solution, then filtering, ultrasonically cleaning the solid phase A3 times by using deionized water, soaking the cleaned solid phase A in a sodium hydroxide aqueous solution with solute mass percentage of 3% again to obtain a mixture, placing the mixture in a sealed container, sealing the container, heating to 120-140 ℃, preserving heat for 1h, cooling to normal temperature after heat preservation, taking out the mixture for solid-liquid separation, washing the solid phase by using the deionized water for 3 times, and drying to obtain ZnO powder.
Example 4
A novel deacidification process for a crude isooctyl nitrate product comprises the following steps:
(1) preparing a polyacrylamide aqueous solution with a polyacrylamide concentration of 38g/500mL, and sequentially adding sodium pyrophosphate and methanol into the polyacrylamide aqueous solution, wherein the mass ratio of the sodium pyrophosphate to the methanol to the polyacrylamide in the polyacrylamide aqueous solution is as follows: sodium pyrophosphate: stirring the solution for 5min with methanol =10:3:0.9, then heating to 50-60 ℃, and keeping the temperature for 60 min;
(2) after the constant temperature is finished, cooling the solution in air to 45-48 ℃ and keeping the temperature constant, adding ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene into the solution again in the constant temperature process, wherein the mass ratio of the added ZnO powder, the sodium carbonate, the dimethyl sulfoxide, the hydrogen peroxide to the polyacrylamide in the solution is that the ZnO powder, the sodium carbonate, the dimethyl sulfoxide and the hydrogen peroxide (20 mass percent of aqueous solution of hydrogen peroxide) and the methyl ketene =10:25:5:0.5:2: 0.3; stirring the solution for 30min after the addition is finished, and cooling the mixture to normal temperature in air;
(3) filtering the mixture, washing the solid phase with acetone for 3 times, and drying to obtain deacidification treatment agent;
(4) mixing the isooctyl nitrate crude product (acidity of 593mgKOH/g and water content of 4530ppm) mixed with acid and water and the deacidification treatment agent according to the weight ratio of 30g of deacidification treatment agent to 1kg of isooctyl nitrate crude product, controlling the temperature of the mixture below 20 ℃ and keeping the temperature for 10 hours, stirring the mixture in the heat preservation process, filtering the mixture after the heat preservation is finished, standing and separating a liquid phase, and removing a water phase to obtain a deacidified isooctyl nitrate fine product.
The preparation method of the ZnO powder described in this example is:
1) preparing a zinc nitrate aqueous solution with the concentration of 1.2g/100mL, adding polyethylene glycol 1000 into the zinc nitrate aqueous solution, wherein the ratio of the adding mass of the polyethylene glycol 1000 to the mass of the zinc nitrate in the solution is zinc nitrate: stirring polyethylene glycol 1000=1:0.4 for 5min to obtain a mixed solution;
2) stirring the mixed solution, adding ammonia water (the mass percentage of solute is 20%) into the mixed solution, wherein the adding weight of the ammonia water is 8 times of the weight of zinc nitrate in the solution, then quickly pouring the mixed solution into a sealed container, sealing the container, heating to 180-190 ℃, preserving heat for 10 hours, and magnetically stirring the solution in the heat preservation process;
3) after stirring, cooling the sealed container in air to normal temperature, then taking out the mixed solution, filtering, washing the solid phase with deionized water, drying, calcining for 1h at the temperature of 450 ℃, and cooling in air to obtain a solid phase A;
4) preparing an oxalic acid aqueous solution with solute mass percentage of 3%, soaking the solid phase A in the oxalic acid aqueous solution for 1min, wherein the mass of the oxalic acid aqueous solution is 10 times of that of the solid phase A soaked in the oxalic acid aqueous solution, then filtering, ultrasonically cleaning the solid phase A3 times by using deionized water, soaking the cleaned solid phase A in a sodium hydroxide aqueous solution with solute mass percentage of 3% again to obtain a mixture, placing the mixture in a sealed container, sealing the container, heating to 120-140 ℃, preserving heat for 1h, cooling to normal temperature after heat preservation, taking out the mixture for solid-liquid separation, washing the solid phase by using the deionized water for 3 times, and drying to obtain ZnO powder.
Comparative example 1
A novel deacidification process for a crude isooctyl nitrate product comprises the following steps:
(1) preparing a polyacrylamide aqueous solution with the polyacrylamide concentration of 36g/500mL, and sequentially adding sodium pyrophosphate and methanol into the polyacrylamide aqueous solution, wherein the mass ratio of the sodium pyrophosphate to the methanol to the polyacrylamide in the polyacrylamide aqueous solution is as follows: sodium pyrophosphate: stirring the solution for 5min with methanol =10:2:0.7, then heating to 50-60 ℃, and keeping the temperature for 60 min;
(2) after the constant temperature is finished, cooling the solution in air to 45-48 ℃ and keeping the temperature constant, adding ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene into the solution again in the constant temperature process, wherein the mass ratio of the added ZnO powder, the sodium carbonate, the dimethyl sulfoxide, the hydrogen peroxide to the polyacrylamide in the solution is that the ZnO powder, the sodium carbonate, the dimethyl sulfoxide and the hydrogen peroxide (20 mass percent of aqueous solution of hydrogen peroxide) and the methyl ketene =10:22:4:0.4:1.8: 0.2; stirring the solution for 30min after the addition is finished, and cooling the mixture to normal temperature in air;
(3) filtering the mixture, washing the solid phase with acetone for 3 times, and drying to obtain deacidification treatment agent;
(4) mixing the isooctyl nitrate crude product (acidity of 593mgKOH/g and water content of 4530ppm) mixed with acid and water and the deacidification treatment agent according to the weight ratio of 20g of deacidification treatment agent to 1kg of isooctyl nitrate crude product, controlling the temperature of the mixture below 20 ℃, preserving the temperature for 10 hours, stirring the mixture in the heat preservation process, filtering the mixture after the heat preservation is finished, standing and separating a liquid phase, and removing a water phase to obtain a deacidified isooctyl nitrate fine product.
The preparation method of the ZnO powder described in this comparative example was:
1) preparing a zinc nitrate aqueous solution with the concentration of 1.1g/100mL, adding polyethylene glycol 1000 into the zinc nitrate aqueous solution, wherein the ratio of the adding mass of the polyethylene glycol 1000 to the mass of the zinc nitrate in the solution is zinc nitrate: stirring polyethylene glycol 1000=1:0.3 for 5min to obtain a mixed solution;
2) stirring the mixed solution, adding ammonia water (the mass percentage of solute is 20%) into the mixed solution, wherein the adding weight of the ammonia water is 8 times of the weight of zinc nitrate in the solution, then quickly pouring the mixed solution into a sealed container, sealing the container, heating to 180-190 ℃, preserving heat for 10 hours, and magnetically stirring the solution in the heat preservation process;
3) and after stirring, cooling the sealed container in air to normal temperature, taking out the mixed solution, filtering, washing the solid phase with deionized water, drying, calcining for 1h at the temperature of 440 ℃, and cooling in air to obtain the ZnO powder of the comparative example.
Comparative example 2
A novel deacidification process for a crude isooctyl nitrate product comprises the following steps:
(1) preparing a polyacrylamide aqueous solution with the polyacrylamide concentration of 36g/500mL, and sequentially adding sodium pyrophosphate and methanol into the polyacrylamide aqueous solution, wherein the mass ratio of the sodium pyrophosphate to the methanol to the polyacrylamide in the polyacrylamide aqueous solution is as follows: sodium pyrophosphate: stirring the solution for 5min with methanol =10:2:0.7, then heating to 50-60 ℃, and keeping the temperature for 60 min;
(2) after the constant temperature is finished, cooling the solution in air to 45-48 ℃ and keeping the temperature constant, adding ZnO powder, sodium carbonate and dimethyl sulfoxide into the solution again in the constant temperature process, wherein the mass ratio of the added ZnO powder, sodium carbonate and dimethyl sulfoxide to the mass ratio of polyacrylamide in the solution is that the ratio of ZnO powder to sodium carbonate to dimethyl sulfoxide is =10:22:4: 0.4; stirring the solution for 30min after the addition is finished, and cooling the mixture to normal temperature in air;
(3) filtering the mixture, washing the solid phase with acetone for 3 times, and drying to obtain deacidification treatment agent;
(4) mixing the isooctyl nitrate crude product (acidity of 593mgKOH/g and water content of 4530ppm) mixed with acid and water and the deacidification treatment agent according to the weight ratio of 20g of deacidification treatment agent to 1kg of isooctyl nitrate crude product, controlling the temperature of the mixture below 20 ℃, preserving the temperature for 10 hours, stirring the mixture in the heat preservation process, filtering the mixture after the heat preservation is finished, standing and separating a liquid phase, and removing a water phase to obtain a deacidified isooctyl nitrate fine product.
The preparation method of the ZnO powder described in this example is:
1) preparing a zinc nitrate aqueous solution with the concentration of 1.1g/100mL, adding polyethylene glycol 1000 into the zinc nitrate aqueous solution, wherein the ratio of the adding mass of the polyethylene glycol 1000 to the mass of the zinc nitrate in the solution is zinc nitrate: stirring polyethylene glycol 1000=1:0.3 for 5min to obtain a mixed solution;
2) stirring the mixed solution, adding ammonia water (the mass percentage of solute is 20%) into the mixed solution, wherein the adding weight of the ammonia water is 8 times of the weight of zinc nitrate in the solution, then quickly pouring the mixed solution into a sealed container, sealing the container, heating to 180-190 ℃, preserving heat for 10 hours, and magnetically stirring the solution in the heat preservation process;
3) after stirring, cooling the sealed container in air to normal temperature, then taking out the mixed solution, filtering, washing the solid phase with deionized water, drying, calcining for 1h at the temperature of 440 ℃, and cooling in air to obtain a solid phase A;
4) preparing an oxalic acid aqueous solution with solute mass percentage of 3%, soaking the solid phase A in the oxalic acid aqueous solution for 1min, wherein the mass of the oxalic acid aqueous solution is 10 times of that of the solid phase A soaked in the oxalic acid aqueous solution, then filtering, ultrasonically cleaning the solid phase A3 times by using deionized water, soaking the cleaned solid phase A in a sodium hydroxide aqueous solution with solute mass percentage of 3% again to obtain a mixture, placing the mixture in a sealed container, sealing the container, heating to 120-140 ℃, preserving heat for 1h, cooling to normal temperature after heat preservation, taking out the mixture for solid-liquid separation, washing the solid phase by using the deionized water for 3 times, and drying to obtain ZnO powder.
Example 5
The acidity values of the isooctyl nitrate fine products obtained in examples 1 to 4 and comparative examples 1 to 2 were measured by a standard KOH/alcohol solution titration method, and the results are shown in Table 1. As shown in Table 1, the method of the invention can obviously remove the acid content in the isooctyl nitrate crude product, which shows that the acidity of the isooctyl nitrate refined product obtained after treatment is obviously reduced. Comparing example 3 with comparative example 1, it can be seen that the treatment method for ZnO can affect the performance of the deacidification treatment agent.
TABLE 1
| Experimental group | Acidity (mgKOH/g) |
| Crude product | 598 |
| Example 1 | 2.8 |
| Example 2 | 2.6 |
| Example 3 | 2.5 |
| Example 4 | 2.6 |
| Comparative example 1 | 231 |
| Comparative example 2 | 60.8 |
The technical solutions provided by the present invention are described in detail above, and for those skilled in the art, the ideas according to the embodiments of the present invention may be changed in the specific implementation manners and the application ranges, and in summary, the content of the present description should not be construed as limiting the present invention.
Claims (7)
1. A novel deacidification process for a crude isooctyl nitrate product is characterized by comprising the following steps:
(1) preparing an aqueous solution of polyacrylamide, sequentially adding sodium pyrophosphate and methanol into the aqueous solution of polyacrylamide, stirring the solution for more than 5min, and then heating to 50-60 ℃ and keeping the temperature for 60-80 min;
(2) after the constant temperature is finished, cooling the solution in air to 45-48 ℃ and keeping the temperature constant, adding ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene into the solution again in the constant temperature process, stirring the solution for 30-40 min after the addition is finished, and cooling the mixture in air to the normal temperature;
(3) filtering the mixture, washing a solid phase with acetone for 2-3 times, and drying to obtain a deacidification treatment agent;
(4) mixing the isooctyl nitrate crude product mixed with acid and water with the deacidification treatment agent, controlling the temperature of the mixture below 20 ℃, preserving the temperature for more than 10 hours, stirring the mixture in the heat preservation process, filtering the mixture after the heat preservation is finished, standing and separating a liquid phase, and removing a water phase to obtain a deacidified isooctyl nitrate fine product.
2. The novel deacidification process for the isooctyl nitrate crude product as claimed in claim 1, wherein the preparation method of the ZnO powder comprises the following steps:
1) preparing an aqueous solution of zinc nitrate, adding polyethylene glycol 1000 into the aqueous solution of zinc nitrate, and stirring for more than 5min to obtain a mixed solution;
2) stirring the mixed solution, adding ammonia water into the mixed solution, then quickly pouring the mixed solution into a sealed container, sealing the container, heating to 180-190 ℃, preserving the temperature for more than 10 hours, and magnetically stirring the solution in the heat preservation process;
3) after stirring, cooling the sealed container in air to normal temperature, then taking out the mixed solution, filtering, washing the solid phase with deionized water, drying, calcining for 1-2 h at 400-450 ℃, and cooling in air to obtain a solid phase A;
4) preparing an oxalic acid solution, soaking the solid phase A in the oxalic acid solution for 1-2 min, then filtering, ultrasonically cleaning the solid phase A2-3 times by using deionized water, soaking the cleaned solid phase A in a sodium hydroxide aqueous solution again to obtain a mixture, placing the mixture in a sealed container, sealing the container, heating to 120-140 ℃, preserving heat for 1-2 h, cooling to normal temperature after heat preservation, taking out the mixture for solid-liquid separation, washing the solid phase with the deionized water for more than 3 times, and drying to obtain ZnO powder.
3. The novel deacidification process for the isooctyl nitrate crude product according to claim 2, wherein the concentration of polyacrylamide in the aqueous solution of polyacrylamide is 30-38 g/500mL, and the balance is water; the mass ratio of the added sodium pyrophosphate to the polyacrylamide in the polyacrylamide aqueous solution is polyacrylamide: sodium pyrophosphate: methanol =10:1 to 3:0.3 to 0.9.
4. The novel deacidification process for the isooctyl nitrate crude product as claimed in claim 2, wherein in the step (2), the mass ratio of the added amount of ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene to the mass ratio of polyacrylamide in the solution is polyacrylamide, ZnO powder, sodium carbonate, dimethyl sulfoxide, hydrogen peroxide and methyl ketene =10: 18-25: 3-5: 0.2-0.5: 1-2: 0.1-0.3, and the hydrogen peroxide is an aqueous solution with the hydrogen peroxide content of 20-30%.
5. The novel deacidification process for the isooctyl nitrate crude product according to claim 2, wherein in the step (4), the mixing weight ratio of the isooctyl nitrate crude product and the deacidification treatment agent is 10-30 g of deacidification treatment agent/1 kg of isooctyl nitrate crude product.
6. The novel deacidification process for the isooctyl nitrate crude product according to claim 2, wherein in the aqueous solution of zinc nitrate, the concentration of zinc nitrate is 0.8-1.2 g/100mL, and the balance is water; the ratio of the added mass of the polyethylene glycol 1000 to the mass of the zinc nitrate in the solution is zinc nitrate: polyethylene glycol 1000=1: 0.1-0.4.
7. The novel deacidification process for the isooctyl nitrate crude product as claimed in claim 2, wherein the solute content in the ammonia water is 20% by mass, the adding weight of the ammonia water is 8-10 times of the weight of the zinc nitrate in the solution, the solute content in the oxalic acid solution is 3-5% by mass, and the balance is water; the mass percentage of solute in the sodium hydroxide aqueous solution is 1% -5%, and the balance is water.
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