Method for recycling electronic-grade and industrial-grade sulfuric acid

A method for recycling electronic-grade and industrial-grade sulfuric acid, comprising:

• constructing a H202 removing and energy-saving spent acid recovery system, which has a first mixing tank connected to a second mixing tank through a filter and then connected to a third mixing tank to produce concentrated clean spent acid, followed by a decomposition furnace to thermally decompose spent acid, and then connected to a first heat exchanger followed by a waste heat boiler and a turbine generator and an organic Rankine cycle generator for heat recovery and electrical energy generation, and then connected to a gas cooling tower and a gas cleaning tower to produce clean process gas containing SO2, and then connected to a converter containing successive converter passes, containing catalyst V205, which linked with a second heat exchanger, a third heat exchanger, and a fourth heat exchanger to convert SO2 to SO3 to reaction temperatures from 380° C. to 460° C. to improve the conversion and heat recovery, then connected to a first absorption tower, and then connected to a first product tower to convert the pure S03 to industrial-grade sulfuric acid, a 3-way valve is connected to a demister containing a PFA filter, to produce high-purity SO3 without any liquid fractions and impurities, and then connected with a second absorption tower and a second product tower to convert the high-purity SO3 to electronic-grade sulfuric acid;
• wherein the fourth heat exchanger is arranged between the second heat exchanger, the third heat exchanger, and the gas cooling tower, absorption towers, and product towers, which is an absorption chiller with a shell-and-tube heat exchanger;
• an ultraviolet radiator is arranged above the second mixing tank, a spent acid inlet is arranged at the high position of the second mixing tank, a spent acid outlet is arranged at the lower position of the second mixing tank, a mixer is arranged in the center of the second mixing tank, a gold/silver bimetallic nanoparticle catalyst is arranged in the second mixing tank, a catalyst collection container is arranged at the bottom of the second mixing tank, and perform the following processing steps:
• step S110, industrial-grade spent acid and electronic-grade spent acid to from various industries are introduced into the first mixing tank to obtain spent acid;
• step S120, then the spent acid passes through the filter and the residual solid impurities and particulate matters are removed, and the spent acid without solid impurities and particulate matters is transferred to the second mixing tank;
• step S130, mixing the gold/silver bimetallic nanoparticle catalyst with the spent acid in the second mixing tank at 60° C. to 120° C., in the presence of UV light by the ultraviolet radiator for 6 to 12 hours, until the residual H202 in the spent acid is less than 2 ppm;
• step S140, transferring the spent acid into the third mixing tank, carrying out distillation to remove the water content from spent acid (0.1 to 1 atm, 60° C. to 100° C.), to obtain a concentrated spent acid (75 wt % to 80 wt %);
• step S150, the spent acid and sulfur, hot combustion air and fuel are fed into the decomposition furnace;
• then the spent acid and sulfur are thermally converted to S03 and H20 at 1000° C. to 1100° C., wherein S03 is further decomposed into SO2 to obtain a processed gas containing SO2;
• step S151, the process gas containing SO2 leaves the decomposition furnace at 900° C. to 1100° C., flows into the first heat exchanger to exchange heat with the combustion air that will enter the decomposition furnace to obtain a hot combustion air and the process gas containing SO2 cooled down at 500° C. to 650° C., and then the process gas containing SO2 leaves the first heat exchanger, then passes through the waste heat boiler to generate a high-pressure steam (40 barg and 450° C.), the high-pressure steam passes through the turbine generator to generate electrical energy;
• and the resulting cooled low-pressure steam (6 barg and 150° C.) passes through the organic Rankine cycle generator to generate electrical energy;
• step S152, the electrical energy generated by pressure steam passing the turbine generator and the organic Rankine cycle generator is used in step S130, heating the second mixing tank and the ultraviolet radiator and step S140, increasing the spent acid concentration in the third mixing tank;
• step S160, the process gas containing SO2 after being cooled to 250° C. to 350° C. flows into the gas cooling tower and the gas cleaning tower, to further cool down, and remove ash particles, S03, acid mist and water, to produce drying process gas containing pure SO2 at 100° C. to 150° C.;
• step S170, under the catalysis of V205, the gas containing SO2 reacts with oxygen to form SO3 and becomes process gas containing SO2 and SO3 in the converter, to maximize the SO2/SO3 conversion efficiency, the converter has successive converter passes and is connected with multiple heat changers, the heat exchangers are used for maintaining conversion temperature (from 380° C. to 460° C.) and improve the heat recovery in this spent acid recovery;
• the dry gas containing pure SO2 flows through the second heat exchange to bring it to the catalyst operating temperature (380° C. to 420° C.) before it contacts V205 in a first converter pass, the gas containing pure SO2 is partially converted to the gas containing SO2 and SO3 in the first converter, the conversion of SO2 to SO3 is highly exothermic and increases the gas temperature to 500° C. to 650° C.;
• the second heat exchanger cools the partially converted gas leaving the first converter pass to 420° C. to 460° C., heat generated by the conversion is recovered and used in the second heat exchanger to bring the gas from the gas cleaning tower to the first converter pass to its optimal operating temperature (380° C. to 420° C.), the cooled gas containing SO2 and S03 (420° C. to 460° C.) flows to a second converter pass where further conversion of SO2 to S03 occurs, generating additional heat, the process gas temperature is raised to 500° C. to 650° C. when leaving the second converter pass and flows to the third heat exchange to cool to desired operating temperature (420° C. to 460° C.) and optimizes heat recovery, the process gas then flows into a third converter pass to convert the remaining SO2 to SO3, the process gas leaving the third converter pass flows through the third heat exchanger to be cooled to 100° C. to 120° C.;
• in step S180, the process gas containing pure S03 passes into the first absorption tower, where SO3 is absorbed by the existing sulfuric acid in the first absorption tower at 80° C. to 100° C., to obtain 35% oleum (108% strength sulfuric acid), the temperature of the sulfuric acid in the first absorption towers increases due to heat transfer from the process gas and absorption of S03, the absorption heat is removed by cooling water produced by the fourth heat exchanger to maintain optimum acid temperatures and energy recovery;
• and
• in step S181, the 35% oleum is introduced into the first product tower and is mixed with pure water (1 wt % to 10 wt %) to obtain industrial-grade sulfuric acid (93 wt % to 98 wt %), the heat of mixing and dilution is also recovered by the fourth heat exchanger.