Method for low-temperature catalytic cracking of organic waste sulfuric acid

Abstract

The invention discloses a method for low-temperature catalytic cracking of organic waste sulfuric acid. The method comprises the following steps: S1, slowly adding sodium percarbonate into a reactor filled with the organic waste sulfuric acid and excessive activated carbon in batches; s2, heating the reactor through a water bath, and reacting until no bubble is generated; and S3, after the reaction is finished, filtering the reaction liquid to obtain the high-purity concentrated sulfuric acid. The organic waste sulfuric acid is subjected to harmless and resourceful treatment by utilizing the adsorption capacity and catalytic capacity of the activated carbon and the strong oxidizing property and environmental friendliness of the sodium percarbonate. Specifically, activated carbon is used as a catalyst, sodium percarbonate is used as an oxidizing agent, and the sodium percarbonate is used for oxidizing organic matters in organic waste sulfuric acid to recover high-purity concentrated sulfuric acid. The method is simple in process, can be carried out at low temperature, is low in energy consumption and high in removal rate, and has a relatively strong industrial prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical engineering, and particularly relates to a method for catalytically cracking organic waste sulfuric acid at low temperature. Background Art

[0002] Organic waste sulfuric acid is a viscous colloidal liquid with a dark red color. It has unstable properties, emits a special odor, and is difficult to treat. The sulfuric acid concentration in waste sulfuric acid is generally relatively low, while the content of organic impurities is relatively high. The organic substances mainly include high-molecular olefins, dienes, quinone organic substances, polycyclic aromatic organic substances, alkyl sulfonic acids, sulfuric acid esters, and sulfides (hydrogen sulfide, mercaptans, etc.) dissolved therein, with more than 300 monomer types. Organic waste sulfuric acid has a wide range of sources. For example, in nitrification, sulfonation, and alkylation chemical fiber enterprises, more or less a certain amount of waste sulfuric acid will be generated in industries that use sulfuric acid in industry.

[0003] Traditional methods for treating organic waste sulfuric acid generally use pyrolysis. That is, the waste sulfuric acid is introduced into a cracking furnace and heated at a high temperature. It is cracked into SO2 at 1000 - 1100 °C, oxidized to SO3, and then sulfuric acid is obtained after absorption. The disadvantages of this method are: (a) In a high-temperature, strong acid and strong oxidizing environment, the equipment is easily corroded; (b) High-temperature reaction is required, with high energy consumption and high operating costs; (c) It requires a large floor area, has a complex process, a huge one-time investment, strong corrosivity of waste sulfuric acid, and high transportation risks, and is not suitable for the treatment of organic waste sulfuric acid by small and medium-sized enterprises.

[0004] Sodium percarbonate, with the chemical formula 2Na2CO3·3H2O2, is an addition compound of hydrogen peroxide and sodium carbonate, commonly known as solid hydrogen peroxide, also known as explosion salt. Sodium percarbonate is a white crystalline granule with a boiling point of 333.6 °C and has strong oxidizing properties. It is easily decomposed into oxygen when exposed to moisture. Therefore, attention should be paid to moisture-proof during its storage, and it should be stored separately from strong reducing agents, etc. Sodium percarbonate has the advantages of being non-toxic, odorless, and pollution-free, and has characteristics such as bleaching, sterilization, washing, and good water solubility.

[0005] Since sodium percarbonate decomposes in water to produce oxygen, it can be used for oxygenation in aquaculture. When placed in a fishpond, it can provide oxygen for aquatic organisms. Additionally, when sodium percarbonate is mixed with a solid containing polyvinyl alcohol and a catalyst such as any compound of Cu, Fe, Co, Mn, etc., it can be used for emergency oxygen supply. Utilizing the strong oxidizing property of sodium percarbonate, it can be used for the removal of pollutants in water bodies. CN2015100580073 reported adding solid sodium percarbonate powder to a contaminated groundwater solution containing benzene derivatives (BTEX), then adding ferrous sulfate to activate the oxidant, and simultaneously adding a chelating agent to enhance the activation effect; achieving the oxidative removal of BTEX in contaminated groundwater. CN2023107757863 reported mixing MnO2@Fe nanozyme and sodium percarbonate powder for the rapid removal of organic pollutants in water bodies. CN2023113487467 reported adding appropriate amounts of sodium percarbonate and formic acid to wastewater containing Cr(III)-EDTA, stirring and dissolving, and then introducing ozone. Through the advanced oxidation-reduction method of ozone / sodium percarbonate / formic acid, the rapid breaking of the chromium complex and the reduction of hexavalent chromium in the wastewater were achieved. CN2022102416302 reported a denture cleaning tablet that uses sodium percarbonate as an oxidation and sterilization component. When it encounters water, it releases a large amount of active oxygen and has excellent deodorizing effects.

[0006] Activated carbon is a porous carbon material obtained through high-temperature carbonization and activation processes. It has a highly developed pore structure and a large specific surface area, thus possessing excellent adsorption performance and certain catalytic properties. Activated carbon is usually prepared from raw materials such as wood, coal, and fruit shells. It appears as black granular or powdered, non-toxic, odorless, and has good chemical stability. Summary of the Invention

[0007] Technical problems to be solved: In view of the above technical problems, the present invention provides a method for catalytic cracking of organic waste sulfuric acid at low temperature, which can effectively solve the deficiencies such as high energy consumption, complexity, and environmental pollution in the above organic waste sulfuric acid process technology.

[0008] Technical solution: A method for catalytic cracking of organic waste sulfuric acid at low temperature includes the following steps:

[0009] S1. Slowly add sodium percarbonate in batches to a reactor filled with organic waste sulfuric acid and activated carbon;

[0010] S2. Heat the reactor through a water bath until no bubbles are generated;

[0011] S3. After the reaction ends, filter the reaction solution to obtain high-purity concentrated sulfuric acid.

[0012] Preferably, the mass ratio of the organic waste in the organic waste sulfuric acid, activated carbon, and sodium percarbonate is 1:30:(3 - 10).

[0013] Preferably, in step S2, water bath heating is carried out at 25-150 °C.

[0014] Preferably, the organic waste sulfuric acid is sulfuric acid containing quinone organic compounds, polycyclic aromatic organic compounds, high molecular olefins, diolefins, alkyl sulfonic acids, sulfuric acid esters, and sulfides.

[0015] Furthermore, the quinone organic compound is chloroquinic acid, and the sulfide is hydrogen sulfide or mercaptan.

[0016] Preferably, the purity of the concentrated sulfuric acid obtained in step S3 is greater than 96%.

[0017] Beneficial effects: The method proposed by the present invention can be carried out at low temperature (50-100 °C), with low energy consumption; the reaction by-products are easy to handle, the process steps are few, the removal rate is high, and the product purity is high. Description of the Drawings

[0018] Figure 1 It is a physical comparison diagram of sodium percarbonate treating organic waste sulfuric acid;

[0019] Figure 2 It is the standard curve of the concentration of the organic waste sulfuric acid solution;

[0020] Figure 3 It is the ultraviolet spectrum diagram of sodium percarbonate treating organic waste sulfuric acid under different sulfuric acid concentrations;

[0021] Figure 4 It is the ultraviolet spectrum diagram of sodium percarbonate treating organic waste sulfuric acid under different addition amounts of sodium percarbonate;

[0022] Figure 5 It is the ultraviolet spectrum diagram of sodium percarbonate treating organic waste sulfuric acid at different temperatures;

[0023] Figure 6 It is the kinetic curve of sodium percarbonate treating organic waste sulfuric acid under preferred conditions;

[0024] Figure 7 It is the ultraviolet spectrum diagram of activated carbon and sodium percarbonate synergistically treating organic waste sulfuric acid under different addition amounts of sodium percarbonate;

[0025] Figure 8 It is the ultraviolet spectrum diagram of the organic waste sulfuric acid treated with sodium percarbonate and the blank control group;

[0026] Figure 9 It is the TOC data of the blank control group, only adding activated carbon treatment, only adding sodium percarbonate treatment, and activated carbon and sodium percarbonate synergistic treatment. Detailed Embodiments

[0027] The present invention will be described in detail below with reference to the drawings and specific embodiments:

[0028] Sources of materials involved in the following examples: sodium percarbonate and chloranilic acid (purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.), sulfuric acid (purchased from Shanghai Lingfeng Chemical Reagent Co., Ltd.), deionized water (resistivity: 18.22 MΩ·cm), activated carbon (Jiangsu Pushida Environmental Protection Technology Co., Ltd.).

[0029] Example 1

[0030] Add 0.1 g of chloranilic acid to 1.41 mL of deionized water, stir to dissolve chloranilic acid at 50 °C, and slowly add 8.59 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 1.0 g of sodium percarbonate in batches, stir and react at 50 °C for 1 hour. After the reaction is completed, filter the obtained solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 96.87%, and the recovered amount of sulfuric acid is 11.2 mL.

[0031] Example 2

[0032] Add 0.1 g of chloranilic acid to 3.77 mL of deionized water, stir to dissolve chloranilic acid at 50 °C, and slowly add 6.23 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 1.0 g of sodium percarbonate in batches, stir and react at 50 °C for 1 hour. After the reaction is completed, filter the obtained solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 99.70%, and the recovered amount of sulfuric acid is 10.9 mL.

[0033] Example 3

[0034] Add 0.1 g of chloranilic acid to 2.43 mL of deionized water, stir to dissolve chloranilic acid at 50 °C, and slowly add 7.57 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 1.0 g of sodium percarbonate in batches, stir and react at 50 °C for 1 hour. After the reaction is completed, filter the obtained solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 95.98%, and the recovered amount of sulfuric acid is 11.3 mL.

[0035] Example 4

[0036] Add 0.1 g of chloranilic acid to 4.24 mL of deionized water, stir to dissolve chloranilic acid at 50 °C, and slowly add 5.76 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 1.0 g of sodium percarbonate in batches, stir and react at 50 °C for 1 hour. After the reaction is completed, filter the obtained solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 98.29%, and the recovered amount of sulfuric acid is 10.9 mL.

[0037] Example 5

[0038] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 1.0 g of sodium percarbonate in batches, stir and react at 50 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity sulfuric acid. The removal rate of chloranilic acid is 100.00%, and the recovered amount of sulfuric acid is 11.0 mL.

[0039] Example 6

[0040] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 0.75 g of sodium percarbonate in batches, stir and react at 50 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity sulfuric acid. The removal rate of chloranilic acid is 98.18%, and the recovered amount of sulfuric acid is 10.8 mL.

[0041] Example 7

[0042] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 0.25 g of sodium percarbonate in batches, stir and react at 50 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity sulfuric acid. The removal rate of chloranilic acid is 95.40%, and the recovered amount of sulfuric acid is 11.2 mL.

[0043] Example 8

[0044] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 0.5 g of sodium percarbonate in batches, stir and react at 50 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity sulfuric acid. The removal rate of chloranilic acid is 98.73%, and the recovered amount of sulfuric acid is 11.3 mL.

[0045] Example 9

[0046] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 0.5 g of sodium percarbonate in batches, stir and react at 25 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity sulfuric acid. The removal rate of chloranilic acid is 87.26%, and the recovered amount of sulfuric acid is 11.1 mL.

[0047] Example 10

[0048] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 0.5 g of sodium percarbonate in batches, stir and react at 150 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 92.18%, and the recovered amount of sulfuric acid is 11.4 mL.

[0049] Example 11

[0050] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 0.5 g of sodium percarbonate in batches, stir and react at 75 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 99.99%, and the recovered amount of sulfuric acid is 11.0 mL.

[0051] Example 12

[0052] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Slowly add 0.5 g of sodium percarbonate in batches, stir and react at 100 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 96.37%, and the recovered amount of sulfuric acid is 10.6 mL.

[0053] Example 13

[0054] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Add 3.0 g of activated carbon to the organic waste sulfuric acid, slowly add 0.3 g of sodium percarbonate in batches, stir and react at 75 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 93.13%, and the recovered amount of sulfuric acid is 10.3 mL.

[0055] Example 14

[0056] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Add 3.0 g of activated carbon to the organic waste sulfuric acid, slowly add 0.4 g of sodium percarbonate in batches, stir and react at 75 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 95.79%, and the recovered amount of sulfuric acid is 10.5 mL.

[0057] Example 15

[0058] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Add 3.0 g of activated carbon to the organic waste sulfuric acid, and slowly add 0.45 g of sodium percarbonate in batches. Stir and react at 75 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 99.98%, and the sulfuric acid recovery is 11.2 mL.

[0059] Example 16

[0060] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Add 3.0 g of activated carbon to the organic waste sulfuric acid, and slowly add 0.5 g of sodium percarbonate in batches. Stir and react at 75 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 100.00%, and the sulfuric acid recovery is 11.5 mL.

[0061] Blank Comparative Example 1

[0062] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Stir and react at 75 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 0%, and the sulfuric acid recovery is 10.0 mL.

[0063] Blank Comparative Example 2

[0064] Add 0.1 g of chloranilic acid to 2.93 mL of deionized water, stir to dissolve the chloranilic acid at 50 °C, and slowly add 7.07 mL of concentrated sulfuric acid to simulate organic waste sulfuric acid. Add 3.0 g of activated carbon to the organic waste sulfuric acid, stir and react at 75 °C for 1 hour. After the reaction, filter the resulting solution to obtain high-purity concentrated sulfuric acid. The removal rate of chloranilic acid is 23.58%, and the sulfuric acid recovery is 9.7 mL.

[0065] The reaction conditions and results of Examples 1-16 and Blank Comparative Examples 1-2 are shown in Table 1 below:

[0066] Table 1 Reaction Conditions and Results of Examples 1-16 and Blank Comparative Examples 1-2

[0067]

[0068]

[0069] A series of tests were carried out on Examples 1-16 and Blank Comparative Examples 1-2:

[0070] Photographs were taken before and after the treatment in Example 16, and the results are as Figure 1 shown: The simulated organic waste sulfuric acid solution was orange-red, and the solution after treatment was transparent and colorless.

[0071] According to Table 2 below, a standard curve of the concentration of the organic waste sulfuric acid solution was established, and the obtained standard curve is as Figure 2 shown: It is used to calibrate the concentration of the organic waste before and after the reaction.

[0072] Table 2 Data of absorbance corresponding to different concentrations of organic waste sulfuric acid

[0073] Concentration (mmol / L) Absorbance 0 0.001 0.1 0.021 0.5 0.071 1 0.120 2 0.328 4 0.596 5 0.757

[0074] The UV spectral test results of Examples 1-5 are as Figure 3 shown: Through the analysis of the data in the figure, it is found that the treatment effect for high-concentration sulfuric acid is very excellent.

[0075] The UV spectral test results of Examples 5-8 are as Figure 4 shown: Through the analysis of the data in the figure, it is determined that when there is no activated carbon, the optimal dosage of sodium percarbonate is 0.5 g.

[0076] The UV spectral test results of Examples 8-12 are as Figure 5 shown: Through the analysis of the data in the figure, it is determined that the optimal treatment temperature is 50 °C - 100 °C.

[0077] Under the preferred conditions (mass percentage concentration of sulfuric acid is 80%, dosage of sodium percarbonate is 0.5 g, treatment temperature is 75 °C, that is, Example 12), the kinetic curve of sodium percarbonate treating organic waste sulfuric acid is as Figure 6 shown: Through the analysis of the data in the figure, it is determined that the optimal reaction time is 33 min.

[0078] The UV spectra of Examples 13-16, the results are as Figure 7 shown: Through the analysis of the data in the figure, it is determined that the optimal dosage of sodium percarbonate is 0.45 g - 0.5 g.

[0079] The UV spectra of Example 15 and blank control Example 1 are as Figure 8 shown: It shows that the organic waste in the organic waste sulfuric acid has been completely treated.

[0080] The TOC data of blank control Example 1, blank control Example 2, Example 11 and Example 16 are as Figure 9 shown: Through the analysis of the data in the figure, it can be found that the synergistic treatment effect of activated carbon and sodium percarbonate is much better than that of activated carbon or sodium percarbonate alone.

[0081] Based on the above embodiments and the blank comparative example, it can be determined that the preferred sulfuric acid concentration for sodium percarbonate to treat organic waste sulfuric acid is 75%-80%, the optimal dosage of sodium percarbonate is 0.5 g, the optimal treatment temperature is 50°C-100°C, and the optimal reaction time is 33 min. The addition of activated carbon can reduce the optimal dosage of sodium percarbonate to 0.45 g, and the treatment effect is better than that of only using sodium percarbonate for treatment. Since activated carbon is a catalyst with low price and can be reused, and the synergistic treatment of activated carbon and sodium percarbonate reduces the optimal dosage of sodium percarbonate to 0.45 g, which greatly reduces the economic cost.

[0082] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for catalytic cracking of organic waste sulfuric acid at low temperature, characterized in that, It includes the following steps: S1. Slowly add sodium percarbonate in batches to a reactor containing organic waste sulfuric acid and activated carbon; S2. Heat the reactor by water bath and react until no bubbles are generated; S3. After the reaction is completed, filter the reaction solution to obtain high-purity concentrated sulfuric acid.

2. The method for catalytically cracking organic waste sulfuric acid at low temperature according to claim 1, characterized in that: The mass ratio of the organic waste in the organic waste sulfuric acid, activated carbon and sodium percarbonate is 1:30:(3-10).

3. A method for catalytically cracking organic waste sulfuric acid at low temperature according to claim 1, characterized in that: In step S2, heat by water bath to 25-150 °C.

4. The method for catalytically cracking organic waste sulfuric acid at low temperature according to claim 1, wherein: The organic waste sulfuric acid is sulfuric acid containing quinone organic compounds, polycyclic aromatic organic compounds, high-molecular olefins, diolefins, alkyl sulfonic acids, sulfuric acid esters and sulfides.

5. A method for catalytically cracking organic waste sulfuric acid at low temperature according to claim 4, characterized in that: The quinone organic compound is chloroquinic acid, and the sulfide is hydrogen sulfide or mercaptan.

6. The method for catalytically cracking organic waste sulfuric acid at low temperature according to claim 1, characterized in that: The purity of the concentrated sulfuric acid obtained in step S3 is greater than 96%.

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