CN112742069A - Method for treating organic matters in sulfonated waste sulfuric acid by using modified attapulgite - Google Patents
Method for treating organic matters in sulfonated waste sulfuric acid by using modified attapulgite Download PDFInfo
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
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Abstract
The invention relates to a method for treating organic matters in sulfonated waste sulfuric acid by using modified attapulgite, which comprises the following steps: taking a attapulgite raw material, and grinding; firstly, carrying out acid washing and then washing, placing the attapulgite particles separated after washing in a sodium chloride solution, then placing the separated attapulgite particles in a saturated solution of sodium dodecyl benzene sulfonate and sodium lignin sulfonate for infiltration, and after solid-liquid separation, calcining to obtain modified attapulgite particles; grinding the modified attapulgite particles to prepare a modified attapulgite material; fully mixing the waste sulfuric acid with the organic-containing waste sulfuric acid of the sulfonator to be treated, and separating solid waste and sulfuric acid. The invention can effectively remove the organic matters in the sulfonated waste sulfuric acid by utilizing the adsorption and separation of the modified attapulgite material, can achieve the adsorption removal efficiency of more than 90 percent through multiple stable treatments, reduces the residual quantity of the organic matters in the sulfonated waste sulfuric acid, and the treated sulfuric acid can be degraded for use or can be used as a raw material for producing byproducts.
Description
Technical Field
The invention belongs to the field of hazardous waste treatment and recycling, and particularly relates to a method for treating organic matters in sulfonated waste sulfuric acid by using modified attapulgite.
Background
With the rapid development of chemical industry in China, the production of industrial waste acid is rapidly increased, and according to statistics, the annual production of waste acid in China reaches 1 hundred million tons, wherein organic waste sulfuric acid is one of relatively high toxicity and prominent environmental risk. The organic waste sulfuric acid is mainly produced in industries such as dye, pesticide, petroleum refining and the like, the annual production amount reaches 1000 ten thousand tons, main harmful components comprise nitro compounds, benzenes, organic phosphorus compounds, alkylated oil and the like, the concentration is 1-5%, the organic waste sulfuric acid is difficult to degrade, and toxicity and odor of different degrees are realized.
Because the sulfonation reaction is a strong exothermic reaction and the sulfuric acid is used as a strong oxidant, a large amount of dark-colored byproducts are generated in the sulfonation process, so that the waste sulfuric acid is brownish black and has a very high COD value. If the waste sulfuric acid is directly discharged, a large amount of resources are wasted, and the environmental pollution is easily caused. The waste sulfuric acid after being purified can be used in the process with low requirement on concentration, or can be recycled after being further concentrated to higher concentration.
At present, the treatment technology of organic waste sulfuric acid mainly comprises an adsorption method, an extraction method and an oxidation method. Adsorption processes are widely used because they selectively enrich certain compounds, and the commonly used adsorbents are activated carbon, adsorption resins and other adsorbent materials. The activated carbon adsorption method has the advantages of early application, wide source, strong acid resistance and strong adsorbability to refractory organic matters, but the activated carbon has high regeneration temperature, high energy consumption, high carbon ablation loss and higher requirement on equipment materials, and limits the industrial large-scale application of the activated carbon adsorption method. The macroporous adsorption resin has larger specific surface area and good acid resistance, has good treatment effect on acid wastewater and waste acid, but needs to select proper regenerant for resin regeneration, has high regeneration cost, and can easily cause secondary pollution to the environment if the waste liquid generated by regeneration cannot be properly treated.
In summary, the prior art for removing organic matters in the sulfonated waste sulfuric acid still has the problems of few treatment methods, high treatment cost, poor popularization and application performance and the like, so that the treatment method which is low in cost, high in adsorption efficiency and easy to operate is provided, and has a good application prospect.
Disclosure of Invention
The invention aims to provide a method for treating organic matters in sulfonated waste sulfuric acid, which has low cost, high removal rate and easy operation on the basis of the prior art.
The technical scheme of the invention is as follows:
a method for treating organic matters in sulfonated waste sulfuric acid by using modified attapulgite comprises the following steps:
(1) grinding attapulgite raw material into particles of not less than 300 meshes;
(2) carrying out acid washing on the ground attapulgite particles, then washing with water until the pH value is 6.5-7.5, placing the attapulgite particles separated after washing with water in a sodium chloride solution, and horizontally oscillating for 3-5 h at the temperature of 90-110 ℃; then placing the separated attapulgite particles into a saturated solution of sodium dodecyl benzene sulfonate and sodium lignin sulfonate for infiltration, and calcining after solid-liquid separation to obtain modified attapulgite particles;
(3) grinding the modified attapulgite particles again to prepare a modified attapulgite material with the particle size of 90-110 mu m;
(4) fully mixing the modified attapulgite material prepared in the step (3) with the organic matter-containing sulfonated waste sulfuric acid to be treated according to the solid-liquid ratio of 1: 90-110, stirring for more than 1h, and carrying out solid-liquid separation to obtain solid waste and sulfuric acid;
(5) and (4) repeating the operation of the step (4) for more than 3 times.
For the present invention, the attapulgite clay raw material is subjected to grinding and modification treatment before the organic matter in the sulfonated waste sulfuric acid is treated. In the step (1), the attapulgite raw material is pretreated and ground by an automatic grinding instrument to prepare particles of not less than 300 meshes so as to disperse other internal components and increase the specific surface area and adsorption sites of the attapulgite.
When the ground attapulgite particles are modified, the ground attapulgite particles are firstly subjected to acid washing to remove substances dissolved in acids in the attapulgite particles. In a preferable scheme, in the step (2), a strong acid with the pH of less than 2 is adopted during acid washing, and the acid washing time is 4-6 h. And after the acid washing is finished, separating the attapulgite particles after the acid washing, and then washing with water until the pH value is 6.5-7.5, wherein the water selected in the water washing process is high-purity water, such as distilled water.
And after the water washing is finished, placing the separated attapulgite particles in a sodium chloride solution, and carrying out sodium treatment on the separated attapulgite particles by horizontal oscillation for 3-5 h at the temperature of 90-110 ℃. In order to obtain better effect, the temperature is generally controlled to horizontally oscillate for 3 hours under the condition of 100 ℃.
In the step (2), in the sodium treatment, in order to obtain a better treatment effect and save cost, the concentration of sodium chloride in the sodium chloride solution can be controlled to be 1mol/L to 3mol/L, for example, 1mol/L, 2mol/L or 3 mol/L.
For the present invention, in step (2), the attapulgite particles separated after washing are placed in a sodium chloride solution, and the water-soil ratio of the sodium chloride solution to the attapulgite particles separated after washing is generally controlled to not less than 2:1 (water-soil ratio ≧ 2: 1), for example, 2: 1. Horizontally oscillating for 3-5 h (e.g. 4 h) under the condition of 90-110 ℃ (e.g. 100 ℃), and soaking the separated attapulgite clay particles in a saturated solution of sodium dodecyl benzene sulfonate and sodium lignin sulfonate for 12-24 h after solid-liquid separation. After infiltration, calcining the separated attapulgite particles at the temperature of 180-220 ℃, wherein the specific calcining temperature can be, but is not limited to, 180 ℃, 200 ℃ or 220 ℃. And controlling the calcination time within 6-12 hours to obtain the modified attapulgite particles. .
In the step (3), the modified attapulgite particles are ground again to prepare the modified attapulgite material with the particle size of 90-110 μm. In a preferred scheme, the modified attapulgite particles are ground again to prepare the modified attapulgite material with the particle size of 100 mu m.
For the purposes of the present invention, the waste sulfonated sulfuric acid is a waste sulfonated sulfuric acid which contains organic substances and is relatively stable, wherein the organic substances are nitrotoluene-o-sulfonic acid, ethylenediaminobenzene sulfonic acid or a mixture of the two.
In a preferable scheme, in the step (4), the modified attapulgite material prepared in the step (3) and the sulfonated waste sulfuric acid containing organic matters to be treated are fully mixed according to the solid-liquid ratio of 1:100, stirred for more than 1h at the stirring speed of 380 r/min-420 r/min, for example, 400r/min, and solid-liquid separation is carried out to obtain solid waste and sulfuric acid.
Chinese patent CN104826854A discloses a regeneration treatment method of dangerous solid waste containing organophosphorus pesticides, which comprises the following steps: taking a attapulgite raw material, and grinding; oxidizing with hydrogen peroxide solution, soaking and eluting with acid to weak acidity, placing in saturated solution of sodium dodecyl benzene sulfonate and sodium lignosulfonate, performing solid-liquid separation, and calcining at high temperature to obtain modified attapulgite; grinding the calcined attapulgite particles to prepare a modified attapulgite material; fully mixing the solid waste with dangerous solid waste containing organophosphorus pesticide to be treated, adding sodium lignosulfonate solution, fully oscillating for more than 1h, and separating solid precipitate after solid-liquid separation. Compared with the patent, the method for treating the organic matters in the sulfonated waste sulfuric acid provided by the invention has the following advantages: (1) the method does not need to carry out hydrogen peroxide oxidation treatment on the ground attapulgite particles, after washing, the attapulgite particles separated after washing are placed in a sodium chloride solution for sodium treatment, and the surfaces of the washed attapulgite particles are organically modified, so that the compatibility and the dispersibility of the washed attapulgite particles and the sulfonated waste sulfuric acid containing organic matters are improved, the adsorption performance of the organic matters in the waste sulfuric acid is improved, and the removal efficiency of the organic matters in the waste sulfuric acid reaches over 90 percent. (2) The modified attapulgite material is adopted to treat the sulfonated waste sulfuric acid containing organic matters, sodium lignosulphonate does not need to be added again in the treatment process, the treatment method is more convenient, and the cost is effectively saved.
Meanwhile, the inventor of the invention fully mixes the modified attapulgite material prepared by the method disclosed in Chinese patent CN104826854A with sulfonated waste sulfuric acid containing organic matters to be treated according to the solid-to-liquid ratio of 1:100, stirs for more than 1h at a stirring speed of 380 r/min-420 r/min, and finds that the removal efficiency of the organic matters in the waste sulfuric acid is about 70%, and even after sodium lignosulfonate is added, the removal efficiency of the organic matters in the waste sulfuric acid is about 72%, the removal efficiency is not obviously increased, and the separated sulfuric acid cannot meet the requirements of degraded use or raw materials as production byproducts. That is, because the objects to be treated are different, a specific modification method needs to be explored to modify the attapulgite raw material, and the obtained modified attapulgite material can obtain better effect.
The sulfonated waste sulfuric acid treated by the modified attapulgite material belongs to hazardous waste with higher environmental risk, and the separated sulfuric acid can be degraded for use or used as a raw material of a production byproduct in the step (4) by adopting the treatment method. In the step (5), the separated solid waste is disposed according to hazardous waste, and wastewater generated in the treatment process enters a sewage treatment system. The whole treatment process adopts a whole-process risk control method, so that the environmental risk is low.
The attapulgite clay raw material adopted by the invention is a relatively abundant mineral product in China, the reserve of the attapulgite clay is abundant in the downstream coastal mountain areas of Huaihe river in China, the reserve accounts for about more than 30% of the total reserve in the world, the quality of the finished attapulgite clay is relatively good, and compared with activated carbon and the like, the utilization cost is low, the large-scale production and processing are easy, and the popularization is easy. When the modified attapulgite material is used for adsorbing and separating organic matters in the sulfonated waste sulfuric acid, the method has the characteristics of low requirement on equipment conditions, organic matter removal efficiency of over 90 percent, less pollutant generation, low treatment cost, wider applicable conditions and the like, is suitable for treating and regenerating hazardous wastes such as sulfonated waste sulfuric acid, and is an efficient and energy-saving hazardous waste treatment and regeneration technology.
In a preferred embodiment, the method for treating heavy metals in inorganic waste sulfuric acid by using the modified attapulgite comprises the following detailed steps:
(1) grinding the attapulgite raw material into particles of not less than 300 meshes, and grinding by using an automatic grinding instrument, wherein the particle size of the particles is controlled to reach 300 meshes so as to disperse other internal components and increase the specific surface area and adsorption sites of the attapulgite.
(2) And (3) carrying out acid washing on the ground attapulgite particles to remove substances dissolved in acids in the attapulgite particles. During acid washing, strong acid with the pH value of less than 2 is adopted, and the acid washing time is 4-6 h (for example, 5 h). And after the acid washing is finished, separating the attapulgite particles after the acid washing, and then washing with water until the pH value is 6.5-7.5, wherein the selected water is distilled water. After the water washing is finished, the separated attapulgite particles after the water washing are placed in 1 mol/L-3 mol/L sodium chloride solution (for example, 1 mol/L), the water-soil ratio is not less than 2:1 (for example, the water-soil ratio is 2: 1), the attapulgite particles are horizontally oscillated for 3 h-5 h (for example, 4 h) under the condition of 90-110 ℃ (for example, 100 ℃), and after the solid-liquid separation, the separated attapulgite particles are placed in a saturated solution of sodium dodecyl benzene sulfonate and sodium lignin sulfonate for infiltration for 12 h-24 h. And after soaking, calcining the separated attapulgite particles at the temperature of 180-220 ℃ (for example, 200 ℃) for 6-12 hours to obtain the modified attapulgite particles.
(3) Grinding the modified attapulgite particles again to prepare a modified attapulgite material with the particle size of 90-110 μm (for example, 100 μm);
(4) and (3) fully mixing the modified attapulgite material prepared in the step (3) with the organic matter-containing sulfonated waste sulfuric acid to be treated according to a solid-liquid ratio of 1: 90-110 (for example, 1: 100), stirring for more than 1h at a stirring speed of 380 r/min-420 r/min (for example, 400 r/min), and carrying out solid-liquid separation to obtain solid waste and sulfuric acid. The separated solid waste is disposed according to the hazardous waste, and the wastewater generated in the treatment process enters a sewage treatment system.
(5) And (4) repeating the operation of the step (4) for more than 3 times. The separated sulfuric acid can be degraded for use or used as a raw material for production by-products.
By adopting the technical scheme of the invention, the advantages are as follows:
aiming at the problem of treatment and regeneration of hazardous waste such as the sulfonated waste sulfuric acid, the invention can effectively remove organic matters in the sulfonated waste sulfuric acid by utilizing the adsorption and separation of the modified attapulgite material, can achieve more than 90 percent of adsorption removal efficiency through multiple times of stable treatment, reduces the residual quantity of the organic matters in the sulfonated waste sulfuric acid, reduces the treatment cost, and can degrade the treated sulfuric acid for use or be used as a raw material for producing byproducts. And the attapulgite clay raw material is a relatively abundant mineral product in China, has high yield, relatively convenient material acquisition and relatively low cost, and is easy to produce and popularize.
The treatment method is simple and easy to implement, has low requirements on equipment conditions, has the characteristics of less pollutant generation, small harmfulness, low treatment cost, wider application conditions and the like, can be applied under extreme conditions such as strong acid and the like, and is an efficient and energy-saving technology for treating and regenerating the sulfonated waste sulfuric acid.
Detailed Description
The method of treating organic matters in sulfonated waste sulfuric acid by using modified attapulgite according to the present invention is further illustrated by the following examples, which are not intended to limit the present invention in any way.
Example 1:
(1) and (3) grinding the attapulgite raw material by using an automatic grinding instrument, and controlling the particle size of attapulgite particles to be 300 meshes.
(2) And after grinding is finished, eluting the ground attapulgite particles by using acid, selecting hydrochloric acid with the pH value of less than 2, pickling for 5 hours, and carrying out solid-liquid separation after pickling. And washing the attapulgite particles separated after acid washing with distilled water until the pH value is 6.5-7.5, and performing solid-liquid separation after washing. And (3) placing the attapulgite particles separated after water washing in 2mol/L sodium chloride solution, horizontally oscillating for 4h at 100 ℃, and performing solid-liquid separation after sodium treatment. Then placing the separated attapulgite particles into a saturated solution of sodium dodecyl benzene sulfonate and sodium lignin sulfonate, soaking for 18h, and carrying out solid-liquid separation after soaking; and calcining the separated attapulgite particles at the temperature of 200 ℃ for 10 hours to obtain the modified attapulgite particles.
(3) And grinding the modified attapulgite particles again to prepare the modified attapulgite material with the particle size of 100 mu m.
(4) And (3) fully mixing the modified attapulgite material prepared in the step (3) with the sulfonated waste sulfuric acid containing p-nitrotoluene-o-sulfonic acid to be treated according to the solid-liquid ratio of 1:100, horizontally stirring for 2h at the stirring speed of 400r/min, and performing solid-liquid separation to obtain solid waste and sulfuric acid. The separated solid waste is disposed according to the hazardous waste, and the wastewater generated in the treatment process enters a sewage treatment system.
(5) The separated sulfuric acid is repeated the above step (4). The separated sulfuric acid can be degraded for use or used as a raw material for production by-products.
After fully stirring once and carrying out solid-liquid separation, the removal effect of the p-nitrotoluene-o-sulfonic acid in the sulfonated waste sulfuric acid containing the p-nitrotoluene-o-sulfonic acid reaches 72 percent. Fully stirring for four times, and performing solid-liquid separation, wherein the removal effect of the p-nitrotoluene-o-sulfonic acid in the sulfonated waste sulfuric acid containing the p-nitrotoluene-o-sulfonic acid reaches 96%. This shows that after one-time full stirring and separation, the removal effect of the p-nitrotoluene-o-sulfonic acid is obvious, and the content of the p-nitrotoluene-o-sulfonic acid can be reduced to a trace level by multiple treatments.
Example 2
(1) And (3) grinding the attapulgite raw material by using an automatic grinding instrument, and controlling the particle size of attapulgite particles to be 300 meshes.
(2) And after grinding is finished, eluting the ground attapulgite particles by using acid, selecting hydrochloric acid with the pH value of less than 2, pickling for 6 hours, and carrying out solid-liquid separation after pickling. And washing the attapulgite particles separated after acid washing with distilled water until the pH value is 6.5-7.5, and performing solid-liquid separation after washing. And (3) placing the attapulgite particles separated after water washing into 3mol/L sodium chloride solution, horizontally oscillating for 5h at the temperature of 100 ℃, and performing solid-liquid separation after sodium treatment. Then placing the separated attapulgite particles into a saturated solution of sodium dodecyl benzene sulfonate and sodium lignin sulfonate, soaking for 18h, and carrying out solid-liquid separation after soaking; and calcining the separated attapulgite particles at the temperature of 200 ℃ for 12h to obtain the modified attapulgite particles.
(3) And (3) grinding the modified attapulgite particles obtained in the step (2) again to prepare the modified attapulgite material with the particle size of 100 mu m.
(4) And (2) grinding the grinded attapulgite particles obtained in the step (1) again to prepare the attapulgite material with the particle size of 100 microns.
(5) And (3) fully mixing the attapulgite material prepared in the step (3) and the attapulgite particles with the particle size of 100 microns prepared in the example 1 of the Chinese patent CN104826854A with sulfonated waste sulfuric acid containing the ethylenediaminobenzene sulfonic acid to be treated according to the solid-liquid ratio of 1:100, horizontally stirring for 3 hours at the stirring speed of 400r/min, and carrying out solid-liquid separation to obtain solid waste and sulfuric acid. The separated solid waste is disposed according to the hazardous waste, and the wastewater generated in the treatment process enters a sewage treatment system.
(6) The separated sulfuric acid is repeated the above step (5). The separated sulfuric acid can be degraded for use or used as a raw material for production by-products.
After fully stirring for four times and carrying out solid-liquid separation, the removal effect of the ethylenediaminobenzene sulfonic acid in the sulfonated waste sulfuric acid treated by using the modified attapulgite material is 94 percent, and the removal effect of the ethylenediaminobenzene sulfonic acid in the sulfonated waste sulfuric acid treated by using the unmodified attapulgite material is 65 percent. This shows that the modified attapulgite material has more obvious effect on removing the ethylenediaminobenzene sulfonic acid. The removal effect of the ethylenediaminobenzene sulfonic acid in the sulfonated waste sulfuric acid treated by the modified attapulgite particles prepared in example 1 in the Chinese patent CN104826854A is 75%, which shows that the removal effect of the modified attapulgite material on the ethylenediaminobenzene sulfonic acid is obviously better than that of the modified attapulgite material disclosed in the Chinese patent CN 104826854A.
Example 3
(1) And (3) grinding the attapulgite raw material by using an automatic grinding instrument, and controlling the particle size of attapulgite particles to be 300 meshes.
(2) And after grinding is finished, eluting the ground attapulgite particles by using acid, selecting hydrochloric acid with the pH value of less than 2, pickling for 5 hours, and carrying out solid-liquid separation after pickling. And washing the attapulgite particles separated after acid washing with distilled water until the pH value is 6.5-7.5, and performing solid-liquid separation after washing.
(3) And (3) placing the attapulgite particles separated after water washing in 2mol/L sodium chloride solution, horizontally oscillating for 4h at 100 ℃, and performing solid-liquid separation after sodium treatment.
(4) Placing the attapulgite particles separated by solid-liquid separation in the step (2) and the step (3) in saturated solutions of sodium dodecyl benzene sulfonate and sodium lignosulfonate respectively, wherein the soaking time is 18h, and carrying out solid-liquid separation after soaking; and calcining the separated attapulgite particles at the temperature of 200 ℃ for 10 hours to obtain sodium modified attapulgite particles and non-sodium modified attapulgite particles.
(5) And grinding the two modified attapulgite particles again to prepare the modified attapulgite material with the particle size of 100 mu m.
(6) Fully mixing the two modified attapulgite materials prepared in the step (5) with waste sulfonated sulfuric acid containing 2 organic matters including p-nitrotoluene-o-sulfonic acid and ethylene diamino benzene sulfonic acid to be treated according to a solid-liquid ratio of 1:100, horizontally stirring for 2h at a stirring speed of 400r/min, and carrying out solid-liquid separation to obtain solid waste and sulfuric acid. The separated solid waste is disposed according to the hazardous waste, and the wastewater generated in the treatment process enters a sewage treatment system.
(7) The separated sulfuric acid is repeated the above step (6). The separated sulfuric acid can be degraded for use or used as a raw material for production by-products.
After fully stirring for four times and carrying out solid-liquid separation, the removal effect of the p-nitrotoluene ortho-sulfonic acid in the sulfonated waste sulfuric acid treated by the sodium modified attapulgite material is 93 percent, and the removal effect of the ethylene diamino benzene sulfonic acid is 92 percent. The removal effect of the p-nitrotoluene-o-sulfonic acid in the sulfonated waste sulfuric acid treated by the non-sodium modified attapulgite material is 80%, and the removal effect of the ethylene diamino benzene sulfonic acid is 76%. This shows that the modified attapulgite material after sodium treatment has more obvious effect on removing organic matters in the sulfonated waste sulfuric acid.
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: modifications of the technical solutions described in the foregoing embodiments are still possible, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for treating organic matters in sulfonated waste sulfuric acid by using modified attapulgite is characterized by comprising the following steps:
(1) grinding attapulgite raw material into particles of not less than 300 meshes;
(2) carrying out acid washing on the ground attapulgite particles, then washing with water until the pH value is 6.5-7.5, placing the attapulgite particles separated after washing with water in a sodium chloride solution, and horizontally oscillating for 3-5 h at the temperature of 90-110 ℃; then placing the separated attapulgite particles into a saturated solution of sodium dodecyl benzene sulfonate and sodium lignin sulfonate for infiltration, and calcining after solid-liquid separation to obtain modified attapulgite particles;
(3) grinding the modified attapulgite particles again to prepare a modified attapulgite material with the particle size of 90-110 mu m;
(4) fully mixing the modified attapulgite material prepared in the step (3) with the organic matter-containing sulfonated waste sulfuric acid to be treated according to the solid-liquid ratio of 1: 90-110, stirring for more than 1h, and carrying out solid-liquid separation to obtain solid waste and sulfuric acid;
(5) and (4) repeating the operation of the step (4) for more than 3 times.
2. The method for treating the organic matters in the sulfonated waste sulfuric acid by using the modified attapulgite clay according to claim 1, wherein in the step (2), the attapulgite clay particles separated after water washing are placed in a sodium chloride solution, and horizontally oscillated for 3h to 5h, preferably for 4h, at the temperature of 100 ℃.
3. The method for treating the organic matters in the sulfonated waste sulfuric acid by using the modified attapulgite clay according to claim 1, wherein in the step (2), the concentration of sodium chloride in a sodium chloride solution is 1 mol/L-3 mol/L, and more preferably 2 mol/L; the water-soil ratio of the sodium chloride solution to the attapulgite particles separated after water washing is not less than 1:2, and the water-soil ratio is preferably 1: 2.
4. The method for treating the organic matters in the sulfonated waste sulfuric acid by using the modified attapulgite clay according to claim 1, wherein in the step (2), a strong acid with a pH of less than 2 is used for acid washing, and the acid washing time is 4-6 h; when washing, the adopted water is distilled water.
5. The method for treating the organic matters in the sulfonated waste sulfuric acid by using the modified attapulgite according to claim 1, wherein in the step (2), the separated attapulgite particles are soaked in a saturated solution of sodium dodecyl benzene sulfonate and sodium lignin sulfonate for 12-24 h; the temperature during calcination is 180-220 ℃, and preferably 200 ℃; the calcining time is 6-12 h.
6. The method for treating organic matters in the sulfonated waste sulfuric acid by using the modified attapulgite clay according to claim 1, wherein in the step (1), the grinding is performed by using an automatic grinder.
7. The method for treating organic matters in the sulfonated waste sulfuric acid by using the modified attapulgite according to claim 1, wherein in the step (3), the modified attapulgite particles are ground again to prepare the modified attapulgite material with the particle size of 100 μm.
8. The method for treating the organic matters in the sulfonated waste sulfuric acid by using the modified attapulgite clay as claimed in claim 1, wherein in the step (4), the solid-to-liquid ratio is 1: 100; the stirring speed is 380 r/min-420 r/min, preferably 400 r/min.
9. The method for treating the organic matters in the sulfonated waste sulfuric acid by using the modified attapulgite clay as claimed in claim 1, wherein in the step (4), the organic matters in the sulfonated waste sulfuric acid are nitrotoluene ortho-sulfonic acid, ethylene diamino benzene sulfonic acid or a mixture of the nitrotoluene ortho-sulfonic acid and the ethylene diamino benzene sulfonic acid.
10. The method for treating organic matters in the sulfonated waste sulfuric acid by using the modified attapulgite clay as claimed in claim 1, wherein in the step (4), the separated solid waste is disposed according to hazardous waste, and wastewater generated in the treatment process enters a sewage treatment system; in step (5), the separated sulfuric acid is used degraded or as a raw material of a production by-product.
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