A method for resourceful treatment of chlorinated organic wastewater

Abstract

The application discloses a resource treatment method of chlorine-containing organic wastewater, which comprises the following steps: mixing a calcium source, an aluminum source and an additive, and then calcining to obtain a calcium-aluminum multi-element compound; adding the calcium-aluminum multi-element compound into the chlorine-containing organic wastewater according to a solid-liquid mass ratio of (0.25-0.4):1, stirring and then standing to obtain a wastewater coagulation product; calcining the wastewater coagulation product to obtain a porous carbon loaded calcium-aluminum chlorine multi-element compound; and using the porous carbon loaded calcium-aluminum chlorine multi-element compound for removal of fluoride ions in fluorine-containing wastewater and / or degradation of carbonyl sulfur in gas. The self-made calcium-aluminum multi-element compound can coagulate the high-chlorine high-concentration organic wastewater in a low amount, and can convert the wastewater from a liquid phase into a solid phase, so that harmless treatment of the wastewater is achieved, and the solidification product can be converted into a high-value-added product for removing fluoride ions in water or hydrolyzing toxic gases in gas, and resource utilization is realized.

Description

TECHNICAL FIELD

[0001] The present application relates to a resource treatment method of chlorinated organic wastewater, and belongs to the harmless and resource treatment technical field of organic wastewater. BACKGROUND

[0002] High-chlorine and high-concentration organic wastewater is a kind of wastewater that is difficult to treat, with strong toxicity and deep color. It contains a large amount of chlorides and high-concentration refractory organic matter, and a certain amount of heavy metals and plant nutrients (ammonia nitrogen, etc.). Among them, the types of organic pollutants are various, including naphthalene / phenanthrene, non-chlorinated aromatic compounds, chlorinated aromatic compounds, phosphates, phthalates, phenolic compounds or aniline compounds, etc., which are difficult to biodegrade.

[0003] At present, the technologies for treating high-chlorine and high-concentration organic wastewater include physical and chemical treatment technology, biological treatment technology, membrane treatment technology, land treatment method and advanced treatment technology, etc. However, the processes of these methods are mostly complex and high in cost. The most common landfill method is relatively simple and low in cost, and can treat a large amount of waste. However, landfill requires a large amount of land, and long-term use will occupy a large amount of land resources, causing waste of land resources. Moreover, harmful substances in waste may seep into groundwater and soil, causing environmental pollution and potential threats to the ecosystem and human health.

[0004] In order to fundamentally solve the problem of high-chlorine and high-concentration organic wastewater, it is necessary to develop new environmental protection agents based on existing research and application to remove or stabilize various anions and cations in wastewater. The coagulation / solidification method is an effective method that can simultaneously achieve the synergistic treatment of multiple pollutants. Chinese patent CN117447170A discloses a phosphogypsum slag-based functional material and a method for solidifying / stabilizing heavy metal contaminated water or soil, which specifically limits the mass percentage components of the slag-based material, and proposes to apply the product as a roadbed material or a building material. However, this method and subsequent resource utilization are not suitable for the treatment of high-chlorine and high-concentration organic wastewater.

[0005] Calcium-aluminum multi-component compounds are a kind of water treatment agents with good anion and cation removal performance. In recent years, they have attracted wide attention due to their advantages such as water resistance, erosion resistance, excellent mechanical properties, stability in reducing atmosphere and the like. However, there are few studies on the preparation and solidification application of calcium-aluminum multi-component compounds at home and abroad, and most of the preparation methods are high-temperature calcination, which not only has high preparation cost, but also has low activity in wastewater treatment. In addition, most of the calcium-aluminum compounds on the market use chemical precipitation method to treat high-chlorine and high-concentration organic wastewater, which has large dosage and still contains some hazardous substances after treatment. Therefore, it is necessary to continue to find a method for treating high-chlorine and high-concentration organic wastewater, which consumes a lot of manpower and material resources and has poor economic benefits. Solidification can effectively avoid the above shortcomings. However, the calcium-aluminum compounds on the market need to be added in a high proportion to make the high-chlorine and high-concentration organic wastewater solidify, which consumes a large amount. SUMMARY

[0006] The purpose of the present application is to provide a resource treatment method for chlorine-containing organic wastewater, which can solidify high-chlorine and high-concentration organic wastewater by adding a small amount of self-made calcium-aluminum multi-component compound, and convert the wastewater from liquid phase to solid phase, so as to obtain harmless treatment of the wastewater, and can convert the solidification product into a high-value-added product for removing fluorine ions in water or toxic gases in hydrolysis gas, and realize resource utilization.

[0007] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0008] A resource treatment method for chlorine-containing organic wastewater, comprising the following steps:

[0009] S1, calcining a mixture of a calcium source, an aluminum source and an additive to obtain a calcium-aluminum multi-component compound;

[0010] S2, adding the calcium-aluminum multi-component compound into chlorine-containing organic wastewater at a solid-liquid mass ratio of (0.25-0.4):1, stirring and then standing to obtain a wastewater solidification product;

[0011] S3, calcining the wastewater solidification product to obtain a porous carbon loaded calcium-aluminum chlorine multi-component compound;

[0012] S4, using the porous carbon loaded calcium-aluminum chlorine multi-component compound for removing fluorine ions in fluorine-containing wastewater and / or degrading carbonyl sulfur in gas.

[0013] Preferably, in step S1, the mass ratio of the calcium-containing precursor, the aluminum-containing precursor and the additive is 1:(0.5-1):(0.02-0.1).

[0014] Preferably, the calcium source is one or more of calcium oxide, calcium hydroxide, carbide slag, limestone, dolomite, gypsum, apatite, montmorillonite and marble;

[0015] The aluminum source is one or more of alumina, aluminum sulfate, bauxite, bayerite, gangue, feldspar, mica, kaolinite and alunite;

[0016] The auxiliary agent is an oil-soluble metal salt, including one or more of naphthenate or sulfonate of magnesium, calcium, iron, manganese, cobalt, nickel and copper.

[0017] Preferably, in step S1, the calcination is performed at 200-700℃ for 2-5h.

[0018] Preferably, in step S2, the concentration of chloride ions in the chlorine-containing organic wastewater is ≥200ppm.

[0019] Preferably, in step S2, the chlorine-containing organic wastewater further contains copper, iron, zinc, potassium, manganese, lead, cadmium and nickel ions.

[0020] Preferably, in step S2, the stirring is performed at 10-40℃ for 1-4h.

[0021] Preferably, in step S3, the calcination is performed at 500-800℃ for 1-4h under nitrogen or argon atmosphere.

[0022] Preferably, in step S4, the specific method for removing fluoride ions in fluorine-containing wastewater by using the porous carbon loaded calcium-aluminum-chlorine multi-element compound is mixing the porous carbon loaded calcium-aluminum-chlorine multi-element compound with fluoride ions in fluorine-containing wastewater at a solid-liquid mass ratio of (0.001-0.01):1, and reacting at 0-60℃ for 10-240min.

[0023] Preferably, in step S4, the specific method for degrading carbonyl sulfur in gas by using the porous carbon loaded calcium-aluminum-chlorine multi-element compound is loading the porous carbon loaded calcium-aluminum-chlorine multi-element compound into a hydrolysis tower at a loading amount of 1-6% of the tower height, with a carbonyl sulfur concentration of 200-1000ppm, nitrogen as the balance gas, a water vapor content of 5-15%, an airspeed of 2000-20000h -1 , a reaction temperature of 50-230℃ and a reaction time of 2-24h.

[0024] The present application has the following advantages:

[0025] The calcium-aluminum multi-element compound has strong activity, and the coagulant produced by the low-temperature calcination one-step method can save a large amount of manpower and electricity, greatly reduce the cost, and has the advantages of simple process equipment and easy to master. At present, the calcium-aluminum compound is mainly produced by high-temperature (1200 DEG C) reaction sintering method, and the obtained calcium-aluminum compound material has problems of high density, low specific surface area, serious particle agglomeration, low activity, excessive addition and the like. The calcium-aluminum multi-element compound prepared by the application can overcome these defects. The calcium-aluminum multi-element compound material can be prepared by mixing sintering method at a temperature of 200-700 DEG C, and is used for treating high-chlorine and high-concentration organic wastewater. A small amount of addition can convert the wastewater from liquid phase to solid phase, greatly reduces the treatment difficulty, and reduces the danger to the environment. The porous carbon loaded with calcium-aluminum chlorine multi-element compound formed by calcination of the coagulation product is used for treating fluorine-containing wastewater and toxic gas carbonyl sulfur or hydrogen sulfide, and realizes the resource utilization.

[0026] In addition, the calcium ions in the calcium-aluminum multi-element compound can reduce the surface charge of the suspended solids and colloids in the wastewater through electro-neutralization, make them lose stability, cause the particles to aggregate with each other, and form larger flocculation. The aluminum ions will undergo hydrolysis reaction in water to form aluminum hydroxyl complexes, and the complexes have strong flocculation and adsorption effect. Moreover, the calcium ions and aluminum ions in the calcium-aluminum multi-element compound can also react with part of the anions in the wastewater to form precipitates with high stability.

[0027] In the preparation process of the calcium-aluminum multi-element compound, the addition of additives can release a large amount of heat during the reaction process, accelerate the reaction rate, make the chemical reaction reach the equilibrium state, reduce the generation of impurity phases, improve the fluidity and diffusivity of the reaction materials, and provide reactive materials, so as to obtain a calcium-aluminum multi-element compound with high purity, which provides a good substrate for subsequent resource utilization. Through morphology characterization, it can be observed that the calcium-aluminum multi-element compound has a coral-like particle morphology, a small amount of flaky crystals, and a material surface containing rich oxygen vacancies, indicating that the charge storage capacity is very strong. Generally, the metal atoms of metal oxides have the characteristics of coordination saturation, and cannot activate oxygen molecules by chemical adsorption. The construction of oxygen vacancy defects of the calcium-aluminum multi-element compound prepared by the application overcomes this defect. The more the surface oxygen vacancies, the more conducive to the hydrolysis / adsorption of the porous carbon loaded with calcium-aluminum chlorine multi-element compound to the fluorine ions and oxygen-containing pollutants.

[0028] In summary, the calcium-aluminum multi-element compound provided by the application has strong water absorption performance and hydration capacity, and can achieve complete coagulation of high-chlorine and high-concentration organic wastewater at a low dosage, greatly reducing the treatment cost and the harm of wastewater to the environment. After calcination at high temperature, the organic pollutants are degraded or carbonized, and the remaining chloride ions and heavy metal ions are stably solidified in the calcium-aluminum-chlorine multi-element compound and are not easily leached in water. The porous carbon loaded calcium-aluminum-chlorine multi-element compound obtained by calcination uses high-purity calcium-aluminum multi-element compound as a matrix, which can effectively promote the removal of fluoride ions and the hydrolysis / adsorption of toxic gases. At the same time, the porous carbon loaded calcium-aluminum-chlorine multi-element compound also contains various metal ions (copper, iron, zinc, potassium, manganese, lead, cadmium, nickel, etc.), providing a large number of active sites, making the hydrolysis and adsorption of toxic gases such as carbonyl sulfur and hydrogen sulfide more significant. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 Figure is the coagulation effect diagram of different dosages of the calcium-aluminum multi-element compound prepared in examples 1 and 2 on wastewater;

[0030] Figure 2 Figure is the SEM diagram of the calcium-aluminum multi-element compound prepared in example 2;

[0031] Figure 3 Figure is the XRD diagram of the calcium-aluminum multi-element compound prepared in example 2;

[0032] Figure 4 Figure is the XRD diagram of the porous carbon loaded calcium-aluminum-chlorine multi-element compound obtained in examples 2-8. DETAILED DESCRIPTION

[0033] Example 1

[0034] The method for resource treatment of high-chlorine and high-concentration organic wastewater comprises the following steps:

[0035] (1) The self-made calcium-aluminum multi-element compound is mixed with high-chlorine and high-concentration organic wastewater (chloride ion concentration is 2000 ppm, and contains metal ions such as copper, iron, zinc, potassium, manganese, lead, cadmium, nickel, etc.) according to a solid-liquid mass ratio of 0.2:1, and is reacted under stirring at 24℃ for 4h, and then is statically placed for 5min. The uncoagulated solid is separated, and then the solid is dried to obtain a calcium-aluminum-chlorine multi-element compound.

[0036] The preparation method of the calcium-aluminum multi-element compound is as follows: a calcium-containing precursor, an aluminum-containing precursor, and an additive are mixed and stirred uniformly according to a mass ratio of 1:1:0.02, and are calcined at 700℃ for 3h.

[0037] The calcium-containing precursor is obtained by mixing calcium oxide, carbide slag, and montmorillonite in a mass ratio of 6:3:1; the aluminum-containing precursor is obtained by mixing alumina, bauxite, and kaolinite in a mass ratio of 5:3:2; and the additive is prepared by mixing calcium petroleum sulfonate and potassium methanesulfonate in a volume ratio of 2:1.

[0038] (2) Using nitrogen as a protective gas, calcium aluminum chloride multi-component compounds were calcined at 500°C for 4 hours to prepare porous carbon-supported calcium aluminum chloride multi-component compounds.

[0039] (3) The porous carbon-supported calcium-aluminum-chlorine multi-component compound was used to remove fluoride ions from fluoride-containing wastewater. Specifically, the solid-liquid mass ratio of the porous carbon-supported calcium-aluminum-chlorine multi-component compound to the fluoride-containing wastewater was 0.007:1, the reaction temperature was 25℃, the reaction time was 180 min, and the fluoride removal efficiency could reach 99.5%.

[0040] A porous carbon-supported calcium-aluminum-chlorine compound was used for the hydrolysis of the toxic gas carbonyl sulfide. The carbonyl sulfide concentration was 500 ppm, nitrogen was used as the equilibrium gas, and the reaction space velocity was 20,000 h⁻¹. -1 The reaction temperature was 170℃, the water vapor content was 15%, and the amount of porous carbon-supported calcium-aluminum-chlorine multi-component compound packed in the hydrolysis tower was 2% of the tower height. Under the above conditions, the hydrolysis efficiency of carbonyl sulfur was 92% after 300 min.

[0041] Example 2

[0042] The resource-based treatment method for high-chlorine, high-concentration organic wastewater includes the following steps:

[0043] (1) The self-made calcium-aluminum multi-component compound was mixed with high-chlorine, high-concentration organic wastewater (chloride ion concentration of 2000 ppm, and containing metal ions such as copper, iron, zinc, potassium, manganese, lead, cadmium, and nickel) at a solid-liquid mass ratio of 0.3:1. The mixture was stirred and reacted at 24°C for 4 hours, and then allowed to stand for 5 minutes until the liquid was completely solidified. The solid was then dried to obtain the calcium-aluminum chloride multi-component compound.

[0044] The preparation method of the calcium-aluminum multi-component compound is as follows: a calcium-containing precursor, an aluminum-containing precursor, and an auxiliary agent are mixed and stirred evenly in a mass ratio of 1:1:0.02, and then calcined at 700℃ for 3 hours.

[0045] The calcium-containing precursor is obtained by mixing calcium oxide, carbide slag, and montmorillonite in a mass ratio of 6:3:1; the aluminum-containing precursor is obtained by mixing alumina, bauxite, and kaolinite in a mass ratio of 5:3:2; and the additive is prepared by mixing calcium petroleum sulfonate and potassium methanesulfonate in a volume ratio of 2:1.

[0046] SEM images of the obtained calcium-aluminum multi-component compounds are shown below. Figure 2 As shown, the XRD pattern is as follows Figure 3 As shown, it mainly consists of CaAl4O7 and Ca.14 Al 12 O 33 etc.

[0047] (2) The porous carbon loaded calcium-aluminum chloro-complex compound is prepared by calcining the calcium-aluminum chloro-complex compound at 200°C for 4h under nitrogen protection.

[0048] (3) The porous carbon loaded calcium-aluminum chloro-complex compound is used for removing fluorine ions in fluorine-containing wastewater. Specifically, the solid-liquid mass ratio of the porous carbon loaded calcium-aluminum chloro-complex compound to the fluorine-containing wastewater is 0.002:1, the reaction temperature is 35°C, the reaction time is 160min, and the fluorine removal efficiency can reach 99.5%.

[0049] The porous carbon loaded calcium-aluminum chloro-complex compound is used for hydrolyzing toxic gas carbonyl sulfide. The concentration of carbonyl sulfide is 500ppm, nitrogen is the balance gas, the reaction space velocity is 15000h-1, the reaction temperature is 150°C, the water vapor content is 10%, and the loading amount in the hydrolysis tower is 4% of the tower height. Under the above conditions, the hydrolysis efficiency of carbonyl sulfide is 96% after 300min. -1

[0050] Figure 1 The calcium-aluminum chloro-complex compound prepared according to the method described in Examples 1-2 is added into high-chlorine and high-concentration organic wastewater (chloride ion concentration is 2000ppm and contains metal ions such as copper, iron, zinc, potassium, manganese, lead, cadmium, and nickel) at different dosing ratios (from left to right, the solid-liquid mass ratio is 0.02:1, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, and 0.6:1) and stirred at 24°C for 4h. The sample picture after standing for 5min is shown in the following figure. Figure 1 As can be seen from the figure, when the dosing amount is 20% (solid-liquid mass ratio 0.2:1), the wastewater does not form a solidified state after standing, and when the dosing amount is 30% (solid-liquid mass ratio 0.3:1), the wastewater completely forms a solidified state after standing. The complete formation of the solidified state makes it unnecessary to discharge residual water bodies, and only calcination is needed in the subsequent process to remove the organic matter, achieving harmless treatment.

[0051] Example 3

[0052] The method is basically the same as that in Example 2, except that in step 2, the porous carbon loaded calcium-aluminum chloro-complex compound is prepared by calcining the calcium-aluminum chloro-complex compound at 300°C for 4h under nitrogen protection.

[0053] Example 4

[0054] The method is basically the same as that in Example 2, except that in step 2, the porous carbon loaded calcium-aluminum chloro-complex compound is prepared by calcining the calcium-aluminum chloro-complex compound at 400°C for 4h under nitrogen protection.​

[0055] Example 5

[0056] The process is basically the same as in Example 2, except that in step 2, nitrogen is used as the protective gas to prepare porous carbon-supported calcium-aluminum-chlorine multi-component compounds by calcination at 500°C for 4 hours.

[0057] Example 6

[0058] The process is basically the same as in Example 2, except that in step 2, nitrogen is used as a protective gas to prepare porous carbon-supported calcium-aluminum-chlorine multi-component compounds by calcination at 600°C for 4 hours.

[0059] Example 7

[0060] The process is basically the same as in Example 2, except that in step 2, nitrogen is used as a protective gas to prepare porous carbon-supported calcium-aluminum-chlorine multi-component compounds by calcination at 700°C for 4 hours.

[0061] Example 8

[0062] The process is basically the same as in Example 2, except that in step 2, nitrogen is used as the protective gas to prepare porous carbon-supported calcium-aluminum-chlorine multi-component compounds by calcination at 800°C for 4 hours.

[0063] The porous carbon-supported calcium, aluminum, and chloride multi-component compounds in Examples 2-8 (named sequentially)

[0064] The crystal phase diagrams of CL-CAOSP-200 / 300 / 400 / 500 / 600 / 700 / 800 are as follows: Figure 4 As shown, by Figure 4 It can be seen that as the calcination temperature increases, the Fred salt phase basically disappears after the calcination temperature reaches 500℃, and is transformed into calcium aluminum chloride compounds, which in turn form porous carbon-based calcium aluminum chloride compounds.

[0065] Example 9

[0066] The resource-based treatment method for high-chlorine, high-concentration organic wastewater includes the following steps:

[0067] (1) The self-made calcium-aluminum multi-component compound was mixed with high-chlorine, high-concentration organic wastewater (chloride ion concentration of 3000 ppm, and containing metal ions such as copper, iron, zinc, potassium, manganese, lead, cadmium, and nickel) at a solid-liquid mass ratio of 0.3:1. The mixture was stirred and reacted at 25°C for 4 hours, and then allowed to stand for 5 minutes until the liquid was completely solidified. The solid was then dried to obtain the calcium-aluminum chloride multi-component compound.

[0068] The preparation method of the calcium-aluminum multi-component compound is as follows: a calcium-containing precursor, an aluminum-containing precursor, and an auxiliary agent are mixed and stirred evenly at a mass ratio of 1:0.9:0.04, and then calcined at 400℃ for 5 hours.

[0069] The calcium-containing precursor is calcium hydroxide, limestone and marble mixed in a mass ratio of 5:1:4; the aluminum-containing precursor is alumina, bauxite and feldspar mixed in a mass ratio of 3:2:1; and the auxiliary agent is copper ethanesulfonate.

[0070] (2) The calcium-aluminum-chlorine multi-component compound is calcined at 600°C for 5h under the protection of helium to obtain the porous carbon loaded calcium-aluminum-chlorine multi-component compound.

[0071] (3) The porous carbon loaded calcium-aluminum-chlorine multi-component compound is used for removing fluorine ions in fluorine-containing wastewater. Specifically, the solid-liquid mass ratio of the porous carbon loaded calcium-aluminum-chlorine multi-component compound to the fluorine-containing wastewater is 0.001:1, the reaction temperature is 40°C, the reaction time is 200min, and the fluorine removal efficiency can reach 98.9%.

[0072] Example 10

[0073] The example 9 is basically the same, except that in step 3, the solid-liquid mass ratio of the porous carbon loaded calcium-aluminum-chlorine multi-component compound to the fluorine-containing wastewater is 0.003:1, and the fluorine removal efficiency can reach 99.0%.

[0074] Example 11

[0075] The example 9 is basically the same, except that in step 3, the solid-liquid mass ratio of the porous carbon loaded calcium-aluminum-chlorine multi-component compound to the fluorine-containing wastewater is 0.005:1, and the fluorine removal efficiency can reach 99.3%.

[0076] Example 12

[0077] The example 9 is basically the same, except that in step 3, the solid-liquid mass ratio of the porous carbon loaded calcium-aluminum-chlorine multi-component compound to the fluorine-containing wastewater is 0.007:1, and the fluorine removal efficiency can reach 99.4%.

[0078] Example 13

[0079] The example 9 is basically the same, except that in step 3, the solid-liquid mass ratio of the porous carbon loaded calcium-aluminum-chlorine multi-component compound to the fluorine-containing wastewater is 0.009:1, and the fluorine removal efficiency can reach 99.6%.

[0080] Example 14

[0081] The method for resourceful treatment of high-chlorine and high-concentration organic wastewater comprises the following steps:

[0082] (1)Self-made calcium-aluminum multi-element compound is mixed with high-chlorine and high-concentration organic wastewater (chloride ion concentration is 3000 ppm, and containing metal ions of copper, iron, zinc, potassium, manganese, lead, cadmium, nickel, etc.) according to solid-liquid mass ratio of 0.3:1, stirring reaction at 25℃ for 4h, then standing for 5min, the liquid is completely solidified, the solid is dried to obtain calcium-aluminum chlorine multi-element compound.

[0083] The preparation method of the calcium-aluminum multi-element compound is as follows: calcium-containing precursor, aluminum-containing precursor and auxiliary agent are mixed and stirred uniformly according to mass ratio of 1:0.6:0.1, and calcination at 700℃ for 5h.

[0084] The calcium-containing precursor is obtained by mixing calcium oxide, limestone and marble according to mass ratio of 3:3:2; the aluminum-containing precursor is obtained by mixing aluminum oxide, vein stone and feldspar according to mass ratio of 3:1:2; and the auxiliary agent is copper sulfobutandioate.

[0085] (2)The calcium-aluminum chlorine multi-element compound is calcined at 800℃ for 2h to obtain porous carbon loaded calcium-aluminum chlorine multi-element compound under the protection of nitrogen.

[0086] (3)The porous carbon loaded calcium-aluminum chlorine multi-element compound is used to hydrolyze toxic gas carbonyl sulfide, the concentration of carbonyl sulfide is 500 ppm, nitrogen is used as balance gas, the reaction space velocity is 20000h-1, the reaction temperature is 50℃, the water vapor content is 15%, and the loading amount of the porous carbon loaded calcium-aluminum chlorine multi-element compound in the hydrolysis tower is 2% of the height of the tower body. -1 Under the above conditions, the hydrolysis efficiency of carbonyl sulfide is 90% after 540min.

[0087] Example 15

[0088] The same as example 14, except that the reaction temperature in step 3 is 80℃, and the hydrolysis efficiency of carbonyl sulfide is 91.5%.

[0089] Example 16

[0090] The same as example 14, except that the reaction temperature in step 3 is 110℃, and the hydrolysis efficiency of carbonyl sulfide is 92%.

[0091] Example 17

[0092] The same as example 14, except that the reaction temperature in step 3 is 140℃, and the hydrolysis efficiency of carbonyl sulfide is 93%.

[0093] Example 18

[0094] The same as example 14, except that the reaction temperature in step 3 is 170℃, and the hydrolysis efficiency of carbonyl sulfide is 95%.

[0095] Example 19

[0096] The procedure of Example 14 was substantially the same, except that in step 3, the reaction temperature was 200°C, and the hydrolysis efficiency of the carboxyl group was 95.4%.

[0097] Example 20

[0098] The procedure of Example 14 was substantially the same, except that in step 3, the reaction temperature was 230°C, and the hydrolysis efficiency of the carboxyl group was 97%.

[0099] Comparative Example 1

[0100] The procedure of Example 2 was substantially the same, except that the commercially available high-temperature mayenite was directly used to solidify the same high-chlorine and high-concentration organic wastewater under the solidification conditions of step 1 of Example 2.

[0101] Comparative Example 3

[0102] The procedure of Example 2 was substantially the same, except that the calcium-aluminum multi-component compound was prepared under the conditions of step 1 of Example 2, but without adding the additive, and then the purity test and solidification experiment were performed, and the solidification experiment was performed under the same conditions as those of step 1 of Example 2.

[0103] Comparative Example 3

[0104] The method for resource utilization of high-chlorine and high-concentration organic wastewater comprises the following steps:

[0105] (1) The self-prepared calcium-aluminum multi-component compound is mixed with the high-chlorine and high-concentration organic wastewater (containing metal ions such as copper, iron, zinc, potassium, manganese, lead, cadmium, and nickel, and the concentration of chloride ions is 3000 ppm) at a solid-liquid mass ratio of 0.3:1, and is stirred and reacted at 25°C for 4h, and then is statically placed for 5 min, and the liquid is completely solidified, and the solid is dried to obtain a calcium-aluminum-chlorine multi-component compound.

[0106] The preparation method of the calcium-aluminum multi-component compound is as follows: the calcium-containing precursor, the aluminum-containing precursor, and the additive are uniformly mixed and stirred at a mass ratio of 1:0.9:0.04, and are calcined at 400°C for 5h.

[0107] The calcium-containing precursor is obtained by mixing calcium hydroxide, limestone, and marble at a mass ratio of 5:1:4; the aluminum-containing precursor is obtained by mixing aluminum oxide, bauxite, and feldspar at a mass ratio of 3:2:1; and the additive is copper ethanesulfonate.

[0108] (2) The calcium-aluminum-chlorine multi-component compound is directly used for removing fluoride ions in the fluoride-containing wastewater, and specifically, the solid-liquid mass ratio of the calcium-aluminum-chlorine multi-component compound to the fluoride-containing wastewater is 0.001:1, the reaction temperature is 40°C, the reaction time is 200 min, and the defluorination efficiency is 50%.

[0109] Comparative Example 4

[0110] The method for resourceful treatment of high-chlorine and high-concentration organic wastewater comprises the following steps:

[0111] (1) mixing self-made calcium-aluminum multi-element compound with high-chlorine and high-concentration organic wastewater (chloride ion concentration is 3000 ppm, and containing metal ions such as copper, iron, zinc, potassium, manganese, lead, cadmium, nickel, etc.) according to solid-liquid mass ratio of 0.3:1, stirring and reacting at 25℃ for 4h, then standing for 5min, completely solidifying the liquid, drying the solid, and obtaining calcium-aluminum chlorine multi-element compound.

[0112] The preparation method of the calcium-aluminum multi-element compound is as follows: mixing calcium-containing precursor, aluminum-containing precursor and additive according to mass ratio of 1:0.9:0.04, uniformly stirring, and calcining at 400℃ for 5h.

[0113] The calcium-containing precursor is obtained by mixing calcium hydroxide, limestone and marble according to mass ratio of 5:1:4; the aluminum-containing precursor is obtained by mixing aluminum oxide, bauxite and feldspar according to mass ratio of 3:2:1; and the additive is copper sulfobutandioate.

[0114] (2) directly using the calcium-aluminum chlorine multi-element compound to hydrolyze toxic gas carbonyl sulfur, the concentration of carbonyl sulfur is 500 ppm, nitrogen is the balance gas, the reaction space velocity is 20000h -1 , the reaction temperature is 50℃, the water vapor content is 15%, the loading amount of the calcium-aluminum chlorine multi-element compound in the hydrolysis tower is 2% of the tower height, under the above conditions, the hydrolysis efficiency of carbonyl sulfur is 45% after 540min.

[0115] Comparative Example 1 and Example 2 are subjected to solidification experiment under the same conditions, it is found that the high-temperature calcium-aluminum stone of Comparative Example 1 cannot effectively solidify the wastewater, while the calcium-aluminum multi-element compound of Example 2 can quickly and effectively solidify the wastewater, it can be seen that the prepared calcium-aluminum multi-element compound has special properties, and the content of Ca 12 Al 14 O 33 is as high as 99%, while the content of Ca 12 Al 14 O 33 in the common calcium-aluminum compound on the market is only 70%, and there is obvious difference between them.

[0116] Comparative Example 2 is prepared without adding additive, but the other conditions are the same as those of the calcium-aluminum multi-element compound of Example 2, and then the purity of the calcium-aluminum multi-element compound is tested, it is found that the purity (calculated by Ca 12 Al 14 O 33 ) of the calcium-aluminum multi-element compound prepared by Comparative Example 2 without adding additive is only 80%, a large amount of by-products (CaO, Al2O3, etc.) are generated, while the purity (calculated by Ca 12 Al14 O 33 The purity of the calcium-aluminum multi-element compound prepared in Example 2 is up to 99%, which indicates that the addition of the auxiliary in the preparation process improves the purity of the calcium-aluminum multi-element compound. The calcium-aluminum multi-element compound synthesized in Comparative Example 2 was subjected to coagulation experiment under the same conditions as Example 2, and it was found that the calcium-aluminum multi-element compound in Comparative Example 2 could only coagulate a small part of the high-chlorine and high-concentration wastewater at the same addition ratio.

[0117] It can be found from the fluorine ion removal performance detection of Comparative Example 3 and Example 9 that the fluorine ion removal efficiency is: Example 9 > Comparative Example 3. The calcium-aluminum chlorine multi-element compound in Comparative Example 3 is not calcined, so there is no loading of porous carbon. The fluorine ion removal efficiency in Example 9 is nearly 2 times that in Comparative Example 3, which shows that the loading of porous carbon can effectively improve the removal efficiency of fluorine ions.

[0118] It can be found from the hydrolysis of carbonyl sulfur performance detection of Comparative Example 4 and Example 14 that the hydrolysis efficiency is: Example 14 > Comparative Example 4. The calcium-aluminum chlorine multi-element compound in Comparative Example 4 is not calcined, so there is no loading of porous carbon. The hydrolysis efficiency of carbonyl sulfur in Example 14 is 2 times that in Comparative Example 4, which shows that the loading of porous carbon can also effectively improve the hydrolysis efficiency of carbonyl sulfur.

[0119] In summary, the method for treating high-chlorine and high-concentration organic wastewater provided by the present application first mixes and stirs the calcium-containing precursor, the aluminum-containing precursor and the auxiliary in a mass ratio of 1:(0.5-1.0):(0.02-0.1) uniformly, then calcines at 200-700°C for 2-5h to prepare a calcium-aluminum multi-element compound, adds the calcium-aluminum multi-element compound as a coagulant to the high-chlorine and high-concentration organic wastewater at a low amount to simultaneously fix the chlorine ions and heavy metals, then calcines the coagulation product to obtain a porous carbon-loaded calcium-aluminum chlorine multi-element compound and use it as an adsorbent for treating fluorine-containing wastewater and toxic gas carbonyl sulfur, thereby realizing the high-value resource treatment of high-chlorine and high-concentration organic wastewater and having good economic benefits. The calcium-aluminum multi-element compound material has the advantages of stable coagulation, resource utilization and high safety, and can be widely used in the treatment of actual wastewater. The high-chlorine and high-concentration organic wastewater and the calcined product of the coagulation product have good effects on removing fluorine ions and degrading carbonyl sulfur; and the chlorine ions and heavy metals in the high-chlorine and high-concentration organic wastewater also have a promoting effect on the removal of fluorine ions and the hydrolysis of carbonyl sulfur.

[0120] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the scope of protection of the present application.

Claims

1. A method for the resource-based treatment of chlorine-containing organic wastewater, characterized in that, Includes the following steps: S1. Calcium source, aluminum source and additives are mixed in a mass ratio of 1:(0.5-1):(0.02-0.1) and then calcined to obtain a calcium-aluminum multi-component compound; wherein the additives are oil-soluble metal salts, including one or more naphthenates or sulfonates of magnesium, calcium, iron, manganese, cobalt, nickel and copper. S2. Add calcium-aluminum multi-component compounds to chlorine-containing organic wastewater at a solid-liquid mass ratio of (0.25-0.4):1, stir, and let stand to obtain wastewater coagulation products; S3. Calcine the coagulated wastewater products to obtain porous carbon-supported calcium, aluminum, and chloride multi-component compounds. S4. Use porous carbon-supported calcium-aluminum-chlorine multi-component compounds for the removal of fluoride ions in fluoride-containing wastewater and / or the degradation of carbonyl sulfides in gases.

2. The method for resource-based treatment of chlorine-containing organic wastewater according to claim 1, characterized in that, The calcium source is one or more of the following: calcium oxide, calcium hydroxide, carbide slag, limestone, dolomite, gypsum, apatite, montmorillonite, and marble. The aluminum source is one or more of the following: alumina, aluminum sulfate, bauxite, bauxite, gangue, feldspar, mica, kaolinite, and alunite.

3. The method for resource-based treatment of chlorine-containing organic wastewater according to claim 1, characterized in that, In step S1, the calcination conditions are: 200-700℃, 2-5h.

4. The method for resource-based treatment of chlorine-containing organic wastewater according to claim 1, characterized in that, In step S2, the concentration of chloride ions in the chlorinated organic wastewater is ≥200ppm.

5. The method for resource-based treatment of chlorine-containing organic wastewater according to claim 1, characterized in that, In step S2, the chlorinated organic wastewater also contains copper, iron, zinc, potassium, manganese, lead, cadmium, and nickel ions.

6. The method for resource-based treatment of chlorine-containing organic wastewater according to claim 1, characterized in that, In step S2, the stirring conditions are: 10-40℃, 1-4h.

7. The method for resource-based treatment of chlorine-containing organic wastewater according to claim 1, characterized in that, In step S3, the calcination conditions are: 500-800℃ for 1-4 hours under a nitrogen or argon atmosphere.

8. The method for resource-based treatment of chlorine-containing organic wastewater according to claim 1, characterized in that, In step S4, the specific method for using porous carbon-supported calcium-aluminum-chlorine multi-component compound to remove fluoride ions from fluoride-containing wastewater is as follows: the porous carbon-supported calcium-aluminum-chlorine multi-component compound is mixed with fluoride ions in fluoride-containing wastewater at a solid-liquid mass ratio of (0.001-0.01):1, and the mixture is reacted at 0-60℃ for 10-240 min.

9. The method for resource-based treatment of chlorine-containing organic wastewater according to claim 1, characterized in that, In step S4, the specific method for using porous carbon-supported calcium-aluminum-chlorine multi-component compounds for the degradation of carbonyl sulfide in gas is as follows: the porous carbon-supported calcium-aluminum-chlorine multi-component compounds are loaded into the hydrolysis tower at a loading rate of 1-6% of the tower height, the carbonyl sulfide concentration is 200-1000 ppm, nitrogen is used as the balance gas, the water vapor content is 5-15%, and the space velocity is 2000-20000 h⁻¹. -1 The reaction temperature is 50-230℃, and the reaction time is 2-24h.

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