Resourceful treatment method of chlorine-containing organic wastewater

Abstract

The invention discloses a resourceful treatment method of chlorine-containing organic wastewater, which comprises the following steps: mixing a calcium source, an aluminum source and an auxiliary agent, and calcining to obtain a calcium-aluminum multi-component compound; the method comprises the following steps: adding a calcium-aluminum multi-component compound into chlorine-containing organic wastewater according to a solid-liquid mass ratio of (0.25-0.4): 1, stirring, and standing to obtain a wastewater solidification product; calcining the wastewater solidification product to obtain a porous carbon loaded calcium-aluminum-chlorine multi-component compound; the porous carbon loaded calcium-aluminum-chlorine multi-component compound is used for removing fluorine ions in fluorine-containing wastewater and / or degrading carbonyl sulfide in gas. According to the method, the high-chlorine and high-concentration organic wastewater can be solidified by adding a small amount of the self-made calcium-aluminum multi-component compound and is converted into a solid phase from a liquid phase, so that harmless treatment on the wastewater is achieved, and a solidified product can be converted into a high-added-value product for removing fluorine ions in a water body or toxic gas in hydrolyzed gas; and resource utilization is realized.

Description

Technical Field

[0001] The invention relates to a resource treatment method for chlorine-containing organic wastewater, belonging to the technical field of harmless and resource treatment of organic wastewater. Background Art

[0002] High-chlorine and high-concentration organic wastewater is highly toxic and dark in color. It is a type of wastewater that is difficult to treat. It contains a large amount of chloride salts and high-concentration difficult-to-degrade organic matter, and there will be a certain amount of heavy metals and plant nutrients (ammonia nitrogen, etc.). Among them, there are many types of organic pollutants, including non-chlorinated aromatic compounds such as naphthalene / phenanthrene, 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 deep treatment technology, but most of these methods are relatively complicated and costly. The most common landfill method is relatively simple and low-cost, and can treat a large amount of waste, but landfill requires a lot of land, and long-term use will occupy a lot of land resources, causing waste of land resources. In addition, harmful substances in the waste may seep into groundwater and soil, causing environmental pollution and posing a potential threat 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 environmentally friendly agents based on existing research and applications to achieve the removal or stabilization of various anions and cations in wastewater, and the solidification / solidification method is an effective method that can simultaneously achieve the coordinated 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. The method defines the mass percentage components of the slag base in detail and proposes to use the product as a roadbed material or building material. However, the method and subsequent resource utilization are not suitable for the treatment of high-chlorine and high-concentration organic wastewater.

[0005] Calcium aluminum polynary compounds are a type of water treatment agent with good anion and cation removal performance. They have received extensive attention in recent years due to their advantages such as resistance to hydration and corrosion, excellent mechanical properties, and high stability in reducing atmospheres. However, there are few studies on the preparation and solidification application of calcium aluminum polynary compounds at home and abroad, and most of the preparations are made by high-temperature calcination, which not only has high preparation costs, but also has low activity in wastewater treatment. In addition, most of the calcium aluminum compounds on the market use chemical precipitation to treat high-chlorine and high-concentration organic wastewater, with a large dosage, and some hazardous substances still remain in the treated high-chlorine and high-concentration organic wastewater. It is necessary to continue to find subsequent treatment methods for high-chlorine and high-concentration organic wastewater, which consumes a lot of manpower and material resources and has poor economic benefits. Solidification effectively avoids the above shortcomings. However, the calcium aluminum compounds used on the market need to be added in high proportions to solidify high-chlorine and high-concentration organic wastewater, and the consumption is huge. Summary of the invention

[0006] The purpose of the present invention is to provide a method for resource recovery treatment of chlorine-containing organic wastewater. By adding a low amount of a homemade calcium-aluminum multi-component compound, high-chlorine and high-concentration organic wastewater can be solidified and converted from a liquid phase to a solid phase, thereby achieving harmless treatment of the wastewater. The solidified product can also be converted into a high-value-added product for removing fluoride ions in water bodies or toxic gases in hydrolyzed gases, thereby achieving resource recovery.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is:

[0008] A method for recycling chlorine-containing organic wastewater comprises the following steps:

[0009] S1, mixing a calcium source, an aluminum source and an additive and calcining the mixture to obtain a calcium-aluminum multinary compound;

[0010] S2, adding calcium aluminum polynary 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 coagulation product;

[0011] S3, calcining the wastewater solidification product to obtain porous carbon loaded with calcium, aluminum and chlorine polyvalent compounds;

[0012] S4. Using porous carbon loaded with calcium aluminum chloride polyvalent compounds to remove fluoride ions from fluoride-containing wastewater and / or degrade carbonyl sulfide in gas.

[0013] Preferably, in step S1, the mass ratio of the calcium-containing precursor, the aluminum-containing precursor and the auxiliary agent 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 aluminum oxide, aluminum sulfate, bauxite, bauxite, gangue, feldspar, mica, kaolinite, and alunite;

[0016] The additive is an oil-soluble metal salt, including one or more of cyclopentane salts or sulfonates of magnesium, calcium, iron, manganese, cobalt, nickel and copper.

[0017] Preferably, in step S1, the calcination conditions are: 200-700°C, 2-5h.

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

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

[0020] Preferably, in step S2, the stirring conditions are: 10-40° C., 1-4 h.

[0021] Preferably, in step S3, the calcination conditions are: under nitrogen or argon atmosphere, 500-800° C., 1-4 h.

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

[0023] Preferably, in step S4, the specific method of using the porous carbon-supported calcium aluminum chloride polynary compound for the degradation of carbonyl sulfide in the gas is: the porous carbon-supported calcium aluminum chloride polynary compound is loaded into the hydrolysis tower in an amount of 1-6% of the tower height, the carbonyl sulfide concentration is 200-1000ppm, nitrogen is the balance gas, the water vapor content is 5-15%, and the space velocity is 2000-20000h -1 , the reaction temperature is 50-230℃, 2-24h.

[0024] The beneficial effects of the present invention are:

[0025] Calcium aluminum polynary compounds have strong activity. The coagulant produced by the one-step method of low-temperature calcination can save a lot of manpower and electricity, and can greatly reduce costs. It also has the advantages of simple process equipment and easy control. At present, most calcium aluminum compounds are produced by high-temperature (1200°C) reaction sintering method. The obtained calcium aluminum compound materials have problems such as high density, low specific surface area, serious particle agglomeration, low activity, and excessive addition. The calcium aluminum polynary compound prepared by the present invention can overcome these defects. This patent can prepare calcium aluminum polynary compound materials by calcining at a temperature of 200-700°C through a mixed sintering method. It is used to treat high-chlorine and high-concentration organic wastewater. It can be converted from liquid phase to solid phase with a low dosage, which greatly reduces the difficulty of treatment and reduces the danger to the environment. The porous carbon formed by calcining the solidified product is used to load the calcium aluminum chlorine polynary compound to treat fluorine-containing wastewater and toxic gases such as carbonyl sulfide or hydrogen sulfide, realizing resource utilization.

[0026] In addition, the calcium ions in the calcium-aluminum polyvalent compound can reduce the surface charge of suspended matter and colloids in the wastewater through electrical neutralization, causing them to lose stability, resulting in the aggregation of particles and the formation of larger flocs. Aluminum ions will undergo hydrolysis in water to form aluminum hydroxy complexes, which have strong flocculation and adsorption effects. In addition, the calcium ions and aluminum ions in the calcium-aluminum polyvalent compound can also undergo precipitation reactions with some anions in the wastewater, and the resulting precipitates have high stability.

[0027] During the preparation of calcium aluminum multinary compounds, additives are added to allow the reaction process to release a large amount of heat, accelerate the reaction rate, allow the chemical reaction to reach a state of equilibrium, reduce the generation of impurity phases, improve the fluidity and diffusivity of the reaction substances, provide reactive substances, and thus obtain high-purity calcium aluminum multinary compounds, providing a good matrix for subsequent resource utilization. Through morphological characterization, it can be observed that the calcium aluminum multinary compound has a coral-like particle morphology, a small amount of flaky crystals, and a rich oxygen vacancy on the surface of the material, indicating that the charge storage capacity is very strong. Usually, 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 in the calcium aluminum multinary compound prepared by the present invention overcomes this shortcoming. The more surface oxygen vacancies, the more conducive it is to the hydrolysis / adsorption of fluoride ions as oxygen-containing pollutants by the porous carbon-loaded calcium aluminum chloride multinary compound obtained by subsequent calcination.

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

[0029] Figure 1 The figure is a graph showing the coagulation effect of different dosages of the calcium aluminum polynary compound prepared in Examples 1 and 2 on wastewater;

[0030] Figure 2 This is a SEM image of the calcium-aluminum multinary compound prepared in Example 2;

[0031] Figure 3 This is the XRD pattern of the calcium aluminum polynary compound prepared in Example 2;

[0032] Figure 4 This is the XRD diagram of the porous carbon loaded with calcium aluminum chloride polyvalent compound obtained in Example 2-8. DETAILED DESCRIPTION

[0033] Example 1

[0034] A method for recycling high-chlorine and high-concentration organic wastewater comprises the following steps:

[0035] (1) The self-made calcium aluminum polynary compound was mixed with high-chloride and high-concentration organic wastewater (chloride ion concentration of 2000 ppm, and containing metal ions such as copper, iron, zinc, potassium, manganese, lead, cadmium, nickel, etc.) at a solid-liquid mass ratio of 0.2:1, and reacted for 4 hours under stirring at 24°C, and then allowed to stand for 5 minutes. The solid-liquid separation was performed for the incomplete solidification, and then the solid was dried to obtain the calcium aluminum chlorine polynary compound.

[0036] The preparation method of the calcium-aluminum multinary 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 the mixture is calcined at 700°C for 3 hours.

[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 aluminum oxide, bauxite and kaolinite in a mass ratio of 5:3:2; and the auxiliary agent is obtained by preparing calcium petroleum sulfonate and potassium methane sulfonate in a volume ratio of 2:1.

[0038] (2) Using nitrogen as a protective gas, the calcium aluminum chloride polyvalent compound was calcined at 500°C for 4 hours to obtain a porous carbon-loaded calcium aluminum chloride polyvalent compound.

[0039] (3) The porous carbon-loaded calcium aluminum chlorine polyvalent compound is used to remove fluoride ions from fluoride-containing wastewater. Specifically, the solid-liquid mass ratio of the porous carbon-loaded calcium aluminum chlorine polyvalent compound to the fluoride-containing wastewater is 0.007:1, the reaction temperature is 25°C, the reaction time is 180 min, and the fluoride removal efficiency can reach 99.5%.

[0040] The porous carbon-supported calcium aluminum chloride polyvalent compound was used to hydrolyze the toxic gas carbonyl sulfide. The carbonyl sulfide concentration was 500 ppm, nitrogen was used as the balance gas, and the reaction space velocity was 20000 h -1 The reaction temperature is 170°C, the water vapor content is 15%, and the loading amount of porous carbon-loaded calcium aluminum chloride polyvalent compounds in the hydrolysis tower is 2% of the tower height. Under the above conditions, the hydrolysis efficiency of carbonyl sulfide is 92% after 300 minutes.

[0041] Example 2

[0042] A method for recycling high-chlorine and high-concentration organic wastewater comprises the following steps:

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

[0044] The preparation method of the calcium-aluminum multinary 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 the mixture is calcined at 700°C 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 aluminum oxide, bauxite and kaolinite in a mass ratio of 5:3:2; and the auxiliary agent is obtained by preparing calcium petroleum sulfonate and potassium methane sulfonate in a volume ratio of 2:1.

[0046] The SEM image of the obtained calcium aluminum multi-component compound is as follows: Figure 2 As shown, the XRD pattern is Figure 3 As shown, it is mainly composed of CaAl4O7, Ca14 Al 12 O 33 wait.

[0047] (2) Using nitrogen as a protective gas, the calcium aluminum chloride polyvalent compound was calcined at 200°C for 4 hours to obtain a porous carbon-loaded calcium aluminum chloride polyvalent compound.

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

[0049] The porous carbon-supported calcium aluminum chloride polyvalent compound was used to hydrolyze the toxic gas carbonyl sulfide. The carbonyl sulfide concentration was 500 ppm, nitrogen was used as the balance gas, and the reaction space velocity was 15000 h -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, after 300 minutes, the hydrolysis efficiency of carbonyl sulfide is 96%.

[0050] Figure 1 The calcium aluminum polyvalent compound was prepared according to the method described in Example 1-2, and different addition ratios (from left to right, the corresponding solid-liquid mass ratios are 0.02:1, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1) were added to 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, nickel, etc.), stirred at 24°C for 4h, and then left to stand for 5min. Figure 1 It can be seen that when the dosage is 20% (solid-liquid mass ratio 0.2:1), the wastewater does not form a solidified state after standing, while when the dosage 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 the residual water additionally. It only needs to be calcined later to achieve the removal of organic matter and achieve harmless treatment.

[0051] Example 3

[0052] It is basically the same as Example 2, except that in step 2, nitrogen is used as the protective gas, and the porous carbon-loaded calcium aluminum chloride polyvalent compound is prepared by calcining at 300° C. for 4 hours.

[0053] Example 4

[0054] It is basically the same as Example 2, except that in step 2, nitrogen is used as the protective gas, and the porous carbon-loaded calcium aluminum chloride polyvalent compound is prepared by calcining at 400° C. for 4 hours.

[0055] Example 5

[0056] It is basically the same as Example 2, except that in step 2, nitrogen is used as the protective gas, and the porous carbon-loaded calcium aluminum chloride polyvalent compound is prepared by calcining at 500° C. for 4 hours.

[0057] Example 6

[0058] It is basically the same as Example 2, except that in step 2, nitrogen is used as the protective gas, and the porous carbon-loaded calcium aluminum chloride polyvalent compound is prepared by calcining at 600° C. for 4 hours.

[0059] Example 7

[0060] It is basically the same as Example 2, except that in step 2, nitrogen is used as the protective gas, and the porous carbon-loaded calcium aluminum chloride polyvalent compound is prepared by calcining at 700° C. for 4 hours.

[0061] Example 8

[0062] It is basically the same as Example 2, except that in step 2, nitrogen is used as the protective gas, and the porous carbon-loaded calcium aluminum chloride polyvalent compound is prepared by calcining at 800° C. for 4 hours.

[0063] The porous carbon-supported calcium aluminum chloride polyvalent compounds obtained in Examples 2-8 (named

[0064] The crystal phase diagram of CL-CAOSP-200 / 300 / 400 / 500 / 600 / 700 / 800) is as follows Figure 4 As shown by Figure 4 It can be seen that with the increase of calcination temperature, after the calcination temperature reaches 500°C, the Friedel salt phase basically disappears and is converted into a calcium aluminum chloride compound, thereby forming a porous carbon multi-calcium aluminum chloride multi-compound.

[0065] Example 9

[0066] A method for recycling high-chlorine and high-concentration organic wastewater comprises the following steps:

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

[0068] The preparation method of the calcium-aluminum multinary 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 1:0.9:0.04, and the mixture is calcined at 400° C. for 5 hours.

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

[0070] (2) Using helium as a protective gas, the calcium aluminum chloride polyvalent compound was calcined at 600°C for 5 hours to obtain a porous carbon-loaded calcium aluminum chloride polyvalent compound.

[0071] (3) The porous carbon-loaded calcium aluminum chloride polyvalent compound is used to remove fluoride ions from fluoride-containing wastewater. Specifically, the solid-liquid mass ratio of the porous carbon-loaded calcium aluminum chloride polyvalent compound to the fluoride-containing wastewater is 0.001:1, the reaction temperature is 40°C, the reaction time is 200 min, and the fluoride removal efficiency can reach 98.9%.

[0072] Example 10

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

[0074] Embodiment 11

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

[0076] Example 12

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

[0078] Embodiment 13

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

[0080] Embodiment 14

[0081] A method for recycling high-chlorine and high-concentration organic wastewater comprises the following steps:

[0082] (1) The self-made calcium aluminum multi-component compound was mixed with high-chloride and high-concentration organic wastewater (chloride ion concentration of 3000 ppm, and containing metal ions such as copper, iron, zinc, potassium, manganese, lead, cadmium, nickel, etc.) at a solid-liquid mass ratio of 0.3:1, stirred and reacted at 25°C for 4 hours, and then allowed to stand for 5 minutes. The liquid was completely solidified, and the solid was dried to obtain a calcium aluminum chlorine multi-component compound.

[0083] The preparation method of the calcium-aluminum multinary 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 1:0.6:0.1, and the mixture is calcined at 700° C. for 5 hours.

[0084] The calcium-containing precursor is obtained by mixing calcium oxide, limestone and marble in a mass ratio of 3:3:2; the aluminum-containing precursor is obtained by mixing aluminum oxide, gangue and feldspar in a mass ratio of 3:1:2; and the auxiliary agent is copper sulfosuccinate.

[0085] (2) Using nitrogen as a protective gas, the calcium aluminum chloride polyvalent compound was calcined at 800°C for 2 hours to obtain a porous carbon-loaded calcium aluminum chloride polyvalent compound.

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

[0087] Embodiment 15

[0088] The process is substantially the same as Example 14, except that in step 3, the reaction temperature is 80° C. and the hydrolysis efficiency of carbonyl sulfide is 91.5%.

[0089] Example 16

[0090] The process is substantially the same as Example 14, except that in step 3, the reaction temperature is 110° C. and the hydrolysis efficiency of carbonyl sulfide is 92%.

[0091] Embodiment 17

[0092] The process is substantially the same as Example 14, except that in step 3, the reaction temperature is 140° C., and the hydrolysis efficiency of carbonyl sulfide is 93%.

[0093] Embodiment 18

[0094] The process is substantially the same as Example 14, except that in step 3, the reaction temperature is 170° C. and the hydrolysis efficiency of carbonyl sulfide is 95%.

[0095] Embodiment 19

[0096] The method is substantially the same as Example 14, except that in step 3, the reaction temperature is 200° C. and the hydrolysis efficiency of carbonyl sulfide is 95.4%.

[0097] Embodiment 20

[0098] The process is substantially the same as Example 14, except that in step 3, the reaction temperature is 230° C., and the hydrolysis efficiency of carbonyl sulfide is 97%.

[0099] Comparative Example 1

[0100] Commercially available high-temperature calcium aluminum stone was directly used to solidify the same high-chlorine and high-concentration organic wastewater according to the solidification conditions in step 1 of Example 2.

[0101] Comparative Example 3

[0102] The calcium aluminum polynary compound was prepared according to the conditions of step 1 of Example 2, but without adding auxiliary agents, and then subjected to purity test and solidification experiment. The solidification experiment conditions were the same as those in step 1 of Example 2.

[0103] Comparative Example 3

[0104] A method for recycling high-chlorine and high-concentration organic wastewater comprises the following steps:

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

[0106] The preparation method of the calcium-aluminum multinary 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 1:0.9:0.04, and the mixture is calcined at 400° C. for 5 hours.

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

[0108] (2) The calcium aluminum chlorine polynary compound is directly used to remove fluoride ions in fluoride-containing wastewater. Specifically, the solid-liquid mass ratio of the calcium aluminum chlorine polynary compound to the fluoride-containing wastewater is 0.001:1, the reaction temperature is 40°C, the reaction time is 200 minutes, and the fluoride removal efficiency is 50%.

[0109] Comparative Example 4

[0110] A method for recycling high-chlorine and high-concentration organic wastewater comprises the following steps:

[0111] (1) The self-made calcium aluminum multi-component compound was mixed with high-chloride and high-concentration organic wastewater (chloride ion concentration of 3000 ppm, and containing metal ions such as copper, iron, zinc, potassium, manganese, lead, cadmium, nickel, etc.) at a solid-liquid mass ratio of 0.3:1, stirred and reacted at 25°C for 4 hours, and then allowed to stand for 5 minutes. The liquid was completely solidified, and the solid was dried to obtain a calcium aluminum chlorine multi-component compound.

[0112] The preparation method of the calcium-aluminum multinary 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 1:0.9:0.04, and the mixture is calcined at 400° C. for 5 hours.

[0113] The calcium-containing precursor is obtained by mixing calcium hydroxide, limestone and marble in a mass ratio of 5:1:4; the aluminum-containing precursor is obtained by mixing aluminum oxide, bauxite and feldspar in a mass ratio of 3:2:1; and the auxiliary agent is copper sulfosuccinate.

[0114] (2) The calcium aluminum chloride polyvalent compound is directly used to hydrolyze the toxic gas carbonyl sulfide. The carbonyl sulfide concentration is 500 ppm, nitrogen is the balance gas, and the reaction space velocity is 20000 h -1 The reaction temperature is 50°C, the water vapor content is 15%, and the calcium aluminum chloride polyvalent compound loading in the hydrolysis tower is 2% of the tower height. Under the above conditions, after 540 minutes, the hydrolysis efficiency of carbonyl sulfide is 45%.

[0115] Comparative Example 1 and Example 2 were subjected to coagulation experiments under the same conditions. It was found that the high-temperature calcium aluminum alloy of Comparative Example 1 could not effectively coagulate the wastewater, while the calcium aluminum alloy of Example 2 could quickly and effectively coagulate the wastewater. It can be seen that the prepared calcium aluminum alloy has particularity, and Ca 12 Al 14 O 33 The content of calcium aluminum compounds is as high as 99%, while the common calcium aluminum compounds on the market, Ca 12 Al 14 O 33 The content of is only 70%, there is a significant difference between the two.

[0116] Comparative Example 2 was prepared without adding an additive but the other conditions were the same as those in Example 2. After the purity test was performed, it was found that the purity of the calcium aluminum polyvalent compound prepared in Comparative Example 2 without adding an additive (measured in terms of Ca 12 Al 14 O 33 The purity of the calcium aluminum polyvalent compound prepared in Example 2 (in terms of Ca 12 Al14 O 33 The calcium aluminum polynary compound synthesized in Comparative Example 2 was subjected to a coagulation experiment under the same conditions as Example 2, and it was found that under the same addition ratio, the calcium aluminum polynary compound in Comparative Example 2 could only coagulate a small portion of high-chlorine and high-concentration wastewater.

[0117] From the fluoride ion removal performance test of Comparative Example 3 and Example 9, it can be found that the fluoride ion removal efficiency is: Example 9>Comparative Example 3. The calcium aluminum chloride polyvalent compound in Comparative Example 3 has not been calcined, so there is no porous carbon loading. The fluoride ion removal efficiency in Example 9 is nearly twice that in Comparative Example 3, which shows that the loading of porous carbon can effectively improve the fluoride ion removal efficiency.

[0118] From the performance test of hydrolyzing carbonyl sulfide of Comparative Example 4 and Example 14, it can be found that the hydrolysis efficiency is: Example 14>Comparative Example 4. The calcium aluminum chloride polyvalent compound in Comparative Example 4 has not been calcined, so there is no porous carbon loading. The hydrolysis efficiency of carbonyl sulfide in Example 14 is twice that of Comparative Example 4, which shows that the loading of porous carbon can also effectively improve the hydrolysis efficiency of carbonyl sulfide.

[0119] In summary, the method for treating high-chlorine and high-concentration organic wastewater provided by the present invention is to first mix and stir the calcium-containing precursor with the aluminum-containing precursor and the auxiliary agent in a mass ratio of 1: (0.5-1.0): (0.02-0.1) and then calcine at 200-700°C for 2-5h to obtain a calcium-aluminum multinary compound, and add the calcium-aluminum multinary compound as a coagulant in a low amount to the high-chlorine and high-concentration organic wastewater to fix chloride ions and heavy metals simultaneously, and then calcine the solidified product to obtain a porous carbon-loaded calcium-aluminum-chlorine multinary compound and use it as an adsorbent for treating fluorine-containing wastewater and toxic gas carbonyl sulfide, thereby realizing high-value resource treatment of high-chlorine and high-concentration organic wastewater, with good economic benefits. Among them, the calcium-aluminum multinary 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 calcination of the solidified product of high-chlorine and high-concentration organic wastewater and calcium-aluminum multi-compound has a good effect on removing fluoride ions and degrading carbonyl sulfide; and the chloride ions and heavy metals contained in the high-chlorine and high-concentration organic wastewater also promote the removal of fluoride ions and the hydrolysis of carbonyl sulfide.

[0120] The above is only a preferred implementation of the patent of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the patent of the present invention. These improvements and modifications should also be regarded as the scope of protection of the patent of the present invention.

Claims

1. A method for recycling chlorine-containing organic wastewater, characterized in that: The steps include: S1, mixing a calcium source, an aluminum source and an additive and calcining the mixture to obtain a calcium-aluminum multinary compound; S2, adding calcium aluminum polynary 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 coagulation product; S3, calcining the wastewater solidification product to obtain porous carbon loaded with calcium, aluminum and chlorine polyvalent compounds; S4. Using porous carbon loaded with calcium aluminum chloride polyvalent compounds to remove fluoride ions from fluoride-containing wastewater and / or degrade carbonyl sulfide in gas.

2. The method for recycling chlorine-containing organic wastewater according to claim 1, characterized in that: In step S1, the mass ratio of the calcium-containing precursor, the aluminum-containing precursor and the auxiliary agent is 1:(0.5-1):(0.02-0.1).

3. The resource treatment method for chlorine-containing organic wastewater according to any one of claims 1 or 2, characterized in that: The calcium source is one or more of calcium oxide, calcium hydroxide, carbide slag, limestone, dolomite, gypsum, apatite, montmorillonite and marble; The aluminum source is one or more of aluminum oxide, aluminum sulfate, bauxite, bauxite, gangue, feldspar, mica, kaolinite, and alunite; The additive is an oil-soluble metal salt, including one or more of cyclopentane salts or sulfonates of magnesium, calcium, iron, manganese, cobalt, nickel and copper.

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

5. The method for recycling chlorine-containing organic wastewater according to claim 1, characterized in that: In step S2, the concentration of chloride ions in the chlorine-containing organic wastewater is ≥200 ppm.

6. The resource treatment method for chlorine-containing organic wastewater according to any one of claims 1 or 2, characterized in that: In step S2, the chlorine-containing organic wastewater also contains copper, iron, zinc, potassium, manganese, lead, cadmium and nickel ions.

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

8. The method for recycling chlorine-containing organic wastewater according to claim 1, characterized in that: In step S3, the calcination conditions are: under nitrogen or argon atmosphere, 500-800° C., 1-4 h.

9. The resource treatment method for chlorine-containing organic wastewater according to claim 1, characterized in that: In step S4, the specific method of using porous carbon-loaded calcium aluminum chloride polynary compound to remove fluoride ions in fluoride-containing wastewater is as follows: the porous carbon-loaded calcium aluminum chloride polynary compound is mixed with fluoride ions in the fluoride-containing wastewater in a solid-liquid mass ratio of (0.001-0.01):1, and reacted at 0-60°C for 10-240 minutes.

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

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