A method for treating coking sulfur paste

Abstract

The present invention relates to the technical field of coal chemical product treatment, and specifically discloses a method for treating coking sulfur paste. The method for treating coking sulfur paste comprises the following steps: adding water to the pretreated coking sulfur paste to separate out water-soluble impurities; after centrifugation, separating out impurities such as coal powder according to density differences; performing microwave-assisted ethanol extraction to separate out benzenes and some polycyclic aromatic hydrocarbons; extracting with a second extractant, separating out phenanthrenes, and further preparing high-purity sulfur. At the same time, the present invention also treats the waste liquid generated in the above method with a composite microbial agent, effectively degrading safety monitoring indicators such as thiosulfates, thiocyanates, and polycyclic aromatic hydrocarbons (PAHs) in the waste liquid. The method for treating coking sulfur paste provided by the present invention has low energy consumption, low cost, no waste gas generation, and takes into account the effective treatment of waste liquid, having good economic and environmental benefits. The present invention can be applied to fields such as the treatment of coking sulfur paste, the preparation of sulfur, and the treatment of coking wastewater.

Description

Technical Field

[0001] The present invention relates to the technical field of coal chemical product treatment, and specifically discloses a method for treating coking sulfur paste. Background Art

[0002] At present, nearly 85% of coal chemical enterprises adopt the wet oxidation method to purify H2S. A large amount of low-grade sulfur is produced during the process of removing H2S by the wet oxidation method, with an annual output of about 800,000 tons nationwide. Among them, coking sulfur paste is the main form. Due to its composition containing, in addition to sulfur, desulfurization by-products such as NH4SCN and (NH4)2S2O3, desulfurization catalysts, and tar-like organic substances and other impurities, it has become a difficult-to-utilize and highly polluting industrial solid waste. At present, there is no economical and effective treatment scheme for coking sulfur paste. How to treat coking sulfur paste has become a technical problem faced by all relevant enterprises, which has severely restricted the sustainable environmental protection development of industries such as coking and chemical fertilizers. Therefore, whether it is to protect the ecological environment or improve the economic benefits of enterprises, it is urgent to carry out research on the resource treatment and utilization of coking sulfur paste.

[0003] In the prior art, the methods for preparing sulfur from coking sulfur paste mainly include three categories: the melting method, the gasification method, and the solvent method. Among them, the melting method requires heating the sulfur-containing material above the melting point of sulfur (119 °C), and the gasification method requires heating the raw material to 450 °C to sublime the sulfur in the coking sulfur paste into sulfur vapor. Both of them not only have relatively high requirements for equipment and high energy consumption, but also cause serious secondary pollution. The solvent method generally has deficiencies such as the extraction agent being more expensive than sulfur, having higher toxicity, poor operating environment, relatively high requirements for equipment, slow reaction speed, and low sulfur quality. It also does not comprehensively consider the treatment of the waste liquid generated during the process of preparing sulfur from coking sulfur paste. Summary of the Invention

[0004] In view of the above technical problems, the present invention provides a method for treating coking sulfur paste with low energy consumption, low cost, no pollution, and the entire process being safe and reliable.

[0005] To solve the above technical problems, the present invention adopts the following technical solutions:

[0006] The present invention provides a method for treating coking sulfur paste, characterized in that the treatment method includes the following steps:

[0007] Step 1: Add water to the pretreated coking sulfur paste, stir, and centrifuge to obtain precipitate I and supernatant I;

[0008] Step 2: Separate the precipitate I according to the layering situation to obtain upper precipitate II and lower precipitate II;

[0009] Step 3: Add ethanol to the lower layer precipitate II and perform the first extraction under microwave conditions to obtain extraction phase I and raffinate phase I;

[0010] Step 4: Add a second extractant to the raffinate phase I and perform the second extraction to obtain extraction phase II and raffinate phase II;

[0011] Step 5: Dry the raffinate phase II to obtain sulfur; concentrate and recover the second extractant from the extraction phase II, and dry it to obtain phenanthrene substances;

[0012] Step 6: Recover ethanol from the extraction phase I to obtain mixture I;

[0013] Step 7: Mix the mixture I with the supernatant I to obtain wastewater, dilute it, inoculate with a composite microbial agent, and perform fermentation culture to obtain treated wastewater;

[0014] Among them, the composite microbial agent includes Micromonospora, Fusarium oxysporum, Bacillus velezensis, Pseudomonas, and Hydrogenophaga palleronii.

[0015] Through the density difference of different substances and their solubility differences in different solvents, the present invention removes water-soluble impurities, other impurities, and organic impurities in coking sulfur paste step by step through dissolution, extraction, and separation, and obtains high-purity sulfur; at the same time, using the biodegradation method, it effectively degrades safety monitoring indicators such as thiosulfate, thiocyanate, and polycyclic aromatic hydrocarbons (PAHs) in the wastewater generated during the treatment of coking sulfur paste. The treated wastewater can be further treated deeply. The treatment method of coking sulfur paste provided by the present invention has low energy consumption, low cost, and no waste gas generation, and has good economic and environmental benefits.

[0016] In Step 1, water is added to the pretreated coking sulfur paste. After stirring and standing, water-soluble impurities such as ammonium thiocyanate, ammonium thiosulfate, ferrous sulfate, PDS, and hydroquinone in the coking sulfur paste dissolve in water.

[0017] In Step 2, coal powder or coke powder inevitably mixed during the preparation of coking sulfur paste. The present invention utilizes the density difference between coal powder or coke powder and sulfur, and according to the stratification situation and color difference of the precipitate I after centrifugation, separates the upper layer precipitate II - coal powder or coke powder from the lower layer precipitate II - a mixture containing sulfur and water-insoluble impurities.

[0018] In Step 3, the microwave-assisted extraction process mainly includes four steps: the target components and the extraction solvent absorb microwave radiation energy; the target components accelerate vibration and separate from the sample; the target components are fully dissolved in the extraction solvent; the target components are collected and the extraction solvent is recovered. Since the dielectric constants of various compounds are different, their absorption of microwave energy is also different. Therefore, the selection of the extraction solvent is crucial. The selection of the extraction solvent is of great importance. First of all, the extraction solvent must have a certain polarity. The greater its polarity, the greater its acceptance of microwave energy, and it can generate a large amount of heat in a short time, with a faster temperature rise, which can accelerate the dissolution of the target components in the solvent. Secondly, the extraction solvent also needs to have good solubility for the target components. If the solubility of the target components in the extraction solvent is low, it will cause incomplete extraction of the target substances or require too much solvent. Selecting appropriate microwave extraction conditions and extraction solvents can significantly improve the extraction speed and save the amount of extraction solvent used. In the present invention, the components in the lower-layer precipitate II are complex, mainly including sulfur, phenanthrene, naphthalene, pyrene, benzene, fluorene, anthracene and other substances. Considering comprehensively the solubility in different solvents, the solvent polarity, the solid-liquid ratio during extraction, the price of the extraction solvent and the operation safety of the lower-layer precipitate II, the extraction solvent preferably used in the present invention is anhydrous ethanol. Through Step 3, sulfur and phenanthrene are separated from naphthalene, pyrene, benzene, fluorene, anthracene and other substances. The extraction phase I mainly includes ethanol, naphthalene, pyrene, and also includes a small amount of benzene, fluorene, anthracene, as well as sulfur and phenanthrene that are slightly soluble in ethanol and other components. The raffinate phase I is mainly sulfur and phenanthrene.

[0019] In Step 4, after adding a second extraction agent to the raffinate phase I for extraction reaction, the extraction phase II mainly contains phenanthrene substances accounting for about 50% in the water-insoluble impurities; the raffinate phase II is mainly sulfur; the purity of the sulfur is greater than 99%.

[0020] In Step 7, through the treatment of the above waste liquid with a composite microbial agent, the degradation rates of safety monitoring indicators such as thiosulfate, thiocyanate and polycyclic aromatic hydrocarbons (PAHs) in the treated wastewater are above 70%, realizing the environmental protection and efficient treatment of the waste liquid in the process of preparing high-purity sulfur.

[0021] Among them, the composite microbial agent includes Micromonospora, Fusarium oxysporum, Bacillus velezensis, Pseudomonas and Hydrogenophaga pauli;

[0022] Specifically, the strain number of the Micromonospora is BNCC229048, and its Latin name is Micromonospora sp.;

[0023] The strain number of the Fusarium oxysporum is BNCC371874, and its Latin name is Fusarium oxysporum Schlechtendahl;

[0024] The strain number of the Bacillus velezensis is BNCC352076, and its Latin name is Bacillus velezensis;

[0025] The strain number of the Pseudomonas is BNCC193134, and its Latin name is Pseudomonas sp.;

[0026] The strain number of the Hydrogenophaga palleronii is BNCC363791, and its Latin name is Hydrogenophaga palleronii.

[0027] During the fermentation culture, the liquid loading is one-fourth to one-third of the volume of the fermentation container; the initial pH value is 6-7, and the above-mentioned various strains work together to effectively degrade safety monitoring indicators such as thiosulfate, thiocyanate, and polycyclic aromatic hydrocarbons (PAHs) in the waste liquid.

[0028] Preferably, in step one, the pretreatment includes crushing treatment and screening through a 60-100 mesh sieve;

[0029] The coking sulfur cream is the coking sulfur cream obtained by the ammonia method HPF coke oven gas desulfurization process.

[0030] Pretreating the coking sulfur cream is, on the one hand, to make the coking sulfur cream better contact with the solvent, and on the other hand, to enable better separation of different components in the coking sulfur cream in the subsequent process; the coking sulfur cream in the present invention is the coking sulfur cream obtained by the ammonia method HPF coke oven gas desulfurization process. After measurement, the wet coking sulfur cream of this type contains 48-54% sulfur, 31-37% water, and 11-17% impurities. Further analyzing and measuring the impurities, the impurities include water-soluble impurities (with a mass ratio of 8-10% in the wet coking sulfur cream), organic solvent-soluble impurities (with a mass ratio of 2-4% in the wet coking sulfur cream), and other impurities (with a mass ratio of 1-2.5% in the wet coking sulfur cream). The mass ratios of ammonium thiocyanate, ferrous sulfate, ammonium thiosulfate, PDS, and hydroquinone in the water-soluble impurities in the wet coking sulfur cream all exceed 0.3%, especially the contents of ammonium thiocyanate and ferrous sulfate are relatively high, and the total mass ratio of ammonium thiocyanate and ferrous sulfate in the water-soluble impurities exceeds 80%. The mass ratios of phenanthrene, naphthalene, and pyrene in the dichloromethane-soluble impurities in the wet coking sulfur cream all exceed 0.3%, especially the total mass ratio of phenanthrene and naphthalene in the dichloromethane-soluble impurities exceeds 70%. In addition, there are also small amounts of benzene, fluorene, and anthracene. The other impurities are mainly coal powder or coke powder substances.

[0031] Preferably, in step three, the power of the microwave is 0.5-5 KW; more preferably 0.8-2 KW.

[0032] During the first extraction reaction, the mass ratio of the lower-layer precipitate II to ethanol is 1:2 to 4, and the reaction time is 0.5 to 1 h.

[0033] Preferably, in step four, during the second extraction reaction, the mass ratio of the raffinate I to the second extractant is 1:2 to 4, and the reaction time is 0.5 to 1 h; the second extractant includes any one of ether, petroleum ether, or dichloromethane.

[0034] Preferably, in step seven, the composite microbial agent is attached to the microbial carrier.

[0035] Preferably, the microbial carrier is polyurethane packing; the mass ratio of the composite microbial agent to the polyurethane packing is 1:2 to 4.

[0036] Preferably, in the composite microbial agent, the viable count of Micromonospora is 1×10 10 ~3×10 10 CFU / g;

[0037] the viable count of Fusarium oxysporum is 5×10 9 ~8×10 9 CFU / g;

[0038] the viable count of Bacillus velezensis is 1×10 10 ~3×10 10 CFU / g;

[0039] the viable count of Pseudomonas is 1.5×10 9 ~3.5×10 9 CFU / g;

[0040] the viable count of Hydrogenophaga palleronii is 1.5×10 9 ~3.5×10 9 CFU / g.

[0041] Preferably, in step seven, the inoculation amount of the composite microbial agent is 3 to 5%.

[0042] Preferably, during the fermentation culture, a fermentation medium is also added.

[0043] After the fermentation culture, the degradation rate of polycyclic aromatic hydrocarbons in the waste liquid is above 80%.

[0044] Preferably, the conditions for the fermentation culture are: culture temperature 27 to 32 °C, culture time 6 to 8 d, rotation speed 150 to 200 r / min;

[0045] After adding the fermentation medium, based on 1 L, the fermentation system includes 0.5 - 1.0 g of NaCl, 5 - 15 g of glucose, and 1.3 - 1.5 g of FeSO4; among them, FeSO4 is derived from the supernatant of Step 1 and does not require additional addition; the fermentation system also includes ammonium thiocyanate, ammonium thiosulfate, PDS, hydroquinone, sulfur, and aromatic hydrocarbons and polycyclic aromatic hydrocarbons such as naphthalene, benzene, fluorene, phenanthrene, and anthracene in Mixture Ⅰ and Supernatant Ⅰ.

[0046] In the present invention, by adsorbing on the composite microbial inoculant, the waste liquid generated in the process of preparing high-purity sulfur from coking sulfur paste is treated, and the concentrations of ammonium thiocyanate, ammonium thiosulfate, and polycyclic aromatic hydrocarbons in the waste liquid can be effectively degraded. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required to be used in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0048] Figure 1 It is the process flow diagram of the treatment method of coking sulfur paste provided in Embodiment 1 of the present invention;

[0049] Figure 2 It is the bar chart of the degradation rate of the main safety monitoring indicators after the diluted waste liquid is treated in Embodiment 1 of the present invention;

[0050] Figure 3 It is the bar chart of the degradation rate of the main safety monitoring indicators after the diluted waste liquid is treated in Embodiment 2 of the present invention;

[0051] Figure 4 It is the bar chart of the degradation rate of the main safety monitoring indicators after the diluted waste liquid is treated in Embodiment 3 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0052] In order to make the purpose, technical solutions, and advantages of the present invention clearer, the following will further elaborate on the present invention in combination with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0053] It should be noted that in the present invention, the determination method of the thiocyanate content is carried out according to "Determination of Thiocyanate Content in Coking Wastewater" (HG / T 6072 - 2022); the determination methods of the remaining indicators are all carried out according to the conventional methods in the art.

[0054] Embodiment 1

[0055] An embodiment of the present invention provides a method for treating coking sulfur paste. The process flow chart of the treatment method is as shown in Figure 1 and specifically includes:

[0056] Step 1: Take the wet coking sulfur paste obtained by the ammonia-based HPF coke oven gas desulfurization process, crush it, and pass it through a 100-mesh sieve to obtain the pretreated coking sulfur paste. After measurement, the components of the above-mentioned wet coking sulfur paste are specifically shown in Table 1 below.

[0057] Table 1

[0058]

[0059] Take 1000 g of the pretreated coking sulfur paste, add 3 L of water, stir, let it stand for 0.5 h, and centrifuge at 3000 rpm for 5 min to obtain precipitate I and supernatant I;

[0060] Step 2: Separate precipitate I according to the layering situation and color difference to obtain upper-layer precipitate II and lower-layer precipitate II; upper-layer precipitate II is mainly coal powder or coke powder, and lower-layer precipitate II is mainly a mixture of sulfur and water-insoluble impurities.

[0061] Step 3: Carry out the first extraction reaction for 1 h under the condition of a microwave power of 1 KW according to the mass ratio of lower-layer precipitate II to absolute ethanol of 1:2.5 to obtain extraction phase I and raffinate phase I;

[0062] Step 4: Mix raffinate phase I and ether according to a mass ratio of 1:2, stir evenly, and carry out the second extraction reaction for 1 h to obtain extraction phase II and raffinate phase II;

[0063] Step 5: Dry raffinate phase II at 0.09 Mpa and 85 °C for 6 h to obtain sulfur; after measurement, 520.5 g of sulfur with a purity of 99.1% is obtained;

[0064] Concentrate extraction phase II by rotary evaporation under reduced pressure, recover ether, and then dry it at 105 °C for 3 h to obtain 15.7 g of phenanthrene substances.

[0065] Step 6: After rotary evaporation to recover ethanol from extraction phase I, a mixture I is obtained. Mixture I mainly includes naphthalene and pyrene in the coking sulfur paste, as well as a small amount of benzene, fluorene, and anthracene, and sulfur and phenanthrene that are slightly soluble in ethanol.

[0066] Step 7: Mix mixture I with supernatant I to obtain 3109.2 g of waste liquid; after diluting the waste liquid by 5 times, after measurement, the statistical table of the main safety monitoring indicators in the diluted waste liquid is shown in Table 2 below.

[0067] Table 2

[0068] Safety monitoring indicators Content (mg / L) Naphthalenes 326.0 Pyrenes 230.4 Fluorenes 126.9 Anthracenes 87.3 Phenanthrenes 117.3 Benzenes 183.5 Ammonium thiocyanate 3561.8 Ferrous sulfate 1504.9 Ammonium thiosulfate 558.2 Hydroquinone 205.6

[0069] Among them, naphthalene, pyrene, fluorene, anthracene and phenanthrene are collectively referred to as polycyclic aromatic hydrocarbons (PAHs for short).

[0070] A composite microbial agent composed of Micromonospora, Fusarium oxysporum, Bacillus velezensis, Pseudomonas and Hydrogenophaga palleronii is made into a bacterial liquid and fixed on a polyurethane filler carrier. Among them, the mass ratio of the composite microbial agent to the polyurethane filler is 1:3.

[0071] The composite microbial agent fixed on the carrier is inoculated into the diluted waste liquid, a fermentation medium is added, and it is cultured in a shaking flask at 30 °C for 7 d, with a rotation speed of 180 r / min and the liquid loading volume during fermentation being one-third of the volume of the fermentation container. After the culture is completed, the treated wastewater is obtained. The statistical table of the main safety monitoring indicators of the treated wastewater is shown in Table 3.

[0072] Among them, the inoculation amount is 4%.

[0073] In the composite microbial agent:

[0074] The strain number of Micromonospora is BNCC229048 (Latin name: Micromonospora sp.), and its viable count is 2×10 10 CFU / g; the strain number of Fusarium oxysporum is BNCC371874 (Latin name: Fusarium oxysporum Schlechtendahl), and its viable count is 6×10 9 CFU / g; the strain number of Bacillus velezensis is BNCC352076 (Latin name: Bacillus velezensis), and its viable count is 2×10 10 CFU / g; the strain number of Pseudomonas is BNCC193134 (Latin name: Pseudomonas sp.), and its viable count is 2.5×10 9 CFU / g; the strain number of Hydrogenophaga palleronii is BNCC363791 (Latin name: Hydrogenophaga palleronii), and its viable count is 2.5×10 9 CFU / g.

[0075] Among them, after adding the fermentation medium, based on 1 L, the fermentation system includes 0.75 g of NaCl, 10 g of glucose, and 1.5 g of FeSO4. In addition, NH4 in the supernatant + can be used as the nitrogen source of the composite microbial agent.

[0076] Table 3

[0077] Safety monitoring indicators Content (mg / L) Naphthalenes 48.6 Pyrenes 17.3 Fluorenes 35.5 Anthracenes 10.5 Phenanthrenes 31.4 Benzenes 32.5 Ammonium thiocyanate 1015.1 Ammonium thiosulfate 140.7 Hydroquinone 56.3

[0078] From the data analysis in Tables 2 - 3, a bar chart of the degradation rate of the main safety monitoring indicators of the treated diluted waste liquid was drawn. For details, see Figure 2 . From Figure 2 it can be seen that after treatment with the composite microbial inoculant provided by the present invention, the degradation rates of the safety monitoring indicators in the diluted waste liquid are between 71.5% and 92.5%. Among them, the degradation rate of polycyclic aromatic hydrocarbons reaches 83.9%. It can be seen that the harmful components in the waste liquid are effectively degraded.

[0079] Example 2

[0080] The embodiment of the present invention provides a method for treating coking sulfur paste. The treatment method specifically includes:

[0081] Step 1: Take the wet coking sulfur paste obtained by the ammonia - based HPF coke oven gas desulfurization process, after crushing and passing through a 60 - mesh sieve, the pretreated coking sulfur paste is obtained. After measurement, the composition of the above - mentioned wet coking sulfur paste is specifically as shown in Table 4 below.

[0082] Table 4

[0083]

[0084] Take 1000 g of the pretreated coking sulfur paste, add 4 L of water, stir, let stand for 0.5 h, and centrifuge at 3000 rpm for 5 min to obtain precipitate I and supernatant I;

[0085] Step 2: According to the layering situation, separate the precipitate I to obtain upper precipitate II and lower precipitate II; the upper precipitate II is mainly coal powder or coke powder, and the lower precipitate II is mainly a mixture of sulfur and water - insoluble impurities.

[0086] Step 3: Carry out the first extraction reaction for 0.5 h under the condition of a microwave power of 2 KW according to the mass ratio of lower precipitate II: absolute ethanol of 1:4 to obtain extraction phase I and raffinate phase I;

[0087] Step 4: Mix the raffinate phase I and dichloromethane according to a mass ratio of 1:4, stir evenly, and carry out the second extraction reaction for 0.5 h to obtain extraction phase II and raffinate phase II;

[0088] Step 5: Dry the raffinate phase II at 0.09 Mpa and 85 °C for 6 h to obtain sulfur; after measurement, 468.5 of sulfur with a purity of 99.3% is obtained;

[0089] Concentrate the extraction phase II by rotary evaporation under reduced pressure, recover dichloromethane, and then dry it at 105 °C for 3 h to obtain 14.3 g of phenanthrene - like substances.

[0090] Step 6: After the extraction phase I is rotary evaporated to recover ethanol, a mixture I is obtained. The mixture I mainly includes naphthalenes, pyrenes in the coking sulfur paste, as well as a small amount of benzenes, fluorenes, and anthracenes, and sulfur and phenanthrenes that are slightly soluble in ethanol.

[0091] Step 7: Mix the mixture I with the supernatant I to obtain 4115.2 g of waste liquid; after diluting the waste liquid by 5 times, upon measurement, the statistical table of the main safety monitoring indicators in the diluted waste liquid is shown in Table 5 below.

[0092] Table 5

[0093] Safety monitoring indicators Content (mg / L) Naphthalenes 242.5 Pyrenes 171.4 Fluorenes 94.5 Anthracenes 64.9 Phenanthrenes 138.8 Benzenes 136.5 Ammonium thiocyanate 2963.3 Ferrous sulfate 1296.4 Ammonium thiosulfate 538.6 Hydroquinone 181.8

[0094] Among them, naphthalenes, pyrenes, fluorenes, anthracenes, and phenanthrenes are collectively referred to as polycyclic aromatic hydrocarbons (PAHs for short).

[0095] Prepare a compound microbial inoculant composed of Micromonospora, Fusarium oxysporum, Bacillus velezensis, Pseudomonas, and Hydrogenophaga pauliensis into a bacterial liquid and fix it on a polyurethane filler carrier. Among them, the mass ratio of the compound microbial inoculant to the polyurethane filler is 1:4;

[0096] Inoculate the compound microbial inoculant fixed on the carrier into the diluted waste liquid, add a fermentation medium, and culture in a shaking flask at 27 °C for 6 d, with a rotation speed of 200 r / min and the liquid loading volume during fermentation being one-third of the volume of the fermentation container. After the culture is completed, the treated wastewater is obtained; the statistical table of the main safety monitoring indicators of the treated wastewater is shown in Table 6.

[0097] Among them, the inoculation amount is 5%;

[0098] In the compound microbial inoculant, the strains are the same as those shown in Example 1, and the specific dosages are as follows:

[0099] The viable count of Micromonospora is 1×10 10 CFU / g; the viable count of Fusarium oxysporum is 5×10 9 CFU / g; the viable count of Bacillus velezensis is 1×10 10 CFU / g; the viable count of Pseudomonas is 1.5×10 9 CFU / g; the viable count of Hydrogenophaga pauliensis is 1.5×10 9 CFU / g.

[0100] Among them, after adding the fermentation medium, based on 1 L, the fermentation system includes 0.5 g of NaCl, 5 g of glucose, and 1.3 g of FeSO4. In addition, NH4 in the supernatant + can be used as the nitrogen source of the compound microbial inoculant.

[0101] Table 6

[0102] Safety monitoring indicators Content (mg / L) Naphthalenes 23.5 Pyrenes 23.7 Fluorenes 28.2 Anthracenes 9.8 Phenanthrenes 26.1 Benzenes 32.6 Ammonium thiocyanate 761.6 Ammonium thiosulfate 133.6 Hydroquinone 48.9

[0103] Based on the data analysis in Tables 5 - 6, a bar chart of the degradation rate of the main safety monitoring indicators of the treated diluted waste liquid was plotted. For details, see Figure 3 . From Figure 3 it can be seen that after treatment with the composite microbial inoculant provided by the present invention, the degradation rates of the safety monitoring indicators in the waste liquid are between 70.2% and 90.3%. Among them, the degradation rate of polycyclic aromatic hydrocarbons reaches 84.3%. It can be seen that the harmful components in the waste liquid are effectively degraded.

[0104] Example 3

[0105] The embodiment of the present invention provides a method for treating coking sulfur paste. The treatment method specifically includes:

[0106] Step 1: Take the wet coking sulfur paste obtained by the ammonia - based HPF coke oven gas desulfurization process, perform crushing treatment, and pass through an 80 - mesh sieve to obtain the pretreated coking sulfur paste. After measurement, the composition of the above - mentioned wet coking sulfur paste is specifically shown in Table 7 below.

[0107] Table 7

[0108]

[0109] Take 1000 g of the pretreated coking sulfur paste, add 3 L of water, stir, let stand for 0.5 h, and centrifuge at 3000 rpm for 5 min to obtain precipitate I and supernatant I;

[0110] Step 2: Separate the precipitate I according to the stratification situation to obtain upper - layer precipitate II and lower - layer precipitate II; the upper - layer precipitate II is mainly coal powder or coke powder, and the lower - layer precipitate II is mainly a mixture of sulfur and water - insoluble impurities.

[0111] Step 3: Carry out the first extraction reaction for 0.6 h under the conditions of a microwave power of 0.8 KW and 55 °C according to the mass ratio of lower - layer precipitate II to absolute ethanol of 1:3 to obtain extraction phase I and raffinate phase I;

[0112] Step 4: Mix the raffinate phase I and petroleum ether according to a mass ratio of 1:3, stir evenly, and carry out the second extraction reaction for 0.5 h to obtain extraction phase II and raffinate phase II;

[0113] Step 5: Dry the raffinate phase II at 0.09 Mpa and 85 °C for 6 h to obtain sulfur; after measurement, 506.5 g of sulfur with a purity of 98.4% is obtained;

[0114] Concentrate the extraction phase II by rotary evaporation under reduced pressure, recover petroleum ether, and then dry it at 105 °C for 3 h to obtain 12.8 g of phenanthrene - like substances.

[0115] Step 6: After the extraction phase I is rotary evaporated to recover ethanol, a mixture I is obtained. The mixture I mainly includes naphthalenes, pyrenes in the coking sulfur paste, and also contains a small amount of benzenes, fluorenes, and anthracenes, as well as sulfur and phenanthrenes that are slightly soluble in ethanol.

[0116] Step 7: Mix the mixture I with the supernatant I to obtain 3081.7 g of waste liquid; after diluting the waste liquid by 5 times, upon measurement, the statistical table of the main safety monitoring indicators in the diluted waste liquid is shown in Table 8 below.

[0117] Table 8

[0118] Safety monitoring indicators Content (mg / L) Naphthalenes 304.3 Pyrenes 180.5 Fluorenes 109.7 Anthracenes 61.0 Phenanthrenes 143.5 Benzenes 132.1 Ammonium thiocyanate 2805.1 Ferrous sulfate 1448.1 Ammonium thiosulfate 588.8 Hydroquinone 159.6

[0119] Among them, naphthalenes, pyrenes, fluorenes, anthracenes, and phenanthrenes are collectively referred to as polycyclic aromatic hydrocarbons (abbreviated as PAHs).

[0120] Prepare a compound microbial inoculant composed of Micromonospora, Fusarium oxysporum, Bacillus velezensis, Pseudomonas, and Hydrogenophaga paeniformis into a bacterial solution and fix it on a polyurethane filler carrier. Among them, the mass ratio of the compound microbial inoculant to the polyurethane filler is 1:3;

[0121] Inoculate the compound microbial inoculant fixed on the carrier into the diluted waste liquid, add a fermentation medium, and culture it in a shaking flask at 32 °C for 8 d, with a rotation speed of 180 r / min. The liquid loading volume during fermentation is one-third of the volume of the fermentation container. After the culture is completed, the treated wastewater is obtained; the statistical table of the main safety monitoring indicators of the treated wastewater is shown in Table 9.

[0122] Among them, the inoculation amount is 3%;

[0123] In the compound microbial inoculant, the bacterial species are the same as those shown in Example 1, and the specific dosages are as follows:

[0124] The viable count of Micromonospora is 3×10 10 CFU / g; the viable count of Fusarium oxysporum is 8×10 9 CFU / g; the viable count of Bacillus velezensis is 3×10 10 CFU / g; the viable count of Pseudomonas is 3.5×10 9 CFU / g; the viable count of Hydrogenophaga paeniformis is 3.5×10 9 CFU / g.

[0125] Among them, after adding the fermentation medium, based on 1 L, the fermentation system includes 1.0 g of NaCl, 15 g of glucose, and 1.44 g of FeSO4. In addition, NH4 in the supernatant + can be used as the nitrogen source for the compound microbial inoculant.

[0126] Table 9

[0127]

[0128]

[0129] From the data analysis of Tables 8 - 9, draw a bar chart of the degradation rates of the main safety monitoring indicators of the treated diluted waste liquid. See Figure 4 . From Figure 4 it can be seen that after treatment with the composite microbial inoculant provided by the present invention, the degradation rates of the various safety monitoring indicators in the waste liquid are between 70.5% and 92.1%. Among them, the degradation rate of polycyclic aromatic hydrocarbons reaches 84.5%. It can be seen that the harmful components in the waste liquid are effectively degraded.

[0130] Comparative Example 1

[0131] In order to investigate the interaction between the selected strains of the present invention, on the basis of the waste liquid prepared in Example 1, in Comparative Example 1, only the strains in the composite microbial inoculant described in Example 1 were adjusted. On the basis of the composite microbial inoculant described in Example 1, Micromonospora and Pseudomonas were simply not added, and the remaining fermentation process parameters were the same as those in Example 1. The statistical table of the main safety monitoring indicators of the treated diluted wastewater is shown in Table 10.

[0132] Table 10

[0133] Safety monitoring indicators Content (mg / L) Naphthalenes 152.6 Pyrenes 79.0 Fluorenes 72.2 Anthracenes 25.1 Phenanthrenes 47.2 Benzenes 160.5 Ammonium thiocyanate 1040.0 Ammonium thiosulfate 139.0 Hydroquinone 97.8

[0134] From the data analysis of Table 1 and Table 10, it can be seen that the composite microbial inoculant provided in Comparative Example 1 can also degrade components such as polycyclic aromatic hydrocarbons, ammonium thiocyanate, ammonium thiosulfate, and hydroquinone in the lung water, but the degradation rate of polycyclic aromatic hydrocarbons is only 57.6%, the degradation rate of hydroquinone is only 52.4%, and the degradation rate of benzene is only 12.5%, which is significantly lower than that in Example 1.

[0135] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, or improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for treating coked sulfur paste, characterized in that: The processing method comprises the following steps: Step 1, adding water to the pretreated coked sulfur paste, centrifuging, and obtaining a precipitate I and a supernatant I; Step 2: Separate the precipitate I according to the stratification to obtain an upper precipitate II and a lower precipitate II; Step 3, adding ethanol to the lower layer precipitate II, and performing a first extraction under microwave conditions to obtain an extraction phase I and a raffinate phase I; Step 4, adding a second extractant to the raffinate phase I, performing a second extraction, and obtaining an extract phase II and a raffinate phase II; Step 5, drying the raffinate phase II to obtain sulfur; concentrating the extract phase II to recover the second extractant, and drying to obtain a phenanthrene-based substance; Step 6, recovering ethanol from the extraction phase I to obtain a mixture I; Step 7, mixing the mixture I with the supernatant I to obtain waste liquid, diluting, inoculating a composite microbial agent, and fermenting to obtain treated wastewater; The composite microbial agent includes Micromonospora, Fusarium oxysporum, Bacillus Velezii, Pseudomonas and Parvibacterium patens for hydrogen-eating and water-producing; The coking sulfur paste is coking sulfur paste prepared by an ammonia-based HPF coke oven gas desulfurization process.

2. The method for treating coked sulfur paste according to claim 1, characterized in that: In step 1, the pretreatment includes crushing and then passing through a 60-100 mesh sieve.

3. The method for treating coked sulfur paste according to claim 1, characterized in that: In step 3, the power of the microwave is 0.5-5KW; In step 3, the mass ratio of the lower layer precipitate II to ethanol is 1:2-4, and the extraction time is 0.5-1h.

4. The method for treating coked sulfur paste according to claim 1, characterized in that: In step 4, the mass ratio of the raffinate phase I to the second extractant is 1:2-4, and the reaction time is 0.5-1h; The second extracting agent includes any one of diethyl ether, petroleum ether or dichloromethane.

5. The method for treating coked sulfur paste according to claim 1, characterized in that: In step seven, the composite microbial agent is attached to the microbial carrier.

6. The method for treating coked sulfur paste according to claim 5, characterized in that: The microbial carrier is a polyurethane filler.

7. The method for treating coked sulfur paste according to any one of claim 1, characterized in that: In the composite microbial agent, the number of viable bacteria of the Micromonospora is 1×10 10 ~3×10 10 CFU / g; The viable count of the Fusarium oxysporum is 5×10 9 ~8×10 9 CFU / g; The viable count of the Velez Bacillus is 1×10 10 ~3×10 10 CFU / g; The viable count of Pseudomonas was 1.5×10 9 ~3.5×10 9 CFU / g; The viable bacteria count of the hydrogen-eating water-producing bacteria is 1.5×10 9 ~3.5×10 9 CFU / g.

8. The method for treating coked sulfur paste according to claim 1, characterized in that: In step seven, the inoculation amount of the composite microbial agent is 3-5%.

9. The method for treating coked sulfur paste according to any one of claims 1 to 8, characterized in that: During the fermentation culture, a fermentation medium is also added.

10. The method for treating coked sulfur paste according to claim 9, characterized in that: In step seven, the fermentation culture conditions are: culture temperature 27-32° C., culture time 6-8 days, and rotation speed 150-200 r / min.

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