CN115216325B - High-efficiency desulfurization process for high-sulfur petroleum coke - Google Patents
High-efficiency desulfurization process for high-sulfur petroleum coke Download PDFInfo
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- CN115216325B CN115216325B CN202210818718.6A CN202210818718A CN115216325B CN 115216325 B CN115216325 B CN 115216325B CN 202210818718 A CN202210818718 A CN 202210818718A CN 115216325 B CN115216325 B CN 115216325B
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- petroleum coke
- desulfurization
- sulfur
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/005—After-treatment of coke, e.g. calcination desulfurization
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a high-efficiency desulfurization process for high-sulfur petroleum coke, in particular relates to a desulfurization process for petroleum coke by photocatalysis synergistic microorganisms, and belongs to the field of clean production of petroleum coke. The invention comprises two aspects of photocatalytic oxidation pretreatment and biological desulfurization of petroleum coke by utilizing the iron-doped titanium dioxide photocatalytic film. The method comprises the following specific steps: (1) Under the irradiation of a mercury lamp, carrying out photocatalytic oxidation pretreatment of 8-12 h on petroleum coke water homogenate (with the liquid-solid ratio of 20-30 mL/g) by utilizing a photocatalytic film; (2) Biological desulfurization is carried out on the pretreated petroleum coke by utilizing the desulfurization bacteria, 0.5-1g of petroleum coke is added into a desulfurization culture medium, and the petroleum coke is cultured at 30 ℃ for 6-16 d; (3) Washing the petroleum coke sample after biological desulfurization with water, filtering and drying to realize the cooperative desulfurization of petroleum coke. The invention fully utilizes the characteristics of mild photocatalysis and microorganism desulfurization conditions, low cost and environmental friendliness, can realize the recycling of the photocatalyst, meets the deep and efficient petroleum coke desulfurization requirement, and has high practical application value.
Description
Technical Field
The invention belongs to the field of clean production of petroleum coke, and particularly discloses a high-efficiency desulfurization process of high-sulfur petroleum coke.
Background
The electrolytic aluminum industry in China is stepping on a road for healthy development, and the demand of petroleum coke is also kept rising steadily. At present, high-quality low-sulfur petroleum coke presents a situation of insufficient supply, so that a plurality of enterprises have to turn the eyes to the high-sulfur petroleum coke market. However, the sulfur content in the high sulfur coke often damages the quality of products, the acid gas released during industrial production also damages production equipment, and in addition, the sulfur content in the petroleum coke is converted into sulfur dioxide which is dissipated into the air to cause atmospheric pollution, thereby causing natural disasters such as acid rain and the like. Therefore, the technical method for efficiently and economically removing the sulfur in the petroleum coke is searched, and has very important significance for expanding the high sulfur coke market and improving the utilization rate of the high sulfur petroleum coke.
The sulfur in petroleum coke is mainly organic sulfur, and the ratio of the sulfur to the organic sulfur is more than 99%, wherein thiophenes and derivatives thereof are most difficult to remove. At present, the research on petroleum coke desulfurization, especially thiophene removal, mainly comprises high-temperature calcination desulfurization, chemical oxidation desulfurization, alkali metal desulfurization, hydrodesulfurization and the like. However, high temperature desulfurization, alkali metal desulfurization and hydrodesulfurization often consume a large amount of energy, and high temperature resistant materials are needed, so that desulfurization cost is high and a large potential safety hazard exists; the chemical oxidation desulfurization can easily destroy the graphite crystal structure of the petroleum coke, reduce the quality of the petroleum coke, and simultaneously bring the problems of environmental pollution, equipment corrosion and the like due to waste liquid which is difficult to treat.
In view of the above, it is necessary to develop a novel petroleum coke desulfurization technology which is mild in condition, green and environment-friendly and is not easy to produce secondary pollution.
Disclosure of Invention
In order to solve the problems of the traditional petroleum coke desulfurization method, the invention provides a high-efficiency desulfurization process for high-sulfur petroleum coke, which utilizes the synergistic desulfurization capability of photocatalysis and microorganisms and combines the respective technical advantages to obtain the high-efficiency and deep desulfurization effect.
In order to achieve the purpose of desulfurization, the invention provides a high-efficiency desulfurization process for high-sulfur petroleum coke, which has the following technical scheme.
The sol-gel method is utilized to prepare the nano titanium dioxide film with the iron doping amount of 1-4 wt percent.
And (5) taking a proper amount of high-sulfur petroleum coke, and crushing the petroleum coke to a particle size smaller than 200 meshes.
Weighing 0.5-1. 1g petroleum coke, adding the petroleum coke into a culture dish containing 14.5-mL deionized water, adding 0.5-1 mL of 30% hydrogen peroxide as an auxiliary oxidant, uniformly stirring, and then adding the iron-doped titanium dioxide film.
The petri dish was placed in a photocatalytic reactor and irradiated with a high-pressure mercury lamp of 200 to 300 to W for 8 to 10 h.
And after the photocatalytic reaction is finished, washing, suction filtering and drying the petroleum coke homogenate.
Will beRhodococcus sp.DQ-07 (deposited in China general microbiological culture collection center, with the deposit number of CGMCC 1.60022) is inoculated into 50 mL BSM culture medium and cultured in a shaking table at 30 ℃ for 2 d.
BSM medium used in the present invention: glucose 10 g, ammonium chloride 2 g, potassium dihydrogen phosphate 2.44 g, disodium hydrogen phosphate dodecahydrate 14.02 g, magnesium chloride hexahydrate 0.2 g, anhydrous calcium chloride 0.04 g, cupric chloride dihydrate 0.01 g, zinc chloride 0.002 g, cobalt chloride hexahydrate 0.004 g, aluminum chloride hexahydrate 0.001 g, boric acid 0.001 g, ferric chloride hexahydrate 0.04 g, sodium molybdate dihydrate 0.001 g, manganese chloride tetrahydrate 0.008 g, and sterilized at 121 ℃ for 20 minutes.
Adding 0.5. 0.5 g pretreated petroleum coke into desulfurization culture medium, culturing at 30-35deg.C for 6-10 d, filtering, cleaning and oven drying the culture solution containing petroleum coke after culturing, and measuring sulfur content.
Technical advantages of the present invention.
1. The two technologies of photocatalytic oxidation desulfurization and biological desulfurization are carried out at normal temperature and normal pressure, and the method has the advantages of mild reaction conditions and safe and controllable reaction process.
2. The nano titanium dioxide has antibacterial effect, and after the photocatalyst is solidified into a glass film, the loss rate of the photocatalyst can be reduced, and the subsequent biological desulfurization can not be influenced.
3. The photocatalytic oxidation simplifies the traditional biological desulfurization 4S path into two steps, and simultaneously utilizes the strong oxidation property to destroy the external structure of the petroleum coke, improves the hydrophilicity of the petroleum coke surface, can furthest exert the desulfurization characteristic of the desulfurization bacteria, and greatly shortens the desulfurization period.
Drawings
FIG. 1 is a scanning electron microscope image (70 K×) of iron doped titanium dioxide.
FIG. 2 contact angle comparison of petroleum coke before pretreatment (a) and after pretreatment (b).
FIG. 3 is a graph showing the synergistic desulfurization effect.
Detailed Description
The technical features of the present invention will be explained below by first preparing a photocatalyst film and then combining with the biological desulfurization embodiment, and it should be noted that the embodiment is only used for explaining the present invention and does not limit the scope of application of the present invention.
Example 1: the high-efficiency desulfurizing process for high-sulfur petroleum coke is as follows.
Ethanol, tetrabutyl titanate, aqueous solution of ferric nitrate and glacial acetic acid are added in sequence according to the volume ratio of 50:10:8:15, and hydrolysis reaction is carried out under magnetic stirring and ultrasonic vibration to obtain titanium dioxide sol with the iron doping amount of 4 and wt percent, and the titanium dioxide sol is aged at room temperature for 24 h.
The iron-doped titanium dioxide sol was fixed on a glass slide in a film-plating manner using an immersion pulling method, and heat-treated at 450 ℃ for 2 h.
Adding petroleum coke with the grain size of less than 200 meshes and 0.5-g into a culture dish containing 14.5-mL deionized water, adding 0.5 mL of 30% hydrogen peroxide as an auxiliary oxidant, uniformly stirring, and then adding 2 iron-doped titanium dioxide films.
In the photocatalytic reactor, 8 h was irradiated with a mercury lamp of 200W.
And carrying out suction filtration, cleaning and drying on the petroleum coke homogenate after photocatalytic oxidation.
Will beRhodococcus sp.DQ-07 was inoculated into 50 mL BSM medium and incubated in a shaker at 30℃for 2 d.
Weighing a petroleum coke sample subjected to photocatalysis pretreatment of 0.5. 0.5 g, and adding the petroleum coke sample into the sampleRhodococcus sp.The culture of DQ-07 was continued in a shaker at 30℃for 8 d.
After the cultivation is finished, the culture solution containing petroleum coke is subjected to suction filtration, cleaning and drying, and the sulfur content is measured, wherein the highest desulfurization rate is 51.92%.
Example 2: the high-efficiency desulfurizing process for high-sulfur petroleum coke is as follows.
Sequentially adding ethanol, tetrabutyl titanate, aqueous solution of ferric nitrate and glacial acetic acid according to the volume ratio of 50:10:8:15, and carrying out hydrolysis reaction under magnetic stirring and ultrasonic vibration to obtain titanium dioxide sol with the iron doping amount of 4 wt%, and aging at room temperature for 24 h;
the iron-doped titanium dioxide sol was fixed on a glass slide in a film-plating manner using an immersion pulling method, and heat-treated at 450 ℃ for 2 h.
Adding petroleum coke with the grain size of less than 200 meshes and 0.5-g into a culture dish containing 14.5-mL deionized water, adding 0.5 mL of 30% hydrogen peroxide as an auxiliary oxidant, uniformly stirring, and then adding 2 iron-doped titanium dioxide films.
In the photocatalytic reactor, 8 h was irradiated with a mercury lamp of 200W.
And carrying out suction filtration, cleaning and drying on the petroleum coke homogenate after photocatalytic oxidation.
Gordonia was inoculated into 50 mL of BSM medium and cultured in a shaker at 30℃for 2 d.
Weighing a petroleum coke sample subjected to photocatalysis pretreatment of 0.5 and g, wrapping with sterilized nylon cloth, putting into a culture medium of Gordonia, and continuously culturing in a shaking table at 30 ℃ for 8 d.
After the cultivation is finished, the culture solution containing petroleum coke is subjected to suction filtration, cleaning and drying, and the sulfur content is measured, wherein the highest desulfurization rate is 29.42%.
Example 3: the high-efficiency desulfurizing process for high-sulfur petroleum coke is as follows.
Ethanol, tetrabutyl titanate, aqueous solution of ferric nitrate and glacial acetic acid are added in sequence according to the volume ratio of 10:50:8:15, and hydrolysis reaction is carried out under magnetic stirring and ultrasonic vibration to obtain titanium dioxide sol with the iron doping amount of 4 and wt percent, and the titanium dioxide sol is aged at room temperature for 24 h.
The iron-doped titanium dioxide sol was fixed on a glass slide in a film-plating manner using an immersion pulling method, and heat-treated at 450 ℃ for 2 h.
Adding petroleum coke with the grain size of less than 200 meshes and 0.5-g into a culture dish containing 14.5-mL deionized water, adding 0.5 mL of 30% hydrogen peroxide as an auxiliary oxidant, uniformly stirring, and then adding 2 iron-doped titanium dioxide films.
In the photocatalytic reactor, 8 h was irradiated with a mercury lamp of 200W.
And carrying out suction filtration, cleaning and drying on the petroleum coke homogenate after photocatalytic oxidation.
HPJ bacteria were inoculated into 50 mL BSM medium and cultured in a shaker at 30℃for 2 d.
The petroleum coke sample after the photocatalysis pretreatment of 0.5. 0.5 g is weighed and added into the culture medium of HPJ bacteria, and the culture is continued in a shaking table at 30 ℃ for 8 d.
After the cultivation is finished, the culture solution containing petroleum coke is subjected to suction filtration, cleaning and drying, and the sulfur content is measured, wherein the maximum desulfurization rate is 34.47%.
Claims (7)
1. The efficient desulfurizing process for high sulfur petroleum coke features the photocatalytic pre-treatment of iron doped titania film to petroleum coke and biological desulfurizing, and the process includes the following steps:
under the irradiation of a mercury lamp, carrying out photocatalytic oxidation pretreatment on petroleum coke water homogenate by utilizing a photocatalytic film;
biological desulfurization is carried out on the pretreated petroleum coke by utilizing the desulfurization bacteria, and the pretreated petroleum coke is added into a desulfurization culture medium for biological desulfurization;
washing the petroleum coke sample after biological desulfurization with water, filtering and drying to obtain the desulfurized petroleum coke.
2. The high-efficiency desulfurization process of high-sulfur petroleum coke according to claim 1, wherein the iron-doped titanium dioxide film is prepared by a sol-gel method, and the iron-doped amount is 1-4 wt%.
3. The high-efficiency desulfurization process of high-sulfur petroleum coke according to claim 1, wherein the liquid-solid ratio of the photocatalytic pretreatment petroleum coke is 10-30 mL/g, and the photocatalytic oxidation pretreatment time is 8-12 h.
4. The efficient desulfurization process for high-sulfur petroleum coke according to claim 3, wherein hydrogen peroxide is added as an auxiliary oxidant in the process of photo-catalytic pretreatment of petroleum coke.
5. The high-efficiency desulfurization process of high-sulfur petroleum coke according to claim 1, wherein desulfurization bacteria are inoculated into a desulfurization medium and cultured for 2-3 d.
6. The efficient desulfurization process for high-sulfur petroleum coke according to claim 5, wherein the pretreated petroleum coke sample is added into desulfurization medium and cultured at 30-35 ℃ for 6-16 d.
7. The high-efficiency desulfurization process for high-sulfur petroleum coke according to claim 6, wherein the liquid-solid ratio of petroleum coke to desulfurization medium is 50-100 mL/g.
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