CN111575039B - Coking desulfurization method - Google Patents
Coking desulfurization method Download PDFInfo
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- CN111575039B CN111575039B CN202010362928.XA CN202010362928A CN111575039B CN 111575039 B CN111575039 B CN 111575039B CN 202010362928 A CN202010362928 A CN 202010362928A CN 111575039 B CN111575039 B CN 111575039B
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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
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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Abstract
The invention relates to a coking desulfurization method, which comprises the steps of mixing a composite catalyst with water, and stirring to obtain an impregnation liquid with the concentration of 0.05-1 wt%; providing high-sulfur coking coal with the granularity not more than 3mm, mixing the high-sulfur coking coal with an impregnation solution, stirring at the speed of 70-100r/min for 1-3h, and drying at the temperature of 90-110 ℃ for 10-14h to obtain a coal sample; and (2) putting the coal sample into a coke oven, heating, introducing hydrogen into the coke oven when the temperature reaches 950-1050 ℃, so that the pressure of the hydrogen in the coke oven is not lower than 1 atmospheric pressure, preserving the heat for 1.5-2.5h, and cooling to obtain coke. The invention can obtain better desulfurization effect and improve the comprehensive performance of coke products.
Description
Technical Field
The invention relates to a coking desulfurization method, belonging to the technical field of coking.
Background
The coke is an important raw material and fuel for metallurgy, chemical industry and non-ferrous industry, and plays an important role in national economic development. The sulfur content in the coke is one of the main indexes for evaluating the quality, price and the like of the coke, and obviously influences the energy consumption, the production capacity, the molten iron quality and the price of the coke in the international market of blast furnace iron making. China is the first coke producing country and export country in the world, but because of the characteristics of the traditional coking process and the lack of low-sulfur coking coal resources, the production of high-quality low-sulfur coke is restrained, and simultaneously, the environment is also severe. The design and development of the low-cost low-energy-consumption pollution-free desulfurization technology in the coal coking process have important significance for industrial production, economic markets and the like, and are also important components of clean coal utilization technology.
Sulfur in coal is divided into two major classes of organic sulfur and inorganic sulfur, and heterocyclic compounds such as thiophene, dibenzothiophene and the like are difficult to remove sulfur in molecules in a desulfurization project. In order to meet the requirements of coal coking desulfurization under the current strict standard, the desulfurization catalyst with higher activity is developed and prepared only by changing the current existing process flow and reaction conditions. For changing the process flow, only the existing reaction device is modified to a certain extent, which can meet the requirement of deep desulfurization of coke to a certain extent, but the equipment investment is increased. If the reaction conditions are changed, such as the conditions of increasing the temperature and pressure of the reaction, side reactions in the process can also be accelerated, so that the yield and the quality of the target product are reduced; the increased pressure also increases the investment and operating costs of the reaction apparatus. Therefore, the best method and the most cost-effective means to solve this problem is to continuously develop a desulfurization catalyst with higher activity to replace the original catalyst material.
The hydrodesulfurization method is characterized in that a catalyst and hydrogen bias are used together, so that a sulfur-containing compound and hydrogen interact in the coal coking process to react and desulfurize to generate a hydrocarbon compound and hydrogen sulfide, the desulfurization reaction is relatively easy to occur for non-heterocyclic sulfur-containing compounds, and the reaction network is very simple. Firstly, the C-S or S-S bond breaking reaction is carried out, then the carbon molecular bone chain is hydrogenated, and finally hydrocarbon and hydrogen sulfide are generated.
Chinese patent specification CN107384503A discloses a method for desulfurizing petroleum coke, and the catalyst used in the method is Al2O3The nickel-molybdenum catalyst is a carrier, the catalyst is columnar with the diameter of 1mm and the length of 10-15mm, and can obtain a good desulfurization effect, but the addition amount of the catalyst is large in a single treatment process, so that the amount of petroleum coke actually treated in the single treatment process is undoubtedly reduced; in addition, after the desulfurization is completed, the catalyst is screened out by particle size screening, which undoubtedly increases the treatment flow and workload, resulting in increased desulfurization cost.
Disclosure of Invention
In view of the disadvantages of the prior art, the present invention aims to provide a coking and desulfurizing method for efficiently obtaining a coke product having a low sulfur content and a high strength at a low cost.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a coking desulfurization method comprises the following steps:
s1, mixing the composite catalyst and water, and stirring to obtain an impregnation liquid with the concentration of 0.05-1 wt%;
the preparation method of the composite catalyst comprises the following steps:
providing a mixed solution; wherein, in the mixed solution, nickel acetate, molybdenum acetate and H3BO3In a molar ratio of 1: (0.3-0.5): (0.05-0.2);
drying the mixed solution to obtain a solid sample;
calcining the solid sample at the temperature of 600-800 ℃ for 2-4h, and grinding to obtain the composite catalyst with the particle size of less than or equal to 0.05 mm;
s2, providing high-sulfur coking coal with the particle size not more than 13mm, mixing the high-sulfur coking coal with the impregnation liquid obtained in the step S1, stirring at the speed of 70-100r/min for 1-3h, and drying at the temperature of 90-110 ℃ for 10-14h to obtain a coal sample;
wherein, the mass ratio of the high-sulfur coking coal to the composite catalyst in the impregnation liquid is (100- & ltSUB & gt 1000-): 1;
s3, loading the coal sample obtained in the step S2 into a coke oven, heating, introducing hydrogen into the coke oven when the temperature reaches 950 ℃ and 1050 ℃, keeping the pressure of the hydrogen in the coke oven not lower than 1 atmospheric pressure, and cooling after 1.5-2.5h of heat preservation to obtain coke.
Further, in S1, a nickel acetate solution, a molybdenum acetate solution and H3BO3The solution is mixed and stirred for 0.5 to 1 hour at the speed of 350-450r/min to obtain a mixed solution. Preferably, the stirring rate is 400 r/min.
Further, in S1, the drying process is performed at 100-150 ℃.
Further, in S1, nickel acetate, molybdenum acetate and H are added to the mixed solution3BO3In a molar ratio of 1: (0.35-0.45): (0.1-0.15).
Further, in S2, high-sulfur coking coal having a particle size of 3mm or less is provided. Optionally, the high-sulfur coking coal is obtained by crushing and screening high-sulfur coking coal with larger particle size.
Further, in S2, stirring is carried out for 1-3h at a speed of 80-90 r/min.
Further, in S2, the coal sample is obtained after drying for 11-13h at 95-105 ℃.
Further, in S2, the mass ratio of the high-sulfur coking coal to the composite catalyst in the impregnation liquid during mixing is (150-: 1, preferably (200- & ltSUB & gt 800-): 1.
further, in S3, the introduction rate of hydrogen is 10-20L/h.
Further, in S3, the core temperature of the coal sample was monitored by a thermocouple.
Further, the sulfur content in the high-sulfur coking coal is more than 2 wt%. Optionally, the high-sulfur coking coal is high-sulfur cleaned coal.
According to the invention, the composite catalyst is mixed with the high-sulfur coking coal in the form of impregnation liquid, compared with conventional solid-solid mixing, the composite catalyst and the high-sulfur coking coal are more easily and uniformly mixed, and the composite catalyst dissolved in water can permeate into the high-sulfur coking coal particles and fully contact with the high-sulfur coking coal, so that the efficient utilization of the composite catalyst is realized.
The composite catalyst containing nickel, molybdenum and boron can improve the desulfurization efficiency of hydrodesulfurization in the coking process and reduce CO in coke in the coking process2The reactivity is improved, and the strength of the coke after reaction is improved, so that the performance of the coke is further improved on the basis of obtaining the low-sulfur coke. The common characteristics of Ni and Mo are that d electron orbitals are not filled, and the unit cell structures of the Ni and the Mo are either body-centered cubic lattices or hexagonal lattices, so that the Ni and the Mo can be used as catalyst materials in terms of electronic characteristics or geometric characteristics, and the catalytic effect can be improved due to the existence of the Ni and the Mo elements. The reason for improving the coke strength is the introduction of the B in the catalyst, so that the porosity of the coke obtained in the coking process is low, the shrinkage of the system is reduced, the reactivity of the coke is reduced, and the strength after the reaction is improved. During secondary heating of coke, coke CO is inhibited due to the existence of boron2Reaction ofGreatly reduces the solubility loss reactivity of the coke and improves the strength of the coke after reaction.
The desulfurization mechanism of the present invention can be explained as follows: firstly, the characteristic that H atoms have good affinity to S atoms is utilized, so that the H atoms can be adsorbed on the S atoms and cause the ring opening of thiophene compounds in the reaction process, but because of the steric hindrance effect of thiophene, H is simply introduced2And do not sufficiently contact with the S atom on the thiophene, thereby reducing desulfurization efficiency. And by adding the composite catalyst containing Ni and Mo, because the d electron orbits of Ni and Mo atoms are not full, Ni and Mo elements can adsorb nearby S atoms and induce the electron density of the adsorbed S atoms to be enhanced, and further S-C bonds are stretched, so that the conjugated structure of thiophene is damaged, the steric effect of thiophene is weakened, and H atoms can be more fully contacted with the S atoms and carry out ring-opening reaction.
During hydrodesulfurization, sulfur is adsorbed on the catalyst surface. Since the H atoms cannot migrate directly to the thiophene molecules, the sulfur adsorbed by the catalyst acts as a "step" for further hydrogenation reactions. It first accepts H to form S-H and then delivers H to C. Eventually the sulfur on the thiophene will adsorb and remain on the catalyst surface. When the degree of sulfiding of the catalyst is not so high, the migration kinetics of H may not be affected, but when the catalyst surface is completely covered with sulfur, the catalyst is deactivated. Therefore, in the desulfurization process, it is necessary to ensure a certain H2Partial pressure is such that sulfur adsorbed on the surface of the catalyst forms H2S gas to restore catalytic activity. Therefore, the invention repeatedly researches while considering the blending degree of the catalyst and the high-sulfur coking coal to obtain the proper H2Pressure and flow rate conditions to ensure that the catalyst surface is not fully sulfided and that high catalytic activity is maintained.
Compared with the prior art, the invention has the following advantages:
(1) the invention realizes the purpose of coke desulfurization in the coking process, reduces the cost and reduces the environmental pollution.
(2) The composite catalyst used in the invention has the advantages of simple preparation, small addition amount and economy.
(3) The composite catalyst used in the invention can improve the strength of coke and the quality of the coke.
(4) According to the invention, through reasonable design of the composite catalyst, the composite catalyst can be prepared into the impregnation liquid and then mixed with the high-sulfur coking coal, so that the effect of uniform mixing can be achieved, and compared with the method of directly adding the solid catalyst into a coal sample, the method improves the mixing effect of the coal and the catalyst; in addition, the introduction of a catalyst carrier is avoided, correspondingly, the amount of coal which can be processed by a single furnace is increased, the subsequent catalyst screening process is not required to be added, the process is simplified, the cost is reduced, the problem of CN107384503A is effectively solved, and the method has a better application prospect.
(5) The invention uses hydrogen to carry out desulfurization treatment on the high-sulfur coking coal, can realize good coke desulfurization in the coal pyrolysis process, and reduces the cost of the subsequent desulfurization treatment of the coke.
Detailed Description
The invention is further illustrated by the following examples, but is not limited thereto.
The high-sulfur cleaned coal used in the examples and comparative examples of the present invention gave a coke sulfur content of 1.65wt% without hydrogenation and catalyst.
Example 1
A small-sized experimental coke oven of 1kg is adopted for coking to realize coke desulfurization, and the method comprises the following specific steps:
crushing the high-sulfur fine-washed coal by using a crusher, screening out coal particles with the particle size range of less than 3mm, and weighing 1kg of coal as an experimental material.
Nickel acetate, molybdenum acetate and boric acid are mixed according to a molar ratio of 1: 0.3: 0.05, preparing a mixed solution, stirring and dispersing the mixed solution at room temperature by using a magnetic stirring rod at 400r/min, uniformly mixing, drying at 120 ℃, putting the dried solid sample into a high-temperature calcining furnace, controlling the calcining temperature at 600 ℃, calcining for 2 hours at the heating rate of 2 ℃/min, recovering the solid sample after the calcining is finished, and grinding the solid sample into powder with the particle size of less than or equal to 0.05mm to obtain the composite catalyst for later use.
According to the mass ratio of coal to the composite catalyst of 200: 1 weighing the composite catalyst, adding clear water, fully stirring to obtain an impregnation liquid with the mass concentration of 0.5wt%, then adding the impregnation liquid into a coal sample used for an experiment, impregnating for 2 hours, and stirring the mixed system at a rotating speed of 80r/min in the impregnating process. After the impregnation was completed, the coal sample was dried at 120 ℃ for 12 hours.
Adding the dried mixture into a reactor (a carbonization chamber) of a coke oven, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing hydrogen into the reactor, setting the aeration rate to be 10L/h, keeping the pressure of the hydrogen at 1 atmosphere, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
Detecting the sulfur content in the coke to obtain the coke with the sulfur content of 0.32wt% and the desulfurization rate of 80.61%, and simultaneously carrying out CO treatment on the coke obtained by the experiment2Reactivity and post-reaction strength tests showed that coke CRI (coke reactivity) was 15.6% and CSR (coke post-reaction strength) was 69.1%. Under the same conditions, coke obtained by coking without adding a catalyst has a CRI of 24.3% and a CSR of 58.4%. The coke CRI obtained by the treatment of this example was reduced by 35.8% and the strength increased by 18.3% after the reaction.
Comparative example 1
The same equipment and process are adopted, high-sulfur fine-washed coal is crushed by a crusher, then coal particles with the particle size of less than or equal to 3mm are screened out, 1kg of coal is weighed as an experimental material, and then a sample is dried.
Adding the dried coal into a reactor (a carbonization chamber) of a coke oven, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing nitrogen into the reactor, setting the aeration rate to be 10L/h, keeping the pressure of the hydrogen at 1 atmosphere, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
The sulfur content in the coke is detected, and the sulfur content of the coke is 0.51wt%, and the desulfurization rate is only 69.1%. Whereas the CRI was 24.3% and the CSR was 58.4%, with no significant change from that obtained by direct coking.
Comparative example 2
The same equipment and process are adopted, high-sulfur fine-washed coal is crushed by a crusher, then coal particles with the particle size of less than or equal to 3mm are screened out, 1kg of coal is weighed as an experimental material, and then a sample is dried.
Nickel acetate and boric acid are mixed according to a molar ratio of 1: 0.05, stirring and dispersing by using a magnetic stirring rod under the condition of 400r/min, drying the mixed solution at 120 ℃ after uniformly mixing, putting the dried solid sample into a high-temperature calcining furnace, controlling the calcining temperature to be 600 ℃, the calcining time to be 2h, the heating rate to be 2 ℃/min, recovering the solid sample after calcining, and grinding to be less than or equal to 0.05mm to obtain the catalyst for later use.
According to the mass ratio of coal to catalyst of 200: 1 weighing the prepared catalyst, adding clear water, fully stirring to obtain an impregnation liquid with the mass concentration of 0.5wt%, then adding the impregnation liquid into a coal sample used for an experiment, impregnating for 2 hours, and stirring the mixed system at a rotating speed of 80r/min in the impregnating process. After the impregnation was completed, the coal sample was dried at 120 ℃ for 12 hours.
Adding the coal sample into a reactor (a carbonization chamber) of a coke oven after drying treatment, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing hydrogen into the reactor, setting the aeration rate to be 10L/h, keeping the pressure of the hydrogen at 1 atmosphere, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
Detecting the sulfur content in the coke to obtain the sulfur content of the coke of 044wt% and a desulfurization degree of 75.93%. Simultaneously, the coke obtained in the experiment is subjected to CO2Reactivity and post-reaction strength tests showed a coke CRI of 15.2% and a CSR of 69.5%. Compared with the example 1, the addition of a proper amount of Mo in the catalyst is helpful for improving the desulfurization efficiency, and the hydrodesulfurization rate is improved by 4.68% after the addition of Mo. In addition, the coke obtained in comparative example 2 has slightly improved CRI and CSR compared to example 1, and analysis suggests that the relative amount of boron in comparative example 2 is increased to result in better performance of CSR and CRI than example 1 while Mo should have no significant effect on coke CRI and CSR, since the relative atomic weight of nickel is less than that of molybdenum, while maintaining the overall catalyst mass.
Comparative example 3
The same equipment and process are adopted, high-sulfur fine-washed coal is crushed by a crusher, then coal particles with the particle size of less than or equal to 3mm are screened out, 1kg of coal is weighed as an experimental material, and then a sample is dried.
Nickel acetate and molybdenum acetate are mixed according to a molar ratio of 1: 0.3, placing the mixture into a beaker, stirring and dispersing the mixed solution at room temperature by using a magnetic stirring rod at 400r/min, uniformly mixing, drying the mixed solution at 120 ℃, placing the dried solid sample into a high-temperature calcining furnace, controlling the calcining temperature at 600 ℃, the calcining time at 2h, the heating rate at 2 ℃/min, recovering the solid sample after the calcining is finished, and grinding the solid sample to be less than or equal to 0.05mm to obtain the catalyst for later use.
According to the mass ratio of coal to catalyst of 200: 1 weighing the prepared catalyst, adding clear water, fully stirring to obtain an impregnation liquid with the mass concentration of 0.5wt%, then adding the impregnation liquid into a coal sample used for an experiment, impregnating for 2 hours, and stirring the mixed system at a rotating speed of 80r/min in the impregnating process. After the impregnation was completed, the coal sample was dried at 120 ℃ for 12 hours.
Adding the dried mixture into a reactor (a carbonization chamber) of a coke oven, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing hydrogen into the reactor, setting the aeration rate to be 10L/h, keeping the pressure of the hydrogen at 1 atmosphere, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
And detecting the sulfur content in the coke to obtain the sulfur content of the coke of 0.30 wt%. The desulfurization rate reaches 81.81 percent. Coke CRI 23.3% and CSR 57.1%. Under the condition of the same catalyst addition amount, B is not added, although the relative contents of Ni and Mo are increased, the desulfurization effect is good, compared with the example 1, the desulfurization effect is improved a little, and the CO of the coke is reduced2Neither reactivity nor post-reaction strength is improved, so that proper addition of B, although it reduces desulfurization efficiency to a small extent, improves the overall performance of the coke.
Comparative example 4
The same equipment and process are adopted, high-sulfur fine-washed coal is crushed by a crusher, then coal particles with the particle size of less than or equal to 3mm are screened out, 1kg of coal is weighed as an experimental material, and then a sample is dried.
Nickel acetate, molybdenum acetate and boric acid are mixed according to a molar ratio of 1: 0.3: 0.05, placing the mixture into a beaker, stirring and dispersing the mixed solution at room temperature by using a magnetic stirring rod at 400r/min, uniformly mixing, drying the mixed solution at 120 ℃, placing the dried solid sample into a high-temperature calcining furnace, controlling the calcining temperature at 600 ℃, the calcining time at 2h, the heating rate at 2 ℃/min, recovering the solid sample after the calcining is finished, and grinding the solid sample to be less than or equal to 0.05mm, thus finishing the preparation of the catalyst.
According to the mass ratio of coal to catalyst of 200: 1 and drying at 120 ℃. Then adding the mixture into a reactor (a carbonization chamber) of a coke oven, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing hydrogen into the reactor, setting the aeration rate to be 10L/h, keeping the pressure of the hydrogen at 1 atmosphere, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
And detecting the sulfur content in the coke to obtain the sulfur content of the coke of 0.41 wt%. The desulfurization rate was 75.15%. Compared with the example 1, under the condition of the same catalyst adding amount, the solid catalyst is directly mixed with the coal sample, and the desulfurization effect is obviously reduced. In addition, the coke CRI was 18.6% which was only 23.4% lower and the CSR was 64.8% higher by 10.9% than the coke obtained without catalyst modification (i.e., comparative example 1). It can be seen that the use of the catalyst for direct mixing with the coal sample is likely to result in the catalyst not being sufficiently and uniformly distributed in the coal sample, which affects the effect of the catalyst.
Example 2
The same equipment and process are adopted, high-sulfur fine-washed coal is crushed by a crusher, then coal particles with the particle size of less than or equal to 3mm are screened out, 1kg of coal is weighed as an experimental material, and then a sample is dried.
Nickel acetate, molybdenum acetate and boric acid are mixed according to a molar ratio of 1: 0.5: 0.15, placing the mixture into a beaker, stirring and dispersing the mixed solution at room temperature by using a magnetic stirring rod at 400r/min, uniformly mixing, drying the mixed solution at 120 ℃, placing the dried solid sample into a high-temperature calcining furnace, controlling the calcining temperature at 600 ℃, the calcining time at 2h, the heating rate at 2 ℃/min, recovering the solid sample after the calcining is finished, and grinding the solid sample to be less than or equal to 0.05mm, thus finishing the preparation of the composite catalyst.
According to the mass ratio of coal to the composite catalyst of 200: 1 weighing the prepared composite catalyst, adding clear water, fully stirring to obtain an impregnation liquid with the mass concentration of 0.5wt%, then adding the impregnation liquid into a coal sample used for an experiment, impregnating for 2 hours, and keeping the rotating speed of 80r/min to stir a mixed system in the impregnating process. After the impregnation was completed, the coal sample was dried at 120 ℃ for 12 hours.
Adding the dried mixture into a reactor (a carbonization chamber) of a coke oven, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing hydrogen into the reactor, setting the aeration rate to be 10L/h, keeping the pressure of the hydrogen at 1 atmosphere, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
The detection result shows that the sulfur content in the coke is 0.26wt% and the desulfurization rate is 84.24%. At the same time, the coke CRI was 14.4%, which is a 40.7% reduction over the coke obtained without the catalyst modification. The CSR was 71.1%, which was 21.7% higher. Compared with analysis, the relative concentration of B is increased, and the CRI and CSR improvement effect of coke is obvious.
Example 3
The same equipment and process are adopted, high-sulfur fine-washed coal is crushed by a crusher, then coal particles with the particle size of less than or equal to 3mm are screened out, 1kg of coal is weighed as an experimental material, and then a sample is dried.
Nickel acetate, molybdenum acetate and boric acid are mixed according to a molar ratio of 1: 0.3: 0.05, preparing a mixed solution, stirring and dispersing the mixed solution at room temperature by using a magnetic stirring rod at 400r/min, uniformly mixing, drying at 120 ℃, putting the dried solid sample into a high-temperature calcining furnace, controlling the calcining temperature at 600 ℃, calcining for 2 hours at the heating rate of 2 ℃/min, recovering the solid sample after the calcining is finished, and grinding the solid sample into powder with the particle size of less than or equal to 0.05mm to obtain the composite catalyst for later use.
According to the mass ratio of coal to the composite catalyst of 200: 1 weighing the composite catalyst, adding clear water, fully stirring to obtain an impregnation liquid with the mass concentration of 0.5wt%, then adding the impregnation liquid into a coal sample used for an experiment, impregnating for 2 hours, and stirring the mixed system at a rotating speed of 80r/min in the impregnating process. After the impregnation was completed, the coal sample was dried at 120 ℃ for 12 hours.
Adding the dried mixture into a reactor (a carbonization chamber) of a coke oven, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing hydrogen into the reactor, setting the aeration rate to be 5L/h, keeping the pressure of the hydrogen at 1 atmosphere, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
The sulfur content in the coke was measured to obtain a coke having a sulfur content of 0.44wt% and a desulfurization rate of 73.33%, which was significantly lower than that of example 1. Simultaneously, the coke obtained in the experiment is subjected to CO2Reactivity and post-reaction strength tests showed that coke CRI (coke reactivity) was 15.6% and CSR (coke post-reaction strength) was 69.1%. The coke CRI decreased by 35.8% and the post-reaction strength increased by 18.3% compared to coke obtained without catalyst modification. According to analysis, H2The flow rate cannot be too low, and too low a flow rate may result in insufficient contact with the coal sample, reducing desulfurization efficiency.
Example 4
The same equipment and process are adopted, high-sulfur fine-washed coal is crushed by a crusher, then coal particles with the particle size of less than or equal to 3mm are screened out, 1kg of coal is weighed as an experimental material, and then a sample is dried.
Nickel acetate, molybdenum acetate and boric acid are mixed according to a molar ratio of 1: 0.3: 0.05, placing the mixture into a beaker, stirring and dispersing the mixed solution at room temperature by using a magnetic stirring rod at 400r/min, uniformly mixing, drying the mixed solution at 120 ℃, placing the dried solid sample into a high-temperature calcining furnace, controlling the calcining temperature at 600 ℃, the calcining time at 2h, the heating rate at 2 ℃/min, recovering the solid sample after the calcining is finished, and grinding the solid sample to be less than or equal to 0.05mm, thus finishing the preparation of the composite catalyst.
According to the mass ratio of coal to the composite catalyst of 200: 1 weighing the prepared composite catalyst, adding clear water, fully stirring to obtain an impregnation liquid with the mass concentration of 0.5wt%, then adding the impregnation liquid into a coal sample used for an experiment, impregnating for 2 hours, and keeping the rotating speed of 80r/min to stir a mixed system in the impregnating process. After the impregnation was completed, the coal sample was dried at 120 ℃ for 12 hours.
Adding the dried mixture into a reactor (a carbonization chamber) of a coke oven, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing hydrogen into the reactor, setting the aeration rate to be 15L/h, keeping the pressure of the hydrogen at 1 atmosphere, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
And detecting the sulfur content in the coke to obtain the sulfur content of the coke of 0.24 percent. The desulfurization rate was 85.45%, while the coke CRI was 14.3%, which was 41.1% lower than that obtained without the catalyst modification. The CSR was 71.3%, which was 22.1% higher.
Example 5
The same equipment and process are adopted, high-sulfur fine-washed coal is crushed by a crusher, then coal particles with the particle size of less than or equal to 3mm are screened out, 1kg of coal is weighed as an experimental material, and then a sample is dried.
Nickel acetate, molybdenum acetate and boric acid are mixed according to a molar ratio of 1: 0.3: 0.05, placing the mixture into a beaker, stirring and dispersing the mixed solution at room temperature by using a magnetic stirring rod at 400r/min, uniformly mixing, drying the mixed solution at 120 ℃, placing the dried solid sample into a high-temperature calcining furnace, controlling the calcining temperature at 600 ℃, the calcining time at 2h, the heating rate at 2 ℃/min, recovering the solid sample after the calcining is finished, and grinding the solid sample to be less than or equal to 0.05mm, thus finishing the preparation of the composite catalyst.
According to the mass ratio of coal to the composite catalyst of 200: 1 weighing the prepared composite catalyst, adding clear water, fully stirring to obtain an impregnation liquid with the mass concentration of 0.5wt%, then adding the impregnation liquid into a coal sample used for an experiment, impregnating for 2 hours, and keeping the rotating speed of 80r/min to stir a mixed system in the impregnating process. After the impregnation was completed, the coal sample was dried at 120 ℃ for 12 hours.
Adding the dried mixture into a reactor (a carbonization chamber) of a coke oven, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing hydrogen into the reactor, setting the aeration rate to be 20L/h, keeping the pressure of the hydrogen at 1 atmosphere, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
And detecting the sulfur content in the coke to obtain the sulfur content of the coke of 0.21 percent. The desulfurization degree was 87.27%, and the desulfurization degree was improved by only 1.82% as compared with example 4. At the same time, the coke CRI was 14.3%, which was 41.1% lower than that obtained without the catalyst modification. The CSR was 71.3%, which was 22.1% higher. It can be seen that in H2The flow rate should not be too high when H2When the flow rate exceeds a certain value, the effect of improving the desulfurization rate is very limited.
Example 6
The same equipment and process are adopted, high-sulfur fine-washed coal is crushed by a crusher, then coal particles with the particle size of less than or equal to 3mm are screened out, 1kg of coal is weighed as an experimental material, and then a sample is dried.
Nickel acetate, molybdenum acetate and boric acid are mixed according to a molar ratio of 1: 0.3: 0.05, preparing a mixed solution, stirring and dispersing the mixed solution at room temperature by using a magnetic stirring rod at 400r/min, uniformly mixing, drying at 120 ℃, putting the dried solid sample into a high-temperature calcining furnace, controlling the calcining temperature at 600 ℃, calcining for 2 hours at the heating rate of 2 ℃/min, recovering the solid sample after the calcining is finished, and grinding the solid sample into powder with the particle size of less than or equal to 0.05mm to obtain the composite catalyst for later use.
According to the mass ratio of coal to the composite catalyst of 200: 1 weighing the composite catalyst, adding clear water, fully stirring to obtain an impregnation liquid with the mass concentration of 0.5wt%, then adding the impregnation liquid into a coal sample used for an experiment, impregnating for 2 hours, and stirring the mixed system at a rotating speed of 80r/min in the impregnating process. After the impregnation was completed, the coal sample was dried at 120 ℃ for 12 hours.
Adding the dried mixture into a reactor (a carbonization chamber) of a coke oven, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing hydrogen into the reactor, setting the aeration rate to be 10L/h, keeping the pressure of the hydrogen at 0.5 atmospheric pressure, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
The sulfur content in the coke was measured to obtain a coke having a sulfur content of 0.53wt% and a desulfurization rate of 67.87%, which was significantly lower than that of example 1. Simultaneously, the coke obtained in the experiment is subjected to CO2Reactivity and post-reaction strength tests showed that coke CRI (coke reactivity) was 15.6% and CSR (coke post-reaction strength) was 69.1%. The coke CRI decreased by 35.8% and the post-reaction strength increased by 18.3% compared to coke obtained without catalyst modification. According to analysis, H2Partial pressure not too low, too low H2Partial pressure can severely reduce desulfurization efficiency.
Example 7
The same equipment and process are adopted, high-sulfur fine-washed coal is crushed by a crusher, then coal particles with the particle size of less than or equal to 3mm are screened out, 1kg of coal is weighed as an experimental material, and then a sample is dried.
Nickel acetate, molybdenum acetate and boric acid are mixed according to a molar ratio of 1: 0.3: 0.05, preparing a mixed solution, stirring and dispersing the mixed solution at room temperature by using a magnetic stirring rod at 400r/min, uniformly mixing, drying at 120 ℃, putting the dried solid sample into a high-temperature calcining furnace, controlling the calcining temperature at 600 ℃, calcining for 2 hours at the heating rate of 2 ℃/min, recovering the solid sample after the calcining is finished, and grinding the solid sample into powder with the particle size of less than or equal to 0.05mm to obtain the composite catalyst for later use.
According to the mass ratio of coal to the composite catalyst of 200: 1 weighing the composite catalyst, adding clear water, fully stirring to obtain an impregnation liquid with the mass concentration of 0.5wt%, then adding the impregnation liquid into a coal sample used for an experiment, impregnating for 2 hours, and stirring the mixed system at a rotating speed of 80r/min in the impregnating process. After the impregnation was completed, the coal sample was dried at 120 ℃ for 12 hours.
Adding the dried mixture into a reactor (a carbonization chamber) of a coke oven, and then charging; after the charging is finished, a thermocouple is installed immediately, a power supply is turned on, and then the heating power or the heating rate of each stage is controlled by using a temperature control system in a computer according to a heating system. When the central temperature of the coke cake reaches 1000 ℃, introducing hydrogen into the reactor, setting the aeration rate to be 10L/h, keeping the pressure of the hydrogen at 1.2 atmospheric pressure, keeping the temperature for 2h, stopping heating, and after the reactor is cooled, pouring out the coke.
Detecting the sulfur content in the coke to obtain the coke with the sulfur content of 0.26wt% and the desulfurization rate of 84.24%, and simultaneously carrying out CO treatment on the coke obtained by the experiment2Reactivity and post-reaction strength tests showed that coke CRI (coke reactivity) was 15.6% and CSR (coke post-reaction strength) was 69.1%. The coke CRI decreased by 35.8% and the post-reaction strength increased by 18.3% compared to coke obtained without catalyst modification. The analysis shows that H is maintained2The partial pressure is not less than 1 atmospheric pressure, which can ensure better desulfurization effect, and the partial pressure is equal to H2The synergistic action with the catalyst is inseparable, and during the reaction, the catalyst is deactivated by the combination of S element, if H2If the partial pressure is too low, the S element cannot be removed in time to maintain the catalyst activity, which inevitably leads to a decrease in desulfurization efficiency.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.
Claims (8)
1. A coking desulfurization method is characterized by comprising the following steps:
s1, mixing the composite catalyst and water, and stirring to obtain an impregnation liquid with the concentration of 0.05-1 wt%;
the preparation method of the composite catalyst comprises the following steps:
providing a mixed solution; wherein, in the mixed solution, nickel acetate, molybdenum acetate and H3BO3In a molar ratio of 1: (0.3-0.5): (0.05-0.2）；
Drying the mixed solution to obtain a solid sample;
calcining the solid sample at the temperature of 600-800 ℃ for 2-4h, and grinding to obtain the composite catalyst with the particle size of less than or equal to 0.05 mm;
s2, providing high-sulfur coking coal with the granularity not more than 13mm, mixing the high-sulfur coking coal with the impregnation liquid obtained in the step S1, stirring at the speed of 70-100r/min for 1-3h, and drying at the temperature of 90-150 ℃ for 10-14h to obtain a coal sample;
wherein, the mass ratio of the high-sulfur coking coal to the composite catalyst in the impregnation liquid is (100- & lt 200-): 1;
s3, loading the coal sample obtained in the step S2 into a coke oven, heating, introducing hydrogen into the coke oven when the temperature reaches 950 ℃ and 1050 ℃, keeping the pressure of the hydrogen in the coke oven not lower than 1 atmospheric pressure, and cooling after 1.5-2.5h of heat preservation to obtain coke;
wherein the introduction rate of the hydrogen is 10-20L/h.
2. The coking desulfurization method according to claim 1, wherein in S1, the nickel acetate solution and the molybdenum acetate solution are mixed with H3BO3The solution is mixed and stirred for 0.5 to 1 hour at the speed of 350-450r/min to obtain a mixed solution.
3. The coking desulfurization method as claimed in claim 1, wherein the drying process in S1 is carried out at 100-150 ℃.
4. The coking desulfurization method according to claim 1, wherein in S1, the mixed solution contains nickel acetate, molybdenum acetate and H3BO3In a molar ratio of 1: (0.35-0.45): (0.1-0.15).
5. The coking desulfurization method according to claim 1, wherein in S2, high-sulfur coking coal having a particle size of 3mm or less is provided.
6. The coking desulfurization method according to claim 1, wherein the stirring in S2 is carried out at a rate of 80 to 90r/min for 1 to 3 hours.
7. The coking desulfurization method according to claim 1, wherein the coal sample is obtained by drying at 95 to 105 ℃ for 11 to 13 hours in S2.
8. The coking and desulfurization method as claimed in claim 1, wherein in S2, the mass ratio of the high-sulfur coking coal to the composite catalyst in the impregnation liquid is (150- & 200): 1.
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