CN111718738B - Coke oven hydrogen utilization method and system - Google Patents
Coke oven hydrogen utilization method and system Download PDFInfo
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- CN111718738B CN111718738B CN202010620326.XA CN202010620326A CN111718738B CN 111718738 B CN111718738 B CN 111718738B CN 202010620326 A CN202010620326 A CN 202010620326A CN 111718738 B CN111718738 B CN 111718738B
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Abstract
The invention relates to the field of coal coke ovens, in particular to a coke oven hydrogen utilization method and a coke oven hydrogen utilization system, which are particularly suitable for a hydrogen-rich comprehensive utilization technical method of raw gas in different coking periods in the coking process of a coke oven. The top of the carbonization chamber has high activation energy of high-temperature hydrogen, and can be subjected to hydrogenation reaction with graphite on the top of the carbonization chamber for secondary cracking of coal tar, so that the coking process of opening the furnace cover 10-20 minutes ahead of the combustion decoking process is eliminated, the tar yield is improved, and the coke oven productivity is improved.
Description
Technical Field
The invention relates to the field of coal coke ovens, in particular to a coke oven hydrogen utilization method and a coke oven hydrogen utilization system, and is particularly suitable for a coke oven coking process, and a hydrogen-rich comprehensive utilization technical method of crude gas in different coking periods.
Background
In the coking process, coking coal is heated and dry distilled in a coke oven in an air-isolated way to generate coke, and simultaneously, a large amount of raw coke gas is generated, the coke oven is usually formed by a plurality of carbonization chambers (hearths) in parallel, each carbonization chamber is provided with a coal feeding port, a raw coke gas outlet, an ascending pipe assembly and a one-way flap valve, the coal is dried to distill high-temperature raw coke gas which reaches about 850 ℃ in the coking process in the carbonization chambers, and the raw coke gas enters the ascending pipe assembly through the raw coke gas outlet of the carbonization chambers and enters a gas collecting pipe after being subjected to ammonia water temperature reduction. In the coking process, the distilled raw gas is different in fractions at different time of the coke, the distilled raw gas dried in the early coking stage mainly contains macromolecular coal tar, the distilled raw gas dried in the later coking stage mainly contains coal gas, and the coal gas contains a large amount of H2 and CH 4. In actual operation, the temperature of the raw gas in the space at the top of the coking chamber needs to be controlled (furnace top space temperature control), according to the regulation of coke oven technical management regulations, the temperature of the furnace top space is preferably controlled to be 800 +/-50 ℃, is not more than 850 ℃, and is too high, so that the coke oven gas is subjected to secondary cracking at the top of the coking chamber, a large amount of deposited carbon is attached to the top of the coking chamber, and the space temperature is too high, which can cause unqualified quality of chemical recovery tar, such as increased specific gravity, increased viscosity and difficult dehydration of the tar. Opening the riser covers (at most, not more than three) 10-20 minutes ahead of the coke pushing plan, closing the bridge pipe water seal flap valve, opening the dust removal hole cover far away from the riser, sucking air, and burning off graphite at the top of the carbonization chamber. In coke oven production, the common methods for eliminating graphite are: the graphite is swept by compressed air, the graphite is swept by an empty furnace, and the graphite is swept by a scraper arranged at the top of a coke pushing head.
The byproduct of the coal tar coking production process is a complex mixture with ten thousand components, and about 500 more single compounds which are separated and identified at present account for about 55 percent of the total amount of the coal tar, wherein the single compounds comprise 174 neutral components such as benzene, dimethylbenzene, naphthalene and the like; phenol, cresol, etc. 63 kinds of acid component and 113 kinds of alkali component. Although some components have high value, the content of the components in coal tar is very small, and only 13 varieties account for more than l percent, and the varieties are naphthalene, phenanthrene, fluoranthene, fluorene, anthracene, pyrene (melting point is 150 ℃), acenaphthene, carbazole, 2-methylnaphthalene, 1-methylnaphthalene, dibenzofuran and cresol. Many compounds in the coal tar are plastics, synthetic rubber, pesticides, medicines, high-temperature resistant materials and valuable raw materials in the national defense industry, and a part of polycyclic hydrocarbon compounds cannot be produced and replaced by the petrochemical industry. Coal tar is mainly used for processing and producing light oil, phenol oil, naphthalene oil, modified asphalt and the like, and then is further processed to prepare various chemical raw materials such as benzene, phenol, naphthalene, anthracene and the like, although the product quantity is large and the application is wide, the product quantity is less than that of more than 500 compounds in the coal tar. The coal tar after simple processing has low utilization value, and the application of the deep processing refined product is generally seen at home and abroad. The processing technology of coal tar at home and abroad is largely the same and different, and is dehydration and fractionation, and the main research direction of coal tar processing is to increase product varieties, improve product quality grade, save energy and protect environment.
The coal tar hydrogenation refinement has the functions of desulfurization, denitrification, deoxidation and hydrogenation saturation, part of unsaturated olefin and aromatic hydrocarbon bonds in the coal tar are saturated in the hydrogenation process, and the desulfurization, denitrification and deoxidation rates of the coal tar in the section respectively reach more than 96%, 85% and 97%, so that the requirements of cracking raw materials are met. The hydrogen/carbon ratio of the product is increased from 1.11 of the raw oil to 1.58, so that the coal tar is partially lightened in the working section. The hydrocracking section further removes hetero atoms such as sulfur, nitrogen, oxygen and the like in the raw oil, further lightens the product, and most of the raw material is hydrocracked to generate light fractions such as gasoline, diesel oil and the like. After the cracking section, the removal rate of the heteroatoms can reach over 99.5 percent, and the hydrogen/carbon ratio can reach 1.62. After the coal tar is subjected to three-stage hydrogenation, the product oil is lighter and cleaner, and high-value naphtha distillate oil and diesel distillate oil can be obtained after rectification.
The hydrogenation of coal tar increases with the conversion rate of heavy oil of the coal tar, the hydrogen consumption increases slowly after increasing rapidly, the oil yield is similar to the hydrogen consumption and increases finally, and the gas yield is in an increasing trend. The hydrogen is a reactant of the hydrocracking reaction of the tar heavy oil, and the oil yield and the gas yield are concurrent products of the hydrocracking reaction of the tar heavy oil. As the reaction temperature and the reaction time increase, the hydrogenation reaction depth of the tar heavy oil increases, and hydrogen gas participating in the reaction increases, so that the hydrogen consumption increases. In the initial stage of the tar heavy oil reaction, a large number of condensed ring cracking intermediate products need to be hydrogenated stably, so that the hydrogen consumption in the initial stage is increased rapidly along with the increase of the reaction depth; in the later reaction stage, most of condensed ring organic matters which are difficult to crack are cracked, and oil products of monocyclic or bicyclic molecules with fewer rings are generated. Although the monocyclic aromatic hydrocarbon is difficult to be hydrocracked in the later period, branched chains on the aromatic ring type compound can undergo further cracking reaction at high temperature to generate organic matters with smaller molecular size, and the cracking rate of the organic matters to obtain the small molecular gas is higher, so that the later generation rate of the gas yield is higher. Because a large amount of polycyclic aromatic hydrocarbon unsaturated hydrogenation is carried out in the early stage, the hydrogen consumption in the later stage is reduced, which shows that the hydrogen consumption in the later stage of the reaction tends to be slowly increased. The change rule of hydrogen consumption and oil yield reflects the rule of the parallel reaction of the hydrocracking reaction of the tar heavy oil. After the fused ring substances are subjected to dehydrogenation, ring opening and dealkylation and decomposed into oil product molecules with smaller molecular weight, the cracking of the fused ring macromolecules is reduced. Meanwhile, the number of small molecule oils increases, the hydrocracking rate increases, and thus the oil yield selectivity goes down. Similarly, the yield selectivity of the generated gas is continuously increased along with the increase of the conversion rate, because the gas amount generated by cracking the micromolecule oil is increased along with the increase of the reaction conversion rate, and the gas yield is increased. From the change rule of the oil yield selectivity and the gas yield selectivity in the later stage of the conversion rate, it can be seen that the proper selection temperature, time and the like are very important for controlling the selectivity of oil products in the catalytic hydrocracking process of the heavy tar oil. Namely, the reaction time and the reaction temperature under the low-temperature reaction condition are the decisive factors influencing the denitrification rate, and the reaction temperature under the high-temperature reaction condition is the decisive factor influencing the denitrification. The denitrification rate can reach more than 95 percent at the temperature of more than 340 ℃, and the higher denitrification rate can be reached by prolonging the reaction time under the low-temperature condition.
Obviously, the coke oven gas containing 50-60% of hydrogen is difficult to separate hydrogen in the process after coking. Resulting in waste of hydrogen resources.
In a word, distilled raw gas is coked at a carbonization chamber, an ascending pipe and a bridge pipe, raw gas resources are wasted, great hidden dangers are brought to safe production, the labor intensity and difficulty of equipment maintenance and repair in the production process are increased, and the coke oven productivity is reduced because macromolecule raw gas is cracked, meanwhile, hydrogenation is needed in the lightening processing of coal tar, 50-60% of hydrogen resources in the coal gas cannot be applied, and a plurality of technical difficulties and pain points exist in the coke oven process:
1. the cracking reaction of macromolecular coal tar can cause a large amount of deposited carbon to be attached to the top of the carbonization chamber, the ascending pipe and the bridge pipe, thereby bringing great hidden danger to safe production and increasing the labor intensity and difficulty of equipment maintenance in the production process;
2. the temperature of the furnace top space is difficult to control;
3. the graphite at the top of the carbonization chamber is burnt and decoked, which wastes energy and resources and reduces the productivity of the coke oven;
4. the yield of tar is reduced by cracking macromolecular coal tar, and the benefit is reduced;
5. the temperature of the coke graphite is high at the low temperature of the raw coke oven gas, the energy consumption of the subsequent ammonia injection is wasted, and the waste heat is wasted
Disclosure of Invention
The invention aims to provide a coke oven hydrogen utilization method and a coke oven hydrogen utilization system, which are based on the principle that hydrogen-rich raw gas dried and distilled at the later coking stage of a coke oven carbonization chamber is led into another carbonization chamber which is just added with coal through a pipe channel, so that macromolecule raw gas dried and distilled by coke coal which is newly added into the carbonization chamber is subjected to cracking and hydrogenation reaction in a hydrogen-rich environment, the coke oven hydrogen utilization system has high reliability and good stability, can effectively solve the problems in the prior art, and is beneficial to long-term stable and safe operation of the system.
The technical method for solving the technical problem is as follows:
a coke oven hydrogen utilization method comprising:
sequentially opening communicating valves of the coking later-stage carbonization chamber furnace top and the pipe duct, sequentially closing a flap valve behind a crude gas riser assembly at the coking later-stage carbonization chamber furnace top, and sequentially opening communicating valves of the coal carbonization chamber and the pipe duct which are just added;
and (3) sequentially leading the hydrogen-rich raw gas in the later coking period from one or more carbonization chambers to one or more carbonization chambers with coal just added through a raw gas pipe duct system, so that the hydrogen-rich raw gas is led into the carbonization chamber with coal just added to form a hydrogen-rich environment, and controlling, adjusting and inducing the cracking reaction of the raw gas to be sequentially circulated.
Preferably, the raw gas pipe duct comprises a cooling waste heat recoverer to adjust and control the temperature of the raw gas, and then the raw gas is introduced into another or other carbonization chambers which are just added with coal, so that hydrogen-rich environment is formed in the carbonization chambers which are just added with coal under the temperature reaction condition by introducing hydrogen-rich raw gas, and the raw gas cracking reaction is controlled, adjusted and induced; after the coal carbonization chamber is added for a certain time to react, the raw gas can also go through the process from heavy component raw gas to the later hydrogen enrichment in the coke cooking process, the hydrogen-enriched raw gas in the carbonization chamber also needs to be introduced into other carbonization chambers which are added with coal, and the flow control is carried out through the respective opening and closing of the pipe channel valve and the flap valve thereof, so that the sequential circulation is realized.
Preferably, the raw gas pipe duct is arranged at the furnace end far away from the raw gas outlet, hydrogen-rich raw gas is injected from the carbonization chamber with just added coal far away from the raw gas outlet end, the hydrogen-rich raw gas enters the top of the carbonization chamber and then flows out from the raw gas outlet of the carbonization chamber; the hydrogen-rich raw gas passes through the length of the top of the carbonization chamber of the coke oven, the reaction time of the raw gas is prolonged, and the initial carbon formation on the top of the carbonization chamber can be reversed again by adding hydrogenThe coke control and the decoking targets at the top of the carbonization chamber are realized by hydrogenation, the coking process is eliminated, the decoking can be realized, the light oil yield can be increased, the hydrogen-rich raw gas is injected from the outlet end of the carbonization chamber, which is far away from the raw gas, into which the coal is just added, and enters the top of the carbonization chamber and then flows out from the raw gas outlet of the carbonization chamber; at the top temperature of 800+50 ℃ at the top of the carbonization chamber, hydrogen has high activation energy, and the coking later period of one carbonization chamber is mainly heated to 850 ℃ by H2And CH4Raw gas which is a main component is led into a carbonization chamber which is just added with coal, the temperature at the top of the carbonization chamber is in a temperature climbing period, so that the temperature at the top of the carbonization chamber reaches about 800 ℃ rapidly to form a high-temperature hydrogen-rich coke oven gas environment, the temperature of the raw gas which is distilled out quickly after the coal which is just added is heated at high temperature is raised rapidly, heavy components of the raw gas are cracked rapidly, hydrogen in the hydrogen-rich environment can participate in the position supplement of broken bonds of cracked molecules to form hydrogenation reaction, and the cracking reaction conditions of the raw gas are controlled, adjusted and induced, so that the target reaction and the control of target products are realized more easily especially when a catalyst fixed bed is arranged on a pipe channel and/or an ascending pipe and/or the top of the carbonization chamber;
preferably, the raw gas pipe duct is arranged at the end of a raw gas outlet furnace, and hydrogen-rich raw gas is injected from the root of the raw gas outlet of the carbonization chamber in which coal is just added, and then is mixed with the raw gas in the carbonization chamber and flows out through the ascending pipe and the components thereof; thereby realizing the temperature condition of cracking hydrogenation, leading the cracking reaction to become a cracking reaction and realizing the lightening of target products or heavy oil; the method is implemented by closing or sequentially closing the hydrogen-rich raw gas at the later coking stage of one or more carbonization chambers of the coke oven through a flap valve, introducing the hydrogen-rich raw gas into another or other carbonization chambers which are just added with coal through a pipe channel, wherein the pipe channel is a high-temperature-resistant pipe channel, introducing the hydrogen-rich raw gas into the carbonization chambers which are just added with coal like a water channel, and the just added coke coal contains certain moisture and is rapidly heated in the carbonization chambers to be distilled out of the raw gas, and macromolecular tar is distilled off along with the increase of the temperature, so that macromolecular bonds of the tar are broken and condensed, and hydrogen molecules can be filled into broken molecular bonds to form a micromolecular light group. The cooler is added at the pipe duct section to control the temperature of the hydrogen-rich raw gas, the raw gas which is newly generated in the carbonization chamber after the coal is just added is introduced and mixed with the raw gas which is newly generated in the carbonization chamber, so that the temperature of the raw gas is reduced, the top temperature of the carbonization chamber is reduced, the top temperature control of the carbonization chamber is realized, the temperature is controlled, the reaction condition of the raw gas is also controlled, the temperature of the raw gas which is output by the carbonization chamber after the coal is added is adjusted, the forming process of a cracking product is adjusted to form a hydrogen-rich environment, and the cracking reaction is converted towards a light target product.
The invention also provides another technical scheme:
a coke oven hydrogen utilization system comprises a coke oven carbonization chamber, a high-temperature valve, a carbonization chamber and pipe channel communicating pipe, a pipe channel, an ascending pipe and a flap valve; the carbonization chamber and the pipe channel communicating pipe is used for communicating the carbonization chamber of the coke oven and the pipe channel; a flap valve is arranged on the ascending pipe; the coke oven carbonization chamber is provided with a raw coke oven gas inlet and outlet at the other end of the ascending pipe side of the original raw coke oven gas outlet, the inlet and outlet are connected with a high-temperature valve, the high-temperature valve is externally connected with a raw coke oven gas pipe duct, the pipe duct is parallel to the side-by-side arrangement line of the coke oven carbonization chamber, the pipe duct is externally connected with a high-temperature valve in a three-way manner, and the high-temperature valve is internally connected with the corresponding coke oven carbonization chamber;
or
The coke oven carbonization chamber is provided with a raw coke oven gas inlet and outlet at one end of the ascending pipe side of the original raw coke oven gas outlet, the inlet and outlet are connected with a high-temperature valve through a three-way type at the root part of the outlet of a raw coke oven gas ascending pipe assembly, the high-temperature valve is externally connected with a raw coke oven gas pipe duct, the pipe ducts are parallel to the side-by-side arrangement line of the coke oven carbonization chamber, the three-way type of the pipe duct is externally connected with the high-temperature valve, and the root part of the ascending pipe; at this time, the high-temperature valve is a three-way high-temperature valve.
Furthermore, the raw coke oven gas pipe duct is a lining heat-insulating pipeline which is connected in a segmented manner, and a cooling waste heat recoverer is arranged in the segment, so that the reaction temperature control of the segment is realized.
Furthermore, the raw coke oven gas ascending pipe is provided with a cooling waste heat recoverer, so that the reaction temperature control of the section is realized.
Further, a fixed catalyst bed is arranged at the top of the pipe duct and/or the ascending pipe and/or the carbonization chamber, so that the reaction condition control of the section is realized.
The invention has the technical effects that:
compared with the prior art, the hydrogen utilization method of the coke oven has the advantages that the hydrogen-rich raw gas in the later coking period is sequentially led into one or more carbonization chambers through a raw gas pipe duct system to one or more other carbonization chambers which are just added with coal, so that the hydrogen-rich environment is formed in the carbonization chambers which are just added with the coal by leading in the hydrogen-rich raw gas, and the cracking reaction is converted towards light target products by controlling, adjusting and inducing the cracking reaction of the raw gas; and has the following advantages:
1. the coke oven hydrogen utilizes the control, adjustment and induction of the cracking reaction of macromolecular coal tar, so that the adhesion of deposited carbon at the top of the carbonization chamber is eliminated;
2. the addition of the catalyst fixed bed can promote the hydrogenation target reaction, promote the lightening of macromolecules after cracking, increase the light yield and improve the added value of coal tar.
3. The invention can control the temperature of the top space of the carbonization chamber through the hydrogen-rich raw gas pipe duct cooler, thereby solving the problem of difficult control of the temperature of the top space of the carbonization chamber;
4. the carbonization chamber top has high activation energy of high-temperature hydrogen, and can be subjected to hydrogenation reaction with graphite at the top of the carbonization chamber for secondary cracking of coal tar, so that the coking process of opening the furnace cover 10-20 minutes ahead of the combustion decoking process is eliminated, the tar yield is improved, and the coke oven productivity is improved;
5. the invention realizes proper hydrogenation reaction through hydrogen-rich cracking control, so that macromolecule coal tar is cracked and hydrogenated, the yield of the coal tar is improved, and the coking benefit is obviously improved.
6. The hydrogen-rich pipe duct provided by the invention is used for cooling waste heat recovery, and is energy-saving and emission-reducing.
7. The temperature of the light raw gas low-temperature coke graphite is reduced, the injection amount of the subsequent ammonia can be obviously reduced, and the waste heat recovery amount is improved.
Drawings
FIG. 1 is a schematic structural diagram of a hydrogen utilization system of a coke oven according to the present invention;
FIG. 2 is a schematic structural diagram of a carbonization chamber with an independent connection of a pipe duct according to the present invention;
FIG. 3 is a schematic view of the side canal structure of the ascending tube according to the present invention;
FIG. 4 is a cross-sectional view taken along line A-A of FIG. 2 according to one embodiment of the present invention;
FIG. 5 is a cross-sectional view taken along line A-A of the alternate embodiment of FIG. 2 of the present invention;
FIG. 6 is a cross-sectional view taken along line B-B of FIG. 3 in accordance with the present invention;
wherein, the carbonization chamber 1, the high temperature valve 2, the carbonization chamber and pipe channel communicating pipe 3, the pipe channel 4, the carbonization chamber furnace top hole 5, the ascending pipe 6, the flap valve 7 and the catalyst fixed bed 8.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
The invention is further illustrated by the following specific examples in combination with the accompanying drawings.
A method for utilizing hydrogen in coke oven features that the hydrogen-enriched raw gas dried out in later coking stage of coking chamber of coke oven is introduced via pipe channel to another coking chamber in which coal has just been added, so cracking and hydrogenating reactions are performed on the macromolecular raw gas dried out from coke coal newly added in said coking chamber in hydrogen-enriched environment. Particularly, the cooler and the catalyst fixed bed are arranged at different positions of each section, so that the hydrogen-rich hydrogenation condition of the raw gas can be optimized, and the targeted reaction control can be realized.
A coke oven hydrogen utilization method comprising:
sequentially opening communicating valves of the top of the carbonization chamber and the pipe duct of the coking later-stage carbonization chamber, sequentially closing a flap valve behind the crude gas riser assembly at the top of the carbonization chamber of the coking later-stage carbonization chamber, and sequentially opening communicating valves of the coal carbonization chamber and the pipe duct which are just added;
and (3) sequentially leading the hydrogen-rich raw gas in the later coking period from one or more carbonization chambers to one or more carbonization chambers with coal just added through a raw gas pipe duct system, so that the hydrogen-rich raw gas is led into the carbonization chamber with coal just added to form a hydrogen-rich environment, and controlling, adjusting and inducing the cracking reaction of the raw gas to be sequentially circulated.
Preferably, the raw gas pipe duct is provided with a cooling waste heat recoverer to adjust and control the temperature of the raw gas, and then the raw gas is introduced into another or other carbonization chambers which are just added with coal, so that hydrogen-rich environment is formed in the carbonization chambers which are just added with coal under the temperature reaction condition by introducing hydrogen-rich raw gas, and the raw gas cracking reaction is controlled, adjusted and induced; after the coal carbonization chamber is added for a certain time to react, the raw gas can also go through the process from heavy component raw gas to the later hydrogen enrichment in the coke cooking process, the hydrogen-enriched raw gas in the carbonization chamber also needs to be introduced into other carbonization chambers which are added with coal, and the flow control is carried out through the respective opening and closing of the pipe channel valve and the flap valve thereof, so that the sequential circulation is realized.
Preferably, a catalyst fixed bed is arranged on the top of the crude gas pipe channel and/or the ascending pipe and/or the carbonization chamber, after a flap valve of the carbonization chamber is closed, the pressure in the carbonization chamber rises, high-temperature hydrogen-rich crude gas flows into the pipe channel under the pressure, macromolecular crude gas which is distilled off after the coal carbonization chamber is added can sharply increase, the pressure in the carbonization chamber rises, the macromolecular crude gas can be driven to flow to the pipe channel, the macromolecular crude gas flows in the pipe channel provided with the fixed window catalyst and meets the converse hydrogen-rich crude gas in the pipe channel provided with the fixed window catalyst, the catalyst can promote the macromolecular crude gas cracking reaction to be carried out in a hydrogen-rich environment, the macromolecule crude gas cracking hydrogenation reaction is promoted, the small molecular groups which are just cracked are combined with hydrogen to form small molecular tar, the small molecular tar enters the carbonization chamber, and the cracking reaction continues to be carried out in the hydrogen-rich environment, Cracking hydrogenation reaction, realizing the micromolecule formation of the raw gas, improving the light yield of the raw gas and realizing the value improvement of the raw gas; similarly, the catalyst fixed bed is arranged in the ascending pipe, so that cracking and cracking hydrogenation reactions can be realized under a hydrogen-rich environment, the raw coke oven gas is subjected to micromolecule formation, the light yield of the raw coke oven gas is improved, and the value of the raw coke oven gas is improved. Meanwhile, the organic sulfur hydrogen-rich environment is subjected to hydrogenation reaction to form inorganic sulfur, which is more favorable for sulfur removal and reduces environmental pollution. And then introduced into another or other carbonization chambers with just added coal, so that the hydrogen-rich raw gas is introduced into the carbonization chambers with just added coal to promote more targeted reaction of cracking and hydrogenation in the raw gas. In order to operate, the movable catalyst fixed bed can be added through the top hole of the carbonization chamber and suspended on the top of the carbonization chamber, so that the catalyst with deactivated reaction can be replaced periodically, the activity of the catalyst is improved, and the real-time reaction catalysis effect of the catalyst is achieved.
Preferably, as shown in fig. 4, the raw gas pipe duct is arranged at the furnace end far away from the raw gas outlet, hydrogen-rich raw gas is injected from the carbonization chamber with just added coal far away from the raw gas outlet end, the hydrogen-rich raw gas enters the top of the carbonization chamber and then flows out from the raw gas outlet of the carbonization chamber; the method has the advantages that the hydrogen-rich raw gas passes through the length of the top of the carbonization chamber of the coke oven, the reaction time of the raw gas is prolonged, the initial carbon formation on the top of the coke oven can be reacted and hydrogenated again by adding hydrogen, the coke control and cleaning targets of the carbonization chamber on the top of the coke oven are realized, the coke cleaning process is eliminated, the yield of light oil can be increased, the hydrogen-rich raw gas is injected from the outlet end of the raw gas far away from the carbonization chamber after coal is added, the hydrogen-rich raw gas enters the top of the carbonization chamber and then flows out from the raw gas outlet of the carbonization chamber; at the top temperature of 800+50 ℃ at the top of the carbonization chamber, hydrogen has high activation energy, and the coking later period of one carbonization chamber is mainly heated to 850 ℃ by H2And CH4Introducing raw coke oven gas as main component into carbonization chamber with coal added, and allowing the top temperature of the carbonization chamber to rapidly reach 800 deg.C in temperature rising period to form high-temperature hydrogen-rich coke oven gas environment, wherein the coal added immediately after high temperature is rapidly heatedThe temperature of the distilled raw gas is rapidly raised, heavy components of the raw gas are rapidly cracked, hydrogen in a hydrogen-rich environment can participate in the position supplement of broken bonds of cracked molecules to form a hydrogenation reaction, the cracking reaction conditions of the raw gas are controlled, adjusted and induced, and the target reaction and the control of a target product are realized;
preferably, as shown in fig. 5, the raw gas pipe duct is arranged at the furnace end of the raw gas outlet, and the hydrogen-rich raw gas is injected from the root of the raw gas outlet of the carbonization chamber to which the coal is just added, and then is mixed with the raw gas in the carbonization chamber and flows out through the ascending pipe and the components thereof; thereby realizing the temperature condition of cracking hydrogenation, leading the cracking reaction to become a cracking reaction and realizing the lightening of target products or heavy oil; the method is implemented by closing or sequentially closing the hydrogen-rich raw gas at the later coking stage of one or more carbonization chambers of the coke oven through a flap valve, introducing the hydrogen-rich raw gas into another or other carbonization chambers which are just added with coal through a pipe channel, wherein the pipe channel is a high-temperature-resistant pipe channel, introducing the hydrogen-rich raw gas into the carbonization chambers which are just added with coal like a water channel, and the just added coke coal contains certain moisture and is rapidly heated in the carbonization chambers to be distilled out of the raw gas, and macromolecular tar is distilled off along with the increase of the temperature, so that macromolecular bonds of the tar are broken and condensed, and hydrogen molecules can be filled into broken molecular bonds to form a micromolecular light group. The cooler is added at the pipe duct section to control the temperature of the hydrogen-rich raw gas, the raw gas which is newly generated in the carbonization chamber after the coal is just added is introduced and mixed with the raw gas which is newly generated in the carbonization chamber, so that the temperature of the raw gas is reduced, the top temperature of the carbonization chamber is reduced, the top temperature control of the carbonization chamber is realized, the temperature is controlled, the reaction condition of the raw gas is also controlled, the temperature of the raw gas which is output by the carbonization chamber after the coal is added is adjusted, the forming process of a cracking product is adjusted to form a hydrogen-rich environment, and the cracking reaction is converted towards a light target product.
Furthermore, a catalyst fixed bed is arranged at the top of the raw gas pipe duct and/or the ascending pipe and/or the carbonization chamber, and then the raw gas is introduced into another or other carbonization chambers which are just added with coal, so that the hydrogen-rich raw gas is introduced into the carbonization chamber which is just added with coal, and the more targeted reaction of cracking hydrogenation in the raw gas is promoted.
The invention also provides a coke oven hydrogen utilization system:
a coke oven hydrogen utilization system, which comprises a carbonization chamber 1, a high-temperature valve 2, a carbonization chamber and pipe channel communicating pipe 3, a pipe channel 4, a rising pipe 6, a flap valve 7 and a catalyst fixed bed 8,
example 1:
as shown in FIGS. 2 and 4, the coke oven hydrogen gas utilization system of the present embodiment is a system in which a pipe duct 4 is provided at the other side position of an ascending pipe 6 of a coking chamber; the carbonization chamber and pipe channel communicating pipe 3 is used for communicating the carbonization chamber 1 of the coke oven and a pipe channel 4; a flap valve 7 is arranged on the ascending pipe 6; the coke oven carbonization chamber 1 is provided with a raw gas inlet and outlet at the other end of the raw gas outlet on the side of an ascending pipe 6, the inlet and outlet is connected into a high-temperature valve 2, the high-temperature valve 2 is externally connected with a raw gas pipe channel, the pipe channels 4 are parallel to the side-by-side arrangement line of the coke oven carbonization chamber 1, the pipe channel three-way type is externally connected with the high-temperature valve 2, the high-temperature valve 2 is internally connected into the corresponding coke oven carbonization chamber 1, and a catalyst fixed bed 8 is arranged in the pipe channel 4 and/or the top of the carbonization chamber 1 and/or the ascending pipe 6; the pipe duct 4 is arranged on the other side of the ascending pipe 6 of the carbonization chamber 1, and has the advantages that the flow of the raw gas in the hydrogen-rich environment is long, and the raw gas can fully react.
Example 2:
as shown in FIGS. 3 and 5, the coke oven hydrogen gas utilization system of the present embodiment is a system in which the pipe duct 4 is provided at the same side position as the rising pipe of the coking chamber; the raw gas inlet and outlet of the coke oven carbonization chamber 1 are arranged on the same side of the ascending pipe 6 of the original raw gas outlet, the inlet and outlet are connected into the high-temperature valve 2 through a three-way type at the root part of the outlet of the raw gas ascending pipe assembly, the high-temperature valve 2 is externally connected with a raw gas pipe duct, the pipe duct 4 is parallel to the side-by-side arrangement line of the coke oven carbonization chamber 1, and a catalyst fixed bed 8 is arranged in the pipe duct 4 and/or the top of the carbonization chamber 1 and/or the ascending pipe 6; the embodiment has the advantages that the technical transformation problem of the existing coke oven can be well solved, and the structure of the carbonization chamber part at the top of the coke oven does not need to be changed.
Example 3:
as shown in figures 2 and 6, the pipe duct 4 is connected with the carbonization chamber 1 of the coke oven by using the hole 5 of the carbonization chamber at the top of the existing oven and is connected with the communicating pipe 3, so that the technical improvement of the technical scheme of the existing coke oven can be smoothly solved by the connection and the disconnection, the invention has the advantages that the existing coke oven does not need to be improved, the pipe duct is connected by using the hole at the top of the carbonization chamber of the existing coke oven, the flow length of the raw gas is increased, and the reaction time is prolonged.
Further, when the coke oven carbonization chamber 1 is provided with a crude gas inlet and outlet at the other end of the crude gas outlet on the side of the ascending pipe 6, the high temperature valve 2 is connected with the corresponding coke oven carbonization chamber 1 through the top carbonization chamber hole 5, or directly connected with the corresponding coke oven carbonization chamber 1, as shown in fig. 4 and 5.
Further, raw coke oven gas pipe 4 is the sectional type connection, and the design can reduce the pipe duct construction degree of difficulty like this, and the maintenance of being convenient for, transformation are equipped with the catalyst fixed bed in every section, and the pipe duct after the segmentation also can realize the construction of catalyst fixed mounting, sets up the catalyst fixed bed in the pipe duct, can realize the rich hydrogen environment of raw coke oven gas early, is favorable to macromolecule raw coke oven gas catalytic hydrogenation to go on.
Furthermore, a catalyst fixed bed 8 is arranged at the top of the raw gas ascending pipe 6 and/or the pipe duct 4 and/or the carbonization chamber 1, and is used for promoting the reaction speed, promoting the reaction to be carried out towards a required direction, promoting the reaction to be carried out unidirectionally, realizing the maximum utilization of rich hydrogen and the maximum utilization of the rich hydrogen.
Furthermore, the raw coke oven gas pipe duct 4 is a lining heat-insulating pipeline and is connected in a segmented mode, a cooling waste heat recoverer is arranged in the segment, and the difficulty of construction, installation and operation maintenance can be reduced by the segment.
Further, the raw coke oven gas ascending pipe 6 is provided with a cooling waste heat recoverer. The waste heat recoverer is arranged for saving energy and controlling the temperature condition of the reaction. The invention leads the hydrogen-rich raw gas in the later coking period from one or more carbonization chambers to another or other carbonization chambers with just finished coal through a raw gas pipe canal system in turn, leads the hydrogen-rich raw gas to form a hydrogen-rich environment in the carbonization chambers with just finished coal, controls, adjusts and induces the cracking reaction of the raw gas, and leads the cracking reaction to be converted towards light target products.
The above embodiments are only specific examples of the present invention, and the protection scope of the present invention includes but is not limited to the product forms and styles of the above embodiments, and any suitable changes or modifications made by those skilled in the art according to the claims of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A coke oven hydrogen utilization method is characterized in that: the principle is that the hydrogen-rich crude gas which is dry distilled in the coking later stage of a coking chamber of a coke oven is led into another coking chamber which is just added with coal through a pipe channel, so that macromolecule crude gas which is dry distilled from the coking coal and is newly added into the coking chamber is subjected to cracking and hydrogenation reaction in a hydrogen-rich environment, and the specific process comprises the following steps:
sequentially opening communicating valves of the furnace top and the pipe duct of the carbonization chamber at the later coking period, sequentially opening communicating valves of the coal carbonization chamber and the pipe duct just after the coal carbonization chamber is added, and sequentially closing a flap valve behind a crude gas riser assembly at the furnace top of the carbonization chamber at the later coking period;
and (2) leading the hydrogen-rich raw gas in the later coking period from one or more carbonization chambers to another or more carbonization chambers which are just added with coal in sequence through a raw gas pipe canal system, so that the hydrogen-rich raw gas is led into the carbonization chambers which are just added with coal to form a hydrogen-rich environment, and controlling, adjusting and inducing the cracking, cracking and hydrogenation reactions of the raw gas to circulate in sequence.
2. The coke oven hydrogen gas utilization method according to claim 1, characterized in that: the raw gas pipe duct comprises a cooling waste heat recoverer to adjust and control the temperature of the raw gas, and then the raw gas is introduced into another or other carbonization chambers which are just added with coal, so that hydrogen-rich environment is formed in the carbonization chambers which are just added with coal under the temperature reaction condition by introducing the hydrogen-rich raw gas, and the raw gas cracking reaction is controlled, adjusted and induced.
3. The coke oven hydrogen gas utilization method according to claim 1, characterized in that: and a catalyst fixed bed is arranged at the top of the raw gas pipe duct and/or the ascending pipe and/or the carbonization chamber and then is introduced into another or other carbonization chambers which are just added with coal, so that the hydrogen-rich raw gas is introduced into the carbonization chamber which is just added with coal, and the more targeted reaction of cracking hydrogenation in the raw gas is promoted.
4. The coke oven hydrogen gas utilization method according to claim 1 or 2, characterized in that: placing the raw gas pipe duct at the furnace end far away from a raw gas outlet, injecting hydrogen-rich raw gas from a carbonization chamber just after coal addition far away from the raw gas outlet end, allowing the hydrogen-rich raw gas to enter the top of the carbonization chamber, and then allowing the hydrogen-rich raw gas to flow out from the raw gas outlet of the carbonization chamber; the hydrogen-rich raw gas passes through the length of the top of the coke oven carbonization chamber, the reaction time of the raw gas is prolonged, and the initial carbon formation on the top of the coke oven can be reacted and hydrogenated again by adding hydrogen.
5. The coke oven hydrogen gas utilization method according to claim 1 or 2, characterized in that: placing the raw gas pipe duct at the furnace end of a raw gas outlet, injecting hydrogen-rich raw gas from the root of the raw gas outlet of a carbonization chamber in which coal is just added, mixing the hydrogen-rich raw gas with the raw gas in the carbonization chamber, and flowing out through a riser and an assembly of the riser; thereby realizing the temperature condition of cracking hydrogenation and leading the cracking reaction to become the cracking reaction.
6. A coke oven hydrogen utilization system comprises a coke oven carbonization chamber, a high-temperature valve, a carbonization chamber and pipe channel communicating pipe, a pipe channel, an ascending pipe and a flap valve; the carbonization chamber and the pipe channel communicating pipe is used for communicating the carbonization chamber of the coke oven and the pipe channel; a flap valve is arranged on the ascending pipe; the coke oven carbonization chamber is provided with a raw coke oven gas inlet and outlet at the other end of the ascending pipe side of the original raw coke oven gas outlet, the inlet and outlet are connected with a high-temperature valve, the high-temperature valve is externally connected with a raw coke oven gas pipe duct, the pipe duct is parallel to the side-by-side arrangement line of the coke oven carbonization chamber, the pipe duct is externally connected with a high-temperature valve in a three-way manner, and the high-temperature valve is internally connected with the corresponding coke oven carbonization chamber;
or
The coke oven carbonization chamber is provided with a raw coke oven gas inlet and outlet at one end of the ascending pipe side of the original raw coke oven gas outlet, the inlet and outlet are connected with a high-temperature valve through a three-way type at the root part of the outlet of a raw coke oven gas ascending pipe assembly, the high-temperature valve is externally connected with a raw coke oven gas pipe duct, the pipe ducts are parallel to the side-by-side arrangement line of the coke oven carbonization chamber, the three-way type of the pipe duct is externally connected with the high-temperature valve, and the root part of the ascending pipe; at this time, the high-temperature valve is a three-way high-temperature valve.
7. The coke oven hydrogen gas utilization system of claim 6, wherein: the pipe channel is connected with the carbonization chamber of the coke oven, and a communicating pipe is connected by using the furnace top hole.
8. The coke oven hydrogen gas utilization system of claim 6, wherein: when the other end of the coke oven carbonization chamber on the side of the riser of the original crude gas outlet is provided with a crude gas inlet and a crude gas outlet, the high-temperature valve is directly connected with the corresponding coke oven carbonization chamber.
9. The coke oven hydrogen gas utilization system of claim 6, wherein: the raw gas pipe duct is a lining heat-insulating pipe and is connected in a segmented mode, a catalyst fixed bed is arranged at the top of each segment and/or the top of the carbonization chamber, and a cooling waste heat recoverer is further arranged in each segment.
10. The coke oven hydrogen gas utilization system of claim 6, wherein: a catalyst fixed bed is arranged at the top of the raw gas ascending pipe and/or the carbonization chamber; and the raw gas ascending pipe is provided with a cooling waste heat recoverer.
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| CN102154049B (en) * | 2011-03-08 | 2014-06-11 | 煤炭科学研究总院 | Method for preparing coking coal by modification by low-order nonadhesive coal |
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| CN206666473U (en) * | 2017-03-03 | 2017-11-24 | 陕西黑猫焦化股份有限公司 | Coke oven gas desulfurization hydro-conversion system |
| CN108102733A (en) * | 2017-07-19 | 2018-06-01 | 湖北申昙环保新材料有限公司 | The method of comprehensive utilization of coke-stove gas |
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