WO2016095464A1 - 一种采用间接加热分段热解方式从中、低阶煤中连续提烃的工艺及装置 - Google Patents

一种采用间接加热分段热解方式从中、低阶煤中连续提烃的工艺及装置 Download PDF

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WO2016095464A1
WO2016095464A1 PCT/CN2015/081693 CN2015081693W WO2016095464A1 WO 2016095464 A1 WO2016095464 A1 WO 2016095464A1 CN 2015081693 W CN2015081693 W CN 2015081693W WO 2016095464 A1 WO2016095464 A1 WO 2016095464A1
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pyrolysis
coke
low
medium
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PCT/CN2015/081693
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English (en)
French (fr)
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程相魁
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程相魁
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Priority to UAA201707635A priority Critical patent/UA120384C2/uk
Publication of WO2016095464A1 publication Critical patent/WO2016095464A1/zh
Priority to ZA2017/04906A priority patent/ZA201704906B/en

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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
    • C10B39/00—Cooling or quenching coke
    • C10B39/02—Dry cooling outside the oven
    • 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
    • C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/18—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge

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  • the invention belongs to the technical field of coal chemical industry, and relates to an indirect heating segmental pyrolysis medium/low rank coal continuous hydrocarbon extraction process and device.
  • low-rank coal brown coal, long-flame coal, non-stick coal, weakly cohesive coal
  • volatiles of medium-rank coal with a volatile content of more than 18% are mainly composed of hydrocarbon materials.
  • the hydrocarbon component In volatiles of medium and low rank coals with a volatile content of more than 25%, the hydrocarbon component generally accounts for more than 75% by weight of the anhydrous radicals.
  • hydrocarbon components In particular, in low-rank coal with a low degree of coalification, hydrocarbon components generally account for more than 25% of the total mass ratio of coal.
  • the hydrocarbon material is pyrolyzed close to the initial component under appropriate process conditions (ie, secondary cracking is inhibited), about 40% of it is a gaseous substance mainly composed of C 1-4 alkane olefin after separation and purification. If the gas is further cryogenically separated, it can extract high value-added clean vehicle fuel LNG (liquid methane) and civil liquefied gas (main component is liquid propane); there are also about 5% liquid light hydrocarbon products; the remaining 50% The left and right are mostly lightweight tars for the production of high-quality motor oil.
  • LNG liquid methane
  • main component main component is liquid propane
  • China is a country that lacks oil, gas, and coal. By the end of 2012, China had identified only 3.33 billion tons of recoverable oil reserves and 4.4 trillion cubic meters of natural gas.
  • the reserves of coal resources were 1.42 trillion tons, of which more than 80% were medium and low-rank coals.
  • the high-efficiency and low-cost hydrocarbon extraction process can extract more than 150 billion tons of processed power oil and extract high-quality alkane gas products (heat value higher than natural gas) by about 140 trillion cubic meters, at least several times as much as natural oil and gas reserves.
  • the medium-low temperature stage pyrolysis technology is more conducive to increasing the light hydrocarbon content of the gas, so that the valuable light hydrocarbon products can be directly extracted and utilized, and the gas after the hydrocarbon is suitable for the synthesis gas.
  • the key to achieving medium and low temperature pyrolysis is the process and furnace type. Although many medium and low temperature dry distillation processes and furnace types can play a role in medium and low temperature pyrolysis, most of these furnaces use an internal heat process using air-rich exhaust gas as a gas source. Not only does a large amount of nitrogen dilute the active constituents of the gas, but even more than 70% of the valuable alkane compounds are severely damaged! Although most people are accustomed to refer to this type of furnace as a dry distillation furnace, strictly speaking, it is not in line with the definition of dry distillation of "insulated air for heating". The key point is that these furnace types are mainly used for dry distillation to produce semi-coke. The thermal decomposition of valuable hydrocarbon chemical products has not been positioned as the main process target, so it is impossible to effectively pyrolyze hydrocarbon compounds in an ideal state. Great destruction and waste of quality resources.
  • Table 1 Medium and low temperature dry distillation furnace types popular in China and their process parameters
  • the oil and gas yield is still low, the asphaltene content in the pyrolysis oil is high, the separation of tar and system dust is difficult, and the blue carbon product can only be ⁇ 6mm.
  • a blast furnace fuel injection or power generation fuel it can not be used for gas production in the fertilizer industry, the use value is reduced and the market space is small, etc.; there is also a kind of internal and external heating type can not use the surface coal as raw material to produce blue carbon, the tar yield is not Up to 50%, and there is a fundamental improvement in gas quality.
  • the waste gas is subjected to strong secondary high-temperature pyrolysis during the derivation process, which reduces the yield and quality of the tar, and at the same time deteriorates the gas composition, resulting in a 70% reduction in the alkane content. Above, the hydrogen content is multiplied.
  • the common problems of the process are the low oil and gas yield, the high content of asphaltene in the pyrolysis oil, and the difficulty in separating the tar from the system dust. Therefore, there is no large-scale industrial application. Moreover, it is generally believed at home and abroad that the key technologies for breakthrough pyrolysis are product separation, light weight of pyrolysis oil and scale up.
  • the object of the present invention is to overcome the deficiencies of the prior art and to provide a process and apparatus for continuously extracting hydrocarbons from medium/low rank coals by means of indirect heating stage pyrolysis.
  • the invention provides a process for heating materials under relatively static conditions, adopting an easy-to-control multi-stage gradient heating, indirect heating of segmental pyrolysis, and gas-solid two-state separation in the process, overcoming dynamic gas and powder in the heating system. Process defects caused by solid two-phase flow.
  • a first object of the present invention is to provide a process for continuously extracting hydrocarbons from medium/low rank coals by indirect heating stage pyrolysis.
  • the process for continuously extracting hydrocarbons from medium/low rank coal by indirect heating segmental pyrolysis includes the following steps:
  • the medium/low-order coal is transported in the whole process of the process in a sealed state by gravity at a speed of less than 0.5 mm/s.
  • the medium/low rank coals of the present invention are conventional intermediate coals and low rank coals well known in the art, and the present invention does not specifically limit its parameters.
  • the medium/low rank coal may be cold powdered coal, which is pressed to obtain a briquette, which can be used for subsequent steps.
  • the indirect heating according to the present invention specifically refers to a process in which the medium/low-order coal is subjected to heat exchange and heat transfer through the partition wall without directly contacting the heat source.
  • the water vapor can be introduced in the ascending process, and the water vapor is directly exchanged with the coke in the coke, single-hole coke quenching, coke and pyrolysis steps in the ascending process to assist the high efficiency. Quenching and generating water gas; the water gas is exported.
  • the quenching section of the present invention comprises a high temperature dry quenching section and a medium and low temperature dry quenching section; in the high temperature dry quenching stage, the high temperature coke is indirectly heat exchanged with the low temperature air, and at the same time, direct heat exchange with water vapor to realize high temperature coke Waste heat recovery; in the medium-low temperature dry quenching stage, the medium and low temperature coke is indirectly heat exchanged with the cooling water, and at the same time, direct heat exchange with the water vapor to realize the waste heat recovery of the medium and low temperature coke.
  • the stage of the gradient heating pyrolysis of the present invention can be determined according to the needs of actual production. Taking three stages of gradient heating pyrolysis as an example, the three stages are: low temperature pyrolysis at 380-450 ° C, medium temperature pyrolysis at 500-600 ° C, and then at 850 ° C or higher. High temperature pyrolysis.
  • the process of the present invention comprises the following steps:
  • the medium-low-grade coal after pre-heat treatment is input into the pyrolysis section, and the indirect heating method is used to carry out low-temperature pyrolysis at 380-450 ° C, and then at a medium temperature pyrolysis at 500-600 ° C, and then High temperature pyrolysis at 850 ° C or higher, continuously collecting gases containing different hydrocarbon components produced in each stage;
  • the medium/low-order coal is conveyed in the whole process of the process in a sealed state by gravity at a speed of less than 0.5 mm/s.
  • the key technology of the process provided by the invention is to realize the step temperature heating of the coal entering the furnace.
  • three or more temperature zones are correspondingly set to extract the waste gas containing different hydrocarbon components.
  • a second object of the present invention is to provide an indirect heating staged pyrolysis medium/low rank coal continuous hydrocarbon raising apparatus.
  • the device comprises a silo sequentially connected from top to bottom, a sealed coal charging device, a pre-storage section, a dry preheating section, a multi-stage gradient heating pyrolysis section, a ⁇ focal length section, a single-hole joint dry quenching section, a focusing device and a sealing device a multi-stage gradient heating pyrolysis section comprising three or more consecutive stages, each stage being respectively connected to a gas outlet; the apparatus further comprising heating for indirect heating of the multi-stage gradient heating pyrolysis section segment.
  • a water atomizer can be provided in the focus device of the present invention.
  • the water vapor generated by the water atomizer and absorbing the sensible heat of the coke passes through a single-hole combined dry quenching section, a ⁇ focal length section, and a multi-stage gradient heating pyrolysis section, and water gas is generated as a product and is led out from the gas outlet.
  • the water vapor acts as a convective heat transfer medium with a large temperature difference between the central coke and the outer coke, so that the indirect heat exchange with the air and the indirect heat exchange with the cooling water are faster and more efficient.
  • the heating section is directly adjacent to the multi-stage gradient heating pyrolysis section, and includes a heating phase corresponding to each pyrolysis phase.
  • the bottom of the heating section is provided with an air inlet and a combustible gas inlet, respectively connected to the air passage and the return gas pipeline; the heating section is further provided with an exhaust gas outlet connected to the exhaust passage located below the heating section.
  • the single-hole combined dry quenching section may include a connected single-hole combined high-temperature dry quenching section and a single-hole combined low-temperature dry quenching heat exchanger from top to bottom.
  • the air passage is located between the single-hole combined high-temperature dry quenching section and the exhaust passage, and is directly adjacent to the two.
  • the combustion air in the air passage indirectly absorbs the heat of the exhaust gas and the sensible heat of the red hot coke on the other side, and is preheated and then enters the bottom of the high temperature heating section to be mixed with the gas for combustion; the exhaust gas transmits the partial heat indirectly to the exhaust gas.
  • the red hot coke transfers part of the heat to the air indirectly, and the descending speed of the shaped coke is less than 0.5 mm/s, preferably less than 0.3 mm/s, so no power and dust are generated during the heat exchange process. .
  • the red hot coke After the red hot coke is cooled in the single-hole high-temperature dry quenching section, it enters the single-hole continuous low-temperature dry quenching section.
  • the coke is softened by the indirect cooling of the cold water in the heat exchanger shell and the direct cooling of the water vapor generated by the water atomizer. It is cooled to below 120 °C.
  • the number of stages of the multi-stage gradient heating pyrolysis section can be adjusted according to actual needs.
  • the multi-stage gradient heating pyrolysis section can be composed of three stages, which are followed by a low temperature pyrolysis section, a medium temperature pyrolysis section, and High temperature pyrolysis section.
  • the device comprises a silo sequentially connected from top to bottom, a sealed coal charging device, a pre-storage section, a dry preheating section, a low temperature pyrolysis section, a medium temperature pyrolysis section, a high temperature pyrolysis section, and a crucible.
  • each pyrolysis section is respectively connected with the gas outlet.
  • the device of the present invention is preferably fully sealed, and the downshifting speed of the material is controlled by the focusing device.
  • the device provided by the invention not only can realize cold coal charging and cold state coking, thereby restraining a large amount of dust generated by thermal buoyancy, and adopts a sealed coal charging device and a sealed decoking device, strictly controls unorganized emission, and the whole process is truly Achieve efficient and fully enclosed production, control the pollution of pollutants to the atmosphere from the source, and reduce environmental protection costs.
  • the pyrolysis section is composed of a pyrolysis temperature section which is heated by a gradient from top to bottom. At the same time, the heating section has different stages from bottom to top, respectively, indirectly heating the pyrolysis chamber, and pyrolyzing in different temperature sections.
  • the waste gas of different components is respectively taken out from the corresponding gas outlet to ensure that the high-quality oil and gas components pyrolyzed in the relatively low temperature zone are not subjected to secondary cracking by high temperature or sub-high temperature.
  • the low-temperature hydrocarbon-rich gas mainly composed of hydrocarbon compounds is mixed with the medium-temperature hydrocarbon gas, and then purified and separated. Extracting high value-added C 1-4 gaseous alkene olefins, light hydrocarbon oil, light tar and a small amount of medium/heavy tar, and extracting the chemical products obtained by direct conversion can be used as needed, or hydrogen can be used, or CO and H 2 are indirectly converted into products such as hydrocarbon products or alcohol ethers, and the rest can be reheated and steam produced.
  • the solid matter with carbon as the main component can be subjected to a corresponding process after pyrolysis as needed, and the synthesis gas CO and H 2 can be used to further convert into a chemical product of market demand; or it can be used as a blast furnace.
  • Injection molding, smokeless fuel or gasification coke can also produce cast coke or metallurgical coke to improve resource utilization.
  • the original intention of the conventional horizontal chamber batch production dry distillation coking unit is mainly for the purpose of producing metallurgical coke or foundry coke.
  • the recovery of gas and chemical products is its derivation process, so it is necessary to uniformly heat the retorting under high temperature conditions.
  • the heating temperature of the carbonization chamber is required to be uniform; the conventional retorting device cannot set the gas outlet at a step temperature, and can only be retorted under a single temperature condition, so that most of the high-quality hydrocarbon compounds in the gas are at high temperature or Secondary cracking at high temperature greatly reduces the valuable high-quality hydrocarbon compounds in the waste gas; if medium and low temperature dry distillation is used, the volatiles in the coal can not be fully released, resulting in the quality of coke not reaching the qualified metallurgical coke and foundry coke. Requirements, the process limits the efficient recycling of chemical products;
  • the indirect heating segmentation pyrolysis low rank coal continuous hydrocarbon extraction process and device developed by the invention extracts hydrocarbon compounds is its largest production purpose, and the production of semi-coke or metallurgical coke is its subordinate purpose;
  • the device can set two, three or more gas outlets of different temperature sections according to different pyrolysis temperature zones according to the requirements of the user for the product; generally, three gas outlets of low temperature, medium temperature and high temperature are set to obtain different
  • the different component gas produced under the temperature condition, that is, the pyrolysis chamber is heated by different temperatures and segmented and exported, and the hydrocarbon compound with low pyrolysis temperature in the volatiles of the coal material is exported at the same time as the low temperature pyrolysis section is distilled off.
  • the hydrocarbon compounds with higher pyrolysis temperature are mostly derived at the same time as the middle temperature pyrolysis section is distilled off, and so on; the staged derivation is effective to control the hydrocarbon compounds contained in the waste gas from the higher temperature zone. Secondary cracking to ensure that the valuable high-quality hydrocarbon compounds are not destroyed; after the coal material enters the high-temperature pyrolysis section, the remaining volatiles are continuously distilled off and taken out from the high-temperature gas outlet.
  • a hydrocarbon-depleted hydrogen-rich gas and hot coke or coke meet other requirements.
  • the alkane component is not guaranteed to be destroyed as much as possible, and the gas of different temperature ranges can be combined or separately purified and separated according to the requirements of downstream products, so that the energy consumption and processing cost of the product can be reduced compared with the indirect conversion process. About 50%, and can recycle higher quality chemical products than indirect conversion.
  • the key of the invention is to realize the step temperature heating of the coal entering the furnace, using segmental indirect heating, the oil and gas which are pyrolyzed by the low temperature section and the middle temperature section from the low temperature gas outlet and the medium temperature gas.
  • the outlets are directly led out, which are not affected by the secondary cracking of the higher temperature zone, which solves the problem of secondary cracking of oil and gas, and ensures that valuable high-quality hydrocarbon compounds are not damaged.
  • the so-called vertical medium-low temperature retorting devices popular in China are mostly internal heating methods using oxygen-containing exhaust gas as a gas source; the process uses oxygen-containing exhaust gas as a gas source to heat the interior of the carbonization chamber, not only in the gas. At least 70% of the hydrocarbons are destroyed, and a large amount of nitrogen is introduced into the air to dilute the concentration of the active ingredient, so that it is impossible to extract the hydrocarbon compounds in the gas (the hydrocarbons are particularly low, the extraction must be a negative benefit), and The heat value of the gas is greatly reduced;
  • the segmental indirect heating developed by the invention that is, the external heating method in which the combustion chamber and the pyrolysis chamber are completely isolated, ensures that valuable hydrocarbon compounds are not damaged by oxygen in the air and are not subjected to nitrogen. Dilution, not only improve the recovery rate of high-quality products, improve resource utilization, and the heat value of gas is at least three times that of the hot-type dry distillation furnace in the air source.
  • the present invention develops a step heating temperature that is easy to control.
  • Zone the low-order coal segment indirect heating pyrolysis, waste gas segmentation derived, thereby controlling the low separation temperature compound from secondary pyrolysis;
  • the block material is relatively static heating at a downward speed of less than 0.5mm per second, so that The gas-solid two states separate themselves in the process, which well solves the common defects of the aforementioned relative dynamic pyrolysis process.
  • the vertical medium-low temperature dry distillation furnace that has been operated or is running all the time is based on low-grade lump coal with low strength, because the lump coal rate in low-grade raw coal is generally only about 30%, about 70%.
  • the end coal rich in hydrocarbon compounds can only be used for direct combustion such as power generation, which not only wastes precious resources greatly, but also increases pollution; if the coal is directly used for pyrolysis, the tar and system dust are still separated. Difficulties such as difficulties; some people have used coal to form coal to replace lump coal into the furnace, but due to defects in its processing technology and the fact that 6 to 13% of volatiles remain in the semi-coke of such processes, the strength is greatly reduced, resulting in its type.
  • the block returns to the powdery shape, which not only worsens the focus of the coke, but also causes the market value of its products to be greatly reduced;
  • the invention increases the high temperature pyrolysis section and the ⁇ focal length in the pyrolysis process on the basis of improving the defects of the conventional process, so that the volatile matter of the coke can be reduced to less than 1.5%, so that the shaped block is not Being destroyed, the block rate is over 95%, which not only broadens the use of coke, but also greatly improves the efficiency of the enterprise.
  • the single-hole combined dry quenching unique process of the present invention completely controls the occurrence of various drawbacks of conventional dry quenching from the source.
  • This new process technology is to transfer some of the sensible heat of the red hot coke to the cooling water and combustion air indirectly before the furnace is discharged, and another part of the sensible heat is directly transmitted to the water vapor participating in the water gas reaction, thereby reducing the coke temperature to 100.
  • Around °C is discharged through the sealing and decoking device. During the whole process, the coke is fully sealed and has no leakage, and the following line operates at a speed of less than 0.5 mm/s.
  • the solution provided by the present invention completely eliminates the heat which inevitably produces unorganized emissions.
  • the intermediate links of coke, coke, and coke not only eliminate the unorganized emission and harmful gas emissions caused by thermal buoyancy, but also recycle the harmful gas resources efficiently, without the need for large-flow medium gas circulation, and save
  • the huge power of the gas circulation and dust removal device greatly reduces the energy consumption, and there is no excess harmful gas emissions to pollute the environment. From the source, the problem of burning loss of coke of about 1.5% of conventional dry quenching is completely controlled, and the problem is eliminated.
  • High-power power consumption process energy consumption reduced by about 80%, completely solved the problem of conventional CDQ pollution gas emissions and high noise pollution from the source.
  • Syngas produced by conventional water gas generators uses water vapor as a gas source.
  • the water vapor device not only has high investment, low heat exchange efficiency, needs to be intermittently fed into the air to be heated, and needs to consume a large amount of fuel, so the energy consumption is high, the gas quality is poor, and there is a safety hazard.
  • the present invention is provided with a water atomizer in the lower part of the low-temperature dry quenching heat exchanger in the single-hole joint process, and the appropriate amount of water is atomized by the atomizer and is about 100 ° C or more.
  • the direct and high-efficiency heat transfer of coke produces water vapor, eliminating the complicated steam transfer device with low heat transfer efficiency and high investment; its water vapor rises along the focal length due to thermal buoyancy, and the coke with high temperature continues during the ascending process.
  • Figure 1 is a schematic view of the structure of the device according to the present invention; wherein: 1, the silo, 2, the sealed coal charging device, 3, the pre-storage section, 4, the dry preheating section, 5, the low temperature pyrolysis section, 6, the low temperature heating section, 7, medium temperature pyrolysis section, 8, medium temperature heating section, 9, high temperature pyrolysis section, 10, high temperature heating section, 11, brick gas channel, 12, ⁇ focal length, 13, exhaust gas, 14, airway, 15, Single hole joint high temperature dry quenching section, 16, air inlet, 17, single hole combined medium and low temperature dry quenching heat exchanger, 18, water atomizer, 19, focusing device, 20, sealing and defocusing machine, 21, low temperature gas guide Export, 22, medium temperature gas outlet, 23, high temperature gas outlet, 24, gas branch, 25, return gas pipeline, 26, exhaust gas outlet, 27, exhaust manifold.
  • the coke obtained from the coke is input into the quenching section, and the high-temperature coke is indirectly exchanged with the air in the high-temperature dry quenching section, and at the same time, it is directly exchanged with water vapor, quenched to about 450 °C, and then enters the medium-low temperature dry quenching section. Indirect heat exchange with cooling water, direct heat exchange with water vapor, quenching to below 120 °C, and then input into the extraction section for pulling After coke treatment, the obtained low temperature coke is discharged through the sealed coke section;
  • the transportation of the intermediate coal in the whole process of the process is realized by gravity down at a speed of less than 0.5 mm/s in a sealed state.
  • the pre-heat treated medium/low-order coal is input into the pyrolysis section, and the indirect heating method is used to carry out low-temperature pyrolysis at about 380 °C, and then to carry out intermediate temperature pyrolysis at about 500 °C, and then at 850 °C.
  • the above is subjected to high temperature pyrolysis, and the gases of different hydrocarbon components generated in each stage are continuously collected separately;
  • the coke obtained from the coke is input into the quenching section, and the high-temperature coke is indirectly heat exchanged with the air in the high-temperature dry quenching section, and at the same time, it is directly exchanged with water vapor, quenched to about 350 °C, and then enters the medium-low temperature dry quenching section. Indirect heat exchange with cooling water, direct heat exchange with water vapor, quenching to below 100 ° C, and then input into the coke section for coke removal treatment, the resulting low temperature coke is discharged through the sealed coke section;
  • the transportation of the low rank coal in the whole process of the process is achieved by gravity down at a speed of less than 0.3 mm/s in a sealed state.
  • a device for continuously extracting hydrocarbons from medium/low-rank coal by indirect heating segmental pyrolysis (partial reference to Fig. 1); the device comprises a silo sequentially connected from top to bottom, a sealed coal charging device 2, and a preserving segment 3 Dry preheating section 4, low temperature pyrolysis section 5, medium temperature pyrolysis section 7, high temperature pyrolysis section 9, ⁇ focal length section 12, single hole joint high temperature dry quenching section 15, single hole combined medium and low temperature dry quenching heat exchanger 17, Focusing device 19 and sealing defocusing machine 20;
  • the low temperature pyrolysis section 5 is also connected to the low temperature gas outlet 21;
  • the intermediate temperature pyrolysis section 7 is also connected to the medium temperature gas outlet 22;
  • the high temperature pyrolysis section 9 is also connected to the high temperature gas outlet 23;
  • the device is a fully enclosed device; the downward speed of the solid material is controlled by the focusing device 19.
  • a device for continuously extracting hydrocarbons from medium/low-rank coal by indirect heating segmental pyrolysis (partially referring to FIG. 1), and comparing with the second embodiment, further comprises a high-temperature heating section 10, a medium-temperature heating section 8, and a low temperature which are sequentially connected in sequence.
  • the low temperature heating section 6 is provided with an exhaust gas outlet that communicates with the exhaust gas passage 13 located below the high temperature heating section 10; the exhaust gas passage 13 is sequentially connected to the exhaust gas outlet 26 and the exhaust gas main pipe 27;
  • the device further includes an air passage 14; one end of the air passage 14 is an air inlet 16 and the other end is connected to an air inlet at the bottom of the high temperature heating section 10; the air passage 14 is located in the exhaust passage 13 and the single hole joint high temperature dry quenching section Between 15 and directly adjacent to the two;
  • the apparatus further includes a return gas pipeline 25, a gas branch pipe 24 and a brick gas passage 11 which are sequentially connected in series, and the outlet of the brick gas passage 11 is connected to the combustible gas inlet at the bottom of the high temperature heating section 10.
  • a water atomizer 18 is further disposed in the focusing device 19;
  • the water vapor generated by the water atomizer 18 and absorbing the sensible heat of the coke passes through the single-hole continuous medium-temperature low-temperature dry quenching heat exchanger 17, the single-hole joint high-temperature dry quenching section 15, the ⁇ focal length 12, and the high temperature pyrolysis section 9
  • the generated water gas is taken out as a product from the gas outlet port 23.
  • the apparatus of the embodiment 5 is used for indirect heating of the segmented pyrolysis low rank coal continuously to extract hydrocarbons according to the method of the invention; the method comprises the following steps:
  • the top of the pyrolysis device of the present invention is provided with a silo 1 and a sealed coal charging device 2; when the coal is loaded, the sealed coal charging device 2 is started, and the pressed coal formed in the silo 1 is sent to the pre-storage section through the sealed coal charging device 2 3.
  • the sealed coal charging device 2 always seals the airflow of the silo 1 and the pre-existing section 3 in the process of running or stopping; the briquette is self-preserved into the preheating section 4 by gravity under the action of gravity; After the briquette enters the low temperature pyrolysis section 5 by gravity; the briquette releases low temperature waste gas containing a large amount of hydrocarbon compounds in the low temperature pyrolysis section 5, and is taken out through the low temperature gas outlet 21 to ensure that the low temperature fraction gas is not After being pyrolyzed by high temperature and sub-high temperature, the briquette after low temperature pyrolysis continues to descend into the intermediate temperature pyrolysis section 7; the briquette releases medium-temperature waste gas with medium hydrocarbon content in the middle temperature pyrolysis section 7 and passes through the medium temperature.
  • the gas outlet 22 is taken out to ensure that the gas from the middle temperature fraction is not cracked by the high temperature, and the coal is gradually formed into a semi-coke after the intermediate temperature pyrolysis, and continues to descend into the high temperature pyrolysis section 9; in the high temperature pyrolysis section 9 pyrolysis Hydrogen-based high temperature and low hydrocarbon
  • the gas is led out through the high-temperature gas outlet 23, and the coal is carbonized into coke after being released from the high-temperature pyrolysis section and descends into the coke section 12; the coke is fully carbonized in the coke section 12 after fully releasing its volatiles, and the coke is fully After carbonization, it is an exothermic process, and the released heat causes the coke to heat up again, and continues to descend into the single-hole high-temperature dry quenching section 15; about 30% of the sensible heat of coke, and heat transfer through indirect heat exchange in the single-hole high-temperature dry quenching section For the combustion air of the air passage 14, after the coke loses
  • the purified gas sent from the return gas pipe 25 is sent through the gas branch pipe 24
  • the brick gas passage 11 entering the bottom of the combustion chamber is then distributed into the bottom of the high temperature heating section 10 by the brick gas passage 11.
  • the air After entering the air inlet 16, the air is distributed to the air passages 14 arranged on both sides, and the air passage 14 is ignited.
  • the exhaust gas Indirectly transferred to the material in the middle temperature pyrolysis section, the exhaust gas once again loses part of the heat and is cooled into the low temperature heating section 6; the exhaust gas is indirectly absorbed by the material in the low temperature pyrolysis section in the low temperature heating section 6, and the exhaust gas is once again lost.
  • the heat is cooled and enters the exhaust passage 13 through the exhaust passage in the partition wall; the exhaust gas in the exhaust passage 13 indirectly transmits a part of the heat to both sides
  • the airway 14 air after the exhaust gas is cooled again into the exhaust outlet 26, the exhaust manifold 27 and then sent through the waste heat recovery boiler heat again;
  • the water atomizer 18 is disposed in the focusing device 19, and an appropriate amount of water is sent from the outside to be atomized by the atomizer 18.
  • the atomized water absorbs the sensible heat of the coke of 100 ° C or more to generate steam and efficiently treat the coke.
  • the water vapor rises into the single-hole low-temperature dry quenching heat exchanger 17 due to the thermal buoyancy, and fully exchanges heat with the hot coke of the focal length; after absorbing the heat of the low-temperature coke, the water vapor continues to rise into the single-hole high-temperature
  • the dry quenching section 15 is heat exchanged with the high temperature red hot coke and continues to heat up; when the water vapor reaches the top of the single hole combined high temperature dry quenching section 15 and the ⁇ focal length 12, it has been heated to about 950 ° C, in which high temperature steam and The water-gas reaction of red hot coke above 950 °C is carried out, and the single-hole coke dry quenching devices 17 and 15 act to strengthen the cooling coke; the water gas after the reaction rises into the high temperature pyrolysis section 9 and is pyrolyzed there.
  • the hydrogen-rich gas is mixed, and the mixed hydrogen-rich gas is led out through the high-temperature gas outlet 23, and then enters the
  • the gas heat value and hydrocarbon recovery rate of the process and equipment provided by the present invention are compared with the JHH-D type external heat furnace of Anshan, China, and the waste heat source internal heat furnace which are currently popular in Inner Mongolia, Shaanxi, Xinjiang, etc.
  • the raw material type, coke bulking rate and conversion benefit were tested. The results are shown in Table 2.
  • the gas obtained by the solution provided by the invention has high calorific value, high recovery rate of hydrocarbon compounds, high coke formation rate, and very good conversion efficiency, and has a strong promotion value.

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Abstract

本发明涉及一种采用间接加热分段热解方式从中/低阶煤中连续提烃的工艺，包括以下步骤：将中/低阶煤压制成型后，输入干燥预热段进行干燥预热；再输入热解段，采用间接加热方式，进行三阶段以上梯度升温热解，分别连续收集每一阶段产生的烃类气体；将热解后所得固体产物依次输入闷焦段、熄焦段、拔焦段进行处理，所得低温焦炭经密封排焦段排出。本发明还涉及了一种采用间接加热分段热解方式从中/低阶煤中连续提烃的装置。本发明提供的工艺和装置从源头彻底解决了污染气体排放和高噪音污染问题；按照不同温度分段热解分段引出保证了煤气中宝贵的烃类化合物不受二次裂解；所述干熄焦回收90％左右焦炭的显热，且比常规干熄焦工艺能耗降低80％左右。

Description

一种采用间接加热分段热解方式从中、低阶煤中连续提烃的工艺及装置 技术领域
本发明属于煤化工技术领域，涉及一种间接加热分段热解中/低阶煤连续提烃工艺及装置。
背景技术
一般情况下，低阶煤(褐煤、长焰煤、不粘煤、弱粘煤)与挥发分大于18％的中阶煤的可挥发物主要是以烃类物质构成的。在挥发分大于25％的中、低阶煤的挥发物中，烃类成分一般占无水基挥发分重量比的75％以上。尤其是煤化度较低的低阶煤中，烃类成分在煤的总质量比中一般占25％以上。若以适当的工艺条件将其烃类物质以接近初始成分热解出来(即克制二次裂解)，经分离净化后，其中约40％左右是以C1～4烷烯烃为主的气态物质，该气体若经进一步深冷分离则可提取高附加值的洁净车用燃料LNG(液态甲烷)和民用液化气(主要成分为液态丙烷)；还有5％左右液态轻烃类产品；其余50％左右多是制取优质车用油的轻质焦油。
中国是一个缺油、少气、富煤的国家。截止2012年底中国查明石油剩余技术可采储量仅为33.3亿吨，天然气4.4万亿立方米；而煤炭资源储量为1.42万亿吨，其中有80％以上是中、低阶煤，若均采用高效低耗提烃工艺，就可提取加工动力油1500亿吨以上、提取优质烷烃气产品(热值高于天然气)约140万亿立方米，至少几十倍于天然油、气储量。采用科学合理的煤化工工艺热解低阶煤提烃制取油和气，是弥补中国缺油少气、突破油气对外依存度、保障能源安全、经济安全、国防安全和国家可持续发展的重大课题。
然而，中国每年却有近二十亿吨富含高附加值烃类成分的中/低阶中、高挥发分煤直接燃烧用于发电、工业供热或做其它民用燃料而付之一炬，不仅极大地浪费了宝贵的资源，而且还大大推高了环 保成本和生产成本。
其次，相当一部分低阶煤用于生产兰炭。但是，由于这类企业所采用的工艺及装置缺陷，多将原料煤中宝贵的烃类化合物至少70％左右被裂解破坏，而且增加了污染源。
另外，还有少部分用于造气以及甲醇、二甲醚、合成氨等生产。但是，由于这类企业目前几乎都采用将原料煤及其中的烃类成分充分裂解后再进行合成的间接转化生产工艺，结果不仅导致其中宝贵的烃类成分被破坏，而且致使其投资特别高、能耗特别高、污染环节特别多、生产成本特别高，致使企业的生存空间受到极大的限制。
目前，中国国内已有少数几家企业用低阶煤做煤制油或煤制气。但是，这些企业多是沿袭世界上最早商业化煤制油企业南非沙索集团间接转化的工艺路线，先将煤进行充分裂解气化，即裂解或反应为CO和H2，然后再将CO和H2合成为烃类化合物。这种工艺不仅仅是将原料中大量更优质的烃类化合物被裂解掉然后再二次合成，更重要的是其裂解与合成过程中需要消耗大量的热能、电能、水资源、尤其是环保资源，从而致使其成为高热耗、高电耗、高水耗、高排放、高成本的五高产品。
对企业来说，由于这类纯粹性间接转化工艺投资特别大、能耗和水耗特别高、污染环节特别多、生产成本特别高，致使企业的生存空间受到极大的限制。
目前，南非煤制油企业沙索集团，采用先进的费-托法工艺已将每t油的水耗从12t降低到6～8t。尽管如此，这对中国90％以上高挥发分低阶煤分布于西北干旱地区来说，仍是一个极其奢侈的水耗指标，必将制约该区域就地规模化煤制油企业使用其工艺的可能性。
在常规炼焦(高温干馏)工艺中，虽然提取了少量的煤化工产品，但其产品的附加值却大打折扣。这是因为常规干馏工艺的主要产品是冶金焦，而冶金焦必须在高温条件下才能生产出质量合格的 产品，在高温条件下煤的挥发分不仅受到低温一次热解，而且又受到高温二次裂解，结果导致大多数宝贵的烃类物质裂解为H2及游离C等廉价物质，使煤气质量变坏，焦油中沥青质大幅度增加。
与高温干馏技术相比，采用中低温分段热解技术更有利于提高煤气轻烃含量，使宝贵的轻烃类化产品可直接提取和利用，且提烃后的煤气适于作合成气，为生产醇醚燃料或合成烷烯等烃类物质创造条件，提高煤气的利用价值；有利于提高焦油收率，进一步改善焦油成分，提高焦油的利用价值；有利于轻烃和酚的回收利用，提高转化为优质能源的效率，不仅大大降低转化过程的能源消耗和产品成本，而且可大大提高产品的附加值。
实现中、低温热解的关键是工艺和炉型。尽管目前已经有不少中、低温干馏的工艺和炉型可以起到一点中、低温热解的作用，但是由于这些炉型大多是采用富含空气的废气做气源的内热式工艺，所以，不仅大量的氮气稀释了煤气的有效成分，更甚的是使70％以上的宝贵烷烃化合物受到了严重的破坏！虽然多数人习惯把这类炉型称为干馏炉，但从严格的概念上讲，它是不符合“隔绝空气进行加热”这一干馏定义的。关键在于，这些炉型是以干馏为主要目的来生产半焦，没有把热解出宝贵的烃类化工产品定位为主要工艺目标，所以无法将烃类化合物以理想状态有效热解出来，造成了对优质资源的极大破坏和浪费。
目前，中国国内不粘和弱粘煤中低温干馏炉型如表1所示。
表1：中国国内流行的中低温干馏炉型及其工艺参数
Figure PCTCN2015081693-appb-000001
Figure PCTCN2015081693-appb-000002
从表1中6种炉型可以看出，有4种属于以空气做气源的烟气内热式，由于空气在煤床内直接燃烧，使大量烃类物质被破坏，导致焦油收率大幅降低，煤气利用价值极差，不能用面煤作原料；另一种热解炉虽也为内热式，虽然采用兰炭粉为热载体，使热解出的焦油和煤气的收率与质量比烟气内热式有了一定程度的提高，但是其无法做到梯级温度加热，仍存在油气收率偏低、热解油中沥青质含量高、焦油与系统粉尘分离困难、兰炭产品≤6mm只能作高炉喷吹燃料或发电燃料，不能供化肥工业造气，利用价值降低且市场空间变小等缺憾；还有一种为内外兼热式同样不能以面煤作原料生产兰炭，焦油收率不到50％，且煤气质量少有根本性改善。可见，迄今为止还没有一种既符合煤资源配置要求，又能生产高附加值油、气等产品回收率高的炉型；且由于煤气不适宜作合成气，迄今尚未建立经济适用的煤气净化、化产品有效回收以及间接转化合成的完整工艺；由于低温干馏的特点，生产废水中富集大量酚类，特别是苯酚，亦未能得到回收利用，反遭其污染。
早期有考伯斯外热立式干馏炉。大连煤气公司曾引建考伯斯炉用 于生产城市煤气，以抚顺弱粘性煤为原料。后利用大同弱粘煤在立式炉内经高温干馏制取城市煤气获得成功，其粒度13～60mm，煤气热值为≦16MJ/m3，接近水平室式焦炉煤气热值。此后鞍山焦耐院先后开发了JLW、JLK、JLH-D立式炉，用于中小煤气厂生产城市煤气。此型立式炉由于结构上的缺陷，荒煤气在导出过程中受到强烈的二次高温热解作用，降低了焦油的收率和质量，同时恶化了煤气组分，致其烷烃含量减少70％以上，而氢的含量则成倍升高。
目前，国内外业内人士多已意识到对低阶煤的最佳利用途径是先进行中低温热解，提取其挥发分中宝贵的烃类成分后，再用残留碳发电或经气化生产合成气，进而间接转化合成气或合成油。并且在低阶煤热解方面做了大量的工作，国内外大都进行了中试或工业示范，但其工艺和装备多是回转炉、移动床、流化床、气流床或固体热载体热解技术，综合这些热解技术的特点多属于固态粉状物料相对快速运动的动态热解工艺思路。因此类工艺的共性问题是油气收率偏低、热解油中沥青质含量高、焦油与系统粉尘分离困难等缺憾，故至今尚无大规模工业应用。且国内外普遍认为：突破热解的关键技术是产品分离、热解油的轻质化和规模的放大。
发明内容
本发明的目的是克服现有技术的缺陷，提供一种采用间接加热分段热解方式从中/低阶煤中连续提烃的工艺及装置。本发明提供的工艺使物料在相对静态下加热，采用易于控制的多阶段梯度升温，间接加热分段热解，气固两态在过程中自行分离，克服了加热系统中动态的气体和粉状固体两相流造成的工艺缺陷。
本发明的第一目的是提供一种采用间接加热分段热解方式从中/低阶煤中连续提烃的工艺。
所述采用间接加热分段热解方式从中/低阶煤中连续提烃的工艺包括以下步骤：
(1)将中/低阶煤压制成型，得到中/低阶型煤，输入干燥预热段进行预热处理；
(2)将经预热处理后的中/低阶型煤输入热解段，采用间接加热方式，进行三阶段以上梯度升温热解，分别连续收集每一阶段产生的烃类气体；
(3)将热解后所得固体产物输入闷焦段进行焖焦处理；
(4)将焖焦所得的焦炭输入熄焦段进行熄焦处理，再输入拔焦段进行拔焦处理，所得低温焦炭经密封排焦段排出；
其中，所述中/低阶型煤在工艺全程中的运输均在密封状态下以小于0.5mm/s的速度靠重力下行实现。
本发明所述中/低阶煤为本领域公知的常规中阶煤和低阶煤，本发明不对其参数做具体限定。所述中/低阶煤可以为冷态的粉末状煤，经压制后得到型煤，可用于后续步骤的处理。
本发明所述间接加热具体是指：中/低阶型煤在不与热源直接接触的情况下通过隔墙传递热量进行热交换升温的过程。
本发明在所述拨焦步骤中，可以引入水蒸汽，所述水蒸汽在上升过程中依次与拨焦、单孔联程干熄焦、焖焦和热解步骤中的焦炭进行直接热交换，辅助高效熄焦，并生成水煤气；将所述水煤气导出。
本发明所述熄焦段包括高温干熄焦段和中低温干熄焦段；在所述高温干熄焦阶段，高温焦炭与低温空气进行间接热交换，同时与水蒸汽进行直接热交换，实现高温焦炭的余热回收；在所述中低温干熄焦阶段，中低温焦炭与冷却水进行间接热交换，同时与水蒸汽进行直接热交换，实现中低温焦炭的余热回收。
本发明所述梯度升温热解的阶段可以根据实际生产的需要决定。以三个阶段梯度升温热解为例，所述三阶段依次为：在380～450℃进行低温热解，再在500～600℃进行中温热解，再在850℃以上进行 高温热解。
作为一种优选方案，本发明所述工艺包括以下步骤：
(1)取冷态粉末状中/低阶煤，压制成型煤后，输入干燥预热段进行预热处理；
(2)将经预热处理后的中/低阶型煤输入热解段，采用间接加热方式，在380～450℃进行低温热解，再在500～600℃进行中温热解，再在850℃以上进行高温热解，分别连续收集每一阶段产生的含不同烃类组分气体；
(3)将热解后所得固体产物输入闷焦段进行焖焦处理；
(4)将焖焦所得的焦炭输入熄焦段，高温焦炭在高温干熄焦段与空气进行间接热交换，同时与水蒸汽进行直接热交换，熄焦至350～450℃，再进入中低温干熄段，与冷却水进行间接热交换，同时与水蒸汽进行直接热交换，焦炭温度降至120℃以下，再输入拔焦段进行拔焦处理，所得低温焦炭经密封排焦段排出；
同时，将水蒸汽与高温焦炭反应生成的水煤气作为产物收集；
其中，所述中/低阶型煤在工艺全程中的输送均在密封状态下以小于0.5mm/s的速度靠重力下行实现。
本发明提供的工艺的关键技术在于实现了对入炉煤的梯级温度加热，根据对煤气组分的不同要求，相应分设三个或三个以上温度区段引出含不同烃类组分的荒煤气，并实现冷态装煤冷态排料的全密闭连续生产工艺，使煤料在热解过程中实现提高优质轻焦油产率，大大提高烷烃在荒煤气中的比例，从而根据需求生产可制取优质油、气的多种组分煤气；同时可生产高炉喷吹料、无烟燃料或气化用焦、也能够生产铸造型焦或冶金型焦，提高资源利用率；为实现热能利用高效化，可对洁净固态物半焦与荒煤气的显热进行回收利用。
本发明的第二目的是提供一种间接加热分段热解中/低阶煤连续提烃装置。
所述装置包括由上至下依次顺序连接的料仓、密封装煤装置、预存段、干燥预热段、多阶段梯度升温热解段、焖焦段、单孔联程干熄焦段、拨焦装置和密封排焦机；所述多阶段梯度升温热解段包括三个以上连续阶段，每个阶段分别与煤气导出口相连；所述装置还包括为所述多阶段梯度升温热解段间接供热的加热段。
本发明所述拨焦装置内可以设有水雾化器。被所述水雾化器雾化并吸收焦炭显热生成的水蒸汽依次经过单孔联程干熄焦段、焖焦段、多阶段梯度升温热解段，生成水煤气作为产物从煤气导出口导出。所述水蒸汽在上升过程中，起到了中心焦炭与外层焦炭较大温差的对流传热的介质作用，使所述与空气间接换热、与冷却水间接换热更快更高效。
作为优选方案，所述加热段与所述多阶段梯度升温热解段直接相邻，且其中包括与每个热解阶段一一对应的加热阶段。
所述加热段的底部设有空气入口和可燃气入口，分别与空气道和回炉煤气管道相连；所述加热段还设有废气出口，其与位于加热段下方的废气道相连。
所述单孔联程干熄焦段由上至下可包括相连单孔联程高温干熄焦段和单孔联程中低温干熄焦换热器。所述空气道位于所述单孔联程高温干熄焦段与所述废气道之间，且分别与二者直接相邻。
在所述装置中，助燃空气在空气道中，间接吸收一边废气的热量和另一边赤热焦炭的显热，被预热后进入高温加热段底部与煤气混合燃烧；废气在将部分热量间接传递给空气后排出炉外；赤热焦炭在将部分热量间接传递给空气，同时型块焦炭下行速度小于0.5mm/s，优选小于0.3mm/s，所以换热过程中均不会消耗动力和产生粉尘。赤热焦炭在单孔联程高温干熄焦段被降温后，进入单孔联程中低温干熄焦段，焦炭在换热器壳体中软化冷水间接冷却和水雾化器产生的水蒸汽的直接冷却共同作用下，被冷却到120℃以下。
所述多阶段梯度升温热解段的阶段数量可以根据实际需要进行调整，例如，所述多阶段梯度升温热解段可以由三个阶段组成，依次为低温热解段、中温热解段和高温热解段。在该情况下，所述装置包括由上至下依次顺序连接的料仓、密封装煤装置、预存段、干燥预热段、低温热解段、中温热解段、高温热解段、焖焦段、单孔联程高温干熄焦段、单孔联程中低温干熄焦换热器、拨焦装置和密封排焦机；各个热解段分别与煤气导出口相连。
为了优化效果，本发明所述装置优选为全密封，由拨焦装置控制物料的下行速度。
本发明提供的装置不仅可以实现冷态装煤、冷态排焦从而克制了由于热浮力产生大量的粉尘，而且采用密封装煤装置和密封排焦装置，严格控制了无组织排放，全过程真正实现了高效的全密闭生产，从源头控制污染物对大气的污染，降低了环保成本。所述热解段向由上到下由梯度升温的热解温度区段组成，同时，加热段由下到上有不同的阶段分别为热解室间接供热，在不同温度区段热解出不同组分的荒煤气分别由对应的煤气导出口引出，以保证相对较低温度区热解出的优质油、气组分不被高温或次高温二次裂解。
在所述装置中，不同温度热解区产生的煤气由多个煤气导出孔引出后，以烃类化合物为主的低温富烃煤气与中温中烃煤气混合后，再经过净化和分离，即可提取出高附加值的C1～4气态烷烯烃、轻烃油、轻质焦油以及少量中/重质焦油，提取直接转化获得的化工产品后的气体可根据需要，或提氢，或用其CO和H2间接转化为烃类产品或醇醚等产品，其余部分可回炉加热以及生产蒸汽等。
热解后以碳为主要成分的固态物，可根据需要在热解后采取相应的工艺，用其生产合成气CO和H2，进一步间接转化为市场需求的化工产品；或用其制作为高炉喷吹料、无烟燃料或气化焦，也可以生产铸造型焦或冶金型焦，以提高资源利用率。
本发明提供的工艺及装置与常规热解工艺及装置相比，存在以下显著的优势：
(1)常规水平室式间歇生产的干馏炼焦装置的设计初衷，主要是以生产冶金焦或铸造焦为目的的，煤气和化产品的回收是其派生工序，故必须在高温条件下均匀加热干馏才能生产出合格的焦炭，因此要求炭化室加热温度一致；常规干馏装置无法以梯级温度分段设置煤气导出口，只能在单一温度条件下干馏，致使煤气中多半优质烃类化合物在高温或次高温下被二次裂解，大大降低了荒煤气中宝贵的优质烃类化合物含量；若采用中、低温干馏则不能充分释放煤料中的挥发分，致使焦炭质量达不到合格冶金焦和铸造焦的要求，其工艺过程限制了化工产品的高效回收；
与现有技术相比，本发明开发的间接加热分段热解低阶煤连续提烃工艺及装置，提取烃类化合物是其最大的生产目的，生产半焦或冶金焦是其从属目的；该装置可以根据用户对产品的要求按不同的热解温度区设置两个、三个或多个不同温度段的煤气导出口；一般情况下设置低温、中温、高温三个煤气导出口，以得到不同温度条件下产生的不同组分煤气，即热解室采用不同温度分段加热、分段导出，煤料挥发分中热解温度低的烃类化合物在低温热解段馏出的同时被导出，热解温度再高一点的烃类化合物多在中温热解段馏出的同时被导出，以此类推；分段导出有效控制荒煤气中所含烃类化合物不受更高一级温度区的二次裂解，从而保证其中宝贵的优质烃类化合物不被破坏；煤料进入高温热解段后继续将剩余挥发分充分馏出并从高温煤气导出口引出，生产出贫烃富氢煤气和高温焦炭或符合其它要求的焦炭。这样，既最大限度地保证了烷烃成分不受破坏，又可根据下游产品要求对不同温度段的煤气进行组合或分别进行净化和分离，从而可将产品能耗及加工成本均比间接转化工艺降低50％左右，而且可回收比间接转化更优质的化工产品。
(2)常规外热立式干馏炉多采用上下交替(换向)加热方式，故燃烧室上下的温度基本一致，炭化室墙上部温度过高，因而被一次热解出的油、气在上升过程中又被高温二次裂解，致使宝贵的烃类化合物大部分受到破坏；
与现有技术相比，本发明的关键是实现了对入炉煤的梯级温度加热，采用分段间接加热，被低温段和中温段热解出的油、气从低温煤气导出口和中温煤气导出口分别直接引出，均使其不受更高一级温度区二次裂解的影响，很好地解决了油、气被二次裂解的问题，保证了宝贵的优质烃类化合物不受破坏。
(3)目前中国国内流行的所谓立式中低温干馏装置，大多是采用以含氧废气做气源的内加热方式；其工艺以含氧废气做气源在炭化室内部加热时，不仅煤气中的烃类物质至少70％以上受到破坏、空气中带进去大量的氮气冲淡了有效成分的浓度，致使无法正效益提取煤气中的烃类化合物(含烃特别低时提取必是负效益)，而且使煤气的热值大幅度降低；
与现有技术相比，本发明开发的分段间接加热，即采用燃烧室与热解室完全隔离的外加热方式，保证了宝贵的烃类化合物不会受空气中氧气的破坏、不被氮气冲淡，不仅提高优质化产品的回收率，提高资源利用率，而且煤气的热值至少是空气源内热式干馏炉的三倍以上。
(4)目前许多国家都在低阶煤热解方面做了大量的工作，且大都进行了中试或工业示范，但其工艺和装备多是回转炉、移动床、流化床、气流床或粉状固体热载体热解技术，综合这些热解工艺的特点，多属于固态粉状物料相对快速运动的动态热解工艺思路，至今尚无大规模工业应用；其共性问题是油气收率偏低、热解油中沥青质含量高、焦油与系统粉尘分离困难等等；
与现有技术相比，本发明开发了设置易于控制的梯级加热温度 区，使低阶煤分段间接加热热解、荒煤气分段导出，从而控制了低分离温度化合物免受次高温裂解；型块化物料以小于每秒0.5mm的下行速度相对静态加热，使气固两态在过程中自行分离，很好地解决了前述相对动态热解工艺的共性缺陷。
(5)一直以来，运行过或正在运行的立式中低温干馏炉，都是以强度很低的低阶块煤为原料，由于低阶原煤中块煤率一般仅30％左右，约70％富含烃类化合物的末煤只能用于发电等直接燃烧，不仅极大地浪费了宝贵的资源，而且还增加了污染；若以末煤直接用于热解，仍存在前述焦油与系统粉尘分离困难等弊端；曾有人将末煤加工成型煤代替块煤入炉，但因其加工工艺存在缺陷以及此类工艺的半焦中仍残留6～13％的挥发物大大降低了强度，导致其型块多返为碎粉状，不仅恶化了排焦环节，而且致使其产品市场价值大打折扣；
与现有技术相比，本发明在改进常规工艺缺陷的基础上，在热解工艺中增加了高温热解段和焖焦段，使焦炭的挥发分可降到1.5％以下，使其型块不被破坏，成块率达到95％以上，不仅拓宽了焦炭的用途，而且可大大提高企业的效益。
(6)在一般的热解工艺过程中，洁净固态物赤热半焦的显热是不回收的；这是因为热解后的半焦强度很低，产生大量的屑粉状物，若采用以惰性气体做热载体的常规干熄焦工艺，首先要经过焦炉热态出焦、热态运焦、热态装入干熄焦炉，不仅这三个环节由于热浮力造成的无组织污染物排放，而且需要大量的惰性气体与赤热焦炭进行直接换热，会导致其系统介质气体阻力大、气固分离困难、锅炉管与风机磨损严重、能耗高、产品烧损率高、因干熄焦过程中有煤气析出而不断送一定量的空气使其燃烧，使循环介质气体不断增加，必然导致含一定量有害物质的介质气体不断排放入大气而污染环境。还有上千千瓦的风机不仅能耗高，而且还会造成高噪音污染 等等弊端；
与现有技术相比，本发明的单孔联程干熄焦独特工艺，从源头上完全控制了常规干熄焦各种弊端的发生。这一全新的工艺技术是将赤热焦炭在出炉前就将其一部分显热间接传递给冷却水和助燃空气，另一部分显热直接传递给参与水煤气反应的水蒸汽，从而将焦炭温度降至100℃左右通过密封排焦装置排出，整个过程中焦炭在全密闭、无任何泄漏、以下行速度＜0.5mm/s的近静态状况运行；本发明提供的方案完全取消了必然产生无组织排放的热态出焦、运焦、装焦等中间环节，不仅杜绝了由于热浮力产生的无组织排放和有害气体排放，而且将其有害气体资源化高效回收，不需要大流量介质气体循环，而且省去了气体循环、除尘装置庞大的动力从而大大降低了能耗，更不会有多余有害气体排放污染环境，从源头上完全控制了常规干熄焦1.5％左右的焦炭被燃烧损失的问题，取消了上千千瓦特大功率的高温循环风机，省去了出焦、装焦、提升运焦装置及循环风机的大功率动力消耗，工艺能耗降低80％左右，从源头彻底解决了常规干熄焦污染气体排放和高噪音污染问题。
(7)常规水煤气发生炉生产合成气均以水蒸汽作气源。其水蒸汽装置不仅投资高、换热效率低、需要间歇式送入空气加热、需要消耗大量的燃料故能耗高、煤气质量差，而且有安全隐患。
与现有技术相比，本发明在单孔联程中低温干熄焦换热器下部的拨焦装置中设有水雾化器，适量的水被雾化器雾化后与100℃左右及以上的焦炭直接高效换热产生水蒸汽，省去了结构复杂换热效率低且投资高的水蒸汽发生装置；其水蒸汽由于热浮力沿焦程上升，并在上升过程中与温度逐高的焦炭继续迅速高效直接换热升温，使水蒸汽温度达950℃左右后，与源源不断下行950℃以上的赤热焦炭进行水煤气反应生产优质合成气；其工艺投资很低、热效率特别高、无须送入空气加热、完全省去了常规水煤气发生炉高额的燃料消耗， 故能耗低、煤气中含N2低质量好、无安全隐患，同时对单孔联程干熄焦装置起到了强化冷却焦炭的作用，从而使焦炭冷却到100℃左右，焦炭90％左右的显热得到回收利用。
附图说明
图1为本发明所述装置结构示意图；其中：1、料仓，2、密封装煤装置，3、预存段，4、干燥预热段，5、低温热解段，6、低温加热段，7、中温热解段，8、中温加热段，9、高温热解段，10、高温加热段，11、砖煤气道，12、焖焦段，13、废气道，14、空气道，15、单孔联程高温干熄焦段，16、空气进口，17、单孔联程中低温干熄焦换热器，18、水雾化器，19、拨焦装置，20、密封排焦机，21、低温煤气导出口，22、中温煤气导出口，23、高温煤气导出口，24、煤气支管，25、回炉煤气管道，26、废气导出口，27、废气总管。
具体实施方式
实施例1
取冷态粉末状中/低阶煤，按照以下步骤进行操作：
(1)取冷态粉末状中/低阶煤，压制成型后，输入干燥预热段进行预热处理；
(2)将经预热处理后的中/低阶型煤输入热解段，采用间接加热方式，在450℃左右进行低温热解，再在600℃左右进行中温热解，再在850℃以上进行高温热解，分别连续收集每一阶段产生的不同烃类组分的气体；
(3)将热解后所得固体产物输入闷焦段进行焖焦处理；
(4)将焖焦所得的焦炭输入熄焦段，高温焦炭在高温干熄焦段与空气进行间接热交换，同时与水蒸汽进行直接热交换，熄焦至450℃左右，再进入中低温干熄段，与冷却水进行间接热交换，同时与水蒸汽进行直接热交换，熄焦至120℃以下，再输入拔焦段进行拔 焦处理，所得低温焦炭经密封排焦段排出；
同时，将水蒸汽与高温焦炭反应生成水煤气作为产物收集；
其中，所述中阶煤在工艺全程中的输送均在密封状态下以小于0.5mm/s的速度靠重力下行实现。
实施例2
取冷态粉末状中/低阶煤，按照以下步骤进行操作：
(1)取冷态粉末状中/低阶煤，压制成型后，输入干燥预热段进行预热处理；
(2)将经预热处理后的中/低阶型煤输入热解段，采用间接加热方式，在380℃左右进行低温热解，再在500℃左右进行中温热解，再在850℃以上进行高温热解，分别连续收集每一阶段产生的不同烃类组分的气体；
(3)将热解后所得固体产物输入闷焦段进行焖焦处理；
(4)将焖焦所得的焦炭输入熄焦段，高温焦炭在高温干熄焦段与空气进行间接热交换，同时与水蒸汽进行直接热交换，熄焦至350℃左右，再进入中低温干熄段，与冷却水进行间接热交换，同时与水蒸汽进行直接热交换，熄焦至100℃以下，再输入拔焦段进行拔焦处理，所得低温焦炭经密封排焦段排出；
同时，将水蒸汽与高温焦炭反应生成水煤气作为产物收集；
其中，所述低阶煤在工艺全程中的输送均在密封状态下以小于0.3mm/s的速度靠重力下行实现。
实施例3
采用间接加热分段热解方式从中/低阶煤中连续提烃的装置(部分参考图1)；该装置包括由上至下依次顺序连接的料仓1、密封装煤装置2、预存段3、干燥预热段4、低温热解段5、中温热解段7、高温热解段9、焖焦段12、单孔联程高温干熄焦段15、单孔联程中低温干熄焦换热器17、拨焦装置19和密封排焦机20；
所述低温热解段5还与低温煤气导出口21相连；
所述中温热解段7还与中温煤气导出口22相连；
所述高温热解段9还与高温煤气导出口23相连；
所述装置为全密闭装置；由拨焦装置19控制固体物料的下行速度。
实施例4
采用间接加热分段热解方式从中/低阶煤中连续提烃的装置(部分参考图1)，与实施例2相比，还包括依次顺序相连的高温加热段10、中温加热段8、低温加热段6；所述高温加热段10与高温热解段9直接相邻；所述中温加热段8与中温热解段7直接相邻；所述低温加热段6与低温热解段5直接相邻；
所述低温加热段6设有废气出口，其与位于高温加热段10下方的废气道13相通；所述废气道13依次与废气导出口26和废气总管27相连；
所述装置还包括空气道14；所述空气道14的一端为空气进口16，另一端与高温加热段10底部的空气入口相连；所述空气道14位于废气道13和单孔联程高温干熄焦段15之间，并分别与二者直接相邻；
所述装置还包括依次顺序相连的回炉煤气管道25、煤气支管24和砖煤气道11，砖煤气道11的出口与高温加热段10底部的可燃气入口相连。
实施例5
采用间接加热分段热解方式从中/低阶煤中连续提烃的装置(如图1所示)，与实施例3相比，所述拨焦装置19内还设有水雾化器18；被所述水雾化器18雾化并吸收焦炭显热生成的水蒸汽依次经过单孔联程中低温干熄焦换热器17、单孔联程高温干熄焦段15、焖焦段12、高温热解段9，生成水煤气作为产物从煤气导出口23导出。
实施例6
采用实施例5所述装置、按照本发明所述方法进行间接加热分段热解低阶煤连续提烃；具体包括以下步骤：
本发明的热解装置顶部设有料仓1和密封装煤装置2；装煤时启动密封装煤装置2，料仓1中的压制而成的型煤经密封装煤装置2被送入预存段3，密封装煤装置2不论在运行或停止过程中，始终将料仓1与预存段3的气流被密封隔断；型煤在重力作用下自预存段落入干燥预热段4；经干燥预热后的型煤靠重力下行进入低温热解段5；型煤在低温热解段5释放含有大量烃类化合物的低温荒煤气，并通过低温煤气导出口21引出，以保证低温馏分出的煤气不被高温和次高温二次裂解，经低温热解后的型煤继续下行进入中温热解段7；型煤在中温热解段7释放以中等烃类化合物含量的中温荒煤气并通过中温煤气导出口22引出，保证中温馏分出的煤气不被高温二次裂解，型煤经中温热解后逐渐形成半焦，并继续下行进入高温热解段9；在高温热解段9热解出以氢气为主的高温低烃荒煤气通过高温煤气导出口23引出，型煤在高温热解段释放挥发物后被炭化为焦炭并下行进入焖焦段12；焦炭在焖焦段12进一步充分释放其挥发物后被充分炭化，焦炭被充分炭化后是一个放热过程，放出的热量使焦炭再次升温，并继续下行进入单孔联程高温干熄焦段15；焦炭30％左右的显热，在单孔联程高温干熄焦段通过间接换热将热量传递给空气道14的助燃空气，焦炭在此失去一部分热量被降温400℃左右后，靠重力下行进入单孔联程中低温干熄焦换热器17；在单孔联程中低温干熄焦换热器17内焦炭的部分显热被换热器17壳体中的软水(入锅炉前的软水)间接冷却后继续下行进入拨焦装置19；焦炭被拨焦装置缓慢有序排出下落进入密封排焦机20，密封排焦机在有效隔断外部空气和内部焦程煤气的条件下，将焦炭排出落入输送机被运出；
自回炉煤气管道25送来的已被净化后的煤气经煤气支管24送 入燃烧室底部的砖煤气道11，再由砖煤气道11分配进入高温加热段10的底部；空气自空气进口16进入后，被分配到两侧上下排列的空气道14，空气道14中助燃空气间接吸收单孔联程高温干熄焦段赤热焦炭的热量和废气道中废气的热量被间接预热到450℃左右，然后进入高温加热段10的底部与自砖煤气道11来的煤气混合燃烧；燃烧后的高温废气在高温加热段10将部分热量间接传给高温热解段正在炭化阶段的物料焦炭，高温废气失去部分热量被降温后进入中温加热段8；废气在中温加热段8又将一部分热量间接传递给中温热解段中的物料，废气又一次失去部分热量被降温后进入低温加热段6；废气在低温加热段6又被低温热解段中的物料间接吸收，废气再一次失去部分热量被降温，并经隔墙中的废气通道进入废气道13；废气在废气道13又将一部分热量间接传递给两侧空气道14中的空气，废气又一次被降温后进入废气导出口26，然后经废气总管27送去余热锅炉再次回收余热；
拨焦装置19中设置有水雾化器18，从外部送入适量的水被雾化器18雾化，被雾化的水吸收100℃以上焦炭的显热产生水蒸汽并对其焦炭进行高效冷却，水蒸汽由于热浮力上升进入单孔联程中低温干熄焦换热器17，并充分与其焦程的热焦炭进行热交换；吸收中低温段焦炭的热量后，水蒸汽继续上升进入单孔联程高温干熄焦段15，又与高温赤热焦炭进行热交换并持续升温；在水蒸汽到达单孔联程高温干熄焦段15顶部和焖焦段12时已被升温到950℃左右，在此段高温水蒸汽与源源不断下行的950℃以上赤热焦炭进行水煤气反应，同时对单孔联程干熄焦装置17与15起到了强化冷却焦炭的作用；反应后的水煤气上升进入高温热解段9与在此热解出的富氢煤气混合，混合后的富氢煤气经高温煤气导出口23被导出，然后进入煤气净化、合成、分离等工序。
实验例
以中国鞍山焦耐院JLH-D式外热炉和中国内蒙古、陕西、新疆等地目前流行的废热源内热炉为对照，对本发明提供的工艺及装置所得煤气热值、烃类化合物回收率、原料类型、焦炭成块率和转化效益进行检测，结果如表2所示。
表2：效果对比
Figure PCTCN2015081693-appb-000003
由表2结果可知，本发明提供的方案所得的煤气热值高，烃类化合物回收率高，焦炭成块率高，转化效益非常好，具有极强的推广价值。
虽然，上文中已经用一般性说明、具体实施方式及试验，对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。

Claims (10)

  1. 一种采用间接加热分段热解方式从中/低阶煤中连续提烃的工艺，其特征在于，包括以下步骤：
    (1)将中/低阶煤压制成型，得到中/低阶型煤，输入干燥预热段进行干燥预热；
    (2)将经预热处理后的中/低阶型煤输入热解段，采用间接加热方式进行三阶段以上梯度升温热解，分别连续收集每一阶段产生的烃类的气体；
    (3)将热解后所得固体产物输入闷焦段进行焖焦处理；
    (4)将焖焦所得的焦炭输入熄焦段进行熄焦处理，再输入拔焦段进行拔焦处理，所得低温焦炭经密封排焦段排出；
    其中，所述中/低阶型煤在工艺全程中的输送均在密封状态下以小于0.5mm/s的速度靠重力下行实现。
  2. 根据权利要求1所述的工艺，其特征在于，在所述拨焦段引入水蒸汽，所述水蒸汽在上升过程中依次与拨焦段、熄焦段、焖焦段和热解段的焦炭进行直接热交换，辅助高效熄焦，并生成水煤气作为产物导出。
  3. 根据权利要求2所述的工艺，其特征在于，所述熄焦段依次包括高温干熄焦段和中低温干熄焦段；
    在所述高温干熄焦段，高温焦炭与空气进行间接热交换，同时与水蒸汽进行直接热交换，实现高温焦炭的余热回收；
    在所述中低温干熄焦段，中低温焦炭与冷却水进行间接热交换，同时与水蒸汽进行直接热交换，实现中低温焦炭的余热回收。
  4. 根据权利要求1～3任意一项所述的工艺，其特征在于，所述梯度升温热解为三个阶段，依次为：在380～450℃进行低温热解，再在500～600℃进行中温热解，再在850℃以上进行高温热解。
  5. 一种采用间接加热分段热解方式从中/低阶煤中连续提烃的 装置，其特征在于，所述装置包括由上至下依次顺序连接的料仓、密封装煤装置、预存段、干燥预热段、多阶段梯度升温热解段、焖焦段、单孔联程干熄焦段、拨焦装置和密封排焦机；
    所述多阶段梯度升温热解段包括三个以上连续阶段，每个阶段分别与煤气导出口相连；
    所述装置还包括为所述多阶段梯度升温热解段间接供热的加热段。
  6. 根据权利要求5所述的装置，其特征在于，所述加热段与所述多阶段梯度升温热解段直接相邻，其中包括与每个热解阶段一一对应的加热阶段；
    所述加热段的底部设有空气入口和可燃气入口；所述空气入口与空气道相连，所述可燃气入口与回炉煤气管道相连；
    所述加热段还设有废气出口，与位于加热段下方的废气道相连。
  7. 根据权利要求6所述的装置，其特征在于，所述单孔联程干熄焦段由上至下包括相连单孔联程高温干熄焦段和单孔联程中低温干熄焦换热器；
    所述空气道位于所述单孔联程高温干熄焦段与所述废气道之间，且分别与二者直接相邻。
  8. 根据权利要求5～7任意一项所述的装置，其特征在于，所述拨焦装置内设有水雾化器；被所述水雾化器雾化并与焦炭直接换热生成的水蒸汽依次经过单孔联程干熄焦段、焖焦段、多阶段梯度升温热解段，生成水煤气作为产物从煤气导出口导出。
  9. 根据权利要求5～8任意一项所述的装置，其特征在于，所述多阶段梯度升温热解段由三个阶段组成，依次为低温热解段、中温热解段和高温热解段。
  10. 根据权利要求5～9任意一项所述的装置，其特征在于，所述装置全密封；其中，拨焦装置控制物料的下行速度。
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CN108485690A (zh) * 2018-05-29 2018-09-04 西北大学 一种粉煤低温静态热解提取油气的装置及方法
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