CN102199434B - Method for direct liquefaction residues of coal by utilizing microwaves quick pyrolysis - Google Patents
Method for direct liquefaction residues of coal by utilizing microwaves quick pyrolysis Download PDFInfo
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- CN102199434B CN102199434B CN 201110092726 CN201110092726A CN102199434B CN 102199434 B CN102199434 B CN 102199434B CN 201110092726 CN201110092726 CN 201110092726 CN 201110092726 A CN201110092726 A CN 201110092726A CN 102199434 B CN102199434 B CN 102199434B
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Abstract
The invention relates to a method for the quick pyrolysis of coal direct liquefaction residues by utilizing microwaves, which comprises the following steps of: heating the coal direct liquefaction residues to the temperature of between 500 and 900 DEG C by utilizing the microwaves as a heating heat source; crushing the coal direct liquefaction residues to less than 30 millimeters, and putting into drying equipment for drying; and putting the dried coal direct liquefaction residues into a microwave pyrolysis reactor, heating to the temperature of between 500 and 900 DEG C to obtain solid coke and pyrolysis gas, and cooling to separate liquid oil from gas. The method is mainly used for recycling the coal direct liquefaction residues comprehensively, and hydrogen-rich gas is obtained while the liquid oil is separated quickly and efficiently, so the method has characteristics of high pyrolysis speed, production efficiency, yield of the liquid oil and hydrogen content in the gas.
Description
Technical field
The invention belongs to the coal pyrolysis technical field, relate to a kind of method of coal directly-liquefied residue pyrolysis, be specifically related to a kind of method of utilizing the microwave quick pyrolysis of coal direct liquefaction residues.
Background technology
The characteristics of China's energy structure are " many coals, few oil, deficencys ", along with the develop rapidly of economy and the raising of living standards of the people, to the demand of the energy particularly the demand of oil entered rapid growth period.Due to a large amount of Imported oils, not only increased the degree of dependence to the external energy, and the fluctuation of international petroleum market and change and can directly affect the economy of China and the safety of power supply.China has abundant coal resources, takes full advantage of the coal resources of China's abundant, and the Devoting Major Efforts To Developing Direct liquefaction technology is one of effective way that solves oil shortage, has important strategy and economic implications.
In the DCL/Direct coal liquefaction process, no matter adopt which kind of liquefaction process and solid-liquid separation technique, all can produce the liquefied residue that accounts for 30% left and right.Liquefied residue is the material of a kind of high-sulfur, high ash and high-carbon, unconverted coal organic substance, mineral substance and catalyzer in the liquefaction raw coal, the main body of formation coal liquefaction residue.Difference in liquefied residue, generally contains the elements such as C, H, O, N, S along with the difference that organic structure forms and inorganic mineral forms of different liquefaction process and coal for the content of liquefied residue and composition, and the content of C element is up to 70%-85%.The classical group of underpressure distillation residue becomes: mink cell focus 30%, asphaltene 20%, preasphaltene 5% and tetrahydrofuran insoluble (unreacted coal and mineral substance) 45%, wherein unreacted coal accounts for 30% left and right.Therefore, from improving the angle of direct coal liquefaction process economy and comprehensive utilization of resources and environment protection, realize that fast, efficiently utilizing of coal directly-liquefied residue is very necessary.
At present, one of the approach that utilizes of liquefied residue is that coal liquefaction residue is used for gasification hydrogen-producing, both for the gelatin liquefaction process provides the part hydrogen source, can be depleted to whole liquefied residues again, realizes the organic coupling that residue comprehensive utilization and gelatin liquefaction are produced.Although adopting liquefied residue gasification hydrogen-producing technique is a kind of effective way that solves the residue comprehensive utilization, but people also are in the starting stage to the understanding of liquefied residue, and the formation condition of liquefied residue, the enrichment of catalyzer and inorganic mineral content still await further research and probe to impact of gasification etc.In China, although Shenhua Group gelatin liquefaction company has completed the research work in early stage of residue gasification hydrogen-producing, and selected Texaco and Shell gasifying process to carry out respectively the liquefied residue gasification and attempted, but not yet find so far a feasible suitability for industrialized production route.
In addition, generally contain have an appointment 30% mink cell focus and asphaltene and the preasphaltene of 25% left and right in liquefied residue, therefore, at first just become another kind by the comprehensive refiltered oil series products of pyrolysis and utilize economically and reasonably approach.The pyrolysis of liquefied residue refers to residue is heated under the condition of isolated air or inert atmosphere, and the complex process of series of physical variation and chemical reaction occurs at different temperature.The pyrolysis of residue is the same with the pyrolysis of coal, be in the trans-utilization processes such as liquefaction, gasification at first and must through reactions steps, it almost occurs in all liquefied residue trans-utilization processes, utilizes process to have a great impact to the subsequent conversion of residue.The pyrolysis of liquefied residue can make the asphaltene in residue be converted into to greatest extent mink cell focus and retortable oil, has increased the liquid product yield of coal liquefaction craft.When liquefied residue and coal carried out mixed pyrolysis, liquefied residue can produce the hydrogen supply effect, can occur simultaneously to interact significantly, and this distribution on product has very large impact.
Microwave heating is a kind of Novel heating technology, has that rate of heating is fast, characteristics of homogeneous heating, efficient energy-saving.In order to prevent that microwave power from causing interference to radio communication, broadcasting, TV and radar etc., general provision 915MHz and 2450MHz are civilian microwave frequency band in the world.Traditional type of heating is first heating object surface, and then to internal delivery, and microwave heating is directly object integral body to be heated to heat, can strengthen to improve heat-transfer effect, reduces the heat transfer loss of pyrolytic process by body surface.At present, microwave heating be widely used in that food-processing, medicine are produced, chemical industry is synthetic, agricultural byproducts are dry, the fields such as the drying of mineral processing, disinfection and coal and biomass etc., desulfurization, pyrolysis.
Present technique is applied to microwave heating in the pyrolysis of liquefied residue, has great importance for improving pyrolysis efficient and oils product yield.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of method of utilizing the microwave quick pyrolysis of coal direct liquefaction residues, the method is mainly used in comprehensive recovery and the utilization of coal directly-liquefied residue, rapidly and efficiently obtaining hydrogen-rich gas in the separating oil series products, have that pyrolysis rate is fast, production efficiency is high, the liquid oils yield is high, the high characteristics of hydrogen richness in coal gas.
To achieve these goals, the technical solution used in the present invention is:
A kind of method of utilizing the microwave quick pyrolysis of coal direct liquefaction residues utilizes microwave as heat source, and coal directly-liquefied residue is heated to 500 ℃～900 ℃.
Specifically comprise the following steps:
The first step utilizes grinding attachment that coal directly-liquefied residue is crushed to below particle diameter 30mm;
Second step is placed in dry 30 ± 10min under 100 ℃ of conditions of drying plant with the coal directly-liquefied residue after pulverizing;
The 3rd step was placed in the microwave-heating reactor with the coal directly-liquefied residue after pulverizing, and power-on is heated to 500 ℃～900 ℃, and the residence time 10 ± 5min obtains solid Jiao and pyrolysis gas;
In the 4th step, solid Jiao collect after water-cooling system is cooled to normal temperature, and pyrolysis gas is collected respectively after the two-stage cooling system is isolated the liquid oil and gas.
Described two-stage cooling system refers to the cold air system of the first step and the liquid phase condensate system of the second stage.
Described heating is the 915MHz of national regulation and the civilian microwave frequency band of 2450MHz with the frequency of microwave.
Compared with prior art, method of the present invention is to utilize the basic fine structure coupling of special wave band that microwave has and material to produce heat to heat, the intensification of liquefied residue is not to transmit by heat but complete by outfield and object interaction, it is fast that it has the heating rate degree, selectivity is good, material is heated evenly, capable of fast starting and stop, easy to operate, energy utilization rate and heating efficiency high.In addition, the volatile matter in residue can obtain sufficient pyrolysis, and the oils product yield is high; Simultaneously can obtain superior in quality solid Jiao and hydrogen-rich gas, be conducive to the comprehensive utilization of resource.
Description of drawings
Accompanying drawing is process flow sheet of the present invention;
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further details.
Embodiment one
As shown in Figure 1, utilize the method for microwave quick pyrolysis of coal direct liquefaction residues, it is characterized in that, comprise the following steps:
The first step utilizes grinding attachment that coal directly-liquefied residue is crushed to particle diameter 30mm;
Second step is placed in dry 20min under 100 ℃ of conditions of drying plant with the coal directly-liquefied residue after pulverizing;
The 3rd step was placed in the microwave-heating reactor with dried coal directly-liquefied residue, power-on, and setting heating is 2450MHz with microwave frequency, is heated to 900 ℃, residence time 15min obtains solid Jiao and pyrolysis gas;
In the 4th step, solid Jiao collect after water-cooling system is cooled to normal temperature, and pyrolysis gas is through main air cooling system and secondary liquid phase condensate system, collects respectively after isolating the liquid oil and gas.
Embodiment two
As shown in Figure 1, utilize the method for microwave quick pyrolysis of coal direct liquefaction residues, it is characterized in that, comprise the following steps:
The first step utilizes grinding attachment that coal directly-liquefied residue is crushed to particle diameter 10mm;
Second step is placed in dry 30min under 100 ℃ of conditions of drying plant with the coal directly-liquefied residue after pulverizing;
The 3rd step was placed in the microwave-heating reactor with dried coal directly-liquefied residue, power-on, and setting heating is 2450MHz with microwave frequency, is heated to 800 ℃, residence time 10min obtains solid Jiao and pyrolysis gas;
In the 4th step, solid Jiao collect after water-cooling system is cooled to normal temperature, and pyrolysis gas is through main air cooling system and secondary liquid phase condensate system, and sub-argument is collected respectively after going out the liquid oil and gas.
Embodiment three
As shown in Figure 1, utilize the method for microwave quick pyrolysis of coal direct liquefaction residues, it is characterized in that, comprise the following steps:
The first step utilizes grinding attachment that coal directly-liquefied residue is crushed to particle diameter 5mm;
Second step is placed in dry 40min under 100 ℃ of conditions of drying plant with the coal directly-liquefied residue after pulverizing;
The 3rd step was placed in the microwave-heating reactor with dried coal directly-liquefied residue, power-on, and setting heating is 915MHz with microwave frequency, is heated to 500 ℃, residence time 5min obtains solid Jiao and pyrolysis gas;
In the 4th step, solid Jiao collect after water-cooling system is cooled to normal temperature, and pyrolysis gas is through main air cooling system and secondary liquid phase condensate system, and sub-argument is collected respectively after going out the liquid oil and gas.
Embodiment four
In the present embodiment, the coal directly-liquefied residue composition analysis is as shown in table 1.
Table 1
Pyrolytic process is as follows:
The first step utilizes grinding attachment that coal directly-liquefied residue is crushed to particle diameter 5～10mm;
Second step is placed in dry 30min under 100 ℃ of conditions of loft drier with the coal directly-liquefied residue after pulverizing;
The 3rd step was placed in the microwave-heating reactor with dried coal directly-liquefied residue, power-on, and setting heating is 2450MHz with microwave frequency, heating stops 15min between 500 ℃～900 ℃, obtain solid Jiao and pyrolysis gas;
In the 4th step, solid Jiao collect after water-cooling system is cooled to normal temperature, and pyrolysis gas is through main air cooling system and secondary liquid phase condensate system, collects respectively after isolating the liquid oil and gas.
After pyrolysis, the analytical results of coal gas is as shown in table 2,
| H 2 | CO 2 | CO | CH 4 |
| Sample 1 | 60.27 | 5.68 | 4.52 | 29.01 |
| Sample 2 | 61.79 | 4.18 | 5.04 | 28.52 |
| Mean value | 61.03 | 4.93 | 4.78 | 28.77 |
Table 2
Experimental result shows, the liquid oils rate of recovery can reach 25% left and right, and in pyrolysis coal gas, hydrogen content is in 60% left and right.
In the present invention, the selection of the grain size after pulverizing, the parameter area of drying plant and microwave heating temperature scope and time is non-limitation of the present invention all, such selection is for no other reason than that consider when guaranteeing to reach best effect and will save cost, as, grain size after pulverizing greater than the temperature of 30mm or heating lower than 500 ℃, the final purpose of pyrolysis still can realize, still can make like this reaction times long, and be unfavorable for Artificial Control.
Claims (6)
1. a method of utilizing the microwave quick pyrolysis of coal direct liquefaction residues, is characterized in that, comprises the following steps:
The first step utilizes grinding attachment that coal directly-liquefied residue is crushed to below particle diameter 30mm;
Second step is placed in dry 30 ± 10min under 100 ℃ of conditions of drying plant with the coal directly-liquefied residue after pulverizing;
The 3rd step was placed in the microwave-heating reactor with dried coal directly-liquefied residue, and power-on is heated to 500 ℃ ~ 900 ℃, and the residence time 10 ± 5min obtains solid Jiao and pyrolysis gas;
In the 4th step, solid Jiao is cooled to normal temperature through water-cooling system, and pyrolysis gas is collected respectively after isolating the liquid oil and gas after the two-stage cooling system.
2. the method for utilizing the microwave quick pyrolysis of coal direct liquefaction residues according to claim 1, is characterized in that, comprises the following steps:
The first step utilizes grinding attachment that coal directly-liquefied residue is crushed to particle diameter 30mm;
Second step is placed in dry 20min under 100 ℃ of conditions of drying plant with the coal directly-liquefied residue after pulverizing;
The 3rd step was placed in the microwave-heating reactor with dried coal directly-liquefied residue, and power-on is heated to 900 ℃, and residence time 15min obtains solid Jiao and pyrolysis gas;
In the 4th step, solid Jiao is cooled to normal temperature through water-cooling system, and pyrolysis gas is collected respectively after isolating the liquid oil and gas after the two-stage cooling system.
3. the method for utilizing the microwave quick pyrolysis of coal direct liquefaction residues according to claim 1, is characterized in that, comprises the following steps:
The first step utilizes grinding attachment that coal directly-liquefied residue is crushed to particle diameter 10mm;
Second step is placed in dry 30min under 100 ℃ of conditions of drying plant with the coal directly-liquefied residue after pulverizing;
The 3rd step was placed in the microwave-heating reactor with dried coal directly-liquefied residue, and power-on is heated to 800 ℃, and residence time 10min obtains solid Jiao and pyrolysis gas;
In the 4th step, solid Jiao is cooled to normal temperature through water-cooling system, and pyrolysis gas is collected respectively after isolating the liquid oil and gas after the two-stage cooling system.
4. the method for utilizing the microwave quick pyrolysis of coal direct liquefaction residues according to claim 1, is characterized in that, comprises the following steps:
The first step utilizes grinding attachment that coal directly-liquefied residue is crushed to particle diameter 5mm;
Second step is placed in dry 40min under 100 ℃ of conditions of drying plant with the coal directly-liquefied residue after pulverizing;
The 3rd step was placed in the microwave-heating reactor with the coal directly-liquefied residue after pulverizing, and power-on is heated to 500 ℃, and residence time 5min obtains solid Jiao and pyrolysis gas;
In the 4th step, solid Jiao is cooled to normal temperature through water-cooling system, and pyrolysis gas is collected respectively after isolating the liquid oil and gas after the two-stage cooling system.
5. the described method of utilizing the microwave quick pyrolysis of coal direct liquefaction residues of arbitrary claim of according to claim 1 to 4, is characterized in that, described two-stage cooling system refers to the cold air system of the first step and the liquid phase condensate system of the second stage.
6. the described method of utilizing the microwave quick pyrolysis of coal direct liquefaction residues of arbitrary claim of according to claim 1 to 4, is characterized in that, described heating is the 915MHz of national regulation and the civilian microwave frequency band of 2450MHz with the frequency of microwave.
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| CN102653683A (en) * | 2012-01-26 | 2012-09-05 | 何巨堂 | Internal heating type coal carbonization gas production process based on pressurization method |
| CN102718383B (en) * | 2012-06-06 | 2017-03-08 | 中国科学院上海高等研究院 | Convert pyrolysis installation and the method containing carbon resource using microwave-assisted pyrolysis on the spot |
| CN102942976A (en) * | 2012-10-19 | 2013-02-27 | 西安建筑科技大学 | Method for preparing formed coke with low metamorphic coal as main raw material in microwave field |
| US9598646B2 (en) | 2013-01-09 | 2017-03-21 | C20 Technologies, Llc | Process for treating coal to improve recovery of condensable coal derived liquids |
| CN104073275A (en) * | 2013-03-29 | 2014-10-01 | 广州市昊晟工程勘察设计有限公司 | Mild-reaction oil residue separation method for coal-based residual oil |
| CN105377794B (en) * | 2013-05-23 | 2020-09-08 | 埃克赛乐公司 | Production of fuels and biofertilizers from biomass |
| CN103788975B (en) * | 2014-01-22 | 2015-10-28 | 中国科学院上海高等研究院 | The method that brown coal microwave-heating utilizes |
| CN105414155A (en) * | 2015-12-28 | 2016-03-23 | 北京中石大能源技术服务有限公司 | Harmless treatment method and harmless treatment device for industrial petroleum wastes |
| CN108106460B (en) * | 2016-11-24 | 2020-08-04 | 神华集团有限责任公司 | Cooling system and method for direct coal liquefaction residues |
| CN110172358A (en) * | 2019-06-27 | 2019-08-27 | 西安建筑科技大学 | A kind of pyrolysis atmosphere furnace and coal hydrogenation microwave-heating system and method |
| CN112625701A (en) * | 2019-09-24 | 2021-04-09 | 王其成 | Rectification residue resource utilization system and process |
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