CN103131448B - Fluidized bed dry distillation method and device for oil shale - Google Patents

Abstract

The invention discloses a fluidized bed dry distillation method and a fluidized bed dry distillation device for oil shale, which aim to solve the problems of high charcoal-burning load borne by a charcoal burner and low shale oil yield in the prior dry distillation technology. The dry distillation method comprises the following steps: A. mixing the oil shale raw material (27) with a high-temperature heat carrier, and then carrying out a first-stage dry distillation reaction in a riser dry distillation reactor (24); B. the oil shale raw material after the first-stage dry distillation reaction enters a bed-type dry distillation reactor (21) to carry out second-stage dry distillation reaction, and the formed mixed semicoke is stripped to obtain entrained oil gas and then enters a tubular char burning device (14); C. the mixed semicoke entering the tubular carbon burning device is subjected to first-stage carbon burning; D. the mixed semicoke after the first-stage carbonization enters a bed-type carbonization device (5) for second-stage carbonization. The invention discloses a fluidized bed dry distillation device for oil shale for realizing the dry distillation method. The invention is mainly used for dry distillation processing of various powder and particle oil shale raw materials.

Description

A fluidized bed dry distillation method and device for oil shale

technical field

The invention belongs to the technical field of oil shale dry distillation, and relates to a fluidized bed dry distillation method and device for oil shale.

Background technique

With the increasing scarcity of oil resources and the advent of the era of high oil prices, the use of oil shale dry distillation technology to produce shale oil in countries around the world has become an important plan to replace and supplement oil resources. Oil shale, also known as kerogen shale, is a sedimentary rock containing organic matter. Organic matter in oil shale is usually composed of two substances: one is asphaltene, and the other is high molecular polymer (called kerogen). Inorganic substances in oil shale mainly include quartz, kaolin, clay, mica, carbonate rock and pyrite. After oil shale is heated and dry-distilled, shale oil, dry distillation gas and shale semi-coke are produced. Shale oil can be directly used as fuel oil, and can also be further processed to produce gasoline, diesel and other vehicle fuels. The fluidized bed dry distillation technology of oil shale has the characteristics of high heat intensity of dry distillation, fast dry distillation speed, good quality of shale oil and high oil recovery rate, etc. "Pilot-scale study on oil shale solid heat carrier fluidized carbonization refining process" (document 1) and other literature introductions.

In the process described in CN101440293A and Document 1, part of the high-temperature heat carrier (circulating hot ash or high-temperature shale ash) generated by charcoal burning in the charcoal burner is discharged from the dry distillation device after being heated, and another part is mixed with the oil shale raw material Mixing and heating; dry distillation reaction to generate mixed semi-coke made of shale semi-coke and heat carrier, and the mixed semi-coke is burned in the charcoal burner to generate high-temperature heat carrier. Using high-temperature heat carrier as the heat source of oil shale carbonization, the energy consumption is low. The composition of the high-temperature heat carrier in the present invention is equivalent to the circulating hot ash generated by the charcoal burner described in CN101440293A (ie, the circulating fluidized bed combustion chamber) or the high-temperature shale ash generated by the charcoal burner described in Document 1.

The above two dry distillation techniques mainly have the following two problems. ① All of the large amount of mixed semi-coke with high calorific value generated after the dry distillation reaction is sent to a charcoal burner for charcoal burning (that is, the coke is burned), so that the charcoal burner bears a high charcoal burning load, making it difficult to control the charcoal burning temperature. The charcoal burner is easily damaged by overheating. ② Only one fluidized bed dry distillation reactor is used for dry distillation reaction. Due to the incomplete reaction of some oil shale raw materials, the yield of shale oil is low, and generally only accounts for 75% to 85% of the oil content of oil shale raw materials. %.

Contents of the invention

The purpose of the present invention is to provide a fluidized bed dry distillation method and device for oil shale, to solve the problem of using a charcoal burner for charcoal burning in the existing oil shale fluidized bed dry distillation technology. The burden of charcoal burning is high, the temperature of charcoal burning is difficult to control, and the charcoal burner is easily damaged by overheating. There is also the problem of low shale oil yield due to the use of a fluidized bed dry distillation reactor for dry distillation reaction .

In order to solve the above problems, the technical solution adopted in the present invention is: a fluidized bed carbonization method for oil shale, characterized in that: the method comprises the following steps in sequence:

A. The pulverized oil shale raw material enters the lower part of the riser carbonization reactor through the oil shale raw material feed pipe, and the high-temperature heat carrier in the bed type charcoal burner enters the riser carbonization reactor through the high-temperature heat carrier delivery pipe In the lower part, after the oil shale raw material is mixed with the high-temperature heat carrier, under the lifting action of the lifting gas introduced from the bottom of the riser carbonization reactor, it goes up along the riser carbonization reactor to perform a stage of carbonization reaction;

B. The oil shale raw material and the heat carrier mixed with it after the first stage of carbonization reaction, as well as the shale oil and carbonization gas generated by the first stage of carbonization reaction, enter the bed type carbonization reactor from the outlet of the riser carbonization reactor, The oil shale raw material after the first-stage carbonization reaction is subjected to the second-stage carbonization reaction in the dense-phase bed of the bed-type carbonization reactor to obtain the shale oil, carbonization gas and shale semi-coke generated by the second-stage carbonization reaction, and the bed-type carbonization reaction The shale semi-coke and heat carrier in the dense-phase bed are mixed together to form mixed semi-coke, and the oil and gas generated by the first-stage and second-stage dry distillation reactions are separated by the cyclone separator installed in the bed-type dry distillation reactor, and then the mixed semi-coke is produced The bed type dry distillation reactor flows out, and the mixed semi-coke in the dense phase bed of the bed type dry distillation reactor flows downwards and enters the stripping section below the bed type dry distillation reactor, and the stripping section is passed into the stripping section. Water vapor is stripped out of the oil and gas entrained in the mixed semi-coke, and the stripped mixed semi-coke in the stripping section flows to the lower part of the stripping section, and enters the bottom of the tubular charcoal burner through the semi-coke conveying pipe;

C. The mixed semi-coke entering the tubular charcoal burner is in contact with a stage of charcoal-burning air, and a stage of charcoal burning is carried out along the tube-type charcoal burner;

D. The mixed semi-coke after the first-stage charcoal burning enters the bed-type charcoal burner from the outlet of the tubular charcoal burner, and contacts with the air of the second-stage charcoal burner in the dense-phase bed of the bed-type charcoal burner to carry out the second-stage charcoal burner. The remaining coke on the mixed semi-coke is burned to generate a high-temperature heat carrier. The flue gas generated by the first-stage charcoal burning and the second-stage charcoal burning is separated from the high-temperature heat carrier by the cyclone separator installed in the bed-type charcoal burner. The high-temperature heat carrier in the dense-phase bed of the bed-type charcoal burner flows out from the bed-type charcoal burner, part of which is discharged from the carbonization device after being cooled by heat extraction, and the other part enters the riser through the high-temperature heat carrier delivery pipe The lower part of the dry distillation reactor, where it is mixed with oil shale feedstock.

The fluidized bed carbonization device for oil shale used to realize the above method includes a bed type carbonization reactor, a bed type charcoal burner, and a bed type charcoal burner connected with the bed type charcoal burner. The heat extraction and discharge device for the high-temperature heat carrier in the phase bed, the bed-type dry distillation reactor and the bed-type charcoal burner are arranged side by side, and the feature is that the fluidized bed dry distillation device for oil shale is also equipped with a riser dry distillation reactor And a tubular charcoal burner, the riser carbonization reactor and the bed type carbonization reactor are arranged side by side, the tubular charcoal burner and the bed type charcoal burner are arranged coaxially, and the lower part of the riser carbonization reactor is equipped with an oil page The rock raw material feed pipe is provided with a lifting gas distributor at the bottom, and the outlet of the riser dry distillation reactor is connected to the bed type dry distillation reactor, and the bed type dry distillation reactor is equipped with a cyclone separator, and the bed type dry distillation reactor There is an oil and gas collection chamber and an oil and gas outlet pipe on the top of the tank, and a stripping section below, which is equipped with a stripping baffle and a stripping steam distributor. The lower part of the stripping section is equipped with a semi-coke conveying pipe. The outlet of the coke conveying pipe is connected to the bottom of the tubular charcoal burner, and the bottom of the tubular charcoal burner is provided with a section of charcoal air distributor, and the outlet of the tubular charcoal burner leads into the bed type charcoal burner, and the bed There is a cyclone separator in the type charcoal burner, the top of the bed type charcoal burner is equipped with a flue gas collection chamber and the flue gas outlet pipe, and the bottom is equipped with a two-stage charcoal burner air distributor. A high-temperature heat carrier delivery pipe is arranged between the riser carbonization reactors, the inlet of the high-temperature heat carrier delivery pipe leads into the bed-type charcoal burner, and the outlet is connected to the lower part of the riser dry distillation reactor, and the bed-type charcoal burner The heat extraction and discharge device for the high-temperature heat carrier in the dense phase bed includes a high-temperature heat carrier discharge pipe. The inlet of the high-temperature heat carrier discharge pipe is connected to the bed-type charcoal burner, and the outlet is connected to the heat collector. The heat collector passes through the pipeline. It is connected with the heat carrier discharge tank, and flow control valves are arranged on the semi-coke conveying pipe, the high-temperature heat transfer pipe and the high-temperature heat carrier discharge pipe.

The present invention adopts the fluidized bed technology to produce shale oil; Adopt the present invention, have the following beneficial effect: (1) the present invention adopts the two-stage composite charcoal-burning technology of pipe-type charcoal burner and bed-type charcoal burner, each charcoal burner The charcoal device only bears a part of the total charcoal burning load, which is relatively low. In this way, the charcoal burning temperatures of the two charcoal burners are all easy to control, which prevents the charcoal burners from being damaged by overtemperature, and can ensure the long-term operation of the charcoal burners. Moreover, the structural size of the tubular charcoal burner and the bed type charcoal burner can be relatively small. (2) The two-stage composite charcoal burning technology of the present invention has strong charcoal burning ability, and the mixed semi-coke charcoal is completely burned (after the mixed semi-coke passes through the two-stage charcoal burning in the tubular charcoal burner and the bed type charcoal burner, usually More than 95% of the coke can be burned), so more coke combustion heat can be recycled. (3) The present invention uses a tubular charcoal burner; compared with conventional bed-type charcoal burners, the tubular charcoal burner has stronger charcoal burning capacity and better operating flexibility. In the tubular charcoal burner, the mixed semi-coke is always in contact with fresh air, so that the charcoal burning rate and efficiency are higher; thus, the storage of high-temperature heat carriers in the bed-type charcoal burner can also be reduced, and the bed size can be reduced. The structural size of the layered charcoal burner saves investment. (4) The present invention adopts the two-stage compound carbonization reaction technology of riser carbonization reactor and bed type carbonization reactor; after the oil shale raw material is subjected to a stage of carbonization reaction in the riser carbonization reactor, the unreacted oil shale raw material The two-stage dry distillation reaction can be carried out in the bed type dry distillation reactor, so that the yield of shale oil can be higher. Under the operating conditions proposed by the present invention, the shale oil yield can account for 80% to 90% of the oil content of the oil shale raw material. (5) The present invention uses a riser dry distillation reactor, which has the advantages of simple structure and good operating flexibility.

The invention is mainly used for dry distillation processing of various powdery oil shale raw materials.

The present invention will be further described in detail below in conjunction with the accompanying drawings, specific embodiments and examples. The drawings, specific implementations and examples do not limit the scope of protection claimed by the present invention.

Description of drawings

Fig. 1 is a schematic diagram of a fluidized bed dry distillation device for oil shale of the present invention.

Detailed ways

Referring to Fig. 1, the fluidized bed carbonization device (abbreviated as carbonization device) of oil shale of the present invention comprises a bed type carbonization reactor 21, a bed type charcoal burner 5, and a bed type charcoal burner 5 The connected bed-type charcoal burner is a heat-taking and discharging device for the high-temperature heat carrier in the dense-phase bed 6; the bed-type dry distillation reactor 21 and the bed-type charcoal burner 5 are arranged side by side. The dry distillation device is also provided with a riser dry distillation reactor 24 and a tubular charcoal burner 14; device 5 is coaxially set. As shown in FIG. 1 , the tube-type charcoal burner 14 extends into the bed-type charcoal burner 5 from the bottom of the bed-type charcoal burner 5 .

The lower part of the riser dry distillation reactor 24 is provided with an oil shale raw material feed pipe 26, and a lift gas distributor 31 is provided at the bottom. The outlet of the riser carbonization reactor 24 leads into the bed-type carbonization reactor 21 , and is generally located above the interface of the dense-phase bed 22 in the bed-type carbonization reactor. The overall structure of the riser carbonization reactor 24 shown in FIG. 1 is similar to the riser reactor of fluidized catalytic cracking (FCC) in petroleum processing. The riser carbonization reactor 24 is made of a metal tube with a circular cross section, and is lined with a heat-insulating and wear-resistant lining (figure omitted); the vertical height (from the top to the bottom) is generally 10-40m, and the inner diameter is generally 200-200m. 5000mm.

The shell of the bed-type dry distillation reactor 21 is mainly composed of a cylindrical metal cylinder on the upper part and an inverted conical metal cylinder on the lower part, and is lined with a heat-insulating and wear-resistant lining (not shown). The bed type dry distillation reactor 21 is provided with a cyclone separator; the cyclone separator shown in Figure 1 is a first cyclone separator 19 and a second cyclone separator 20 installed in series, and the legs of the two cyclone separators extend into the dense-phase bed 22 of the bed-type dry distillation reactor (extending into the upper part of the dense-phase bed 22 of the bed-type dry distillation reactor). The top of the bed-type dry distillation reactor 21 is provided with an oil-gas collection chamber 18 and an oil-gas outlet pipe 33 , and a stripping section 28 is arranged below; the top of the stripping section 28 is connected to the bottom of the bed-type dry distillation reactor 21 . The shell of the stripping section 28 is mainly composed of a cylindrical metal cylinder lined with a heat-insulating and wear-resistant lining (figure omitted). The stripping section 28 is provided with a stripping baffle (shown in FIG. 1 as a herringbone stripping baffle) and a stripping steam distributor 29 . The overall structure of the bed-type dry distillation reactor 21-stripping section 28 shown in Figure 1 is similar to the FCC settler.

The lower part of the stripping section 28 is provided with a semi-coke conveying pipe 25, on which a flow control valve 11 is arranged to control the flow of the mixed semi-coke in the pipe. The outlet of the semi-coke delivery pipe 25 is connected to the bottom of the tubular charcoal burner 14, and the bottom of the tubular charcoal burner 14 is provided with a charcoal burner air distributor 15.

The outlet of the tubular charcoal burner 14 leads into the bed-type charcoal burner 5, generally above the interface of the dense-phase bed 6 of the bed-type charcoal burner. The overall structure of the tubular charcoal burner 14 shown in Fig. 1 is similar to that of the FCC riser reactor. The tubular charcoal burner 14 is made of a metal tube with a circular cross section, and is lined with a heat-insulating and wear-resistant lining (figure omitted); the vertical height (from top to bottom) is generally 10-40m, and the inner diameter is generally 200-200m. 5000mm.

The shell of the bed-type charcoal burner 5 is mainly composed of a cylindrical metal cylinder at the top and an inverted circular table-shaped metal cylinder at the bottom, and is lined with a heat-insulating and wear-resistant lining (not shown). The bed-type charcoal burner 5 is provided with a cyclone separator; the cyclone separator shown in Figure 1 is the third cyclone separator 3 and the fourth cyclone separator 4 installed in series, and the material legs of the two cyclone separators extend Into the dense-phase bed 6 of the bed-type charcoal burner (into the upper part of the dense-phase bed 6 of the bed-type charcoal burner). The top of the bed-type charcoal burner 5 is provided with a flue gas collection chamber 2 and a flue gas outlet pipe 34 , and a second-stage charcoal-burning air distributor 12 is provided at the bottom. The overall structure of the bed type charcoal burner 5 shown in Fig. 1 is similar to that of the FCC regenerator.

A high-temperature heat carrier delivery pipe 23 is provided between the bed-type charcoal burner 5 and the riser carbonization reactor 24 . The entrance of the high-temperature heat carrier delivery pipe 23 leads into the bed-type charcoal burner 5 and is located in the dense-phase bed 6 of the bed-type charcoal burner (generally located in the middle or lower part of the height of the dense-phase bed 6 of the bed-type charcoal burner The outlet of the high-temperature heat carrier delivery pipe 23 is connected to the bottom of the riser dry distillation reactor 24. The high-temperature heat carrier delivery pipe 23 is provided with a flow control valve 11 to control the flow of the high-temperature heat carrier in the pipe.

The heat-taking and discharging device of the high-temperature heat carrier in the dense-phase bed 6 of the bed type charcoal burner comprises a high-temperature heat carrier discharge pipe 7; carrier flow. The inlet of the high-temperature heat carrier discharge pipe 7 is connected to the bed-type charcoal burner 5, and is generally connected to the middle or lower position of the dense-phase bed 6 height of the bed-type charcoal burner. The outlet of the high-temperature heat carrier discharge pipe 7 is connected to the bottom of the heat collector 8 , and the top of the heat collector 8 is connected to the top of the heat carrier discharge tank 10 through a pipeline 9 . The heat extractor 8 can use various FCC external heat extractors, and the heat medium generally uses water at ambient temperature (figure omitted). The heat carrier discharge tank 10 is a metal container.

Each pipeline in the retort device uses circular metal tubes with a heat-insulating and wear-resistant lining (figure omitted). The inner diameter of each pipeline is mainly determined according to the flow rate and density of the material and/or medium in each pipeline.

The flow control valve 11 set on the semi-coke delivery pipe 25, the high-temperature heat carrier delivery pipe 23 and the high-temperature heat carrier discharge pipe 7 can use various commonly used flow control valves for controlling the flow of solid powder, such as using a slide valve. The lifting gas distributor 31 , the stripping steam distributor 29 , the first-stage charcoal-burning air distributor 15 and the second-stage charcoal-burning air distributor 12 can use commonly used annular distributors or dendritic distributors.

Adopt the dry distillation device shown in Fig. 1 to carry out the method for oil shale fluidized bed dry distillation of the present invention (being called for short dry distillation method), comprise the following steps successively:

A. The pulverized oil shale raw material 27 enters the lower part of the riser carbonization reactor 24 through the oil shale raw material feed pipe 26, and the high-temperature heat carrier in the bed-type charcoal burner 5 enters the lifting pipe through the high-temperature heat carrier delivery pipe 23. The lower part of the tube retort reactor 24. After the oil shale raw material 27 and the high-temperature heat carrier are mixed in the lower part of the riser carbonization reactor 24, they are lifted along the lift under the action of the lift gas 32 introduced from the lift gas distributor 31 installed at the bottom of the riser carbonization reactor 24. Pipe carbonization reactor 24 goes up, and carries out one stage of carbonization reaction.

B. The oil shale raw material after a stage of carbonization reaction and the heat carrier mixed with it, as well as the shale oil and carbonization gas generated by a stage of carbonization reaction, enter the bed type carbonization reactor from the outlet of the riser carbonization reactor 24 21. The oil shale raw material and the heat carrier mixed with it fall down into the dense-phase bed 22 of the bed type carbonization reactor after a stage of carbonization reaction. The oil shale raw material after the first-stage dry distillation reaction is subjected to the second-stage dry distillation reaction in the dense-phase bed 22 of the bed-type dry distillation reactor, and the shale oil, dry distillation gas and shale semi-coke generated by the second-stage dry distillation reaction are obtained.

The shale semi-coke and the heat carrier in the dense-phase bed 22 of the bed-type dry distillation reactor are mixed with each other to form mixed semi-coke. The oil and gas 17 generated by the first-stage and second-stage dry distillation reactions, as well as the water vapor after stripping the mixed semi-coke in the stripping section 28 and the oil and gas entrained by the stripped mixed semi-coke, pass through the bed-type dry distillation reactor together. After the first cyclone separator 19 and the second cyclone separator 20 in 21 separate the mixed semi-coke, it flows out from the top of the bed-type dry distillation reactor 21 through the oil and gas collection chamber 18 and the oil and gas outlet pipe 33, and enters the fractionation system for further processing. Fractional distillation (same as in Example 1 to Example 6; Figure omitted). The oil and gas mentioned above refer to shale oil and dry distillation gas produced by the first-stage and second-stage dry distillation reactions. The mixed semi-coke separated by the first cyclone separator 19 and the second cyclone separator 20 falls into the dense-phase bed 22 of the bed-type dry distillation reactor through the dipleg.

The mixed semi-coke in the dense-phase bed 22 of the bed-type dry distillation reactor flows downwards and enters the stripping section 28 arranged below the bed-type dry distillation reactor 21 . The stripping steam 30 is introduced into the stripping section 28 through the stripping steam distributor 29, and the oil and gas entrained in the mixed semi-coke are stripped out. The mixed semi-coke stripped in the stripping section 28 flows to the lower part of the stripping section 28 and enters the bottom of the tubular charcoal burner 14 through the semi-coke delivery pipe 25 .

C. The mixed semi-coke entering the tubular charcoal burner 14 is in contact with a section of charcoal-burning air 16 (compressed air) introduced by a section of charcoal-burning air distributor 15, and carries out a section of charcoal burning along the tube-type charcoal burner 14 upwards.

D. The mixed semi-coke after the first-stage charcoal burning and the flue gas generated by the first-stage charcoal burning enter the bed-type charcoal burner 5 through the outlet of the tubular charcoal burner 14 . The mixed semi-coke after one stage of charcoal burning falls into the dense-phase bed 6 of the bed-type charcoal burner downwards, and in the dense-phase bed 6 of the bed-type charcoal burner, it is connected with the second-stage charcoal-fired air distributor 12 that is passed into the second-stage charcoal burner. Stage charcoal-burning air 13 (compressed air) is contacted to carry out two-stage charcoal-burning, and the remaining coke on the mixed semi-coke is burned to generate high-temperature heat carrier.

The flue gas 1 generated by the first-stage charcoal burning and the second-stage charcoal burning passes through the third cyclone separator 3 and the fourth cyclone separator 4 installed in the bed type charcoal burner 5 to separate the high-temperature heat carrier, and collects the gas through the flue gas. The chamber 2 and the flue gas outlet pipe 34 are discharged from the top of the bed type charcoal burner 5 . The high-temperature heat carrier separated by the third cyclone separator 3 and the fourth cyclone separator 4 falls into the dense-phase bed 6 of the bed-type charcoal burner through the material leg.

The high-temperature heat carrier in the dense-phase bed 6 of the bed-type charcoal burner flows out from the bed-type charcoal burner 5, and part of it is discharged from the carbonization device after being cooled by heat extraction. Referring to Fig. 1, a part of the high-temperature heat carrier enters the heat extractor 8 through the high-temperature heat carrier discharge pipe 7, and the heat-extracted heat medium takes heat and cools down (usually the temperature is lowered to below 100°C to become a low-temperature heat carrier). The high-temperature heat carrier enters the heat carrier discharge tank 10 through the pipeline 9 after cooling down, and finally the heat carrier discharge tank 10 is discharged from the carbonization device (which can be used as a building material). In the present invention, the amount of a part of the high-temperature heat carrier discharged from the retort device is determined according to the material balance calculation of the retort device.

Another part of the high-temperature heat carrier in the dense-phase bed 6 of the bed-type charcoal burner flowing out from the bed-type charcoal burner 5 enters the lower part of the riser carbonization reactor 24 through the high-temperature heat carrier delivery pipe 23, and is mixed with the oil shale raw material 27 mixed.

The above-mentioned steps A to D are carried out continuously and cyclically.

The operating conditions of the above-mentioned dry distillation method are generally as follows:

In step A, the particle size of the oil shale raw material 27 is not greater than 3mm, the oil content is 5%-35%, and the water content is not higher than 15%. The ratio of the weight flow rate of the high-temperature heat carrier entering the riser dry distillation reactor 24 to the oil shale raw material 27 is 2 to 7; Embodiment 1～embodiment 6 are the same), it is 650～750 ℃. The temperature of the oil shale raw material 27 entering the oil shale raw material feed pipe 26 is the ambient temperature (the same as in Embodiment 1 to Embodiment 6). Lifting gas 32 can be dry gas (the main components are carbon 1 and carbon 2), which is compressed dry gas formed by compressing dry gas at ambient temperature (the same as in embodiment 1 to embodiment 6), with an absolute pressure of 0.15 ~0.6 MPa. The lifting gas 32 can also be water vapor, and the temperature is 450-550°C. The residence time of the oil shale raw material 27 in the riser carbonization reactor 24 (that is, the time for a stage of carbonization reaction) is 3 to 8 minutes; the temperature at the outlet of the riser carbonization reactor 24 is 450 to 550° C., and the absolute pressure is 0.1 ~0.4MPa [substantially the same as the absolute pressure at the top of the bed type carbonization reactor 21 (the same applies to embodiments 1 to 6)]; s[the average air linear velocity refers to the average linear velocity of the lift gas 32 flowing upward after entering the riser carbonization reactor 24 (calculated under the temperature and absolute pressure conditions at the outlet of the riser carbonization reactor 24)]. The oil shale raw material 27 entering the riser dry distillation reactor 24 has a conversion rate of 20% to 30% after a stage of dry distillation reaction. The conversion rate is the conversion rate of the one-stage dry distillation reaction, which is defined as the weight percentage of the shale oil generated by the one-stage dry distillation reaction in the oil content of the oil shale raw material 27 .

The vertical height of the riser carbonization reactor 24 is mainly determined according to its operating conditions and the total height of the bed type carbonization reactor 21 and the stripping section 28, and the inner diameter is mainly determined according to the variation range of the average linear velocity of the lifting gas 32.

In step B, the oil shale raw material after the first-stage carbonization reaction is subjected to the second-stage carbonization reaction in the dense-phase bed 22 of the bed-type carbonization reactor for 2 to 10 minutes, and the temperature of the dense-phase bed 22 in the bed-type carbonization reactor is (i.e. the second-stage dry distillation reaction temperature) is 450 to 550°C, the linear velocity of the gas in the dilute phase section of the bed dry distillation reactor 21 is 0.2 to 1.2m/s, and the absolute pressure at the top of the bed dry distillation reactor 21 is 0.1 to 1.2m/s. 0.4MPa. The dilute-phase section of the bed-type dry distillation reactor 21 refers to the section above the interface of the dense-phase bed 22 of the bed-type dry distillation reactor. The gas mainly includes water vapor after the mixed semi-coke is stripped in the stripping section 28, oil and gas entrained in the stripped mixed semi-coke, and oil and gas generated by the first-stage and second-stage dry distillation reactions. During operation, the dense-phase bed 22 of the bed-type dry distillation reactor is in an aerated and fluidized state.

The time for the oil shale raw material after the one-stage dry distillation reaction to carry out the second-stage dry distillation reaction in the dense-phase bed 22 of the bed-type dry distillation reactor is preferably 3 to 6 minutes, and the temperature of the dense-phase bed 22 in the bed-type dry distillation reactor is preferably 470～530℃.

The time for the oil shale raw material after the first-stage carbonization reaction to undergo the second-stage carbonization reaction in the dense-phase bed 22 of the bed-type carbonization reactor is preferably 3.5 to 4.5 minutes, and the temperature of the dense-phase bed 22 in the bed-type carbonization reactor is the best It is 480～520℃.

The inner diameter of the cylindrical shell on the upper part of the bed type carbonization reactor 21 is mainly calculated and determined according to the fluctuation range of the gas linear velocity in the dilute phase section of the bed type carbonization reactor 21, and the height of the dense phase bed 22 in the bed type carbonization reactor is mainly determined According to the calculation and determination of the time for the oil shale raw material after the first-stage dry distillation reaction to carry out the second-stage dry distillation reaction in the dense-phase bed 22 of the bed-type dry distillation reactor and the storage amount of mixed semi-coke in the bed-type dry distillation reactor 21, the bed type The height of the dilute phase section of the dry distillation reactor 21 is mainly calculated and determined according to the sedimentation height of the mixed semi-coke.

The present invention uses a bed-type dry distillation reactor 21, whose operation and control are less complicated. Moreover, the water vapor after stripping the mixed semi-coke in the stripping section 28, the oil and gas entrained by the stripped mixed semi-coke, and the oil and gas generated by the second-stage carbonization reaction in the dense-phase bed 22 of the bed-type carbonization reactor can all be As the fluidization medium, the dense-phase bed 22 of the bed-type carbonization reactor is in a state of aeration and fluidization, without using dry gas, so the energy consumption of the bed-type carbonization reactor 21 is relatively low. In addition, the temperature of the dense-phase bed 22 in the bed-type dry distillation reactor can be kept relatively stable.

In step B, the temperature of the mixed semi-coke bed in the stripping section 28 is 480-520°C. After the mixed semi-coke entering the stripping section 28 is stripped, usually more than 95% of the entrained oil and gas can be stripped (the same as in Embodiment 1 to Embodiment 6). The coke content of the mixed semi-coke after stripping in the stripping section 28 is generally 3% to 15%.

In step C, the time for the mixed semi-coke entering the tubular charcoal burner 14 for a period of charcoal burning in the tubular charcoal burner 14 is 5-40s; the temperature at the outlet of the tubular charcoal burner 14 is 600-750 ℃, the absolute pressure is 0.1 ~ 0.4MPa; the average air velocity in the tubular charcoal burner 14 is 1 ~ 10m/s The average linear velocity of upward flow (calculated under the temperature and absolute pressure conditions at the outlet of tubular charcoal device 14)]. The absolute pressure at the outlet of the tube type charcoal burner 14 is substantially the same as the absolute pressure at the top of the bed type charcoal burner 5 (the same applies to Embodiment 1 to Embodiment 6). The mixed semi-coke entering the tubular charcoal burner 14 can usually be burned off 30% to 70% of the coke after a stage of charring; the weight percentage of the burned coke is equal to the coke contained in the mixed semi-coke before and after the stage of charring The difference in weight percentage is divided by the weight percentage of coke contained in the mixed semi-coke before first-stage charring (ie after stripping), and then multiplied by 100%. In the tubular charcoal burner 14, the remaining entrained oil and gas of the stripped mixed semi-coke are burned off.

The vertical height of the tubular charcoal burner 14 is mainly calculated and determined according to its operating conditions and the total height of the bed type charcoal burner 5 and the stripping section 28, and the inner diameter is mainly determined according to the variation range of the average air velocity.

In step D, the time for the mixed semi-coke after the first-stage charcoal burning to be carried out in the dense-phase bed 6 of the bed-type charcoal burner for the second-stage charcoal burning is 3 to 8 minutes, and the temperature of the dense-phase bed 6 of the bed-type charcoal burner ( That is, the second-stage charcoal burning temperature) is 650-750°C, the gas linear velocity in the dilute phase section of the bed-type charcoal burner 5 is 0.1-1.2m/s, and the absolute pressure at the top of the bed-type charcoal burner 5 is 0.1-0.4 MPa. The dilute-phase section of the bed-type charcoal burner 5 refers to the section above the interface of the dense-phase bed 6 of the bed-type charcoal burner. The gas mentioned above is mainly the flue gas generated by the first-stage charcoal burning and the second-stage charcoal burning. During the operation, the dense-phase bed 6 of the bed-type charcoal burner is in a gas-filled fluidized state.

The inner diameter of the upper cylindrical shell of the bed-type charcoal burner 5 is mainly calculated and determined according to the variation range of the gas linear velocity in the dilute phase section of the bed-type charcoal burner 5, and the height of the dense-phase bed 6 of the bed-type charcoal burner is mainly determined. According to the calculation and determination of the time for the mixed semi-coke after the first-stage charcoal burning to perform the second-stage charcoal burning in the dense-phase bed 6 of the bed-type charcoal burner and the storage amount of high-temperature heat carrier in the bed-type charcoal burner 5, the bed-type charcoal burner The height of the dilute phase section of the charcoal device 5 is mainly calculated and determined according to the settlement height of the high-temperature heat carrier. After the mixed semi-coke stripped in the stripping section 28 is burned in two stages in the tubular charcoal burner 14 and the bed-type charcoal burner 5, usually more than 95% of the coke can be burned off.

In the technique described in CN101440293A, the particle size of the oil shale raw material is relatively large (less than 30mm); although the crushing cost of the oil shale raw material can be reduced, there are the following problems: 1. the yield of shale oil is reduced; The fluidization and transportation of raw materials in the retort device are difficult, which is not conducive to the large-scale construction of the retort device; ③ channeling and partial flow of the retort heat fluidized medium in the fluidized bed retort chamber results in uneven heat transfer of the oil shale raw material, and It affects the carbonization effect of oil shale raw materials and the quality of shale oil produced. Compared with this process, the process described in Document 1 cited in this specification uses oil shale raw materials with a particle size not greater than 3mm, which is more suitable. The present invention also uses the oil shale raw material 27 of this particle size, can make oil shale raw material 27 can be fluidized and carbonized normally in riser dry distillation reactor 24 and bed type dry distillation reactor 21 like this, improves shale oil At the same time, it can also make the coke on the mixed semi-coke burn better during the first-stage and second-stage charcoal burning, thereby recovering more heat. Use the oil shale raw material 27 whose particle diameter is not greater than 3mm. Under the operating conditions of the present invention, the shale oil yield can account for 80% to 90% of the oil content of the oil shale raw material 27 (the shale described in the present invention The oil yields are the actual yields obtained).

According to the instructions or requirements of the present invention, those skilled in the field of oil shale retort can select the retort operation conditions proposed by the present invention and various equipment components to design, operate and control the retort device according to the specific operation conditions.

In the present invention, both the first-stage charcoal-burning air 16 and the second-stage charcoal-burning air 13 are compressed air formed by compressing air at ambient temperature (the same applies to Embodiment 1 to Embodiment 6). The ambient temperature in the present invention is 25-35°C, the pressure is absolute pressure, the percentages are weight percentages, and the inner diameter refers to the inner diameter of the metal cylinder or the heat-insulating and wear-resistant lining of the pipeline lining. In FIG. 1 , arrows without reference numerals indicate the flow directions of various materials and/or media.

Example

On the small-scale test device of the fluidized bed carbonization device shown in FIG. 1 , 6 groups of tests (Example 1 to Example 6) were carried out according to the steps of the oil shale carbonization method described in the specific embodiment section of this specification. The oil shale raw material 27 is made of ylang-ylang oil shale powder raw material, and its properties are shown in Table 1; the feed rate (the weight flow rate of the oil shale raw material 27 entering the oil shale raw material feed pipe 26) is 150kg/day.

In Examples 1 to 6, the gas linear velocity in the dilute phase section of the bed-type dry distillation reactor 21 is all 0.65 m/s. The temperature of the mixed semi-coke bed in the stripping section 28 is 500°C, and the stripping medium is the stripping steam 30 at 500°C. The high-temperature heat carrier that enters the heat collector 8 through the high-temperature heat carrier discharge pipe 7 is cooled to 100° C. by the heat-taking medium (water at ambient temperature). The lifting gas 32 is compressed dry gas of 0.3MPa (absolute pressure), the first-stage charcoal-burning air 16 and the second-stage charcoal-burning air 13 are compressed air of 0.4MPa (absolute pressure), and the test environment temperature is 25-26°C.

The remaining operating conditions, product distribution and properties of some products in Examples 1 to 6 are shown in Tables 2 to 8, respectively. Wherein, the product distribution in Table 2 to Table 7 all refer to the total product distribution of the retort device. In each embodiment, the coke content of the high-temperature heat carrier flowing out from the bed-type charcoal burner 5 is the same as that of the mixed semi-coke after stripping in the stripping section 28 described in Table 2 to Table 7. The coke content of the high-temperature heat carrier generated after the two-stage charcoal burning in the charcoal device 14 and the bed-type charcoal device 5 is the same. The ratio of a part of the high-temperature heat carrier in the dense-phase bed 6 of the bed-type charcoal burner described in Table 2 to Table 7 is discharged from the carbonization device after taking heat and cooling down, all means that the part of the high-temperature heat carrier is densely packed by the bed-type charcoal burner. The weight flow of the phase bed 6 flowing out through the high-temperature heat carrier discharge pipe 7 accounts for the percentage of the weight flow of the oil shale raw material 27 entering the oil shale raw material feed pipe 26 .

The property of table 1 oil shale raw material (embodiment 1～embodiment 6)

project data Bulk specific gravity (sedimentation state), g/ml 1.04 Specific heat, cal/kg·℃ 0.259 Oil content (measured by aluminum retort method), % 8.5 Moisture content, % 6.9 Ash content (determined by combustion method), % 70.4 Particle size distribution,% Below 20μm 16.5 20～40μm 6 40～80μm 5.1 80～110μm 2.3 110～149μm 3.1 149～500μm 18.2 500～1000μm 20 1000～1500μm 18.5 1500～3000μm 10.3

Operating conditions and product distribution of table 2 embodiment 1

[Note]: Embodiment 2～Example 6 are the same.

Operating conditions and product distribution of table 3 embodiment 2

Operating conditions and product distribution of table 4 embodiment 3

Operating conditions and product distribution of table 5 embodiment 4

Operating conditions and product distribution of table 6 embodiment 5

Operating conditions and product distribution of table 7 embodiment 6

Table 8 Embodiment 1～The character of embodiment 6 part products

Claims (2)

1. a fluidized bed dry distillation method for resinous shale, is characterized in that: the method in turn includes the following steps:

A. the resinous shale raw material (27) after pulverizing enters the bottom of riser tube dry distillation reactor device (24) through resinous shale material feeding tube (26), the high-temperature heat carrier that bed formula is made charcoal in device (5) enters the bottom of riser tube dry distillation reactor device (24) through high-temperature heat carrier transfer lime (23), after resinous shale raw material (27) mixes with high-temperature heat carrier, up along riser tube dry distillation reactor device (24) under the castering action of the lift gas (32) being passed into by the bottom of riser tube dry distillation reactor device (24), carry out one section of dry distillation reactor;

B. the resinous shale raw material after one section of dry distillation reactor and the thermal barrier mixing with it, the shale oil and the carbonization gas that also have one section of dry distillation reactor to generate, by the outlet of riser tube dry distillation reactor device (24), enter bed formula dry distillation reactor device (21), resinous shale raw material after one section of dry distillation reactor carries out two sections of dry distillation reactors in bed formula dry distillation reactor device dense bed (22), obtain the shale oil that two sections of dry distillation reactors generate, carbonization gas and shale semicockes, shale semicockes and thermal barrier in bed formula dry distillation reactor device dense bed (22) are mixed to form mixing semicoke mutually, the cyclonic separator of the oil gas (17) that one section and two sections of dry distillation reactors generate through being located at bed formula dry distillation reactor device (21) in isolates that mixing half is defocused is flowed out by bed formula dry distillation reactor device (21), mixing semicoke in bed formula dry distillation reactor device dense bed (22) flows downward, enter the stripping stage (28) of being located at bed formula dry distillation reactor device (21) below, in stripping stage (28), pass into water stripping steam (30), stripping goes out to mix semicoke entrained oil gas, mixing semicoke in stripping stage (28) after stripping flows to the bottom of stripping stage (28), through semicoke transfer lime (25), enter the make charcoal bottom of device (14) of tubular type,

C. enter the mixing semicoke that tubular type makes charcoal in device (14) and contact with one section of air of making charcoal (16), along tubular type, making charcoal, device (14) is up to carry out one section and makes charcoal;

D. one section of mixing semicoke after making charcoal enters the bed formula device (5) of making charcoal by the make charcoal outlet of device (14) of tubular type, in bed formula is made charcoal device dense bed (6), contact with two sections of air of making charcoal (13) and carry out two sections and make charcoal, remaining coke on burning-off mixing semicoke, generate high-temperature heat carrier, one section make charcoal and two sections make charcoal the flue gas (1) that generates after the cyclonic separator of being located at bed formula and making charcoal device (5) in is isolated high-temperature heat carrier by device (5) discharge of making charcoal of bed formula, the high-temperature heat carrier that bed formula is made charcoal in device dense bed (6) is flowed out by the bed formula device (5) of making charcoal, a part is discharged destructive distillation device after heat-obtaining cooling, another part enters the bottom of riser tube dry distillation reactor device (24) through high-temperature heat carrier transfer lime (23), mix with resinous shale raw material (27),

In steps A, the particle diameter of resinous shale raw material (27) is not more than 3mm, oleaginousness is 5%～35%, water content is not higher than 15%, the ratio that enters the weight rate of the interior high-temperature heat carrier of riser tube dry distillation reactor device (24) and resinous shale raw material (27) is 2～7, the residence time of resinous shale raw material (27) in riser tube dry distillation reactor device (24) is 3～8min, the temperature in riser tube dry distillation reactor device (24) exit is 450～550 ℃, absolute pressure is 0.1～0.4MPa, the average linear speed of the interior lift gas of riser tube dry distillation reactor device (24) (32) is 7～15m/s, enter the interior resinous shale raw material (27) of riser tube dry distillation reactor device (24) after one section of dry distillation reactor, transformation efficiency is 20%-30%, in step B, the time that resinous shale raw material after one section of dry distillation reactor carries out two sections of dry distillation reactors in bed formula dry distillation reactor device dense bed (22) is 2～10min, the temperature of bed formula dry distillation reactor device dense bed (22) is 450～550 ℃, the linear gas velocity of bed formula dry distillation reactor device (21) dilute phase section is 0.2～1.2m/s, the absolute pressure at bed formula dry distillation reactor device (21) top is 0.1～0.4MPa, in step C, entering mixing semicoke that tubular type makes charcoal in device (14), in tubular type is made charcoal device (14), to carry out one period of making charcoal be 5～40s, the make charcoal temperature in device (14) exit of tubular type is 600～750 ℃, absolute pressure is 0.1～0.4MPa, the average air linear speed that tubular type is made charcoal in device (14) is 1～10m/s, enter mixing semicoke that tubular type makes charcoal in device (14) after one section is made charcoal, by the coke of burning-off 30%～70%, in step D, it is 3～8min that one section of mixing semicoke after making charcoal carries out two periods of making charcoal in bed formula is made charcoal device dense bed (6), the make charcoal temperature of device dense bed (6) of bed formula is 650～750 ℃, the make charcoal linear gas velocity of device (5) dilute phase section of bed formula is 0.1～1.2m/s, the make charcoal absolute pressure at device (5) top of bed formula is 0.1～0.4MPa,

In step C and step D, one section of air of making charcoal (16) and all pressurized air for being formed by the air compressing under envrionment temperature of two sections of air of making charcoal (13).

2. one kind for realizing the fluidized bed dry distillation device of the resinous shale of method described in claim 1, comprise a bed formula dry distillation reactor device (21), the bed formula device (5) of making charcoal, and with bed formula the make charcoal heat-obtaining discharger of the interior high-temperature heat carrier of device dense bed (6) of bed formula that device (5) is connected of making charcoal, bed formula dry distillation reactor device (21) and the bed formula device (5) of making charcoal is set up in parallel, it is characterized in that: the fluidized bed dry distillation device of resinous shale is also provided with a riser tube dry distillation reactor device (24) and the tubular type device (14) of making charcoal, riser tube dry distillation reactor device (24) is set up in parallel with bed formula dry distillation reactor device (21), tubular type device (14) and the bed formula device (5) of making charcoal of making charcoal coaxially arranges, the bottom of riser tube dry distillation reactor device (24) is provided with resinous shale material feeding tube (26), bottom is provided with lift gas sparger (31), the outlet of riser tube dry distillation reactor device (24) passes in bed formula dry distillation reactor device (21), in bed formula dry distillation reactor device (21), be provided with cyclonic separator, the top of bed formula dry distillation reactor device (21) is provided with oil gas collection chamber (18) and oil gas vent pipe (33), below is provided with stripping stage (28), stripping stage is provided with stripping baffles in (28), stripped vapor sparger (29), the bottom of stripping stage (28) is provided with semicoke transfer lime (25), the make charcoal bottom of device (14) of the outlet of semicoke transfer lime (25) and tubular type is connected, the make charcoal bottom of device (14) of tubular type is provided with one section of air-distributor of making charcoal (15), the make charcoal outlet of device (14) of tubular type passes into bed formula and makes charcoal in device (5), bed formula is made charcoal in device (5) and is provided with cyclonic separator, the make charcoal top of device (5) of bed formula is provided with flue gas collection chamber (2) and smoke outlet tube (34), bottom is provided with two sections of air-distributors of making charcoal (12), bed formula is made charcoal and is provided with high-temperature heat carrier transfer lime (23) between device (5) and riser tube dry distillation reactor device (24), the entrance of high-temperature heat carrier transfer lime (23) passes into bed formula and makes charcoal in device (5), outlet is connected in the bottom of riser tube dry distillation reactor device (24), the make charcoal heat-obtaining discharger of the interior high-temperature heat carrier of device dense bed (6) of described bed formula comprises high-temperature heat carrier drainage conduit (7), the entrance of high-temperature heat carrier drainage conduit (7) and the bed formula device (5) of making charcoal is connected, outlet is connected with heat collector (8), heat collector (8) is connected with thermal barrier blow-down drum (10) by pipeline (9), semicoke transfer lime (25), in high-temperature heat carrier transfer lime (23) and high-temperature heat carrier drainage conduit (7), be equipped with flowrate control valve (11).

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