阅读说明：本技术 一种微波耦合液氧辅助木本油料剩余物热解气化方法 (Microwave coupling liquid oxygen assisted pyrolysis gasification method for woody oil residues ) 是由 张爱华 肖志红 李昌珠 李培旺 李力 李启刚 缪一夫 于 2019-11-18 设计创作，主要内容包括：一种微波耦合液氧辅助木本油料剩余物热解气化方法,将木本油料加工剩余物收集并作为原料,将其干燥至含水量8～14％后,通过粉碎和成型机械压缩并粉碎制粒,形成标准化颗粒物A；然后将所述标准化颗粒物A在反应容器中,在900～1200℃的催化剂环境下进行热解反应,其产生的产物进行分离收集,得到生物气B和生物炭C；然后将生物气B依次经过粗过滤、水洗和干燥工序后进入储气系统；而生物炭C则进入储存箱。本发明。(A microwave coupling liquid oxygen assisted pyrolysis gasification method for woody oil residues is characterized in that woody oil processing residues are collected and used as raw materials, the raw materials are dried until the water content is 8-14%, and then the raw materials are crushed and mechanically compressed by a forming machine and crushed and granulated to form standardized particles A; then, carrying out pyrolysis reaction on the standardized particles A in a reaction container at the temperature of 900-1200 ℃ in the presence of a catalyst, and separating and collecting the generated products to obtain biogas B and biochar C; then the biogas B enters a gas storage system after being subjected to coarse filtration, water washing and drying in sequence; and the biochar C enters the storage tank. The invention relates to a method for preparing a high-temperature-resistant ceramic material.)

1. A reaction device for pyrolysis and gasification of woody oil residues is characterized by comprising a pyrolysis reactor and a feeding device, wherein the pyrolysis reactor is a reactor with a composite structure and comprises a lower air-suction type fixed fluidized bed gasification furnace arranged at the upper part and an upper air-suction type fluidized bed gasification furnace arranged at the lower part; the lower air-suction type fixed fluidized bed gasification furnace is sleeved on the upper air-suction type fluidized bed gasification furnace, the upper part of the lower air-suction type fixed fluidized bed gasification furnace is connected with a feeding device for feeding, a liquid oxygen tank is arranged beside the upper part of the lower air-suction type fixed fluidized bed gasification furnace for supplying oxygen for liquid oxygen in the furnace body, and a plurality of microwave emitters are arranged on the side wall of the lower air-suction type fixed fluidized bed gasification furnace for providing microwave assistance for the lower air-suction type fixed fluidized bed gasification furnace; the upper air-breathing fluidized bed gasification furnace is provided with an air-breathing position connected with an oxygen supply pipeline and a water vapor supply pipeline, and the upper part of the upper air-breathing fluidized bed gasification furnace is provided with a fuel gas outlet connected with a fuel gas collecting pipe through the fuel gas outlet.

2. The reaction device for pyrolysis gasification of wood oil residues according to claim 1, wherein the feeding device is a continuous closed material distributor.

3. The reaction device for pyrolysis and gasification of wood oil residues according to claim 1, wherein water jackets are arranged on the furnace bodies of the lower air-breathing fixed fluidized bed gasification furnace and the upper air-breathing fluidized bed gasification furnace corresponding to the pyrolysis reactor, and the water jackets are connected with the steam cavity and connected with the steam supply pipeline through the steam cavity so as to use self-generated steam of equipment as an auxiliary gasification agent.

4. The reaction device for pyrolysis and gasification of wood oil residues according to claim 1, wherein a rotary water tank is arranged at the lower bottom of a furnace body of the pyrolysis reactor, a rotary ash knife is arranged in the rotary water tank, and the furnace body realizes wet-type discharge of the biochar C through relative rotation of the rotary ash knife and the rotary water tank.

5. The reaction device for pyrolysis and gasification of wood oil residues as claimed in claim 4, wherein the inclination of the rotary ash knife is 20-30 °.

6. The reaction device for pyrolysis and gasification of the remainder of the woody oil material according to claim 1, wherein the rear part of the gas collecting pipe is sequentially connected with a heat exchanger, a spray tower and a cooler, the bottoms of the heat exchanger, the spray tower and the cooler are communicated sedimentation tanks, and the spray water of the spray tower is treated by the sedimentation tank and then recycled without being discharged outside; and high-calorific-value biomass such as ash, tar and the like deposited in the sedimentation tank is separated and then returned to the gasification furnace to be used as a raw material to enter a hall for gasification.

7. A microwave-coupled liquid oxygen-assisted pyrolysis gasification method for woody oil residues, which utilizes the apparatus as claimed in claim 2 as a reactor to perform microwave-coupled liquid oxygen-assisted pyrolysis gasification treatment for the woody oil residues, and specifically comprises the following operation steps:

s1, collecting and classifying the remainder of the woody oil, drying branches, shells and fallen leaves of the woody oil at the temperature of 70-120 ℃, and controlling the water content of the materials to be 8-14%; then crushing the mixture to particles with the particle size of 1-5 mm by a crusher; then, using cake dregs obtained after processing woody oil as an adhesive for forming particles, crushing the particles to 1-5 mm, mixing the two particles, controlling the amount of the cake dregs particles to be 10-30% of the total material, homogenizing the cake dregs with the aid of a stirrer, and compressing the homogenized material under the condition that the compression ratio of a ring die is 3.5-6.5 to obtain a standardized particle material A;

s2, taking a reaction device for pyrolysis and gasification of the remainder of the woody oil as a reactor, filling the standardized granular material A into the reactor through a feeding device, adding an active catalyst accounting for 0.2-1.5% of the raw material in the filling process, uniformly mixing the active catalyst with the material, and performing catalytic pyrolysis in the reactor, wherein a liquid oxygen tank is adopted for supplying oxygen in the catalytic pyrolysis process, and the oxygen flow is controlled to be 1-4 m³Per ton of raw material, performing microwave assistance by using a 1.5KW microwave emitter, introducing oxygen and water vapor into the bottom of an upper air-breathing fluidized bed gasification furnace, controlling the gasification temperature in a reactor to be 900-1200 ℃, and reacting for 30-70 min;

s3, collecting fuel gas in the catalytic pyrolysis process of the reactor, cooling the fuel gas from the gasification furnace through a heat exchanger, washing the fuel gas through a spray tower, cooling the fuel gas to room temperature through a two-stage indirect cooler, removing water and tar, pressurizing the fuel gas through a booster fan, and sending the pressurized fuel gas to a gas storage cabinet through a check valve to obtain a product biogas B; the bottom of the furnace body of the reactor is provided with a rotary water tank with a rotary ash knife, and the biochar C is subjected to wet stripping through relative rotation between the rotary ash knife and the rotary water tank.

8. The microwave-coupled liquid oxygen-assisted pyrolysis gasification method for woody oil residues according to claim 1, wherein the active catalyst comprises a microwave catalyst and a pyrolysis catalyst.

9. The microwave coupling liquid oxygen-assisted pyrolysis gasification method for wood oil residues according to claim 1, wherein the active catalyst is SiO with a mass ratio of 1: 3-1: 4₂And KF/CaO.

10. The microwave-coupled liquid oxygen-assisted pyrolysis and gasification method for the remainder of the woody oil material according to claim 1, wherein the reactor controls the temperature in the upper suction type fluidized bed gasifier to be 800-1200 ℃, the temperature in the lower suction type fixed fluidized bed gasifier to be 700-800 ℃ and the flow rate of water vapor to be 1-2 m during the catalytic pyrolysis reaction³/h/And (4) ton of material.

Technical Field

The invention belongs to the technical field of biomass processing, and particularly relates to a microwave coupling liquid oxygen-assisted pyrolysis gasification method for woody oil residues.

Background

Tea-oil trees, tung oil trees and litsea cubeba seeds are used as representatives of large woody oil resource types such as woody edible oil, industrial oil, aromatic oil and the like, and the planting of the camellia-oil trees and the tung oil trees is gradually increased year by year in recent years. Above-mentioned woody oil resource is being processed, can be accompanied with the processing remainder that produces great quantity usually, and present woody oil processing remainder mainly uses to burn and abandon as leading, not only causes the waste of resource, and can bring ecological environment's pollution problem, causes negative effects.

With the falling of relevant policies, the transformation and upgrading of the traditional industry are required to be promoted, the development of the emerging industry is accelerated, the energy structure optimization is promoted, the high-efficiency utilization of the woody oil processing residues becomes a new development point of the development of the relevant industry, and the considerable economic value can be generated; meanwhile, the biogas obtained by utilizing the high-efficiency thermochemical conversion of the woody oil processing residues can effectively compensate the shortage of the existing fossil energy, belongs to the category of green renewable energy, has great development potential and also has social benefit.

In the prior art, the biomass gasification process is a good processing way for processing the woody oil processing residues. The existing biomass gasification process has various technical types and routes, but generally has the defects of high requirement specificity on raw materials, poor raw material universality, difficult treatment of tar components in byproducts and the like, and the prepared biogas product has lower heat value. For example, patent 201820262555.7 discloses a biomass gasification furnace, which comprises a furnace body, a furnace cover and a device for supplying gasification medium, and has the advantages of simple operation and high gasification efficiency, but has the defects of poor continuity and heat value; patent 201510740284.2 discloses a biomass pyrolysis gasification method and a biomass pyrolysis system, which have the advantages of high pyrolysis speed, low energy consumption, and good quality of obtained biomass fuel gas, but have the disadvantages of high energy consumption, and further improved heat value and gasification efficiency of the biomass gas.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a microwave coupling liquid oxygen assisted pyrolysis gasification method for woody oil residues, which can effectively reduce the production cost and improve the heat value and gasification efficiency of biogas so as to solve the defects in the technical background.

The technical problem solved by the invention is realized by adopting the following technical scheme:

a microwave coupling liquid oxygen assisted pyrolysis gasification method for woody oil residues is characterized in that woody oil processing residues are collected and used as raw materials, the raw materials are dried until the water content is 8-14%, and then the raw materials are crushed and mechanically compressed by a forming machine and crushed and granulated to form standardized particles A; then, carrying out pyrolysis reaction on the standardized particles A in a reaction container at the temperature of 900-1200 ℃ in the presence of a catalyst, and separating and collecting the generated products to obtain biogas B and biochar C; then the biogas B enters a gas storage system after being subjected to coarse filtration, water washing and drying in sequence; and the biochar C enters the storage tank.

The invention also discloses a reaction device for pyrolysis and gasification of the woody oil residues, which comprises a pyrolysis reactor and a feeding device, wherein the pyrolysis reactor is a composite structure reactor and comprises a lower air suction type fixed fluidized bed gasification furnace arranged at the upper part and an upper air suction type fluidized bed gasification furnace arranged at the lower part; the lower air-suction type fixed fluidized bed gasification furnace is sleeved on the upper air-suction type fluidized bed gasification furnace, the upper part of the lower air-suction type fixed fluidized bed gasification furnace is connected with a feeding device for feeding, a liquid oxygen tank is arranged beside the upper part of the lower air-suction type fixed fluidized bed gasification furnace for supplying oxygen for liquid oxygen in the furnace body, and a plurality of microwave emitters are arranged on the side wall of the lower air-suction type fixed fluidized bed gasification furnace for providing microwave assistance for the lower air-suction type fixed fluidized bed gasification furnace; the upper air-breathing fluidized bed gasification furnace is provided with an air-breathing position connected with an oxygen supply pipeline and a water vapor supply pipeline, and the upper part of the upper air-breathing fluidized bed gasification furnace is provided with a fuel gas outlet connected with a fuel gas collecting pipe through the fuel gas outlet.

As a further limitation, the feeding device is a continuous closed cloth feeder.

As a further limitation, the furnace bodies of the lower air-breathing fixed fluidized bed gasification furnace and the upper air-breathing fluidized bed gasification furnace corresponding to the pyrolysis reactor are respectively provided with a water jacket, and the water jackets are connected with the steam cavity and are connected with the steam supply pipeline through the steam cavity so as to utilize the steam self-produced by the equipment as an auxiliary gasification agent.

As a further limitation, a rotary water tank is arranged at the lower bottom of a furnace body of the pyrolysis reactor, a rotary ash knife is arranged in the rotary water tank, and the furnace body realizes wet-type discharge of the biochar C through the relative rotation of the rotary ash knife and the rotary water tank; in order to obtain the best discharging effect, the inclination of the rotary ash knife is 20-30.

As a further limitation, the rear part of the fuel gas collecting pipe is sequentially connected with a heat exchanger, a spray tower and a cooler, the bottoms of the heat exchanger, the spray tower and the cooler are communicated sedimentation tanks, and the spraying water of the spray tower is recycled after being treated by the sedimentation tanks and is not discharged outside; and high-calorific-value biomass such as ash, tar and the like deposited in the sedimentation tank are separated and then returned to the gasification furnace to be used as a raw material for gasification.

A microwave coupling liquid oxygen assisted pyrolysis gasification method for woody oil residues specifically comprises the following operation steps:

s1, collecting and classifying the remainder of the woody oil, drying branches, shells and fallen leaves of the woody oil at the temperature of 70-120 ℃, and controlling the water content of the materials to be 8-14%; then crushing the mixture to particles with the particle size of 1-5 mm by a crusher; and then, using the cake dregs after the processing treatment of the woody oil as an adhesive for forming particles, crushing the particles to 1-5 mm, mixing the two particles, controlling the amount of the cake dregs particles to be 10-30% of the total material, homogenizing the cake dregs with the aid of a stirrer, and compressing the homogenized material under the condition that the compression ratio of a ring die is 3.5-6.5 to obtain a standardized particle material A.

S2, filling the standardized granular material A into a reactor through a feeding device, adding an active catalyst accounting for 0.2-1.5% of the raw material in the filling process, uniformly mixing the active catalyst with the material, and performing catalytic pyrolysis in the reactor, wherein a liquid oxygen tank is adopted for supplying oxygen in the catalytic pyrolysis process, and the oxygen flow is controlled to be 1-4 m³Per ton of raw material, using 1.5KAnd (3) carrying out microwave assistance by the W microwave emitter, introducing oxygen and water vapor into the bottom of the upper air-breathing fluidized bed gasification furnace, and reacting for 30-70 min.

S3, collecting fuel gas in the catalytic pyrolysis process of the reactor, cooling the fuel gas from the gasification furnace through a heat exchanger, washing the fuel gas through a spray tower, cooling the fuel gas to room temperature through a two-stage indirect cooler, removing water and tar, pressurizing the fuel gas through a booster fan, and sending the pressurized fuel gas to a gas storage cabinet through a check valve to obtain a product biogas B; the bottom of the furnace body of the reactor is provided with a rotary water tank with a rotary ash knife, and the biochar C is subjected to wet stripping through relative rotation between the rotary ash knife and the rotary water tank.

By way of further limitation, the active catalyst includes a microwave catalyst and a pyrolysis catalyst, wherein the microwave catalyst is SiO₂And the pyrolysis catalyst is KF/CaO; preferably, SiO₂The mass ratio of KF to CaO is 1: 3-1: 4.

By further limiting, the reactor controls the bed temperature of the upper air-suction type fluidized bed gasification furnace to be 800-1200 ℃, the bed temperature of the lower air-suction type fixed fluidized bed gasification furnace to be 700-800 ℃ and the flow rate of water vapor to be 1-2 m when the catalytic pyrolysis reaction is carried out³H/ton of material.

The invention has the advantages and beneficial effects that:

the gasification mode combining the fluidization and the immobilization of the biomass is developed, the gas is produced by combining the upper part and the lower part, and the full gasification technology is realized, so that the gasification process is strengthened.

The method has the advantages that water vapor and oxygen are mixed to serve as a gasifying agent to further convert fixed carbon in forest product substances into combustible gas, so that the heat value and the gasification efficiency of the combustible gas are improved, the gas yield is improved by 10%, the heat value is improved by 5%, and the effect is obvious.

The wet-type biomass charcoal production method overcomes the defects that the biogas is easy to lose and leak in the traditional biomass gasification process and the dry-type biomass charcoal carries a large amount of waste heat, reduces the hidden danger and can effectively improve the working environment.

The development technology has strong universality, simple equipment and convenient operation and popularization.

Drawings

FIG. 1 is a schematic structural diagram of a reaction apparatus according to a preferred embodiment of the present invention.

Wherein: 1. continuously sealing the material distributing feeder; 2. a microwave emitter; 3. a liquid oxygen tank interface; 4. a lower suction type fixed bed gasification furnace; 5. an upper air suction type fluidized bed gasification furnace; 6. a gas outlet; 7. an air inlet is combined.

Detailed Description

In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further described below by combining the specific drawings and the embodiments.

In the following examples, it will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

Referring to fig. 1, an embodiment of a reaction apparatus for pyrolysis gasification of woody oil residues, in which the reaction apparatus for pyrolysis gasification of woody oil residues includes a pyrolysis reactor including a lower suction-type fixed fluidized-bed gasification furnace 4 at an upper portion and an upper suction-type fluidized-bed gasification furnace 5 disposed at a lower portion; a feeding hole is formed in the upper portion of the lower air suction type fixed fluidized bed gasification furnace 4, a continuous closed cloth blanking device 1 serving as a feeding device is arranged at the position of the feeding hole, a plurality of liquid oxygen tank connectors 3 are arranged beside the upper portion of the lower air suction type fixed fluidized bed gasification furnace 4, the lower air suction type fixed fluidized bed gasification furnace 4 is connected with the liquid oxygen tanks through the liquid oxygen tank connectors 3 to supply oxygen for liquid oxygen in the furnace body, and three 1.5KW microwave emitters 2 are further arranged on the side wall of the lower air suction type fixed fluidized bed gasification furnace 4.

The lower air suction type fixed fluidized bed gasification furnace 4 is sleeved on the upper air suction type fluidized bed gasification furnace 5, a lower suction port of the upper air suction type fluidized bed gasification furnace 5 is a combined air inlet and is respectively connected with an oxygen supply pipeline and a water vapor supply pipeline, meanwhile, a fuel gas outlet 6 is also arranged at the upper part of the lower air suction type fixed fluidized bed gasification furnace 4, the fuel gas outlet 6 is connected with a fuel gas collecting pipe, the product fuel gas generated by the lower air suction type fixed fluidized bed gasification furnace 4 can be collected, and the product fuel gas is subjected to purification treatment by once connecting a heat exchanger, a spray tower and a cooler through the fuel gas collecting pipe.

In this embodiment, in order to improve the energy efficiency of the equipment, water jackets are disposed on the furnace bodies of the lower suction type fixed fluidized bed gasification furnace 4 and the upper suction type fluidized bed gasification furnace 5, and the water jackets are connected with the steam chamber and connected with the steam supply pipeline through the steam chamber so as to utilize the steam self-produced by the equipment as the auxiliary gasification agent.

A rotary water tank is arranged at the lower bottom of a furnace body of the pyrolysis reactor, a rotary ash knife with the inclination of 20-30 degrees is arranged in the rotary water tank, and the furnace body realizes wet-type discharge of the biochar C through relative rotation of the rotary ash knife and the rotary water tank.

In an embodiment, when the microwave coupling liquid oxygen assisted wood oil residue pyrolysis gasification method is performed by using the reaction device for wood oil residue pyrolysis gasification, the operation steps are as follows:

firstly, drying tea-oil tree branches, fruit shells, fallen leaves and the like at a low temperature of 100 ℃, controlling the drying moisture at 11%, and crushing the tea-oil tree branches, the fruit shells, the fallen leaves and the like to a particle size of 3mm by a crusher; meanwhile, crushing the camellia oleifera cake, controlling the particle size to be 2mm, adding camellia oleifera cake crushed particles into the crushed particles, and controlling the adding amount of the camellia oleifera cake particles to be 20% of the total material; the homogeneous mass was compressed to a standardized granular mass a at a ring die compression ratio of 4.5.

Filling the standardized granular material A into a reactor from top to bottom through a continuous closed material distributing feeder 1, and adding 0.2-1.5% of active catalyst (SiO) in the filling process₂And KF/CaO in a ratio of 1: 3), and uniformly mixing the mixture with the materials; in the catalytic pyrolysis process, the system adopts the liquid oxygen tank to supply oxygen through a liquid oxygen tank connector 3, and the oxygen flow is controlled to be 2m by a flowmeter³Per hour/tonRaw material and microwave assisted using three 1.5KW microwave emitters 2. Measuring temperature change by a K-index thermocouple at 0-1300 ℃ in the catalytic pyrolysis process, controlling the gasification temperature at 900-1000 ℃ to ensure that the duration of the whole catalytic pyrolysis process is 60min, and controlling the flow rate of water vapor to be 1.5m in the process³H/ton of material.

The embodiment also adopts a totally-enclosed wet ash discharging technology. The lower bottom of the furnace body, namely the upper air suction type fluidized bed gasification furnace 5, is provided with a rotary water tank, a rotary ash knife with the inclination of 36 degrees is arranged in the rotary water tank, a 7Mpa hydraulic oil cylinder is configured, the water tank is pushed to rotate by hydraulic pressure to realize the relative rotation of the rotary ash knife and the rotary water tank, and therefore, the rotary ash knife is used for scraping out biochar C to realize the totally-closed wet ash discharge.

Meanwhile, through the arrangement of the gas outlet 6, the gas is discharged from the upper air suction type fluidized bed gasification furnace 5 and is cooled by the heat exchanger, and the heat exchanger provides a heat source for part of the gasification agent through heating air. Washing the fuel gas with water in a spray tower, cooling to room temperature in a two-stage indirect cooler, removing water (less than 0.5%) and tar (less than 30 mg/m)³) And the gas is pressurized by the booster fan and then is sent to the gas storage cabinet through the check valve, and the product biogas B is obtained.

Under the process conditions of this example, the various indexes of biogas B were measured as shown in the following table:

in order to fully utilize the raw materials, interconnected sedimentation tanks are arranged at the bottoms of the heat exchanger, the spray tower and the cooler, and the spray water of the spray tower is recycled after being treated by the sedimentation tanks and is not discharged outside; and high-calorific-value biomass raw materials such as ash, tar and the like deposited in the sedimentation tank are separated and then returned to the gasification furnace to be used as raw materials for gasification.

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.