Biomass oil-gas co-production device and method based on chemical chain

文档序号：1682887 发布日期：2020-01-03 浏览：16次中文

阅读说明：本技术 一种基于化学链的生物质油气联产装置及方法 (Biomass oil-gas co-production device and method based on chemical chain ) 是由廖艳芬莫菲马晓茜刘桂才于 2019-10-28 设计创作，主要内容包括：本发明公开了一种基于化学链的生物质油气联产装置及方法；包括热解炉、化学链气化反应器以及冷凝装置；热解炉顶部设有第一旋风分离器；燃料反应室侧面与第二螺旋进料器连通,底部设有流化气管道入口,氧化反应室的侧面连接氧化气管道入口,顶部连接第一旋风分离器；生物质与载氧体在热解反应器发生热解反应,热解气经过冷凝装置冷却后生物油存储在储油罐同时不凝结气体被排出,固体产物进入燃料反应室气化,反应后在流化气的作用下产物进入氧化反应室,在水蒸气的氧化条件下生成富氢气化气,同时载氧体经过气固分离重新进入热解反应器。该装置及方法采用生物质作为原料,通过梯级利用同时制备生物油与气化气,提高生物质的利用品质。(The invention discloses a biomass oil-gas co-production device and method based on a chemical chain; comprises a pyrolysis furnace, a chemical chain gasification reactor and a condensing device; the top of the pyrolysis furnace is provided with a first cyclone separator; the side surface of the fuel reaction chamber is communicated with the second spiral feeder, the bottom of the fuel reaction chamber is provided with a fluidized gas pipeline inlet, the side surface of the oxidation reaction chamber is connected with an oxidation gas pipeline inlet, and the top of the oxidation reaction chamber is connected with a first cyclone separator; the biomass and the oxygen carrier are subjected to pyrolysis reaction in the pyrolysis reactor, the pyrolysis gas is cooled by the condensing device, the bio-oil is stored in the oil storage tank, simultaneously, non-condensable gas is discharged, a solid product enters the fuel reaction chamber for gasification, the reacted product enters the oxidation reaction chamber under the action of the fluidized gas, hydrogen-rich gasification gas is generated under the oxidation condition of water vapor, and simultaneously, the oxygen carrier enters the pyrolysis reactor again through gas-solid separation. The device and the method adopt biomass as raw materials, and biological oil and gasified gas are simultaneously prepared through cascade utilization, so that the utilization quality of the biomass is improved.)

1. The utility model provides a living beings oil gas coproduction device based on chemical chain which characterized in that: the device comprises a biomass pyrolysis reactor (2), a chemical chain gasification reactor, a first cyclone separator (10), a second cyclone separator (11), a condensing device and a fluidization gas pipeline;

the chemical-looping gasification reactor is divided into a fuel reaction chamber (8) and an oxidation reaction chamber (9);

the condensing device comprises a condenser (4) and an oil storage tank (5);

the fluidizing gas conduit comprises intercommunicating: a non-condensation pyrolysis gas pipeline I, a main fluidizing gas pipeline II, a gasification gas branch pipeline III and CO₂A pipeline IV;

the bottom of the fuel reaction chamber (8) is provided with an air distribution plate (7) and is connected with a main fluidizing gas pipeline II;

the top wall of the biomass pyrolysis reactor (2) is provided with two interfaces, the first interface is sequentially communicated with the condenser (4) and the oil storage tank (5) through a pipeline, and the second interface is connected with the bottom of the first cyclone separator (10); the upper part of the oil storage tank (5) is connected with a non-condensable pyrolysis gas pipeline I;

the top of the oxidation reaction chamber (9) is communicated with a side gas inlet of the first cyclone separator (10) through a pipeline; a gas outlet at the top of the first cyclone separator (10) is communicated with a gas inlet at the side of the second cyclone separator (11), and a gas outlet at the top of the second cyclone separator (11) is connected with a gasified gas branch pipeline III through a gasified gas main pipeline V;

a plurality of baffle plates (3) which are inclined downwards and are mutually spaced are arranged on the corresponding side wall in the biomass pyrolysis reactor (2) in a staggered manner from top to bottom;

and a spiral feeder (6) for conveying the reacted solid product to a fuel reaction chamber (8) is arranged at the bottom of the biomass pyrolysis reactor (2).

2. The chemical-looping-based biomass oil-gas co-production device according to claim 1, characterized in that: a first screw feeder (1) is arranged on the upper side wall of the biomass pyrolysis reactor (2); the side wall of the fuel reaction chamber (8) is provided with a second screw feeder (12).

3. The chemical-looping-based biomass oil-gas co-production device according to claim 2, characterized in that: the side wall of the oxidation reaction chamber (9) is provided with a steam inlet pipeline which is connected upwards at 45 degrees, and steam is generated by a steam generator.

4. The chemical-looping-based biomass oil-gas co-production device according to claim 3, characterized in that: the condenser (4) is a shell-and-tube heat exchanger, and circulating water is driven by a pump to cool.

5. The chemical-looping-based biomass oil-gas co-production device according to claim 4, characterized in that: the non-condensation pyrolysis gas pipeline I, the gasified gas branch pipeline III and CO₂And valves are arranged on the pipelines of the pipeline IV.

6. A chemical-chain-based biomass oil-gas co-production method is realized by the chemical-chain-based biomass oil-gas co-production device of claim 5, and comprises the following steps:

the method comprises the following steps: the second spiral feeder (12) loads oxygen carrier particles into the fuel reaction chamber (8) as bed materials, and the bed materials are preheated to 800-900 ℃; the steam generator is opened to ensure that the whole oxidation reaction chamber (9) is filled with steam and kept stable; opening a fluidizing gas valve on a fluidizing gas main pipeline II to ensure that oxygen carrier particles stably and circularly flow between the biomass pyrolysis reactor (2) and the gasification reactor, and controlling the temperature of the biomass pyrolysis reactor (2) to be maintained at 400-500 ℃ all the time by adjusting the fluidizing gas flow;

step two: biomass raw materials enter a biomass pyrolysis reactor (2) from a first spiral feeder (1) for pyrolysis, an oxygen carrier enters the biomass pyrolysis reactor (2) from the bottom of a first cyclone separator (10), and an inclined baffle plate (3) enhances the contact and heat conduction of the biomass and the oxygen carrier in the falling process; under the catalytic tempering effect of an oxygen carrier, biomass is cracked into biomass charcoal and pyrolysis gas, after reaction, solid products enter a gasification reactor from the bottom of a biomass pyrolysis reactor (2) through a spiral feeder (6), the pyrolysis gas enters a condenser (4) from the top of the biomass pyrolysis reactor (2) for condensation, the biomass oil condensed into liquid state is stored in an oil storage tank, and the non-condensable gas enters the gasification reactor through a non-condensable pyrolysis gas pipeline I and a fluidized gas main pipeline II;

step three: the bottom of the fuel reaction chamber (8) is provided with an air distribution plate (7), and the solid product and the fluidized gas react in the fuelIs gasified in the chamber (8) and thereby converted into H₂、CO、CO₂、CH₄Small molecule, simultaneous biomass char and CO in the fluidizing gas₂And H₂Carrying out oxidation-reduction reaction on O;

step four: the steam entering the fuel reaction chamber (8) reacts with the biomass charcoal, part of the reduced oxygen carrier is oxidized, the gasified gas and the solid product generated by the reaction of the fuel reaction chamber (8) enter the oxidation reaction chamber (9), and under the oxidation action of the steam, the reduced oxygen carrier is continuously oxidized and the steam is converted into H₂And simultaneously, generating water gas reaction in the oxidation reaction chamber (9) to generate hydrogen-rich gasified gas, wherein the generated chemical reaction formula is as follows:

Fe+CaO+H₂O→Ca₂Fe₂O₅+H₂

CO+H₂O→CO₂+H₂；

step five: and the reacted product enters a first cyclone separator (10) for separation, the oxygen carrier enters a biomass pyrolysis reactor (2) from the bottom of the first cyclone separator (10) again, the gas and biomass ash enter a second cyclone separator (11), the biomass ash is collected from the bottom of the second cyclone separator (11) after separation, a gas outlet of the second cyclone separator (11) is introduced into a gasification reactor again to be used as fluidizing gas, and a part of gas is extracted from the fluidizing gas to be used as a gasification gas product.

7. The chemical-chain-based biomass oil-gas co-production method according to claim 6, wherein the oxygen carrier in the step one is a calcium-iron composite oxide, and comprises: ca₂Fe₂O₅、Ca₂Fe₂O₅/MgO、Ca₂Fe₂O₅/CaO。

Technical Field

The invention relates to the field of chemical industry and energy utilization of biomass oil-gas co-production, in particular to a biomass oil-gas co-production device and method based on a chemical chain.

Background

The biomass which is abundant in reserves and easy to obtain is an important fuel capable of replacing fossil energy, and the development and utilization of the biomass has important significance for relieving the problems of insufficient energy and environmental pollution. The high-grade fuels such as the biofuel oil, the synthesis gas and the like are prepared by the biomass pyrolysis and gasification process, and the high-quality utilization of the biomass is improved.

Biomass pyrolysis is a complex physicochemical process that forms three products by cracking the hydrocarbons in biomass: liquid (bio-oil), solid (coke), gas (combustible gas). The traditional thermal cracking technology realizes the full-component thermal cracking of biomass to prepare high-yield bio-oil in inert atmosphere, medium temperature and normal pressure and short retention time, and produces a small amount of pyrolysis gas and coke, but the byproduct combustible gas is diluted by the inert gas, so the recycling is difficult, and the heat value is lower.

The current biomass chemical chain gasification technology utilizes oxygen carrier to provide lattice oxygen to prepare high-yield gasified gas and a small amount of tar, but the gasified gas still has a small amount of tar after being condensed. In order to obtain qualified biomass gas, most of the existing processes adopt a water washing or secondary cracking method to reduce tar in the gas, so that a large amount of water resources are wasted, energy contained in the tar is wasted, or a catalyst is added in secondary pyrolysis to increase the preparation cost of gasified gas.

Based on the design, the biomass oil-gas co-production device based on the chemical chain realizes the cascade utilization of biomass. The method has the advantages that the pyrolyzed biological oil is collected, and high-value chemicals (such as levoglucosan) are extracted from the biological oil, so that high-value utilization of biomass resources and flexible and adjustable target products can be realized; also collects the gasified gas, and realizes high-quality utilization.

Disclosure of Invention

The invention aims to provide a biomass oil-gas co-production device and method based on a chemical chain by combining a biomass pyrolysis technology and a chemical chain gasification mode, so that high-quality biological oil and gasified gas are obtained, and efficient and gradient utilization of biomass is realized. The method has the advantages that the pyrolyzed biological oil is collected, and high-value chemicals (such as levoglucosan) are extracted from the biological oil, so that high-value utilization of biomass resources and flexible and adjustable target products can be realized; also collects the gasified gas, and realizes high-quality utilization.

The invention is realized by the following technical scheme:

a biomass oil-gas co-production device based on a chemical chain comprises a biomass pyrolysis reactor 2, a chemical chain gasification reactor, a first cyclone separator 10, a second cyclone separator 11, a condensing device and a fluidization gas pipeline;

the chemical-looping gasification reactor is divided into a fuel reaction chamber 8 and an oxidation reaction chamber 9;

the condensing device comprises a condenser 4 and an oil storage tank 5;

the fluidizing gas conduit comprises intercommunicating: a non-condensation pyrolysis gas pipeline I, a main fluidizing gas pipeline II, a gasification gas branch pipeline III and CO₂A pipeline IV;

the bottom of the fuel reaction chamber 8 is provided with an air distribution plate 7 and is connected with a main fluidizing gas pipeline II;

the top wall of the biomass pyrolysis reactor 2 is provided with two interfaces, the first interface is sequentially communicated with a condenser 4 and an oil storage tank 5 through a pipeline, and the second interface is connected with the bottom of a first cyclone separator 10; the upper part of the oil storage tank 5 is connected with a non-condensable pyrolysis gas pipeline I;

the top of the oxidation reaction chamber 9 is communicated with a side gas inlet of a first cyclone separator 10 through a pipeline; a gas outlet at the top of the first cyclone separator 10 is communicated with a side gas inlet of the second cyclone separator 11, and a gas outlet at the top of the second cyclone separator 11 is connected with a gasified gas branch pipeline III through a gasified gas main pipeline V;

a plurality of baffle plates 3 which are inclined downwards and are spaced from each other are arranged on the corresponding side wall in the biomass pyrolysis reactor 2 in a staggered manner from top to bottom;

the bottom of the biomass pyrolysis reactor 2 is provided with a spiral feeder 6 for conveying the reacted solid product to a fuel reaction chamber 8.

A first screw feeder 1 is arranged on the upper side wall of the biomass pyrolysis reactor 2; the side wall of the fuel reaction chamber 8 is provided with a second screw feeder 12.

The non-condensation pyrolysis gas pipeline I, the gasified gas branch pipeline III and CO₂And valves are arranged on the pipelines of the pipeline IV.

The outlet gas of said second cyclone 11 is reintroduced into the gasification reactor as fluidizing gas and a part of the gas is withdrawn therefrom as gasification gas product, the branch being provided with a flow control valve.

The fuel reaction chamber 8 is connected with the oxidation reaction chamber 9 and is a fast fluidized bed, and CO is introduced in the starting stage₂As fluidizing gas, the product gas is recycled as fluidizing gas after stable operation without introducing CO₂。

The condenser is a shell-and-tube heat exchanger, and circulating water is driven by a pump to cool.

A steam inlet pipeline is arranged at the side end of the oxidation reaction chamber 9 and is connected upwards at 45 degrees, and steam is generated by a steam generator.

A biomass oil-gas co-production method based on a chemical chain comprises the following steps:

the method comprises the following steps: the second screw feeder 12 loads the oxygen carrier particles into the fuel reaction chamber 8 as bed materials, and the bed materials are preheated to 800-900 ℃; the steam generator is opened to make the whole oxidation reaction chamber 9 filled with steam and kept stable; opening a fluidizing gas valve on a fluidizing gas main pipeline II to ensure that oxygen carrier particles stably and circularly flow between the biomass pyrolysis reactor 2 and the gasification reactor, and controlling the temperature of the biomass pyrolysis reactor 2 to be maintained at 400-500 ℃ all the time by adjusting the fluidizing gas flow;

step two: biomass raw materials enter a biomass pyrolysis reactor 2 from a first spiral feeder 1 for pyrolysis, an oxygen carrier enters the biomass pyrolysis reactor 2 from the bottom of a first cyclone separator 10, and an inclined baffle plate 3 enhances the contact and heat conduction of the biomass and the oxygen carrier in the falling process; under the catalytic tempering effect of an oxygen carrier, biomass is cracked into biomass charcoal and pyrolysis gas, after reaction, solid products enter a gasification reactor from the bottom of a biomass pyrolysis reactor 2 through a spiral material conveyer 6, the pyrolysis gas enters a condenser 4 from the top of the biomass pyrolysis reactor 2 for condensation, the biomass oil condensed into liquid state is stored in an oil storage tank, and the non-condensable gas enters the gasification reactor through a non-condensable pyrolysis gas pipeline I and a fluidized gas main pipeline II;

step three: the bottom of the fuel reaction chamber 8 is provided with an air distribution plate 7, and solid products (including biomass charcoal and oxygen carrier) and fluidized gas are gasified in the fuel reaction chamber 8 and are converted into H₂、CO、CO₂、CH₄The same small molecules are added, and the biomass carbon and CO in the fluidized gas are simultaneously added₂And H₂Carrying out oxidation-reduction reaction on O; with an oxygen carrier Ca₂Fe₂O₅For example, the oxygen carrier is reduced to elemental Fe and CaO, the main chemical reaction taking place:

C+Ca₂Fe₂O₅→CO+CO₂+Fe+CaO

C+CO₂→2CO

CH₄+Ca₂Fe₂O₅→CO+CO₂+H₂+H₂O+Fe+CaO

Tar+Ca₂Fe₂O₅→CO+CO₂+H₂+H₂O+C_mH_n+Fe+CaO

C+H₂O→CO+H₂

step four: the steam entering the fuel reaction chamber 8 not only reacts with the biomass charcoal, but also oxidizes part of the reduced oxygen carrier, the gasified gas and the solid products generated by the reaction in the fuel reaction chamber 8 enter the oxidation reaction chamber 9, and under the oxidation action of the steam, the reduced oxygen carrier is continuously oxidized and the steam is converted into H₂And simultaneously, the water gas reaction is carried out in the oxidation reaction chamber 9 to generate hydrogen-rich gasified gas, and the chemical reaction formula is as follows:

Fe+CaO+H₂O→Ca₂Fe₂O₅+H₂

CO+H₂O→CO₂+H₂；

step five: the reacted product enters a first cyclone separator 10 for separation, the oxygen carrier enters a biomass pyrolysis reactor 2 from the bottom of the first cyclone separator 10 again, the gas and biomass ash enter a second cyclone separator 11, the biomass ash is collected from the bottom of the second cyclone separator 11 after separation, a gas outlet of the second cyclone separator 11 is introduced into a gasification reactor as fluidized gas, and a part of gas is extracted from the fluidized gas as a gasification gas product.

The oxygen carrier is a calcium-iron composite oxide, and comprises: ca₂Fe₂O₅、Ca₂Fe₂O₅/MgO、Ca₂Fe₂O₅/CaO。

In the first step, the oxygen carrier in the fuel reactor is supplied by a second screw feeder;

the water vapor injection flow rate which plays a role in supplementing and adjusting in the fourth step is lower so as to reduce the energy consumption of the steam generator. The energy of the steam generator supplies heat exchanged from the condenser.

Compared with the prior art, the invention has the following advantages and effects:

1) using Ca₂Fe₂O₅、Ca₂Fe₂O₅/MgO、Ca₂Fe₂O₅the/CaO is used as an oxygen carrier, releases lattice oxygen in the reduction stage of the reaction with the biochar, and directly recovers the original lattice oxygen under the oxidation of water vapor, so that an air reactor can be omitted, and the complexity of the system is reduced.

2) The calcium-iron composite oxide oxygen carrier not only provides oxygen for biomass gasification, but also plays a role in catalyzing and tempering in the stage of preparing bio-oil by pyrolysis, and pyrolysis gas enters a chemical-looping gasification furnace to realize secondary reaction, so that the tar content in the gasification gas is reduced while energy is utilized.

3) The high-temperature oxygen carrier enters the pyrolysis furnace from the oxidation reaction chamber, and the self-heating balance of biomass pyrolysis can be realized.

4) The water vapor is used as the oxidizing gas, so that the introduction of nitrogen is avoided, and the H in the gasified gas is increased₂And (4) content.

5) The design of the baffle plate in the biomass pyrolysis furnace can enhance the contact and heat conduction of oxygen carrier particles and biomass raw materials, prolong the retention time and ensure the sufficient pyrolysis of biomass.

Drawings

FIG. 1 is a schematic structural diagram of a biomass oil-gas co-production device based on a chemical chain.

Description of reference numerals: a first screw feeder 1; a biomass pyrolysis reactor 2; a striker plate 3; a condenser 4; an oil storage tank 5; a screw feeder 6; an air distribution plate 7; a fuel reaction chamber 8; an oxidation reaction chamber 9; a first cyclone 10; a second cyclone 11; a second screw feeder 12; a represents non-condensable pyrolysis gas; b represents the fluidization gas; c represents an oxidizing gas; d represents the product of the gasification gas; a non-condensing pyrolysis gas pipeline I; a main fluidizing gas pipeline II; a gasified gas branch pipeline III; CO 2₂A pipeline IV; a main gasification gas pipeline V.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

As shown in fig. 1. The invention discloses a biomass oil-gas co-production device based on a chemical chain, which comprises a biomass pyrolysis reactor 2, a chemical chain gasification reactor, a first cyclone separator 10, a second cyclone separator 11, a condensing device and a fluidized gas pipeline, wherein the chemical chain gasification reactor is arranged on the biomass oil-gas co-production device;