阅读说明：本技术 一种碱金属或碱土金属可控去除和添加的化学链气化重整装置及方法 (Chemical chain gasification reforming device and method for controllably removing and adding alkali metal or alkaline earth metal ) 是由 胡志锋 蒋恩臣 王明峰 任永志 吴家威 张键鑫 杨锋 林宗杰 黄祥能 苗桢武 于 2019-08-27 设计创作，主要内容包括：本发明公开一种碱金属或碱土金属可控去除和添加的化学链气化重整装置及方法,装置包括依次连接的去除组件、添加组件、螺旋进料器、化学链气化重整装置、旋风分离器和气体净化装置,还包括分别收集去除组件和添加组件中的液体的液体净化装置,液体净化装置与化学链气化重整装置连接并向化学链气化重整装置提供水蒸气；方法为生物质原料在磁力搅拌去除装置中与酸溶液搅拌酸洗,经压滤淋洗后进入磁力搅拌添加装置与碱金属或碱土金属溶液搅拌浸渍,经压滤后在化学链气化重整装置中与氧载体、水蒸气连续搅动混合均匀并反应,调节水蒸气加入量以可控调节合成气比例,氧载体继续在空气反应器中反应重新与预处理后生物质混合,继续下一个循环。(The invention discloses a chemical chain gasification reforming device and a chemical chain gasification reforming method for controllably removing and adding alkali metal or alkaline earth metal, wherein the device comprises a removing component, an adding component, a spiral feeder, a chemical chain gasification reforming device, a cyclone separator and a gas purification device which are sequentially connected, and also comprises a liquid purification device for respectively collecting liquid in the removing component and the adding component, wherein the liquid purification device is connected with the chemical chain gasification reforming device and provides water vapor for the chemical chain gasification reforming device; the method comprises the steps of stirring and pickling biomass raw materials with an acid solution in a magnetic stirring removal device, entering a magnetic stirring adding device after filter pressing and leaching, stirring and dipping with an alkali metal or alkaline earth metal solution, continuously stirring, uniformly mixing and reacting with an oxygen carrier and water vapor in a chemical chain gasification reforming device after filter pressing, adjusting the adding amount of the water vapor to controllably adjust the proportion of synthesis gas, continuously reacting the oxygen carrier in an air reactor, mixing with pretreated biomass again, and continuing the next cycle.)

1. The chemical-looping gasification reforming device capable of controllably removing and adding the alkali metal or the alkaline earth metal is characterized by comprising a removing component, an adding component, a spiral feeder, a chemical-looping gasification reforming device, a cyclone separator and a gas purifying device which are sequentially connected, and further comprising a liquid purifying device for respectively collecting liquid in the removing component and the adding component, wherein the liquid purifying device is connected with the chemical-looping gasification reforming device and provides water vapor for the chemical-looping gasification reforming device;

get rid of the subassembly including the magnetic stirring remove device who connects gradually, get rid of coil formula pressure filter and get rid of chain conveyor, add the subassembly including the magnetic stirring who connects gradually add the device, add coil formula pressure filter and add chain conveyor.

2. The chemical looping gasification reforming device for removing and adding alkali metals or alkaline earth metals controllably as claimed in claim 1, wherein the liquid phase channel of the removal coil type filter press is connected with a liquid purification device, the solid phase channel of the removal coil type filter press is connected with a removal looping conveyor belt, a leaching device is arranged above the removal looping conveyor belt, and leaching water is introduced into the liquid purification device.

3. The chemical looping gasification reforming device for the controlled removal and addition of alkali metals or alkaline earth metals as claimed in claim 1, wherein the liquid phase channel of the additional spiral tube type pressure filter is connected with a liquid purification device, the solid phase channel of the additional spiral tube type pressure filter is connected with an additional looping conveyor belt, and the outlet end of the removal looping conveyor belt is connected with a magnetic stirring and adding device.

4. The chemical looping gasification reforming device for removing and adding alkali metals or alkaline earth metals in a controlled manner as claimed in claim 1, wherein the screw feeder is a shaftless screw reactor, an inlet of the screw feeder is connected with an outlet end of the adding chain conveyor belt, and an outlet of the screw feeder is connected with the chemical looping gasification reforming device.

5. The chemical looping gasification reforming device for removing and adding the alkali metal or the alkaline earth metal controllably according to claim 1, characterized in that the chemical looping gasification reforming device adopts a shaftless spiral reactor, the chemical looping gasification reforming device comprises a feed inlet, a water vapor channel, an oxygen carrier circulation channel and a discharge outlet, the feed inlet is connected with a spiral feeder, the water vapor channel is connected with a liquid purification device, a peristaltic pump is arranged between the water vapor channel and the liquid purification device, the discharge outlet is connected with a cyclone separator, a gas outlet of the cyclone separator is connected with the gas purification device and a gas storage tank, a solid outlet of the cyclone separator is connected with an air reactor, and the air reactor leads to the chemical looping gasification reforming device to form the oxygen carrier circulation channel.

6. A chemical looping gasification reforming process with controlled removal and addition of alkali or alkaline earth metals, the process comprising:

feeding the biomass raw material into a magnetic stirring removal device, adding an acid solution, continuously stirring in the magnetic stirring removal device for acid washing, separating water into a liquid purification device through a liquid phase channel by a removal rotary tube type filter press for purification treatment, and feeding the filter-pressed biomass into a removal chain conveyor belt through a solid phase channel;

during the process of removing chain conveyor belt and transporting biomass, continuously washing an acid solution on the biomass by a leaching device, conveying the washed biomass to a magnetic stirring adding device, simultaneously adding an alkali metal or alkaline earth metal solution into the magnetic stirring adding device, continuously stirring and dipping in the magnetic stirring adding device, separating water into a liquid purifying device through an adding coil type filter press through a liquid phase channel for purifying treatment, and conveying the filter-pressed biomass to a spiral feeder through a solid phase channel by an adding chain conveyor belt;

the biomass after passing through the spiral feeder, the high-temperature oxygen carrier after being oxidized by the air reactor and the water vapor provided by the liquid purification device after treating the wastewater are respectively sent to the chemical-looping gasification reforming device and are uniformly mixed, and the biomass, the water vapor and the oxygen carrier react in the chemical-looping gasification reforming device;

products obtained by reaction in the chemical chain gasification reforming device are separated by a cyclone separator, and synthetic gas is treated by a gas purification device and then is sent into a gas storage tank; the solid product enters an air reactor from a solid outlet of the cyclone separator, the reduced oxygen carrier reacts with air in the air reactor to form an oxidized oxygen carrier, and the oxidized oxygen carrier is sent into the chemical-looping gasification reforming device again to complete the primary circulation of preparing the synthesis gas by the chemical-looping gasification reforming of the biomass with the controllable removal and addition of alkali metal or alkaline earth metal; the above circulation is repeatedly operated, and biomass pretreatment of continuously and controllably removing and adding alkali metals or alkaline earth metals can be realized.

7. The chemical looping gasification reforming method for controllably removing and adding alkali metals or alkaline earth metals as claimed in claim 6, wherein the biomass raw material is stirred and pickled for 1-5 hours in a magnetic stirring removal device, the mass ratio of the acid solution to the biomass raw material is 10: 1-90: 1, the acid solution is hydrochloric acid, sulfuric acid, nitric acid or acetic acid, and the mass concentration of the acid solution is not more than 9%.

8. The chemical looping gasification reforming method for removing and adding alkali metals or alkaline earth metals controllably according to claim 6, characterized in that the mass concentration of the alkali metal or alkaline earth metal solution added in the magnetic stirring adding device is not more than 24%, the alkali metal or alkaline earth metal solution adopts corresponding inorganic salt or organic salt solution, and one salt solution is added singly or a plurality of salt solutions are added in a mixing way.

9. The chemical looping gasification reforming method for removing and adding alkali metals or alkaline earth metals in a controllable manner according to claim 6, wherein the reaction time of the biomass, the steam and the oxygen carrier in the chemical looping gasification reforming device is 15-40 min, the ratio of hydrogen to carbon monoxide in the synthesis gas is adjusted by controlling the adding amount of the steam in the chemical looping gasification reforming device, and the ratio of the hydrogen to the carbon monoxide can be adjusted within the range of 0.5-6.0.

10. The chemical looping gasification reforming method for removing and adding alkali metals or alkaline earth metals controllably according to claim 9, characterized in that, in the circulation process, when the hydrogen concentration value in the synthesis gas is reduced by 5%, 10% of oxygen carriers are required to be taken out from the solid outlet of the cyclone for activation, and 10% of fresh oxygen carriers are required to be fed into the chemical looping gasification reforming device.

Technical Field

The invention relates to the technical field of chemical-looping gasification reforming, in particular to a chemical-looping gasification reforming device and a chemical-looping gasification reforming method capable of removing and adding alkali metal or alkaline earth metal controllably.

Background

Chemical looping gasification is a novel gasification technology. Chemical looping gasification systems typically consist of two reactors in series (a fuel reactor and an air reactor) with an oxygen carrier circulating between the two reactors. The lattice oxygen in the oxygen carrier serves as a medium for conventional gasification reactions throughout the cycle and provides the necessary oxygen element for the fuel gasification reaction. Furthermore, by controlling the ratio of lattice oxygen to fuel, H can be obtained₂And syngas with CO as the main constituent. The technology has the advantages that oxygen carriers are used for circularly supplying oxygen, so that the cost is saved; can control H₂And the proportion of CO, so that the ideal synthesis gas required by chemical products can be obtained conveniently; the oxygen carrier can catalyze and promote the reaction and improve the gasification reaction efficiency. Therefore, the exploration and development of the biomass chemical-looping gasification technology have extremely high application value.

The agricultural and forestry wastes have various types and large performance difference, and the types and the content of alkali metals in the biomass also have large difference. In the biomass gasification process, alkali metal and alkaline earth metal (AAEM) are used as trace elements with the largest content in agricultural and forestry waste, so that the problems of furnace hearth material slagging, heating surface ash deposition corrosion and the like are easily caused, and the combustion, pyrolysis and gasification reaction of biomass are hindered. Meanwhile, researches show that alkali metal or alkaline earth metal plays a certain role in catalysis or inhibition in the biomass pyrolysis, gasification and combustion processes, and the reaction process is uncontrolled, so that the differences of the reaction performance, the dynamic characteristic, the gas product precipitation characteristic and other performances of the biomass are obvious, and the efficiency and the safety of biomass centralized treatment are further influenced; in the gasification reaction, the gasification efficiency greatly fluctuates, and the gas quality is unstable, thereby affecting the quality of chemical products or the combustion condition.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a device for preparing synthesis gas by biomass chemical-looping gasification reforming, wherein alkali metals or alkaline-earth metals are removed and added controllably, the device can efficiently and continuously remove the alkali metals or the alkaline-earth metals of a biomass raw material, slow down the inhibition effect of the alkali metals or the alkaline-earth metals, and can controllably add the needed alkali metals or the alkaline-earth metals with the catalytic action, thereby achieving the purpose of efficiently pretreating the raw material of the chemical-looping gasification reaction.

Another object of the present invention is to provide a method for preparing synthesis gas by chemical looping gasification reforming of biomass, in which alkali metals or alkaline earth metals can be controllably removed and added, the method can combine raw material pretreatment and chemical looping gasification reforming reaction, reduce agglomeration of biomass and oxygen carriers during the reaction process, improve the reaction efficiency, and controllably adjust the composition of combustible gas during the reaction process.

The technical scheme of the invention is as follows: a chemical chain gasification reforming device for controllably removing and adding alkali metal or alkaline earth metal comprises a removing component, an adding component, a spiral feeder, a chemical chain gasification reforming device, a cyclone separator and a gas purification device which are sequentially connected, and further comprises a liquid purification device for respectively collecting liquid in the removing component and the adding component, wherein the liquid purification device is connected with the chemical chain gasification reforming device and provides water vapor for the chemical chain gasification reforming device;

get rid of the subassembly including the magnetic stirring remove device who connects gradually, get rid of coil formula pressure filter and get rid of chain conveyor, add the subassembly including the magnetic stirring who connects gradually add the device, add coil formula pressure filter and add chain conveyor.

The liquid phase channel of the removal coil type filter press is connected with the liquid purification device, the solid phase channel of the removal coil type filter press is connected with the removal chain type conveyer belt, a leaching device is arranged above the removal chain type conveyer belt, and leaching water is introduced into the liquid purification device.

The liquid phase channel of the adding coil type filter press is connected with the liquid purification device, the solid phase channel of the adding coil type filter press is connected with the adding chain type conveyer belt, and the outlet end of the removing chain type conveyer belt is connected with the magnetic stirring adding device.

The spiral feeder adopts a shaftless spiral reactor, the inlet of the spiral feeder is connected with the outlet end of the adding chain type conveying belt, and the outlet of the spiral feeder is connected with the chemical chain gasification reforming device.

The chemical chain gasification reforming device adopts a shaftless spiral reactor, and comprises a feed inlet, a steam channel, an oxygen carrier circulation channel and a discharge port, wherein the feed inlet is connected with a spiral feeder, the steam channel is connected with a liquid purification device, a peristaltic pump is arranged between the steam channel and the liquid purification device, the discharge port is connected with a cyclone separator, a gas outlet of the cyclone separator is connected with a gas purification device and a gas storage tank, a solid outlet of the cyclone separator is connected with an air reactor, and the air reactor leads to the chemical chain gasification reforming device to form the oxygen carrier circulation channel.

A chemical looping gasification reforming process with controlled removal and addition of alkali or alkaline earth metals, the process comprising:

feeding the biomass raw material into a magnetic stirring removal device, adding an acid solution, continuously stirring in the magnetic stirring removal device for acid washing, separating water into a liquid purification device through a liquid phase channel by a removal rotary tube type filter press for purification treatment, and feeding the filter-pressed biomass into a removal chain conveyor belt through a solid phase channel;

during the process of removing chain conveyor belt and transporting biomass, continuously washing an acid solution on the biomass by a leaching device, conveying the washed biomass to a magnetic stirring adding device, simultaneously adding an alkali metal or alkaline earth metal solution into the magnetic stirring adding device, continuously stirring and dipping in the magnetic stirring adding device, separating water into a liquid purifying device through an adding coil type filter press through a liquid phase channel for purifying treatment, and conveying the filter-pressed biomass to a spiral feeder through a solid phase channel by an adding chain conveyor belt;

the biomass after passing through the spiral feeder, the high-temperature oxygen carrier after being oxidized by the air reactor and the water vapor provided by the liquid purification device after treating the wastewater are respectively sent to the chemical-looping gasification reforming device and are uniformly mixed, and the biomass, the water vapor and the oxygen carrier react in the chemical-looping gasification reforming device;

products obtained by reaction in the chemical chain gasification reforming device are separated by a cyclone separator, and synthetic gas is treated by a gas purification device and then is sent into a gas storage tank; the solid product enters an air reactor from a solid outlet of the cyclone separator, the reduced oxygen carrier reacts with air in the air reactor to form an oxidized oxygen carrier, and the oxidized oxygen carrier is sent into the chemical-looping gasification reforming device again to complete the primary circulation of preparing the synthesis gas by the chemical-looping gasification reforming of the biomass with the controllable removal and addition of alkali metal or alkaline earth metal; the above circulation is repeatedly operated, and biomass pretreatment of continuously and controllably removing and adding alkali metals or alkaline earth metals can be realized.

The biomass raw materials are stirred and pickled for 1-5 hours in a magnetic stirring removal device, the mass ratio of an acid solution to the biomass raw materials is 10: 1-90: 1, the acid solution is hydrochloric acid, sulfuric acid, nitric acid or acetic acid, and the mass concentration of the acid solution is not more than 9%.

The mass concentration of the alkali metal or alkaline earth metal solution added into the magnetic stirring and adding device is not more than 24%, the alkali metal or alkaline earth metal solution adopts corresponding inorganic salt or organic salt solution, and one salt solution is added singly or a plurality of salt solutions are mixed and added.

The reaction time of the biomass, the steam and the oxygen carrier in the chemical chain gasification reforming device is 15-40 min, the ratio of hydrogen to carbon monoxide in the synthesis gas is adjusted by controlling the adding amount of the steam in the chemical chain gasification reforming device, and the adjustable range of the ratio of the hydrogen to the carbon monoxide is 0.5-6.0.

In the circulation process, when the hydrogen concentration value in the synthesis gas is reduced by 5%, 10% of oxygen carrier is required to be taken out from the solid outlet of the cyclone separator for activation, and 10% of fresh oxygen carrier is required to be fed into the chemical chain gasification reforming device.

Compared with the prior art, the invention has the following beneficial effects:

1. the biomass is pickled by magnetic stirring, so that alkali metals or alkaline earth metals of the biomass raw material are efficiently removed, the inhibition effect of the biomass raw material on chemical chain gasification reforming reaction is slowed down, and the agglomeration and caking phenomena of the biomass and an oxygen carrier are reduced.

2. The method can controllably add the needed alkali metal or alkaline earth metal with catalytic action, improve the reaction efficiency of biomass chemical-looping gasification reforming, and control the adding amount of water vapor to controllably adjust the combustible gas components in the reaction process under the action of the alkali metal or alkaline earth metal.

3. The device has low price and strong practicability, the adopted method is simple and easy to implement, meets the environmental protection requirement, can be widely used in the agricultural and forestry waste thermochemical energy conversion processes such as biomass continuous pretreatment, continuous gasification reforming, rural distributed energy and the like, and has wide application prospect.

Drawings

FIG. 1 is a schematic view of the structure of the apparatus of the present invention.

FIG. 2 is a process flow diagram of the method of the present invention.

FIG. 3 shows the test results of example 2.

The reference numbers and corresponding part names in the figures are: the device comprises a magnetic stirring removal device 1, a removal coil type press filter 2, a leaching device 3, a liquid purification device 4, a chain conveyor belt 5, a magnetic stirring adding device 6, an addition coil type press filter 7, an addition chain conveyor belt 8, a peristaltic pump 9, a spiral feeder 10, a chemical chain gasification reforming device 11, a cyclone separator 12, an air reactor 13, a gas purification device 14 and a gas storage tank 15.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.