阅读说明：本技术 一种生物质热解处理用助剂及其制法和应用 (Auxiliary agent for biomass pyrolysis treatment and preparation method and application thereof ) 是由 王鑫 宋永一 张彪 赵丽萍 吴斯侃 于 2019-10-30 设计创作，主要内容包括：本发明公开了一种生物质热解处理用助剂及其制法和应用,所述助剂包括组分A、组分B和组分C；所述组分A为液体油浆,所述组分B为具有微波吸收性的物质,所述具有微波吸收性的物质包括生物焦和吸波陶瓷；所述组分C为具有催化裂解活性的物质,包括IA、IIA族金属盐及其氢氧化物、VIII和IB族金属盐及其氧化物。所述助剂制备方法首先将组分A和组分B混合,然后进行打浆处理,得到均匀状粘流态浆液,然后再与组分C混合打浆处理。采用所述助剂后的生物质热解气化方法可以提高合成气收率,且得到的合成气产品中焦油含量极低,工艺经济性高,具有良好应用前景。(The invention discloses an auxiliary agent for biomass pyrolysis treatment and a preparation method and application thereof, wherein the auxiliary agent comprises a component A, a component B and a component C; the component A is liquid oil slurry, the component B is a substance with microwave absorbability, and the substance with microwave absorbability comprises biological coke and wave-absorbing ceramic; the component C is a substance with catalytic cracking activity and comprises IA and IIA metal salts and hydroxides thereof, and VIII and IB metal salts and oxides thereof. The preparation method of the auxiliary agent comprises the steps of mixing the component A and the component B, pulping to obtain uniform viscous state slurry, and mixing and pulping with the component C. The biomass pyrolysis gasification method adopting the auxiliary agent can improve the yield of the synthesis gas, and the obtained synthesis gas product has extremely low tar content, high process economy and good application prospect.)

1. An auxiliary agent for biomass pyrolysis treatment, which comprises a component A, a component B and a component C;

the component A is liquid oil slurry which can generate coking reaction at normal pressure and 200-600 ℃, the liquid oil slurry is one or more of pyrolysis tar, catalytic oil slurry, pyrolysis tar in a biorefinery process and heavy tar in a coal carbonization process, and the pyrolysis tar in the biorefinery process is preferred;

the component B is a substance with microwave absorbability, and the substance with microwave absorbability comprises biological coke and/or wave-absorbing ceramic;

the component C is a substance with catalytic cracking activity and comprises one or more of IA group metal salt, IIA group metal salt, IA group metal hydroxide, IIA group metal hydroxide, VIII group metal salt, VIII group metal oxide, IB group metal salt and IB group metal oxide.

2. The biomass pyrolysis treatment aid of claim 1, wherein: the pyrolysis tar from the biorefinery process comprises any biological tar, and specifically comprises one or more of straw tar, forest tar, wheat straw tar, rice hull tar, microalgae tar and seaweed tar.

3. The biomass pyrolysis treatment aid of claim 1, wherein: the pyrolysis tar is tar obtained in the urban industry and domestic waste treatment process, and specifically is one or more of tire tar, plastic tar, resin tar, paint tar and kitchen waste tar.

4. The biomass pyrolysis treatment aid of claim 1, wherein: the heavy tar in the coal dry distillation process is one or more of low-temperature coal tar, medium-temperature coal tar and high-temperature coal tar.

5. The biomass pyrolysis treatment aid of claim 1, wherein: the liquid oil slurry is forest tar and seaweed tar.

6. The biomass pyrolysis treatment aid of claim 1, wherein: the biological coke is one or more selected from pyrolysis biological coke at 600-1000 ℃.

7. The biomass pyrolysis treatment aid of claim 1, wherein: the wave-absorbing ceramic is one or more selected from SiC, SiN, Si-C-N, Si-C-B, Si-N-B, Si-C-N-B and Si-C-Al-N ceramic materials.

8. The biomass pyrolysis treatment aid of claim 1, wherein: the component B is pyrolytic biological coke, and is further preferably pyrolytic biological coke at 800 ℃.

9. The biomass pyrolysis treatment aid of claim 1, wherein: the component C is one or more of potassium carbonate, sodium carbonate, lithium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, iron oxide, nickel oxide, cobalt oxide and copper oxide, and preferably potassium carbonate and nickel oxide.

10. The biomass pyrolysis treatment aid of claim 1, wherein: based on the weight content of the auxiliary agent, the content of the component A is 70-90 wt%, the content of the component B is 5-15 wt%, and the content of the component C is 5-15 wt%.

11. A method of making an aid for the pyrolysis treatment of biomass as claimed in any one of claims 1 to 10, the method comprising:

(1) firstly, mixing the component A and the component B, and then pulping to obtain uniform viscous state slurry;

(2) and (2) mixing the slurry obtained in the step (1) with the component C for pulping treatment, and obtaining the biomass pyrolysis treatment auxiliary agent after treatment.

12. The process for producing an assistant for pyrolysis of biomass according to claim 11, wherein: the pulping treatment is realized by a grinder, and a ball mill is further preferred.

13. The process for producing an assistant for pyrolysis of biomass according to claim 11, wherein: the pulping treatment temperature in the step (1) is 15-40 ℃.

14. Use of the biomass pyrolysis treatment auxiliary according to any one of claims 1 to 10 in a biomass pyrolysis gasification treatment process comprising:

(1) mixing a biomass raw material and an auxiliary agent, and carrying out molding treatment to obtain a biomass reaction material;

(2) and (2) allowing the biomass reaction material obtained in the step (1) to enter a biomass pyrolysis reactor for reaction, and separating reaction products to obtain biomass synthesis gas and biological coke.

15. The use of an auxiliary for biomass pyrolysis treatment according to claim 14 in a biomass pyrolysis gasification process, wherein: the mixing and forming process of the biomass raw material and the auxiliary agent in the step (1) is as follows: mixing the biomass raw material with the auxiliary agent, uniformly mixing, and then carrying out hot press forming to obtain a formed biomass reaction material, wherein the maximum dimension of the material in the direction is not more than 40mm, and preferably 10-20 mm.

16. The use of an auxiliary for biomass pyrolysis treatment according to claim 14 in a biomass pyrolysis gasification process, wherein: the hot-press molding conditions are as follows: the temperature is 60-120 ℃ and 20-50 kg/cm²Hot pressing for 1-10 min, heating to 150-180 deg.C, and 60-100 kg/cm²Carrying out hot pressing for 1-10 minutes under the condition, and then cooling for later use.

17. The use of an auxiliary for biomass pyrolysis treatment according to claim 14 in a biomass pyrolysis gasification process, wherein: the mass ratio of the biomass raw material to the auxiliary agent is 4-20: 1.

18. the use of an auxiliary for biomass pyrolysis treatment according to claim 14 in a biomass pyrolysis gasification process, wherein: the biomass raw material is any substance containing lignocellulose, and specifically is one or more of corn straw, rice hull, wheat straw, wood block, tree leaf and branch.

19. The use of an auxiliary for biomass pyrolysis treatment according to claim 14 in a biomass pyrolysis gasification process, wherein: the reaction temperature in the biomass pyrolysis reactor in the step (2) is 700-900 ℃, and the reaction time is 10-30 minutes.

20. Use of an auxiliary agent for biomass pyrolysis treatment according to claim 14 or 19 in a biomass pyrolysis gasification process, wherein: the reaction in the step (2) is carried out under the microwave condition, and the microwave power density is 1 multiplied by 10⁵～10×10⁵W/m³。

21. The use of an auxiliary for biomass pyrolysis treatment according to claim 14 in a biomass pyrolysis gasification process, wherein: the reaction in the step (2) is carried out in the presence of oxygen-containing gas, the reaction pressure is 0-0.6 MPa, wherein the oxygen-containing gas is one or more of oxygen, air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and flue gas, a mixed gas of oxygen and water vapor or a mixed gas of oxygen and inert gas, the volume fraction of the oxygen in the mixed gas is 10-40%, and the flow rate of the oxygen-containing gas is 0.01-0.1 m³/h。

Technical Field

The invention belongs to the field of biomass processing, and relates to an auxiliary agent for biomass pyrolysis treatment, and a preparation method and application thereof.

Background

In recent years, biomass microwave pyrolysis gasification technology is widely applied and a plurality of pilot-scale experimental demonstration devices are established, but in specific engineering practice, biomass microwave heating has the defects of small tolerance to raw material difference, too fast tar formation and the like, and particularly, the tar can seriously influence the operation of a gasification system. In order to solve the problem of low tolerance of microwave to raw materials, a wave absorber (activated carbon, biological coke and silicon carbide) is usually mixed into biomass to improve the microwave energy utilization efficiency of the biomass, but the microwave absorption property of the biomass, which is differentiated due to factors such as type, batch and production place, can directly influence the microwave heating assisted effect of the wave absorber, and researches show that the microwave absorption performance of the biomass can be inhibited by adding inappropriate and inappropriate amounts of the wave absorber, so that the overall pyrolysis efficiency is influenced, and how to reasonably use the wave absorber still remains one of the problems troubling the microwave pyrolysis technology of the biomass.

Aiming at the problem of too fast tar formation, a tar cracking reaction system is usually added outside a pyrolysis reactor to carry out on-line upgrading on a gasification product, but the requirement on the tolerance of a catalyst is higher, and the conventional ZSM-5 and Me have higher requirements on the tolerance of the catalyst_xO_y、Me/Al₂O₃The catalyst still has the problem of poor timeliness; the in-reactor catalysis is in-situ catalytic tar removal in the biomass pyrolysis process, and is an ideal tar removal method, but in view of the severe conditions of the pyrolysis working condition, the commonly used cheap catalysts (coke and natural ore) have the common problems of incomplete tar removal and quick inactivation.

201810126555.9 mixing the biomass raw material and the carbonized material, extruding and molding under the action of the thermosetting adhesive, then blending the extruded and molded material with a metal or metal oxide catalyst and then performing microwave pyrolysis to obtain a high-quality biochar product and a gasification product, wherein no obvious tar is generated in the pyrolysis process, and the method has the advantages of high product quality and environment-friendly pyrolysis process. 201811022722.1 the AnBm type metal mixture is directly loaded on the semi-coke powder with wave absorption property and is evenly mixed with the pyrolysis material to form even hot spots in the microwave field, so that the overall temperature distribution of the material is more even, and the catalytic active component loaded on the semi-coke is in the high energy field, thus enhancing the catalytic active point position, greatly reducing the catalyst cost and not introducing too much impurities. However, the metal oxide and the metal mixture with catalytic activity are commonly added in the method, and the bottleneck problems that the metal catalyst is difficult to recover, the quality of the biochar product is influenced and the like exist.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides the auxiliary agent for biomass pyrolysis treatment and the preparation method and the application thereof, the biomass pyrolysis gasification method adopting the auxiliary agent can improve the yield of the synthesis gas, and the obtained synthesis gas product has extremely low tar content, high process economy and good application prospect. Solves the problems of low synthesis gas yield and poor quality in the existing process for preparing synthesis gas by using biomass as a raw material through pyrolysis.

The invention provides an auxiliary agent for biomass pyrolysis treatment, which comprises a component A, a component B and a component C;

the component A is liquid oil slurry, preferably liquid oil slurry capable of undergoing coking reaction at normal pressure and at 200-600 ℃, the liquid oil slurry can be one or more of pyrolysis tar, catalytic oil slurry, pyrolysis tar in a biorefinery process and heavy tar in a coal carbonization process, and is preferably pyrolysis tar in a biorefinery process; wherein the pyrolysis tar from the biorefinery process comprises any biological tar, and specifically can be one or more of straw tar, forest tar, wheat straw tar, rice hull tar, microalgae tar and seaweed tar; the cracked tar is tar obtained in the urban industry and domestic waste treatment process, and specifically can be one or more of tire tar, plastic tar, resin tar, paint tar and kitchen waste tar; the heavy tar in the coal carbonization process can be one or more of low-temperature coal tar, medium-temperature coal tar and high-temperature coal tar; catalytic slurries include, but are not limited to, cracked slurries of several feedstocks such as vacuum residuum, atmospheric residuum, ethylene tar, and the like; the component A is further preferably forest tar and seaweed tar, wherein the mass ratio of the forest tar to the seaweed tar is 1-10: 1.

the component B is a substance with microwave absorbability, the substance with microwave absorbability comprises biological coke and/or wave-absorbing ceramic, wherein the biological coke is one or more selected from pyrolytic biological coke at 600-1000 ℃, and the wave-absorbing ceramic is one or more selected from SiC, SiN, Si-C-N, Si-C-B, Si-N-B, Si-C-N-B and Si-C-Al-N ceramic materials; the pyrolytic biological coke is preferred, and the pyrolytic biological coke at 800 ℃ is further preferred.

The component C is a substance with catalytic cracking activity, and comprises one or more of IA group metal salt, IIA group metal salt, IA group metal hydroxide, IIA group metal hydroxide, VIII group metal salt, VIII group metal oxide, IB group metal salt and IB group metal oxide, and specifically can be one or more of potassium carbonate, sodium carbonate, lithium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, iron oxide, nickel oxide, cobalt oxide and copper oxide, and preferably is potassium carbonate and nickel oxide, wherein the mass ratio of the potassium carbonate to the nickel oxide is 1-5: 1.

In the assistant for biomass microwave pyrolysis treatment, the content of the component A is 70wt% -90 wt%, the content of the component B is 5wt% -15 wt%, and the content of the component C is 5wt% -15 wt% based on the weight content of the assistant.

In a second aspect, the present invention provides a method for preparing the above assistant for biomass pyrolysis treatment, the method comprising the following steps:

(1) firstly, mixing the component A and the component B, and then pulping to obtain uniform viscous state slurry;

(2) and (2) mixing the slurry obtained in the step (1) with the component C for pulping treatment, and obtaining the biomass pyrolysis treatment auxiliary agent after treatment.

In the above method for preparing the assistant for biomass pyrolysis treatment, the pulping treatment can be carried out by any device capable of forming a slurry of solid and liquid phases, such as a grinder, and further preferably a ball mill.

In the preparation method of the auxiliary agent for biomass pyrolysis treatment, the pulping treatment temperature in the steps (1) and (2) is 15-40 ℃.

In the above method for preparing an assistant for biomass pyrolysis treatment, the third aspect of the present invention provides an application of the assistant for biomass pyrolysis treatment in a biomass pyrolysis gasification treatment process, where the pyrolysis gasification treatment process is as follows:

(1) mixing a biomass raw material and an auxiliary agent, and carrying out molding treatment to obtain a biomass reaction material;

(2) and (2) allowing the biomass reaction material obtained in the step (1) to enter a biomass pyrolysis reactor for reaction, and separating reaction products to obtain biomass synthesis gas and biological coke.

In the application of the assistant for biomass pyrolysis treatment in the biomass pyrolysis gasification treatment process, the biomass raw material and the assistant in the step (1) are mixed and formed as follows: mixing the biomass raw material with the auxiliary agent, uniformly mixing, and then carrying out hot press forming to obtain a formed biomass reaction material, wherein the maximum dimension of the material in the direction is not more than 40mm, and preferably 10-20 mm. Further preferably, the hot press molding conditions are as follows: the temperature is 60-120 ℃ and 20-50 kg/cm²Hot pressing for 1-10 min, heating to 150-180 deg.C, and 60-100 kg/cm²Carrying out hot pressing for 1-10 minutes under the condition, and then cooling for later use.

In the application of the auxiliary agent for biomass pyrolysis treatment in the biomass pyrolysis gasification treatment process, the mass ratio of the biomass raw material to the auxiliary agent is (4-20): 1.

in the application of the auxiliary agent for biomass pyrolysis treatment in the biomass pyrolysis gasification treatment process, the biomass raw material is any substance containing lignocellulose, and can be one or more of corn straw, rice hull, wheat straw, wood block, leaves and branches.

In the application of the assistant for biomass pyrolysis treatment in the biomass pyrolysis gasification treatment process, the assistant for biomass pyrolysis treatment in the step (1) is the assistant for biomass pyrolysis treatment.

The application of the auxiliary agent for biomass pyrolysis treatment in the biomass pyrolysis gasification treatment process comprises the step (2)The reaction temperature in the biomass pyrolysis reactor is 700-900 ℃, the reaction time is 10-30 minutes, the reaction is preferably carried out under the microwave condition, and the microwave power density is 1 multiplied by 10⁵～10×10⁵W/m³(ii) a Further preferably, the reaction is carried out in the presence of oxygen-containing gas with the reaction pressure of 0-0.6 MPa, wherein the oxygen-containing gas is one or more of oxygen, air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and flue gas, a mixed gas of oxygen and water vapor or a mixed gas of oxygen and inert gas, the volume fraction of the oxygen in the mixed gas is 10-40%, and the flow rate of the oxygen-containing gas is 0.01-0.1 m³/h。

In the application of the assistant for biomass pyrolysis treatment in the biomass pyrolysis gasification treatment process, the gas-solid separation in the step (2) is based on one or more of gravity settling, centrifugal separation, filter screen separation, electrostatic separation, adsorption separation and the like, but is not limited to the above modes, and specifically comprises one or more of cyclone separation, cloth bag filtration, electrostatic dust removal and filler adsorption separation.

Compared with the prior art, the auxiliary agent for biomass pyrolysis treatment, the preparation method and the application thereof have the following advantages:

1. the auxiliary agent for biomass pyrolysis treatment comprises a component A, a component B and a component C, wherein the component A in the auxiliary agent is carbonized due to poor thermal stability in the temperature rising process to form a carbon layer for removing tar generated in the pyrolysis process; the component B can regulate and control the carbonization process of the component A due to the adjustable microwave absorption performance of the component B, so that tar generated in the biomass pyrolysis process can be synchronously removed in situ in a carbon layer, and the outward release behavior of the tar is inhibited; the component C can promote the carbonization degree of the component A and inhibit the component A from generating new tar molecules due to the dual functions of catalytic carbonization and cracking, and is favorable for obtaining high-quality biomass synthesis gas products.

2. According to the biomass microwave pyrolysis gasification treatment method, a biomass reaction material suitable for microwave pyrolysis is obtained by adopting a biomass raw material and auxiliary agent hot press forming method, the hot press forming method is firstly carried out at a lower temperature and under a lower pressure, so that part of viscous-state auxiliary agent slowly permeates and moves outwards and gradually forms a coating layer on the surface of the biomass raw material, then the coating layer is polymerized at a higher temperature and under a higher pressure to form a compact coating layer, and meanwhile, the auxiliary agent dispersed inside is further fully contacted with the biomass material to form the biomass forming reaction material suitable for microwave pyrolysis.

3. The biomass microwave pyrolysis gasification treatment method provided by the invention utilizes the added auxiliary agent to gradually form a compact carbon layer on the surface of the material in the pyrolysis process to crack and remove tar and reformed gas, so that the quality of the biomass synthesis gas is improved. Compared with the conventional method for directly adding the microwave absorbent in the microwave pyrolysis process, the method for directly adding the microwave absorbent in the microwave pyrolysis process has the advantages that the distribution of a microwave field in the biomass heating process is not changed by adding the auxiliary agent, namely the added auxiliary agent does not obviously influence the microwave heating performance and the pyrolysis efficiency of the biomass, the bottleneck problems of reduced microwave absorption of the biomass and poor pyrolysis intensity caused by adding the conventional wave absorbent are effectively solved, and the heating advantage of the microwave body for pyrolysis when the biomass absorbs the microwave is ensured.

4. The additive added in the biomass microwave pyrolysis gasification treatment method can form a carbonized coating and synchronously crack and remove tar through optimized regulation and control during biomass pyrolysis, so that the aim of producing high-quality synthesis gas through pyrolysis and gasification in a one-stage microwave reactor is fulfilled, subsequent processes such as gas separation, purification and the like are greatly simplified, the addition of exogenous substances in the whole pyrolysis process is remarkably reduced, and better technical feasibility and economic performance are generally presented.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

Example 1

Taking 70 percent of component A1, 15 percent of component B1 and 15 percent of component C1 according to mass fraction, wherein the component A1 is plastic tar, the component B1 is SiC, and the component C1 is Ca (OH)₂. Components A1 and B1 were first ball milled at 40 ℃ at 200 rpm in a high speed ball millAnd then, obtaining uniform viscous state slurry, mixing the slurry with the component C1, and carrying out low-speed ball milling treatment at 15 ℃ at 80 rpm to obtain the auxiliary agent MWA1 for biomass microwave pyrolysis treatment.

Example 2

According to the mass fraction, 90% of component A2, 5% of component B2 and 5% of component C2 are taken, wherein component A2 is high-temperature coal tar, component B2 is SiN, and component C2 is KOH. Firstly, carrying out high-speed ball milling treatment on the components A2 and B2 at 15 ℃ at 200 rpm to obtain uniform viscous state slurry, then mixing the slurry with the component C2, and carrying out low-speed ball milling treatment at 40 ℃ at 80 rpm to obtain the auxiliary agent MWA2 for biomass microwave pyrolysis treatment.

Example 3

According to the mass fraction, 80% of component A3, 5% of component B3 and 15% of component C3 are taken, wherein the mass ratio of forest tar to seaweed tar in component A3 is 1:1, component B3 is pyrolytic biological coke, and the mass ratio of potassium carbonate to nickel oxide in component C3 is 1: 5. Firstly, carrying out high-speed ball milling treatment on the components A3 and B3 at 15 ℃ at 200 rpm to obtain uniform viscous state slurry, then mixing the slurry with the component C3, and carrying out low-speed ball milling treatment at 40 ℃ at 80 rpm to obtain the auxiliary agent MWA3 for biomass microwave pyrolysis treatment.

Example 4

According to the mass fraction, 82.35 percent of component A1 and 17.65 percent of component B1 are taken. Firstly, carrying out high-speed ball milling treatment on the components A1 and B1 at 40 ℃ at 200 r/min to obtain uniform viscous state slurry, and carrying out low-speed ball milling treatment at 15 ℃ at 80 r/min to obtain the auxiliary agent MWA4 for biomass microwave pyrolysis treatment.

Example 5

According to the mass fraction, 84.21 percent of component A2 and 15.79 percent of component C2 are taken. And (3) performing low-speed ball milling treatment on the components A2 and C2 at 40 ℃ at 80 rpm to obtain the assistant MWA5 for microwave pyrolysis treatment of the biomass.

Example 6

According to the mass fraction, 25 percent of component B3 and 75 percent of component C3 are taken. And (3) performing low-speed ball milling treatment on the components B3 and C3 at 40 ℃ at 80 rpm to obtain the auxiliary agent MWA6 for biomass microwave pyrolysis treatment.

Example 7

According to the mass percentage, 80 percent of biomass raw material and 20 percent of auxiliary agent MWA1 are mixed, and the mixture is evenly mixed at 60 ℃ and 20kg/cm²Hot pressing for 10 min, heating to 150 deg.C, and 60kg/cm²Hot pressing for 10 minutes under the condition, and cooling for later use to obtain a formed biomass reaction material MWM1 with the maximum direction size of 10 mm.

Example 8

According to the mass percentage, 95 percent of biomass raw material and 5 percent of auxiliary agent MWA2 are mixed, and are evenly mixed at 120 ℃ and 50kg/cm²Hot pressing for 1 min, heating to 180 deg.C, and 100kg/cm²And (3) carrying out hot pressing for 1 minute under the condition, and cooling for later use to obtain a formed biomass reaction material MWM2 with the maximum direction size of 20 mm.

Example 9

According to the mass percentage, 85 percent of biomass raw material and 15 percent of auxiliary agent MWA3 are mixed, and the mixture is evenly mixed at 100 ℃ and 30kg/cm²Hot pressing for 5 min, heating to 160 deg.C, and 100kg/cm²Hot pressing for 2 minutes under the condition, and cooling for later use to obtain a formed biomass reaction material MWM3 with the maximum direction size of 10 mm.

Example 10

According to the mass percentage, 85 percent of biomass raw material and 15 percent of auxiliary agent MWA3 are mixed, and the mixture is evenly mixed at 160 ℃ and 100kg/cm²Hot pressing for 7 minutes under the condition, and cooling for later use to obtain a molded biomass reaction material MWM3-1 with the maximum direction size of 10 mm.

Example 11

According to the mass percentage, 80 percent of biomass raw material and 20 percent of auxiliary agent MWA4 are mixed, and the mixture is evenly mixed at 60 ℃ and 20kg/cm²Hot pressing for 10 min, heating to 150 deg.C, and 60kg/cm²Hot pressing for 10 minutes under the condition, and cooling for later use to obtain a formed biomass reaction material MWM4 with the maximum direction size of 10 mm.

Example 12

According to the mass percentage, 95 percent of biomass raw material and 5 percent of auxiliary agent MWA5 are mixed, and are evenly mixed at 120 ℃ and 50kg/cm²Hot pressing for 1 min, heating to 180 deg.C and 100 deg.Ckg/cm²Hot pressing for 1 minute under the condition, and cooling for later use to obtain a molded biomass reaction material MWM5 with the maximum direction size of 10 mm.

Example 13

According to the mass percentage, 85 percent of biomass raw material and 15 percent of auxiliary agent MWA6 are mixed, and the mixture is evenly mixed at 100 ℃ and 30kg/cm²Hot pressing for 5 min, heating to 160 deg.C, and 100kg/cm²Hot pressing for 2 minutes under the condition, and cooling for later use to obtain a formed biomass reaction material MWM6 with the maximum direction size of 10 mm.

Example 14 (shaped Biomass reaction mass MWM 1)

The biomass reaction material MWM1 obtained by the molding treatment enters a biomass pyrolysis reactor, and the microwave power density is 1 multiplied by 10 at the reaction temperature of 700 DEG C⁵W/m³Air flow of 0.02m³Reaction is carried out under the conditions of 0.1MPa of reaction pressure and 30 minutes of reaction time to obtain a pyrolysis product of which the main part is gaseous product and a small amount of biological coke, wherein the gaseous product is subjected to gas-solid separation to obtain a biomass synthesis gas product, the yield of the synthesis gas is 1.11m³Perkg, syngas content 65%, H₂a/CO ratio of 1.74 and a tar content of 150mg/Nm³。

Example 15 (shaped Biomass reaction mass MWM 2)

The biomass reaction material MWM2 obtained by the molding treatment enters a biomass pyrolysis reactor, and the microwave power density is 10 multiplied by 10 at the reaction temperature of 900 DEG C⁵W/m³The oxygen flow rate was 0.04m³H, water vapor flow of 0.06m³The reaction is carried out under the conditions of 0.6MPa of reaction pressure and 10 minutes of reaction time to obtain a pyrolysis product of which the main part is gaseous product and a small amount of biological coke, wherein the gaseous product is subjected to gas-solid separation to obtain a biomass synthesis gas product, the yield of the synthesis gas is 1.86m³Perkg, syngas content 85%, H₂a/CO ratio of 1.47 and a tar content of 220mg/Nm³。

Example 16 (shaped Biomass reaction mass MWM 3)

The biomass reaction material MWM3 obtained by the molding treatment enters a biomass pyrolysis reactor at the reaction temperatureAt 900 deg.C and microwave power density of 10 × 10⁵W/m³Oxygen flow rate of 0.08m³H, water vapor flow rate of 0.08m³Reaction is carried out under the conditions of 0.2MPa of reaction pressure and 10 minutes of reaction time to obtain a pyrolysis product of which the main part is gaseous product and a small amount of biological coke, wherein the gaseous product is subjected to gas-solid separation to obtain a biomass synthesis gas product, the yield of the synthesis gas is 2.53m³Perkg, 90% syngas content, H₂a/CO ratio of 1.93 and a tar content of 50mg/Nm³。

Example 17 (shaped Biomass reaction mass MWM 3-1)

The biomass reaction material MWM3-1 obtained by molding treatment enters a biomass pyrolysis reactor, and the microwave power density is 10 multiplied by 10 at the reaction temperature of 900 DEG C⁵W/m³Oxygen flow rate of 0.08m³H, water vapor flow rate of 0.08m³Reaction is carried out under the conditions of 0.2MPa of reaction pressure and 10 minutes of reaction time to obtain a pyrolysis product of which the main part is gaseous product and a small amount of biological coke, wherein the gaseous product is subjected to gas-solid separation to obtain a biomass synthesis gas product, the yield of the synthesis gas is 2.35m³Perkg, syngas content 85%, H₂a/CO ratio of 1.82 and a tar content of 85mg/Nm³。

Example 18 (shaped Biomass reaction mass MWM 4)

The biomass reaction material MWM4 obtained by the molding treatment enters a biomass pyrolysis reactor, and the microwave power density is 1 multiplied by 10 at the reaction temperature of 700 DEG C⁵W/m³Air flow of 0.02m³Reaction is carried out under the conditions of 0.1MPa of reaction pressure and 30 minutes of reaction time to obtain a pyrolysis product of which the main part is gaseous product and a small amount of biological coke, wherein the gaseous product is subjected to gas-solid separation to obtain a biomass synthesis gas product, the yield of the synthesis gas is 0.87m³Per kg, syngas content 52%, H₂a/CO ratio of 1.22 and a tar content of 480mg/Nm³。

Example 19 (shaped Biomass reaction mass MWM 5)

The biomass reaction material MWM5 obtained by the molding treatment enters a biomass pyrolysis reactor, and the microwave power density is 10 multiplied by 10 at the reaction temperature of 900 DEG C⁵W/m³The oxygen flow rate was 0.04m³H, water vapor flow of 0.06m³The reaction is carried out under the conditions of 0.6MPa of reaction pressure and 10 minutes of reaction time to obtain a pyrolysis product of which the main part is gaseous product and a small amount of biological coke, wherein the gaseous product is subjected to gas-solid separation to obtain a biomass synthesis gas product, the yield of the synthesis gas is 1.62m³Per kg, syngas content 79%, H₂a/CO ratio of 1.38 and a tar content of 360mg/Nm³。

Example 20 (shaped Biomass reaction mass MWM 6)

The biomass reaction material MWM6 obtained by the molding treatment enters a biomass pyrolysis reactor, and the microwave power density is 10 multiplied by 10 at the reaction temperature of 900 DEG C⁵W/m³Oxygen flow rate of 0.08m³H, water vapor flow rate of 0.08m³Reaction is carried out under the conditions of 0.2MPa of reaction pressure and 10 minutes of reaction time to obtain a pyrolysis product of which the main part is gaseous product and a small amount of biological coke, wherein the gaseous product is subjected to gas-solid separation to obtain a biomass synthesis gas product, the yield of the synthesis gas is 2.22m³Perkg, syngas content 82%, H₂a/CO ratio of 1.75 and a tar content of 185mg/Nm³。

Comparative example 1 (without using an auxiliary for microwave pyrolysis of Biomass, comparative example 16)

The biomass raw material is processed at 100 ℃ and 30kg/cm²Hot pressing for 5 min, heating to 160 deg.C, and 100kg/cm²Hot pressing for 2 minutes under the condition, and cooling for later use to obtain the formed biomass raw material with the maximum dimension of 10mm in the direction. The biomass raw material obtained by the molding treatment enters a biomass pyrolysis reactor, and the microwave power density is 10 multiplied by 10 at the reaction temperature of 900 DEG C⁵W/m³Oxygen flow rate of 0.08m³H, water vapor flow rate of 0.08m³Reaction is carried out under the conditions of 0.2MPa of reaction pressure and 10 minutes of reaction time to obtain a pyrolysis product of which the main part is gaseous product and a small amount of biological coke, wherein the gaseous product is subjected to gas-solid separation to obtain a biomass synthesis gas product, the yield of the synthesis gas is 2.05m³Perkg, synthesis gas content 75%, H₂a/CO ratio of 1.28, a tar content of 2000mg/Nm³。

Comparative example 2 (direct microwave pyrolysis of Biomass bulk Material, comparison with example 16)

Directly feeding loose biomass raw material into a biomass pyrolysis reactor, and performing microwave power density of 10 multiplied by 10 at the reaction temperature of 900 DEG C⁵W/m³Oxygen flow rate of 0.08m³H, water vapor flow rate of 0.08m³Reaction is carried out under the conditions of 0.2MPa of reaction pressure and 10 minutes of reaction time to obtain a pyrolysis product of which the main part is gaseous product and a small amount of biological coke, wherein the gaseous product is subjected to gas-solid separation to obtain a biomass synthesis gas product, the yield of the synthesis gas is 1.99m³77% of synthesis gas/kg, H₂a/CO ratio of 1.33 and a tar content of 1800mg/Nm³。