阅读说明：本技术 一种湿生物质制取可燃性生物气的连续式反应系统 (A kind of wet biomass produces the continuous reaction system of flammable biogas ) 是由 徐东海 柳亮 郭树炜 王瀚 郝博天 于 2019-07-26 设计创作，主要内容包括：本发明公开了一种湿生物质制取可燃性生物气的连续式反应系统,包括进行水热液化反应与催化超临界水气化反应的两级连续式反应器,进行液化产物和超临界水气化产物各自分离的分离系统,以及水相产物的循环回收利用系统；水热液化预热器与水热液化反应器依次连接在反应系统的进料口,并与液化产物的分离系统相连；超临界水气化预热器与超临界水气化反应器依次连接在液化水相产物的出口,并与气化产物的分离系统相连；水相产物的循环回收利用系统经由气化反应后分离水相产物后的出口与超临界水气化反应的进料口相连,储存在气化储液箱内的残余水相,经水相高压泵泵入到超临界水气化反应系统中,达到水相中有机质的循环利用。(The invention discloses the continuous reaction systems that a kind of wet biomass produces flammable biogas, two-stage flow reactor including carrying out hydrothermal liquefaction reaction and catalysis and supercritical water gasification reaction, carry out the recycling system of liquefaction products and individually separated separation system and the water-phase product of supercritical water gasification product；Hydrothermal liquefaction preheater and hydrothermal liquefaction reactor are connected to the feed inlet of reaction system in turn, and are connected with the separation system of liquefaction products；Supercritical water gasification preheater and supercritical water gasification reactor are connected to the outlet of liquefaction water-phase product in turn, and are connected with the separation system of gasification product；The recycling system of water-phase product is connected via the feed inlet that the outlet after separating water-phase product after gasification reaction is reacted with supercritical water gasification, the remaining water phase being stored in gasification liquid reserve tank, it is pumped into supercritical water gasification reaction system through water phase high pressure, reaches recycling for organic matter in water phase.)

1. the continuous reaction system that a kind of wet biomass produces flammable biogas, which is characterized in that including two-stage continous way Reaction member, liquefaction products separative unit, gasification product separative unit and water-phase product recycling unit；Two cascades Continuous formula reaction member is made of hydrothermal liquefaction reaction member and supercritical water gasification reaction member；

The hydrothermal liquefaction reaction member, including the hydrothermal liquefaction preheater (3) and hydrothermal liquefaction reactor being connected by pipeline (4)；The supercritical water gasification reaction member, including the supercritical water gasification preheater (23) and overcritical being connected by pipeline Water reactor (22)；

Wet biomass enters hydrothermal liquefaction preheater (3) by feed inlet, enters hydrothermal liquefaction reactor (4) after preheated processing Hydrothermal liquefaction reaction is carried out, the product after reaction enters the processing of liquefaction products separative unit；The water phase of liquefaction products separative unit Product exit end is connected with the arrival end of supercritical water gasification preheater (23), the outlet end of supercritical water gasification preheater (23) It is connected with gasification product separative unit；Water-phase product recycling unit separates the outlet of water-phase product via gasification reaction It is connected with the feed inlet of supercritical water gasification reaction member, the remaining water phase of storage, which can be passed through to supercritical water gasification, reacts single It is recycled in member.

2. the continuous reaction system that wet biomass according to claim 1 produces flammable biogas, which is characterized in that Hydrothermal liquefaction preheater (3) outlet is connected with hydrothermal liquefaction reactor (4) entrance, hydrothermal liquefaction reactor (4) outlet warp Hydrothermal liquefaction preheater (3) is connected with liquefaction products separative unit；Supercritical water gasification preheater (23) outlet is faced with super Boundary's water reactor (22) entrance is connected, and supercritical water gasification reactor (22) is exported through supercritical water gasification preheater (23) It is connected with gasification product separative unit；Liquid can be separately recovered in hydrothermal liquefaction preheater (3), supercritical water gasification preheater (23) Waste heat after changing reaction, gasification reaction.

3. the continuous reaction system that wet biomass according to claim 1 produces flammable biogas, which is characterized in that Liquefaction products separative unit includes solid-liquid separator (29), liquefaction gas-liquid separator (28), the first centrifuge (26)；It is separated by solid-liquid separation The entrance of device (29) is connected through liquefaction counterbalance valve (30) with the outlet of hydrothermal liquefaction preheater (3), and solid-liquid separator (29) goes out Mouth one end is connect with dreg-storing box (27), and the other end is connected with liquefaction gas-liquid separator (28), and liquefaction gas-liquid separator (28) goes out Mouth one end connects the first centrifuge (26) by the first supercharger (6) connection storage cylinder (7), the other end.

4. the continuous reaction system that wet biomass according to claim 3 produces flammable biogas, which is characterized in that Oil-phase product and water-phase product after the first centrifuge (26) centrifugation are high by liquefaction oil high-pressure pump (5) and liquefaction water respectively Press pump (25) pump is into oil storage tank (8) and liquefaction liquid reserve tank (24).

5. the continuous reaction system that wet biomass according to claim 3 produces flammable biogas, which is characterized in that Gasification product separative unit includes gasification gas-liquid separator (19), the second centrifuge (17) and shielded box (11)；Overcritical aqueous vapor Change preheater (23) and is connected through gasification counterbalance valve (21) with gasification gas-liquid separator (19), gasification gas-liquid separator (19) one end warp Shielded box (11) is connect with fuel gas storage cylinder (13), and the other end is connected with the second centrifuge (17).

6. the continuous reaction system that wet biomass according to claim 5 produces flammable biogas, which is characterized in that It further include the solvent pipe being connected with the second centrifuge (17), solvent pipe is equipped with connected solvent high-pressure pump (18) and fluid Contact tower (10) is loaded with the solvent for extracting the tar phase after gasification in water phase in fluid contacting column (10)；Second centrifugation After destilling tower (16), the tar of generation is mutually placed in tar storage bin (14) for one end of machine (17), the other end and gasification liquid storage Case (15) connection.

7. the continuous reaction system that wet biomass according to claim 6 produces flammable biogas, which is characterized in that Derivative liquid phase in gasification liquid reserve tank (15) is pumped into super face through water phase high pressure pump (9) by water-phase product recycling unit Continue the utilization of remnant organic matter in the water reaction member in boundary.

8. the continuous reaction system that wet biomass described according to claim 1~any one of 7 produces flammable biogas System, which is characterized in that further include body feed tank (1), the wet biomass stored in body feed tank (1) is pumped into hydro-thermal by high-pressure pump (2) In liquefaction preheater (3).

9. the continuous reaction system that wet biomass described according to claim 1~any one of 7 produces flammable biogas System, which is characterized in that supercritical water gasification inside reactor loads the catalyst wall (20) containing catalyst.

Technical field

The invention belongs to biomass energy technology field, it is related to the preparation system of a kind of bio oil, flammable biogas, especially It is the continuous reaction system that a kind of wet biomass produces flammable biogas.

Background technique

Consuming excessively for fossil fuel causes the energy securities problem such as atmosphere pollution and greenhouse effects and fuel reserve to cause Biomass energy is set to be mined and utilize extensively.Biomass energy can pass through biochemistry as a kind of reproducible clean energy resource Method and thermochemical method are converted into Novel clean liquid fuel (such as biodiesel, bio-crude oil), can be realized carbon using process Closed circulation, control CO₂Discharge to reduce greenhouse effects, for high efficiency of energy utilize and alleviate energy shortages have it is very big It is promoted.Biomass contains protein, unsaturated fatty acid and other physiological activators, bioavailable efficiency and oil-producing efficiency It is higher, it can also grow up in extreme environment, have good adsorption effect and decomposition to heavy metal ion, as subsequent deposit Fuel has extensive development prospect and prospect of the application.

Hydrothermal liquefaction technology (HTL) refers to using thermochemical method, under the action of with or without catalyst, subcritical Condition (280~350 DEG C, 5~20MPa) hot pressing continues 5~60 minutes processes for being converted into liquid phase biology oil product in shrinking.It is wet Biomass HTL is that one kind has promising liquefaction technology very much, has many advantages.Firstly, HTL not only can be by wet biomass In grease be converted to bio-oil, the protein that can be also contained to greatest extent, glucide, lignin and cellulose It is converted to the bio-oil of high heating value.Secondly, the thermochemical study technology (as gasified and being pyrolyzed) that comparison is traditional, wet biomass Undried raw material can be directly converted into the bio-oil of energy-intensive by HTL, so as to avoid needed for drying process High energy, therefore there is higher capacity usage ratio.Again, HTL can promote as nitrogen, phosphorus, iron, calcium, magnesium, potassium and other The recycling of nutriment needed for the separation of the nutrients such as minerals and polar organic compound and wet biomass growth.It is super Critical gasification technology (SCWG) is that one kind is hopeful to convert high-moisture biomass or waste water slurry to biology base synthesis very much The promising technology of natural gas, typical gas include the C of methane, hydrogen, carbon dioxide, carbon monoxide and low concentration₂-C₃ Gas.Hydrogen can be widely applied to commercially producing for fuel cell, gas renormalizing and a large amount of ammonia synthesis, other combustibility gas Volumetric combustion also can produce heat.

For the application study of wet biomass, most of is all that single-stage (catalysis) liquefaction is carried out using single reaction vessel Reaction, and reaction of high order system can be attempted to improve an important trend of technology after being.Using molten after hydrothermal liquefaction Agent extracts available bio-crude oil, but in large-scale continuous production, addition this method of solvent can improve it is economical at This is simultaneously polluted the environment.Contain remaining organic matter and alkyl-substituted cricoid nitrogenous in water-phase product after liquefaction With oxygen containing compound, direct emission will also result in the loss and environmental pollution of organic matter.

Therefore, to the scale application of realization wet biomass processing technique, it is also necessary to solve following problems:

Firstly, while guaranteeing to improve quality of bio-oil obtained by reaction as much as possible, reduce the operation of reaction system at Sheet and Energy in use, improve the utilization efficiency of energy；Secondly, the water phase still organic matter containing high-content and nutrition after liquefaction Substance distributes the resource utilization that water-phase product realizes reaction raw materials, effectively to improve the ecological environment.Do not have both at home and abroad at present About the research for the multilevel device that wet biomass liquefaction is coupled with catalysis supercritical gasification, existing reaction unit is also generally deposited It is higher in system energy consumption, the problems such as separation of product is not thorough, and the quality of oily phase is low.

Summary of the invention

In order to overcome the disadvantages of the above prior art, flammable biogas is produced the purpose of the present invention is to provide a kind of Continuous reaction system, the system structure design is reasonable, can effectively solve the problem that times of water-phase product after wet biomass hydrothermal liquefaction The problem that meaning is discharged, the loss of organic matter and oil-phase product quality are low.

In order to achieve the above object, the present invention is achieved by the following scheme:

The invention discloses the continuous reaction system that a kind of wet biomass produces flammable biogas, including two-stage are continuous Formula reaction member, liquefaction products separative unit, gasification product separative unit and water-phase product recycling unit；Two-stage Continuous reaction unit is made of hydrothermal liquefaction reaction member and supercritical water gasification reaction member；

The hydrothermal liquefaction reaction member is reacted including the hydrothermal liquefaction preheater being connected by pipeline and hydrothermal liquefaction Device；The supercritical water gasification reaction member, including the supercritical water gasification preheater being connected by pipeline and overcritical aqueous vapor Change reactor；

Wet biomass enters hydrothermal liquefaction preheater by feed inlet, after preheated processing enter hydrothermal liquefaction reactor into The reaction of row hydrothermal liquefaction, the product after reaction enter the processing of liquefaction products separative unit；The water phase of liquefaction products separative unit produces Object outlet end is connected with the arrival end of supercritical water gasification preheater, the outlet end of supercritical water gasification preheater and gasification product Separative unit is connected；Outlet and supercritical water of the water-phase product recycling unit via gasification reaction separation water-phase product The feed inlet of gasification reaction unit is connected, and the remaining water phase of storage, which can be passed through into supercritical water gasification reaction member, to be followed Ring utilizes.

Preferably, the hydrothermal liquefaction preheater outlet is connected with hydrothermal liquefaction reactor inlet, hydrothermal liquefaction reactor Outlet is connected through hydrothermal liquefaction preheater with liquefaction products separative unit；Supercritical water gasification preheater outlet with it is overcritical Water reactor inlet is connected, and supercritical water gasification reactor outlet is separated through supercritical water gasification preheater with gasification product Unit is connected；Hydrothermal liquefaction preheater, supercritical water gasification preheater can be separately recovered remaining after liquefaction reaction, gasification reaction Heat.High temperature and high pressure flow after two kinds of reactions is known from experience carrying heat and is preheated to the raw material in preheater, thus recovery waste heat.

Preferably, liquefaction products separative unit includes solid-liquid separator, liquefaction gas-liquid separator, the first centrifuge；

The entrance of solid-liquid separator is connected through liquefaction counterbalance valve with the outlet of hydrothermal liquefaction preheater, and solid-liquid separator goes out Mouthful one end connect with dreg-storing box, and the other end is connected with the gas-liquid separator that liquefies, and the exit end for the gas-liquid separator that liquefies passes through the One supercharger connects storage cylinder, and the other end connects the first centrifuge.

It is further preferred that oil-phase product and water-phase product after the centrifugation of the first centrifuge, pass through liquefaction oil height respectively Press pump and liquefaction high-pressure water pump are pumped into oil storage tank and liquefaction liquid reserve tank.

It is further preferred that gasification product separative unit includes gasification gas-liquid separator, the second centrifuge and shielded box；It is super Critical water preheater is connected through gasification counterbalance valve with gasification gas-liquid separator, gas-liquid separator one end of gasifying through shielded box and The connection of fuel gas storage cylinder, the other end are connected with the second centrifuge.

It is further preferred that further including the solvent pipe being connected with the second centrifuge, solvent pipe is molten equipped with what is be connected Agent high-pressure pump and fluid contacting column are loaded with the solvent for extracting the tar phase after gasification in water phase in fluid contacting column；The After destilling tower, the tar of generation is mutually placed in tar storage bin for one end of two centrifuges, and the other end is connect with gasification liquid reserve tank.

It is further preferred that water-phase product recycling unit is by the derivative liquid phase in the liquid reserve tank that gasifies through water phase height Press pump is pumped into the utilization for continuing remnant organic matter in supercritical water gasification reaction member.

It preferably, further include body feed tank, the wet biomass stored in body feed tank is pumped into hydrothermal liquefaction by high-pressure pump and preheats In device.

Preferably, supercritical water gasification inside reactor loads the catalyst wall containing catalyst

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

The present invention reacts the two stages continous way being coupled with catalysis and supercritical water gasification reaction by setting hydrothermal liquefaction Reaction member, synchronize realize wet biomass produce high-quality biological oil and liquefaction water-phase product through gasification produce flammable biogas Process, the water phase after gasification participates in catalysis and supercritical water gasification process again through recirculation system and realizes organic matter Recycle.It is provided with preheater in two-stage continuous reaction unit, the waste heat after can recycling reaction reduces The whole energy consumption of entire reaction system.In addition, the comprehensive use of liquefaction products separative unit and gasification product separative unit can be with Realize that oily phase, burnt oil-phase product are completely separated.The extraction and separation of bio oil are without solvent extraction process, only centrifugation behaviour Make, the effect of the fluid contacting column of this system is exactly that the simple extraction for tar phase after gasification provides organic solvent, final to steam Hair falls solvent to recycle tar phase, therefore the resulting oil-phase product quality of the present invention is high.At other wet biomass Reason system, present system raw material fully reacting, thoroughly, oily phase quality is high for product separation, and realizing has in liquefaction water-phase product The recycling of machine matter and producing for flammable biogas can be widely applied to wet biomass processing.

Detailed description of the invention

Fig. 1 is the schematic diagram of reaction system of the present invention.

In figure: 1, material storing box；2, high-pressure pump；3, hydrothermal liquefaction preheater；4, hydrothermal liquefaction reactor；5, liquefaction oil high pressure Pump；6, the first supercharger；7, storage cylinder；8, oil storage tank；9, water phase high pressure pumps；10, fluid contacting column；11, shielded box；12, Two superchargers；13, fuel gas storage cylinder；14, tar storage bin；15, gasify liquid reserve tank；16, destilling tower；17, the second centrifugation Machine；18, solvent high-pressure pump；19, gasify gas-liquid separator；20, catalyst wall；21, gasify counterbalance valve；22, supercritical water gasification Reactor；23, supercritical water gasification preheater；24, liquefy liquid reserve tank；25, liquefy high-pressure water pump；26, the first centrifuge；27, Dreg-storing box；28, liquefy gas-liquid separator；29, solid-liquid separator；30, liquefy counterbalance valve.

Specific embodiment

In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work It encloses.

It should be noted that description and claims of this specification and term " first " in above-mentioned attached drawing, " Two " etc. be to be used to distinguish similar objects, without being used to describe a particular order or precedence order.It should be understood that using in this way Data be interchangeable under appropriate circumstances, so as to the embodiment of the present invention described herein can in addition to illustrating herein or Sequence other than those of description is implemented.In addition, term " includes " and " having " and their any deformation, it is intended that cover Cover it is non-exclusive include, for example, the process, method, system, product or equipment for containing a series of steps or units are not necessarily limited to Step or unit those of is clearly listed, but may include be not clearly listed or for these process, methods, product Or other step or units that equipment is intrinsic.

The invention will be described in further detail with reference to the accompanying drawing:

Referring to Fig. 1, the present invention provides the continuous reaction systems that a kind of wet biomass produces flammable biogas, including Two-stage preheater, respectively hydrothermal liquefaction preheater 3 and supercritical water gasification preheater 23, the hydrothermal liquefaction reaction of first stage The supercritical water gasification reactor 22 of device 4 and second stage, liquefaction products separative unit, gasification product separative unit and water phase Product circulation recycles unit.Two stage preheater is connected with corresponding reactor, liquefied and gasification process after it is anti- It answers waste heat to can be used for preheater heating, reduces unnecessary energy loss.

Further, it is mounted with catalyst wall 20 in supercritical water gasification reactor 22, promotes supercritical water gasification reaction Progress.

The liquefaction products separative unit includes solid-liquid separator 29, liquefy gas-liquid separator 28 and the first centrifuge 26, Hydrothermal liquefaction preheater 3 is connect through liquefaction counterbalance valve 30 with solid-liquid separator 29,29 one end of solid-liquid separator and liquefaction gas-liquid point It is connected from device 28, the other end connects dreg-storing box 27.Liquefaction 28 the first supercharger of one end 6 of gas-liquid separator is connect with storage cylinder 7, The other end is connect with the first centrifuge 26.One end of first centrifuge 26 is connect through liquefaction oil high-pressure pump 5 with oil storage tank 8, another End is connect through liquefaction high-pressure water pump 25 with liquefaction liquid reserve tank 24.

The separation system of the gasification product includes gasification gas-liquid separator 19, fluid contacting column 10, the second centrifuge 17 With destilling tower 16, the preheater 23 that gasifies is connect through gasification counterbalance valve 21 with gasification gas-liquid separator 19, and gasify gas-liquid separator 19 One end is connect through shielded box 11 with fuel gas storage cylinder 13, sodium hydrate solid particle is covered in shielded box 11, for absorbing Carbon dioxide in gas.The other end and solvent pipe of gasification gas-liquid separator 19 are connected to the second centrifuge 17.Solvent is used Tar phase after extraction gasification in water phase, pumps out solvent phase through solvent high-pressure pump 18 from fluid contacting column 10.Second centrifugation After destilling tower 16, the tar of generation is mutually placed in tar storage bin 14 for one end of machine 17, and the other end and gasification liquid reserve tank 15 connect It connects.

The water-phase product recycling unit passes through the derivative liquid phase recycled in gasification liquid reserve tank 15 after gasification Water phase high pressure pump 9 is pumped into supercritical water gasification reaction member, is continued the utilization of remnant organic matter, is reached wet biomass The recycling and recycling of organic principle.

The wet biomass of certain useful load is pumped into hydrothermal liquefaction preheater 3 through high-pressure pump 2 in body feed tank 1, is completed pre- It is entered after heat in hydrothermal liquefaction reactor 4, after the completion of hydrothermal liquefaction process, product reduces loine pressure through liquefaction counterbalance valve 30 Afterwards, it is filtered through solid-liquid separator 29, solid product is stored in dreg-storing box 27, and gas phase and liquid product are through the gas-liquid separator that liquefies After 28, gas-phase product is collected through the first supercharger 6 to storage cylinder 7, and liquid product is separated into water phase after the first centrifuge 26 With oily phase, oil is mutually pumped into oil storage tank 8 through liquefaction oil high-pressure pump 5, and aqueous phase by-product is pumped into liquid through liquefaction high-pressure water pump 25 Change in liquid reserve tank 24, continues the catalysis and supercritical water gasification reaction of second stage.Water-phase product enters the overcritical of second stage In water preheater 23, completes to enter in supercritical water gasification reactor 22 after preheating and complete gasification reaction, carried on the back through gasification After pressure valve 21 reduces loine pressure, mix products are gasified after gas-liquid separator 19, and gas-phase product passes through solid containing sodium hydroxide After the shielded box 11 of body, carbon dioxide gas is absorbed, and flammable biogas is pumped into fuel gas through the second supercharger 12 and stores up In gas cylinder 13.Water-phase product passes through the solvent mixing pumped out from fluid contacting column 10, after extraction after the separation of the second centrifuge 17, Solvent is mutually after the distillation of destilling tower 16, and obtained tar is mutually saved to tar storage bin 14, the water-phase product separated after gasification It saves to gasification liquid reserve tank 14.Still organic matter containing part in water phase after gasification is pumped into overcritical through water phase high pressure pump 9 In water reaction member, continue the gasification of subsequent organic matter.

In conclusion the advantage that wet biomass of the invention produces the continuous reaction system of flammable biogas is summarized such as Under:

1, two stages preheater is coupled with two stages reactor, the oily phase of hydrothermal liquefaction realization of first stage wet biomass, The separation of solid phase and aqueous phase by-product obtains the bio-crude oil of high-quality without solvent extraction, second stage water-phase product The recycling of water-soluble organic matter and producing for flammable biogas, two stages coupling technique are realized in catalysis and supercritical water gasification Realize the resource utilization of wet biomass.

2, still there are also part organic matters in the water phase collected after catalysis and supercritical water gasification, again through recirculation system It is transferred in supercritical water gasification system, continues the cycle gasification process for realizing organic matter, it is ensured that the organic matter in wet biomass Without loss.

3, the comprehensive use of solid-liquid separator, gas-liquid separator and two-stage centrifugal machine makes reaction product separation thoroughly, obtains The tar of the bio oil of higher quality, flammable biogas and extraction phase.

The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention Protection scope within.