CN107151560B - A kind of lignin separation and steam cracking system and method - Google Patents
A kind of lignin separation and steam cracking system and method Download PDFInfo
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- CN107151560B CN107151560B CN201710444589.8A CN201710444589A CN107151560B CN 107151560 B CN107151560 B CN 107151560B CN 201710444589 A CN201710444589 A CN 201710444589A CN 107151560 B CN107151560 B CN 107151560B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
Abstract
The present invention relates to agricultural fossil datas to utilize technical field, disclose a kind of lignin separation and steam cracking system and method, including sequentially connected cooking reaction kettle, preheating device, radiation cleavage device, quenching apparatus and recovery processing mechanism, lignin is isolated from lignocellulose raw material using lye, and using steam as oxidant after cracking lignin, bio oil and biological flue gas are generated by hydrogenation reaction, residue enzymatic saccharification rich in cellulose and hemicellulose is high-efficient, and equipment is simple, whole system operating temperature is lower, cracking process is stablized, it is simple for process, it is environment-friendly and low-toxicity, the lignin extraction rate of recovery is high, holocellulose saccharification efficiency is high, it is easily industrialized.
Description
Technical field
The present invention relates to agricultural fossil datas to utilize technical field, more particularly to a kind of lignin separation and steam cracking
System and method.
Background technique
The energy and environmental crisis are one of the major obstacles that 21 century human social is faced.Utilize the earth
On most abundant, most cheap renewable lignocellulose raw material produce biomass fuel and biobased products are to solve above-mentioned obstacle
One of effective way.
Cellulose accounts for 35%~45% in lignocellulose raw material, and hemicellulose accounts for 20%~40%, and lignin accounts for 20%~
30%.Cellulose and hemicellulose can prepare a series of sugared platform chemicals, including bio-ethanol, biological fourth through hydrolysis and saccharification
Chemicals such as the liquid fuels such as alcohol and furfural, xylitol etc., cellulose can also prepare functional fiber cellulosic material.As natural
Although the lignin of high molecular material also has higher utility value, for lignin product also up to several hundred kinds, lignin is sharp
Also it is far from making full use of with situation.
Carrying out gasification technology to biomass such as lignocellulose raw materials is a kind of the new of the comprehensive energy utilization occurred 21 century
Technology.Existing biomass gasification technology mainly includes techniques and the equipment such as fixed bed gasification, fluidized gasification, two-part gas
Deng.Implement thermal reforming or steam reformation further after biomass can also be carried out to thermal cracking to manufacture the mode of high heat gas
Carry out gasifying electricity generation.Existing gasification, cracking technique are to be directed to lignocellulose raw material generally speaking mostly at present, and there is no separate
Out cellulose, hemicellulose and lignin and studied respectively.Cellulose and hemicellulose have except non-vaporized cracking
More extensive application prospect, and many application technologies are mature or close to mature industry.And lignin is because of complicated component,
Its product and utilization are mostly also in starting conceptual phase.Therefore, the direct gas of the lignocellulose raw material containing holocellulose is utilized
Change, the limitation of Study on Cleavage are extremely limited, and do not give full play to biomass material advantage and be used.
There is also following deficiencies for biomass direct gasification technique at present: due to material composition complexity, calorific value is extremely unstable,
The running temperature of gasification furnace is difficult to control；When using air as oxidant, nitrogen content is excessively high and leads to available gas and calorific value
It is relatively low；It can gasify containing alkali metal oxides such as a large amount of K, Na when temperature is higher than 800 DEG C in biomass and mix in gasification
In product, gaseous mass not only will affect, can be also adhered in equipment and pipeline together with tar and cause seriously corroded.Cracking
A large amount of cleaved fragment free radical can be generated in the process and cause lytic activity very high, it is extremely unstable, it is necessary to be protected from light, avoid with
Air contact saves.
In view of the drawbacks of the prior art, it is isolated in this application provides a kind of slave lignocellulose raw material with universality
Lignin and the method for being subject to steam cracking.
Summary of the invention
(1) technical problems to be solved
The object of the present invention is to provide a kind of lignin separation and steam cracking system and method, solve in the prior art
Gasification furnace is difficult to control, and calorific value is low, and product quality is low, and equipment is easily damaged, the unstable defect of cracking process.
(2) technical solution
In order to solve the above technical problem, the present invention provides a kind of lignin separations and steam cracking system, feature to exist
In, comprising:
Cooking reaction kettle is equipped with lignocellulose raw material feeding inlet, holocellulose discharge port, lignin mixture boiling outlet
With lye feeding inlet, the holocellulose discharge port is connect with holocellulose collector；
Preheating device is equipped with lignin mixture preheating entrance, hydrogen inlet, the second steam entry, hydrogen water and steams
Gas mixed export and lignin mixture preheating outlet, the lignin mixture preheating entrance and the lignin mixture steam
Mouth connection is cooked, the lignin mixture for being fed into heats vaporization, and hydrogen and vapor pass through the hydrogen inlet respectively
It is passed through the preheating device preheating with the second steam entry, forms the vapor stream of hydrogen, and mixed by hydrogen vapor
Outlet discharge；
Radiation cleavage device comprising lignin mixture radiation cleavage entrance and lignin mixture radial shake solve
Mouthful, the radiation cleavage entrance and lignin mixture boiling outlet connect, and the hydrogen vapor mixed export is in institute
It states and is connect inside radiation cleavage device with the neighbouring lignin mixture radiation cleavage exit；
Quenching apparatus, including chilling feeding inlet, gas discharge mouth and solid-liquid discharge port, the chilling feeding inlet and the wood
Quality mixture radiation cleavage outlet connection；
It is recycled mechanism, is connect with the gas discharge mouth and solid-liquid discharge port, it is after cooling for recycling and separating
Product.
Wherein, the recovery processing mechanism includes gas cleaning plant and solid-liquid separation column, the gas discharge mouth and institute
The entrance connection of gas cleaning plant is stated, the solid-liquid discharge port is connect with the entrance of the solid-liquid separation column, and the gas is net
Disguise the outlet set to connect with gas receiver, the outlet of the solid-liquid separation column is also connect with oil storage tank and with solid calcining furnace respectively
Tail gas absorber connection.
Wherein, the recovery processing mechanism further includes soda recovery unit and alkali storage tank, the soda recovery unit difference
It is connect with the alkali storage tank and solid calcining furnace, the alkali storage tank is connect with lye feeding inlet, for recycling circulation
Use alkali.
Wherein, the recovery processing mechanism further includes Steam Recovery heat exchanger, Steam Recovery heat exchanger be equipped with first entrance,
First outlet, second entrance and second outlet, the cooking reaction kettle is additionally provided with the first steam outlet and the first vapor enters
Mouthful, first steam outlet connect with the first entrance, and first outlet passes through pipeline across the preheating device and the
The connection of one steam entry, is recycled steam；The second entrance and second outlet are connect with the quenching apparatus respectively, are followed
Ring uses high steam.
It wherein, further include sequentially connected belt conveyor, feed hopper and screw feeding machine, the screw feeding machine and institute
State the connection of lignocellulose raw material feeding inlet.
Invention additionally discloses a kind of lignin separation and steam cracking methods characterized by comprising
Lignin fibre raw material is passed through by the lignocellulose raw material feeding inlet of cooking reaction kettle, and lye is led to by lye feeding inlet
Enter, isolates holocellulose by holocellulose discharge port and be expelled to the collection of holocellulose collector, the lignin mixture of extraction
It exports discharge by lignin mixture boiling and preheating device is passed through by lignin mixture preheating entrance and carry out heating vapour
Change；
After hydrogen and vapor are preheated by preheating device, the vapor stream of hydrogen is formed；
Lignin mixture after heating vaporization carries out preliminary cracking reaction by radiation cleavage device, is tentatively cracked
Product；
Preliminary pyrolysis product and the vapor stream of hydrogen are mixed in neighbouring lignin mixture radiation cleavage exit
Hydrocracking reaction is carried out, and product after reaction is passed through refrigerated separation in quenching apparatus；
Product after quenching apparatus refrigerated separation is by recovery processing organizational separation and recycling.
Wherein, the product after quenching apparatus refrigerated separation is by recovery processing organizational separation and recycling including the use of gas
Body purification device purification gas, and collected by gas receiver；Liquid after being separated using solid-liquid separation column is by oil storage tank, after separation
The gas that solid is generated through solid calcining furnace is passed through tail gas absorber.
Wherein, the solid generated through solid calcining furnace is passed through soda recovery unit recycling, then is passed through the storage of lye feeding inlet
It deposits.
It wherein, further include Steam Recovery heat exchanger, the steam being discharged by cooking reaction kettle is exchanged heat by the Steam Recovery
One circuit of device, and with after heat transferring medium heat exchange, preheating device is passed through as heat medium, is returned again to cooking reaction kettle, is followed
Ring uses steam；The high steam of quenching apparatus discharge is passed through another circuit of Steam Recovery heat exchanger, returns to quenching apparatus,
High steam is recycled.
Wherein, it is 5%~25% that the caustic dosage in cooking reaction kettle, which is lignocellulose raw material weight,；The hydrogen
It is 0.1%~2% that hydrogen, which accounts for the weight ratio of vapor, in vapor stream；The weight ratio of hydrogen and preliminary pyrolysis product is 0.1~
1.5%；Temperature after lignin mixture heats in preheating device is 120~300 DEG C, and the vapor stream of hydrogen is preheating
Temperature in device after preheating is 560~660 DEG C；Temperature is 560~660 DEG C at radiation cleavage device portal, radiation cleavage dress
Setting outlet temperature is 770~850 DEG C.
(3) beneficial effect
A kind of lignin separation and steam cracking system and method provided by the invention, have the advantages that
1, lignin is isolated from lignocellulose raw material using lye, and using steam as oxidant after cracking lignin,
Bio oil and biological flue gas are generated by hydrogenation reaction, the residue enzymatic saccharification rich in cellulose and hemicellulose is high-efficient, and
Equipment is simple, and whole system operating temperature is lower, and cracking process is stablized, simple for process, environment-friendly and low-toxicity, and lignin extraction is returned
High income, holocellulose saccharification efficiency are high, it is easy to accomplish industrialization；
2, air-liquid and solid product are subjected to initial gross separation recycling, reduce the pollution to environment；
3, after by the steam of cooking reaction kettle by Steam Recovery heat exchanger and heat transferring medium heat exchange heating, it is passed through pre- hot charging
It sets as heat transferring medium, after hydrogen, steam heating and lignin preheating, returns again to cooking reaction kettle, realize steam circulation benefit
With；The high steam of quenching apparatus discharge also returns again to after Steam Recovery heat exchanger, and high steam is recycled；
4, the alkali collection in product is utilized using solid calcining furnace and soda recovery unit.
Detailed description of the invention
Fig. 1 is the schematic diagram of a kind of lignin separation of the present invention and steam cracking system；
Fig. 2 is the flow chart of a kind of lignin separation of the present invention and steam cracking method；
In figure, 1, belt conveyor；2, feed hopper；3, screw feeding machine；4, cooking reaction kettle；5, holocellulose is collected
Device；6, hydrogen inlet；7, the second steam entry；8, air blower；9, preheating device；10, radiation cleavage device；11, chilling fills
It sets；12, gas cleaning plant；13, gas receiver；14, solid-liquid separation column；15, oil storage tank；16, tail gas absorber；17, alkali collection
Device；18, solid calcining furnace；19, Steam Recovery heat exchanger；20, admission port；21, alkali storage tank；22, infusion pump.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Following instance
For illustrating the present invention, but it is not intended to limit the scope of the invention.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；It can
To be mechanical connection, it is also possible to be electrically connected；It can be directly connected, can also can be indirectly connected through an intermediary
Connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood at this with concrete condition
Concrete meaning in invention.
As shown in Figure 1, the present invention discloses a kind of lignin separation and steam cracking system, comprising: cooking reaction kettle 4, if
There are lignocellulose raw material feeding inlet, holocellulose discharge port, lignin mixture boiling outlet and lye feeding inlet, the comprehensive fibre
Plain discharge port is tieed up to connect with holocellulose collector 5；
Preheating device 9 is equipped with lignin mixture preheating entrance, hydrogen inlet, the second steam entry, hydrogen water and steams
Gas mixed export and lignin mixture preheating outlet, the lignin mixture preheating entrance and the lignin mixture steam
Mouth connection is cooked, the lignin mixture for being fed into heats vaporization, and hydrogen and vapor pass through the hydrogen inlet respectively
The preheating device 9 is passed through with the second steam entry to preheat, and forms the vapor stream of hydrogen, and mixed by hydrogen vapor
Outlet discharge；
Radiation cleavage device 10 comprising lignin mixture radiation cleavage entrance and lignin mixture radial shake solve
Mouthful, the radiation cleavage entrance and lignin mixture boiling outlet connect, and the hydrogen vapor mixed export is in institute
10 inside of radiation cleavage device is stated to connect with the neighbouring lignin mixture radiation cleavage exit；
Quenching apparatus 11, including chilling feeding inlet, gas discharge mouth and solid-liquid discharge port, the chilling feeding inlet with it is described
Lignin mixture radiation cleavage outlet connection；
It is recycled mechanism, is connect with the gas discharge mouth and solid-liquid discharge port, it is after cooling for recycling and separating
Product.
Specifically, lignin fibre raw material is transported to feed hopper 2 from belt conveyor 1, entered by screw feeding machine 3
The lignocellulose raw material feeding inlet of cooking reaction kettle 4, lye enter the lye pan feeding of cooking reaction kettle 4 from alkali storage tank 21
Mouthful, lignocellulosic material goes out holocellulose with lye hybrid separation and is collected by holocellulose collector 5, and remaining lignin is mixed
Conjunction object is passed through preheating device 9 and carries out the vapor stream that heating vaporization, vapor and hydrogen form hydrogen in preheating device 9,
Preheating device 9 is also connected to realize material Convective Heating with air blower 8.It is mixed in the middle lignin that radiation cleavage device 10 vaporizes
Close object and first carry out preliminary cracking reaction, the neighbouring exit of radiation cleavage device 10 be passed through the vapor stream of hydrogen with it is wooden
Hydrocracking reaction is carried out after plain preliminary pyrolysis product mixing, obtained product injection quenching apparatus 11 carries out refrigerated separation, point
Recycling and further separation are carried out from after.
A kind of lignin separation and steam cracking system provided by the invention, are isolated using lye from lignocellulose raw material
Lignin, and using steam as oxidant after cracking lignin, bio oil and biological flue gas are generated by hydrogenation reaction, rich in fibre
The residue enzymatic saccharification of dimension element and hemicellulose is high-efficient, and equipment is simple, and whole system operating temperature is lower, and cracking process is steady
Fixed, simple for process, environment-friendly and low-toxicity, the lignin extraction rate of recovery is high, and saccharification of cellulose is high-efficient, it is easy to accomplish industrialization.
Wherein, the recovery processing mechanism includes gas cleaning plant 12 and solid-liquid separation column 14, the gas discharge mouth
It is connect with the entrance of the gas cleaning plant 12, the solid-liquid discharge port is connect with the entrance of the solid-liquid separation column 14, institute
The outlet for stating gas cleaning plant 12 is connect with gas receiver 13, the outlet of the solid-liquid separation column 14 also respectively with oil storage tank 15 and
The tail gas absorber 16 connecting with solid calcining furnace 18 connects.Specifically, after cooling, gas is passed through gas cleaning plant 12
It is collected in gas receiver 13 after purification, other products by solid-liquid separation column 14, collect in oil storage tank 15 by the liquid isolated, point
The solid separated out is handled by the tail gas that solid calcining furnace 18 is isolated by tail gas absorber 16, is realized and is produced air-liquid and solid
Object carries out initial gross separation recycling, reduces the pollution to environment.
Further, the recovery processing mechanism further includes soda recovery unit 17 and alkali storage tank 21, the alkali collection
Device 17 is connect with the alkali storage tank 21 and solid calcining furnace 18 respectively, and the alkali storage tank 21 connects with lye feeding inlet
It connects, for recycling alkali.Alkali is recycled by soda recovery unit 17 by the solid that solid calcining furnace 18 generates, and is stored in
Alkali storage tank 21 realizes the recycling of alkali for the use of alkali in cooking reaction kettle 4.Specifically, in alkali storage tank 21
Lye injects cooking reaction kettle 4 using infusion pump 22.
Wherein, the recovery processing mechanism further includes Steam Recovery heat exchanger 19, and Steam Recovery heat exchanger 19 is equipped with first
Entrance, first outlet, second entrance and second outlet, the cooking reaction kettle 4 are additionally provided with the first steam outlet and the first water
Vapour inlet, first steam outlet are connect with the first entrance, and first outlet passes through the pre- hot charging by pipeline
It sets 9 to connect with the first steam entry, steam is recycled；The second entrance and second outlet respectively with the quenching apparatus
11 connections, are recycled high steam.Specifically, the steam that cooking reaction kettle 4 generates is passed through Steam Recovery heat exchanger 19, and change
It is passed through in preheating device 9 after thermal medium heat exchange heating and serves as heat-storage medium, as heat source and lignin mixture, the hydrogen being passed through
It exchanges heat with vapor, wherein Steam Recovery heat exchanger 19 is equipped with admission port 20, for supplementing steam；Steam Recovery heat exchanger 19
Another circuit is used to recycle the high steam in quenching apparatus 11.
It wherein, further include sequentially connected belt conveyor 1, feed hopper 2 and screw feeding machine 3, the screw feeding machine 3
It is connect with the lignocellulose raw material feeding inlet, transmits and screen raw material for going out.
As shown in Fig. 2, invention additionally discloses a kind of lignin separation and steam cracking methods, comprising:
Lignin fibre raw material is passed through by the lignocellulose raw material feeding inlet of cooking reaction kettle, and lye is led to by lye feeding inlet
Enter, isolates holocellulose by holocellulose discharge port and be expelled to the collection of holocellulose collector, the lignin mixture of extraction
It exports discharge by lignin mixture boiling and preheating device is passed through by lignin mixture preheating entrance and carry out heating vapour
Change；
After hydrogen and vapor are preheated by preheating device, the vapor stream of hydrogen is formed；
Lignin mixture after heating vaporization carries out preliminary cracking reaction by radiation cleavage device, is tentatively cracked
Product；
Preliminary pyrolysis product and the vapor stream of hydrogen are mixed in neighbouring lignin mixture radiation cleavage exit
Hydrocracking reaction is carried out, and product after reaction is passed through refrigerated separation in quenching apparatus；
Product after quenching apparatus refrigerated separation is by recovery processing organizational separation and recycling.
Specifically, lignocellulose raw material includes the straws such as agricultural crop straw, timber, bamboo, bagasse, branch, stem
Leaf or two or more of mixtures in them etc..The method for extracting lignin are as follows: by lignocellulose raw material and inorganic base
Aqueous solution (solid-to-liquid ratio is 1:1~1:10) is placed in cooking reaction kettle 4, and 0.5~3h of boiling is kept the temperature after being heated to 50~220 DEG C
Afterwards, filtering squeezing obtains the pretreatment fluid rich in lignin.Wherein, inorganic alkali solution is sodium hydroxide, sodium carbonate, bicarbonate
One of sodium, potassium hydroxide, potassium carbonate, saleratus or a variety of aqueous solutions with vulcanized sodium or NaHS, optimization add
It is 5%~25% that alkali number (in terms of sodium hydroxide), which is lignocellulose raw material weight,；The amount of optimization plus vulcanized sodium or NaHS
For wood fibre 0~20%.Temperature of the pretreatment fluid rich in lignin in preheating device 9 after heat is 120~300 DEG C, is contained
Temperature after the vapor stream of hydrogen preheats in preheating device 9 is 560~660 DEG C.The condition of preliminary cracking reaction are as follows: radiation
Section inlet temperature is 560~660 DEG C, and the outlet temperature of radiant section is 770~850 DEG C, and the reaction time is 0.1~15 second.Wherein,
It is 0.1%~2% that hydrogen, which accounts for the weight ratio of vapor, in the vapor stream of hydrogen；The weight ratio of hydrogen and preliminary pyrolysis product
It is 0.1~1.5%.
The separating lignin provided by the invention from the lignocellulose raw material and method for being subject to steam cracking can sufficiently subtract
The generation of charcoal in few raw material generates CO and H since high-temperature vapor can be reacted with charcoal2, to reduce the generation of carbon deposit.It introduces
Hydrogen the radical reaction that can be cracked to form with lignin of vapor stream, to substantially increase the stabilization of bio oil
Property, also improve the calorific value of bio oil.Simple for process, environment-friendly and low-toxicity, lignin extraction rate of recovery height, isolated is comprehensive
Saccharification of cellulose is high-efficient, it is easy to accomplish industrialization has a extensive future.
Wherein, the product after quenching apparatus refrigerated separation by recovery processing organizational separation and recycles net including the use of gas
Purification gas is set in makeup, and is collected by gas receiver；Solid of the liquid by oil storage tank, after separation after being separated using solid-liquid separation column
The gas generated through solid calcining furnace is passed through tail gas absorber.Lignin steam cracking product gas can be used for biological flue gas and conjunction
At gas, liquid can be used as liquid fuel etc. after being used as biological oil refinement；Lye is had to pass through before calcining obtained gas discharge
Processing absorbs therein such as H2S、SO2Etc. the gas for having pollution.
Wherein, the solid generated through solid calcining furnace is passed through soda recovery unit recycling, then is passed through the storage of lye feeding inlet
It deposits.Specifically, solid calcining, which carries out alkali collection, refers to the solid for obtaining solid product calcining evaporation.Solid product in alkali collection
The solid base that calcining evaporation obtains can repeat recycling and use in the aqueous slkali extraction lignin technique of lignocellulose raw material.And
The bio oil that hydrogen can be obtained by lignocellulose raw material rapid cleavage is produced, to ensure that the reproducibility of hydrogen.
It wherein, further include Steam Recovery heat exchanger, the steam being discharged by cooking reaction kettle is exchanged heat by the Steam Recovery
One circuit of device, and with after heat transferring medium heat exchange, preheating device is passed through as heat medium, is returned again to cooking reaction kettle, is followed
Ring uses steam；It returns after treatment in another circuit that the high steam of quenching apparatus discharge is passed through Steam Recovery heat exchanger
Quenching apparatus is returned, high steam is recycled.
Wherein, it is 5%~25% that the caustic dosage in cooking reaction kettle, which is lignocellulose raw material weight,；The hydrogen
It is 0.1%~2% that hydrogen, which accounts for the weight ratio of vapor, in vapor stream；The weight ratio of hydrogen and preliminary pyrolysis product is 0.1~
1.5%；Temperature after lignin mixture heats in preheating device is 120~300 DEG C, and the vapor stream of hydrogen is preheating
Temperature in device after preheating is 560~660 DEG C；Temperature is 560~660 DEG C at radiation cleavage device portal, radiation cleavage dress
Setting outlet temperature is 770~850 DEG C.
Embodiment 1: lignin and steam cracking are extracted in Bamboo leftover
Include the following steps:
(1) Bamboo leftover is crushed to partial size less than 2cm, 100g bamboo powder is taken to be added to the sodium hydroxide of 500mL
(4%) it and in the aqueous solution of vulcanized sodium (2%), is heated to keeping the temperature 1h at 180 DEG C, be filtered by vacuum after natural cooling with solid-liquid point
From obtaining the filtrate containing lignin.
(2) after the filtrate preheating obtained step (1), preliminary cracking reaction is carried out into radiant section；At the same time, will contain
There is the vapor stream of 0.2% hydrogen to preheat, in radiant section exit, the logistics of hydrogen and the preliminary pyrolysis product of radiant section are mixed
It closes, carries out further Hydrocracking reaction；
(3) cleavage reaction product finally obtained in step (2) is injected in rapid-cooling heat exchanger and carries out refrigerated separation, separated
At high steam, cracking gas and coarse biometric oil.High steam repetitive cycling uses, and cracking gas enters later separation device, biology
Oil enters subsequent bio device for purifying fuel after being separated by solid-liquid separation, and solid recycles alkali and reused after being evaporated calcining.
Wherein, the recovery rate of lignin is 97%, and the temperature after the vapor stream of hydrogen preheats in preheating device is
560~660 DEG C, it is preheated after lignin steam stream temperature be 600 DEG C, the radiant section outlet temperature of pyrolysis furnace is 840 DEG C,
The cracking reaction time is 0.22 second in radiant section.
The holocellulose being collected into does following processing: in 100mL plastic bottle, it is residual that bamboo powder of the 2g rich in holocellulose is added
Slag, adjusting pH value with 40mL NaAc_HAc buffer solution (0.05M) is 4.8, and the cellulase of 15FPU/g glucan is added,
48h is hydrolyzed under 50 DEG C, 180rpm.Show that cellulose is converted into the yield of glucose up to 100%, reduced sugar yield then exists
94%.
Inorganic salts (g/L) is added in above-mentioned enzyme hydrolyzate: peptone, 5.0；Potassium dihydrogen phosphate, 2.0；Magnesium sulfate, 1.0；Chlorine
Change calcium, 0.25, sterilize 20min at 121 DEG C.After taking-up, adjusting pH value is 5.5 ± 0.1.Activated yeast juice is inoculated into
In hydrolyzate.Yeast-inoculated amount is the 2% of glucose amount.Solution, which is placed in shaking table, starts alcohol fermentation, controlled at 37 DEG C,
Revolving speed is 150rpm.After fermentation 24 hours, ethanol content is measured by sampling, calculate glucose is converted into ethanol yield and is
95.1%.
The saccharification efficiency of the holocellulose obtained using the method for the present invention is up to 94%.And the saccharification of untreated bamboo wood
Efficiency is generally between 2~5%.Glucose is converted into ethanol yield and is up to 95.1%.Bamboo wood is greatly improved using the technology
Bio-ethanol efficiency is produced, there is wide prospects for commercial application.
Embodiment 2:
The difference of the present embodiment and embodiment 1 is only that in step (2) will be pre- containing 0.5% hydrogen vapor stream
Heat.
Embodiment 3:
The difference of the present embodiment and embodiment 1 be only that in step (1) 100g poplar wood powder is added to it is above-mentioned water-soluble
In liquid.
The present invention discloses a kind of lignin separation and steam cracking system and method, has the advantages that
1, lignin is isolated from lignocellulose raw material using lye, and using steam as oxidant after cracking lignin,
Bio oil and biological flue gas are generated by hydrogenation reaction, the residue enzymatic saccharification rich in cellulose and hemicellulose is high-efficient, and
Equipment is simple, and whole system operating temperature is lower, and cracking process is stablized, simple for process, environment-friendly and low-toxicity, and lignin extraction is returned
High income, holocellulose saccharification efficiency are high, it is easy to accomplish industrialization；
2, air-liquid and solid product are subjected to initial gross separation recycling, reduce the pollution to environment；
3, after by the steam of cooking reaction kettle by Steam Recovery heat exchanger and heat transferring medium heat exchange heating, it is passed through pre- hot charging
It sets as heat transferring medium, after hydrogen, steam heating and lignin preheating, returns again to cooking reaction kettle, realize steam circulation benefit
With；The high steam of quenching apparatus discharge also returns again to after Steam Recovery heat exchanger, and high steam is recycled；
4, the alkali collection in product is utilized using solid calcining furnace and soda recovery unit.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of lignin separation and steam cracking system characterized by comprising
Cooking reaction kettle (4), exported equipped with lignocellulose raw material feeding inlet, holocellulose discharge port, lignin mixture boiling,
Lye feeding inlet and the first steam entry, the holocellulose discharge port are connect with holocellulose collector (5)；
Preheating device (9) is equipped with lignin mixture and preheats entrance, hydrogen inlet, the second steam entry, hydrogen vapor
Mixed export and lignin mixture preheating outlet, the lignin mixture preheating entrance and the lignin mixture boiling
Outlet connection, lignin mixture for being fed into heat vaporization, hydrogen and vapor pass through respectively the hydrogen inlet and
Second steam entry is passed through the preheating device (9) preheating, forms the vapor stream of hydrogen, and mixed by hydrogen vapor
Outlet discharge；
Radiation cleavage device (10) comprising lignin mixture radiation cleavage entrance and lignin mixture radial shake solve
Mouthful, the radiation cleavage entrance and lignin mixture preheating outlet connection, the hydrogen vapor mixed export is in institute
Radiation cleavage device (10) inside is stated to connect with the neighbouring lignin mixture radiation cleavage exit；
Quenching apparatus (11), including chilling feeding inlet, gas discharge mouth and solid-liquid discharge port, the chilling feeding inlet and the wood
Quality mixture radiation cleavage outlet connection；
It is recycled mechanism, is connect with the gas discharge mouth and solid-liquid discharge port, for recycling and separating product after cooling.
2. lignin separation as described in claim 1 and steam cracking system, which is characterized in that recovery processing mechanism packet
Include gas cleaning plant (12) and solid-liquid separation column (14), the entrance of the gas discharge mouth and the gas cleaning plant (12)
Connection, the solid-liquid discharge port are connect with the entrance of the solid-liquid separation column (14), the outlet of the gas cleaning plant (12)
Connect with gas receiver (13), the outlet of the solid-liquid separation column (14) also respectively with oil storage tank (15) and with solid calcining furnace (18)
The tail gas absorber (16) of connection connects.
3. lignin separation as claimed in claim 2 and steam cracking system, which is characterized in that the recovery processing mechanism is also
Including soda recovery unit (17) and alkali storage tank (21), the soda recovery unit (17) respectively with the alkali storage tank (21)
It is connected with solid calcining furnace (18), the alkali storage tank (21) connect with lye feeding inlet, for recycling alkali.
4. lignin separation as described in claim 1 and steam cracking system, which is characterized in that the recovery processing mechanism is also
Including Steam Recovery heat exchanger (19), Steam Recovery heat exchanger (19) is equipped with first entrance, first outlet, second entrance and second
Outlet, the cooking reaction kettle (4) are additionally provided with the first steam outlet, and first steam outlet and the first entrance connect
It connects, first outlet passes through the preheating device (9) by pipeline and connect with the first steam entry, and steam is recycled；It is described
Second entrance and second outlet are connect with the quenching apparatus (11) respectively, and high steam is recycled.
5. lignin separation as described in claim 1 and steam cracking system, which is characterized in that further include sequentially connected skin
Belt conveyor (1), feed hopper (2) and screw feeding machine (3), the screw feeding machine (3) and the lignocellulose raw material pan feeding
Mouth connection.
6. a kind of lignin separation and steam cracking method characterized by comprising
Vapor is passed through by the first steam entry of cooking reaction kettle, lignin fibre raw material by cooking reaction kettle wooden fibre
Dimension raw material feeding inlet be passed through, lye is passed through by lye feeding inlet, isolate holocellulose be expelled to by holocellulose discharge port it is comprehensive
Cellulose collector is collected, and the lignin mixture of extraction is by lignin mixture boiling outlet discharge and mixed by lignin
Conjunction object preheating entrance is passed through preheating device and carries out heating vaporization；
After hydrogen and vapor are preheated by preheating device, the vapor stream of hydrogen is formed；
Lignin mixture after heating vaporization carries out preliminary cracking reaction by radiation cleavage device, obtains preliminary crack and produces
Object；
Preliminary pyrolysis product and the vapor stream of hydrogen are mixed in neighbouring lignin mixture radiation cleavage exit and carried out
Hydrocracking reaction, and product after reaction is passed through refrigerated separation in quenching apparatus；
Product after quenching apparatus refrigerated separation is by recovery processing organizational separation and recycling.
7. lignin separation as claimed in claim 6 and steam cracking method, which is characterized in that described cooling through quenching apparatus
Product after separation is received by recovery processing organizational separation and recycling including the use of gas cleaning plant purification gas, and by gas receiver
Collection；By oil storage tank, the gas that the solid after separation is generated through solid calcining furnace is passed through liquid after being separated using solid-liquid separation column
Tail gas absorber.
8. lignin separation as claimed in claim 7 and steam cracking method, which is characterized in that described to be produced through solid calcining furnace
Raw solid is passed through soda recovery unit recycling, then is passed through the storage of lye feeding inlet.
9. lignin separation as claimed in claim 6 and steam cracking method, which is characterized in that further include Steam Recovery heat exchange
Device, the steam being discharged by cooking reaction kettle by a circuit of the Steam Recovery heat exchanger, and with after heat transferring medium heat exchange,
Preheating device is passed through as heat medium, cooking reaction kettle is returned again to, steam is recycled；The high steam of quenching apparatus discharge
It is passed through another circuit of Steam Recovery heat exchanger, returns to quenching apparatus, high steam is recycled.
10. lignin separation as claimed in claim 6 and steam cracking method, which is characterized in that adding in cooking reaction kettle
Alkali number is that lignocellulose raw material weight is 5%~25%；Hydrogen accounts for the weight of vapor in the vapor stream of the hydrogen
Than being 0.1%~2%；The weight ratio of hydrogen and preliminary pyrolysis product is 0.1~1.5%；Lignin mixture is in preheating device
Temperature after interior heating is 120~300 DEG C, and the temperature after the vapor stream of hydrogen preheats in preheating device is 560~660
℃；Temperature is 560~660 DEG C at radiation cleavage device portal, and radiation cleavage device outlet temperature is 770~850 DEG C.
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| CN103347984B (en) * | 2010-12-20 | 2016-01-20 | 国际壳牌研究有限公司 | Intermediate oxygenatedchemicals platinum catalysis hydrogenation deoxidation is then fuel by cellulosic aqueous hydrolysis |
| WO2017052454A1 (en) * | 2015-09-22 | 2017-03-30 | Ren Fuel K2B Ab | Continuous production of fuel grade hydrocarbons by hydrotreatment of forestry byproduct lignin |
| CN206872741U (en) * | 2017-06-13 | 2018-01-12 | 国际竹藤中心 | A kind of lignin separation and steam cracking system |
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| CN103347984B (en) * | 2010-12-20 | 2016-01-20 | 国际壳牌研究有限公司 | Intermediate oxygenatedchemicals platinum catalysis hydrogenation deoxidation is then fuel by cellulosic aqueous hydrolysis |
| WO2017052454A1 (en) * | 2015-09-22 | 2017-03-30 | Ren Fuel K2B Ab | Continuous production of fuel grade hydrocarbons by hydrotreatment of forestry byproduct lignin |
| CN206872741U (en) * | 2017-06-13 | 2018-01-12 | 国际竹藤中心 | A kind of lignin separation and steam cracking system |
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