CN102701898A - Method for directionally preparing benzene by utilizing xylogen - Google Patents
Method for directionally preparing benzene by utilizing xylogen Download PDFInfo
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Abstract
The invention relates to a method for directionally preparing benzene by utilizing xylogen. The method comprises the following steps of: selecting a cylindrical fixed bed catalytic reactor with a conductive metal wire arranged in a cavity; depolymerizing to converte xylogen to an aromatic monomer, wherein a led raw material is the xylogen, a catalyst is powder zeolite catalyst or modified zeolite catalyst containing transition metal nickel element, the usage amount is characterized in that the weight ratio of the catalyst to the xylogen is 0.3-10 per hour, and a product is a liquid-state aromatic monomer mixer; and directionally converting the aromatic monomer mixer into benzene, wherein a led raw material is the aromatic monomer mixer which is preheat to be 200-250 DEG C, a catalyst is powder zeolite catalyst containing an Re element, the usage amount is characterized in that the weight ratio of the aromatic monomer mixer to the zeolite catalyst containing the Re element is 0.2-15 per hour, and a product is mixed liquid taking the benzene as the main part. According to the method, an external hydrogen source is not needed, the raw material resources are rich, and higher benzene yield and benzene selectivity can be obtained at intermediate temperature and constant pressure as well as under a green and mild reaction environment.
Description
Technical field
The present invention relates to a kind of method of utilizing xylogen beam system benzene.
Background technology
Benzene is the important basic chemical industry raw material of petrochemical industry.The tar light oil that in the coal coking process, generates contains a certain amount of benzene.From 1 ton of coal, can extract about 1 kilogram of benzene.Global most benzene derives from non-renewable fossil feedstock now, and producing the most important three kinds of technologies of benzene at present is oil CR, toluene hydrodealkylation and steam cracking.Along with the mass consumption of coal and oil traditional resource and the attention of environment protection, press for the reproducible green alternative materials of exploitation.
The annual biomass total amount that is generated by photosynthesis surpasses 2,000 hundred million tons on the earth, is the abundantest renewable resources.Xylogen is to be only second to cellulosic second largest natural organic matter in plant; According to estimates; Xylogen is regenerated with annual about 50,000,000,000 tons speed; Only the xylogen sub product that produces of paper-making industry just reaches 5,000 ten thousand tons/year, the large sub product during the s-generation alcohol fuel that xylogen also is based on agricultural waste material is produced.But xylogen still fails to obtain fully effectively to utilize so far.The lignin conversion research of having reported comprises mainly that xylogen hydrogenating reduction, catalyzed oxidation, thermo-cracking, bio oil are concise, xylogen gasification and biochemical conversion etc.Document for example: (1) Zakzeski J., Bruijnincx P. C. A., Jongerius A. L., Weckhuysen B. M., Chem. Rev., 2010,110 (6): 3552-3599; (2) Pandey M. P., Kim C. S., Chem. Eng. Technol., 2011,34 (1): 29-41; (3) Effendi, A.; Gerhauser, H.; Bridgwater, A.V., Renewable and Sustainable Energy Reviews, 2008,12 (8): 2092-2116; (4) Suhas, Carrott, P.J.M., Ribeiro Carrott M.M.L., Bioresour. Technol., 2007,98 (12): 2301-2312; E) Sena-Martins, G., Almeida-Vara, E., Duarte, J.C., Ind. Crops Prod., 2008,27 (2): 189-195).The xylogen catalytic hydrogenating reduction is through high-pressure hydrogenation, forms mainly to contain compounds such as phenols, alkyl benzene and alkanes.The xylogen catalyzed oxidation is (like O at oxygenant
2/ H
2O
2) and catalyst action under, obtain comprising mix products such as aldehyde, acid, aromatic alcohol and quinones.In addition, xylogen is at 400-600
oThe organic liquid that gentle oxygen free condition produces through thermo-cracking down among the C is called the lignin-base bio oil, this bio oil complicated component, and its kind can reach hundreds of (comprising phenols, benzene class, furan nanmu class, alcohols, lipid and tar etc.).The xylogen catalytic pyrolysis is under the effect of catalyzer, obtains compounds such as simple aromatic hydrocarbon, naphthalene and phenols, and wherein the selectivity of benzene is lower.In addition; Xylogen and Wooden Biomass gasification produce biomass synthesis gas, can be used for heat supply and generating, also can be used for preparing chemicals and liquid fuel; Consider the constitutional features of xylogen aromatic polymer, xylogen is more suitable to be used as the raw material of producing aromatic compounds.
In the prior art; That has reported mainly contains two kinds of technology approach from xylogen system benzene: a kind of is to adopt the xylogen catalytic hydrogenation method; The product that obtains is the aromatics that phenols, benzene class and alkanes etc. are formed; The selectivity of benzene generally is lower than 10%, and this arts demand uses outside hydrogen source and under condition of high voltage, reacts.Another kind of xylogen system benzene process is the xylogen Deep Catalytic Cracking process; This method is to utilize xylogen on zeolite catalysts such as ZSM-5 molecular sieve, to carry out catalytic pyrolysis; The product that forms mainly contains materials such as toluene, YLENE, naphthalene, methylnaphthalene, benzene and phenols to be formed, and the selectivity of benzene generally is no more than 20% in the aromatic product that obtains.Can find out that the products distribution that xylogen system benzene obtains in the existing technology is very wide, and the selectivity of title product-benzene is very low, can't reach the purpose of xylogen beam system benzene.
In sum, xylogen is the unique non-oil resource that reproducible large compound aromatic base can be provided of occurring in nature.The xylogen system benzene of utilization can provide an important flat molecule of basic chemical industry raw material and the high-end chemical of development for petrochemical industry, still, does not see as yet so far with orientation and prepares the relevant report that benzene is the controlled transformation technology of xylogen of target.
Summary of the invention
The objective of the invention is to, controllably produce the technical barrier of benzene to the xylogen orientation that waits in the prior art to solve, providing a kind of can need not under external hydrogen source, middle normal temperature and pressure and the green gentle reaction environment, makes the directed method for preparing benzene of xylogen.
The object of the invention is realized through following technical scheme.
The directed method for preparing benzene of xylogen of utilizing of the present invention; Comprise the reactor drum of selecting for use the tubular fixed bed catalytic reactor that is provided with conductive wire in the chamber to be prepared as benzene as xylogen; Said powder catalyst is filled in around the built-in metal silk and the wire surface uniform contact, starts reactor drum then and connect the external source of conductive wire, make to feed raw material generation conversion reaction; Described conductive wire is Ni-Cu or Ni-Cr, or a kind of among the Fe-Cr-Al; On the feed pipe of reactor drum and catalyticreactor, be provided with heating unit; It is characterized in that; Said conversion reaction be divided into two the step carry out: the first step utilizes the tubular fixed bed catalytic reactor that the xylogen catalytic degradation is converted into the aromatics monomer; The feeding raw material is an xylogen; Catalyst system therefor is pulverous zeolite catalyst or the modified zeolite catalyst that contains the transition metal nickel element; Its usage quantity is that to make the weight ratio of catalyzer hourly and xylogen be 0.3-10, and the product that obtains is an aromatic liquid class monomer mixture, and reaction conditions is: the inherent rare gas element of reactor cavity is (like N
2Gas) under the atmosphere, temperature is at 450-650
oIn the C scope, the feeding electric current of conductive wire is between the 0A-5A; Second step was to utilize the tubular fixed bed catalytic reactor to make aromatics monomer mixture orientation be converted into benzene, fed raw material for being preheating to 200-250
oThe aromatics monomer mixture of C; Catalyst system therefor is the zeolite catalyst of the pulverous Re of containing element; It is 0.2-15 that its usage quantity per hour makes aromatics monomer mixture and the weight ratio that contains the zeolite catalyst of Re element, and reaction conditions is: the inherent rare gas element of reactor cavity is (like N
2Gas) under the atmosphere, temperature is at 450-650
oIn the C scope, the feeding electric current of conductive wire is 0A-5A; The product that finally obtains is to be main mixing liquid with benzene.
In practical application; For realizing serialization production; Can use two tubular fixed bed catalytic reactors; With the reactor drum that is used for lignin depolymerization of the first step and the aromatics monomer set in second step to the integrated production line of the reactors in series that is converted into benzene; That is: the xylogen of feeding changes into the aromatics monomer mixture at first reactor drum that is used for lignin depolymerization, and it directly gets into second aromatics monomer set to the reactor drum that is converted into benzene from this reactor drum output back, and accomplishing therein that conversion reaction obtains with benzene is main mixing liquid.
In practical application, be the flow process that simplifies the operation, also can described xylogen catalytic degradation and aromatics monomer set be carried out in a catalytic bed reactor to the two step PROCESS COUPLING that are converted into benzene simultaneously, that is:
Earlier with zeolite catalyst or contain the transition metal nickel element modified zeolite catalyst, mix according to mass ratio 1:10-5:1 with the zeolite catalyst of rhenium-containing (Re) element; And add sticker and mix and obtain having lignin depolymerization and the bifunctional mixed catalyst of aromatics conversion of monomer, wherein the mass content of sticker accounts for the 2-40wt% of total difunctional mixed catalyst quality; Again said difunctional mixed catalyst is filled in the tubular fixed bed catalytic reactor around the wire and with the wire surface uniform contact; Start reactor drum then and connect the external source of conductive wire, make the inherent rare gas element of reactor drum (like N
2Gas) under the atmosphere, temperature is at 450-650
oIn the C scope, the feeding electric current of conductive wire is 0-5.0A, will be preheating to 200-250
oThe xylogen powder stock of C is passed in the reactor drum; Its feeding amount is to make that the weight ratio of catalyzer and xylogen is 0.3-10; Make xylogen that lignin depolymerization reaction and the conversion reaction of aromatics monomer set to preparation benzene take place in the one-part form catalytic bed reactor simultaneously, obtaining with benzene is the mixing liquid of leading.
Employed zeolite catalyst in the above process, the zeolite catalyst that contains the modified zeolite catalyst of transiting metal nickel and contain the Re element all can directly be buied from market, also can be prepared by following method:
Preparation contains the zeolite catalyst of transition metal nickel element: compound concentration is the nickelous nitrate of 0.05-0.5mol/L or the solution of nickel acetate; The active ingredient zeolite of selecting for use is impregnated in the above solution, obtains the zeolite catalyst through the modification of transition metallic element through dry, sintering then, wherein the mass content of transition metal is the 0-40 wt% of zeolite catalyst quality; Said active ingredient zeolite is one or more a mixture of ZSM-5 series zeolite, β zeolite, HY zeolite, overtemperature Y zeolite; With said modified zeolite catalyst and sticker mixed grinding is powder, and wherein the mass content of sticker accounts for the 2-35wt% of total mixed powder quality, and described sticker is the smart powder in kaolin or field; With above-mentioned mixed powder compressing tablet, drying, to sieve and obtain particle diameter be 40-80 purpose fine-particle powder in fragmentation again, is the zeolite catalyst finished product that contains the transition metal nickel element.
Preparation contains the element modified zeolite catalyst of Re: compound concentration is the nitric acid rhenium solution of 0.05-0.5mol/L; The active ingredient zeolite of selecting for use is impregnated in the above solution; Obtain element modified zeolite catalyst through dry, sintering then through Re; Wherein the content of Re is 0-20 wt%, and said active ingredient zeolite is one or more a mixture of ZSM-5 series zeolite, β zeolite, HY zeolite, overtemperature Y zeolite; With above-mentioned modified zeolite catalyst and sticker mixed grinding is powder, and wherein the content of sticker accounts for the 2-35wt% of total mixed powder quality, and described sticker is the smart powder in kaolin or field; With above-mentioned mixed powder compressing tablet, drying, to sieve and obtain particle diameter be 40-80 purpose fine-particle powder in fragmentation again, promptly contains the zeolite catalyst finished product of Re element.
In the inventive method, the feeding electric current of said conductive wire is 0-5.0A, and this expression can have the external source of connection or disconnect two kinds of situation of external source.When feeding electric current wiry was zero, the said lignin depolymerization system aromatics monomer process and the aromatics monomer set in second step all only were under catalyst action, to carry out to the process that is converted into benzene; When feeding electric current wiry is non-vanishing; Thermal electron emission principle according to the metallic surface; The energising wire is that catalyst surface provides a large amount of thermoelectrons, and the lignin depolymerization system aromatics monomer process and the aromatics monomer set in second step all are under the synergy of thermoelectron and catalyzer, to carry out to the process that is converted into benzene.Compare two kinds of situation, the transformation efficiency when feeding electric current is apparently higher than disconnecting the external source situation.This be because, contain the dissociated aromatics polymer of a large amount of difficulties in the xylogen, the synergy of thermoelectron and catalyzer can promote in the xylogen ehter bond and carbon-to-carbon rupture and induce the free radical chain chemical reaction; Also can be to the aromatics monomer mixture of multi-component complex and the characteristic of a spot of oligomer; Promote functional group's fracture and regrouping process in the aromatics monomer; Thereby realize that making the efficient depolymerization of xylogen is the aromatics monomer, makes aromatics monomer efficiently and directionally be converted into title product-benzene.
Actual measurement shows; As being that lignin depolymerization is used catalyzer with 15 wt% Ni/HZSM-5 (load weight content be the HZSM-5 zeolite catalyst of 15% nickel); Under the condition of 600 ℃ of temperature of reaction and electric current 0A, the aromatics monomer mixture productive rate that lignin depolymerization forms is 0.20 (kg monomer/kg xylogen); Under the condition of 550 ℃ of temperature of reaction and electric current 4A, the aromatics monomer mixture productive rate that lignin depolymerization forms is 0.29 (kg monomer/kg xylogen).For with aromatics monomer catalytic cracking benzene the time; As being that the aromatics conversion of monomer is used catalyzer with 10 wt% Re/Y type zeolites (load weight content be the y-type zeolite catalyzer of 10% rhenium); The aromatics monomer that obtains with the xylogen catalytic pyrolysis is as raw material; Under the condition of 650 ℃ of temperature of reaction and electric current 0A, the productive rate of title product-benzene is 0.10 (kg benzene/kg xylogen), and the selectivity of benzene is 96.0%; Under the condition of 550 ℃ of temperature of reaction and electric current 4A, the productive rate of title product-benzene is 0.13 (kg benzene/kg xylogen), and the selectivity of benzene is up to 95.5%.In addition; If lignin depolymerization and aromatics monomer set are carried out in the one-part form catalytic bed reactor to the two step PROCESS COUPLING that are converted into benzene; When with 15 wt% Ni/HZSM-5 as the lignin depolymerization catalyzer, be that 2:1 mix the dual-function catalyst that obtain lignin depolymerization-aromatics conversion of monomer as aromatics conversion of monomer catalyzer by mass ratio with 10wt % Re/Y type zeolite; With xylogen as starting raw material; Under the condition of 650 ℃ of temperature of reaction and electric current 0A, the productive rate of title product-benzene is 0.07 (kg benzene/kg xylogen), and the selectivity of benzene reaches 90.0wt%; Under the condition of 550 ℃ of temperature of reaction and electric current 5A, the productive rate of benzene is 0.08 (kg benzene/kg xylogen), and the selectivity of benzene reaches 93.0wt%.This shows, adopt the xylogen catalysis system benzene (electric current is zero) of no current effect and have the xylogen catalysis system benzene (electric current is non-vanishing) of galvanic action to operate, all can realize the purpose of the directed preparation of xylogen benzene; But adopt when feeding electric current, can be at benzene productive rate and the benzene selective higher than acquisition under the low reaction temperatures.
Method of the present invention can orientation efficiently changes into benzene under external hydrogen source, middle normal temperature and pressure and the green gentle reaction environment need not with xylogen; And all raw materials that use are various reproducible biomass; For example; Can use xylogen that separation such as wood chip, stalk, rice husk obtain or the various xylogen that derive from the pulping process of paper industry, its raw material has the advantage of aboundresources, environmental friendliness and aspect such as renewable, and xylogen system benzene can be petrochemical industry the basic chemical industry raw material is provided; Also be an important flat molecule of the high-end chemical of development, help realizing the recycle of the sustainability of resource-environmental integration.
Embodiment
Below do through embodiment and to further describe.
Embodiment 1Making lignin depolymerization is the aromatics monomer
In the present embodiment process, the xylogen raw material is available from the blue rising sun bio tech ltd in Hefei City.Principal element consists of carbon, hydrogen and oxygen element (element ratio is C:H:O=62.55:5.83:31.62) in the xylogen raw material.Lignin depolymerization is 15 wt%Ni/HZSM-5 modified zeolite catalysts with catalyzer.This Preparation of catalysts step is: weighing 37.5 g Nickelous nitrate hexahydrates, add the 100mL deionized water, and be configured to nickel nitrate solution; Be in 25 the HZSM-5 zeolite powder 20g adding in the nickel nitrate solution with the weighing silica alumina ratio then; Shake the powder that makes solution not have ZSM-5; Leave standstill dipping moisture in the evaporate to dryness solution in the 80 degree water-baths again after 24 hours; Then in baking oven after the 120 degree dryings, 550 degree sintering 6 hours in retort furnace.15 wt%Ni/HZSM-5 catalyzer that will prepare again and sticker (kaolin or field smart powder) carry out mixed grinding and obtain mixed powder, and wherein sticker accounts for 10 wt% of total mixed powder quality, with behind the above-mentioned mixed powder compressing tablet in temperature 110
oDrying is 8 hours under the condition of C, and sieving and obtaining particle diameter is 40-80 purpose microparticle, promptly is used for the modified zeolite catalyst that the contains the transition metal nickel element 15 wt%Ni/HZSM-5 finished products of lignin depolymerization.
Used lignin depolymerization catalyticreactor is a tubular fixed bed catalytic reactor that has indirect heating and thermal insulation layer; Be connected with the feeding pipeline and the reaction product output channel of reaction raw materials (xylogen) and carrier gas at its two ends; The xylogen hold-up vessel links to each other with feeder; Carrier gas channel and reactant feed pipeline and connect, and are respectively equipped with gas control valve and reactant flow amount controller, and the access tube pipeline outer wall is provided with the outer heating unit that is used for preheating; On the reaction product output channel, be connected with in turn and comprise double-condenser, product liquid scoop, solid product scoop and exhaust collection device; The wire that in the inner chamber of barrel reactor, is provided with ceramic insulating layer and is communicated with external source, power wiry is selected by desired reaction temperature and reactor volume, and said built-in metal silk is the Ni-Cu wire.
In the present embodiment; The 15 wt%Ni/HZSM-5 zeolite catalysts that at first will be used for lignin depolymerization be filled in around the built-in wire of reactor drum and with the wire surface uniform contact; Catalyst levels is 10g, opens the valve of carrier gas nitrogen steel cylinder, and the flow of regulating carrier gas is 1000ml/min; After air in the question response device was discharged from, the flow of regulating carrier gas was 450 ml/min.Connect the power supply wiry be used to provide thermoelectron and internal heating again, make feeding electric current wiry be separately positioned on 0,2,4A is constant, through the power of conditioned reaction device externally heated oven, makes temperature in the reactor drum inner chamber at 450-650
oRegulate in the C scope.Behind the temperature-stable in the reactor drum; Open the valve of the feeder on the xylogen raw material storage tanks outlet pipe; The lignin feed amount is 10g, and xylogen and carrier gas get into the catalyticreactor inner chamber through feeding pipeline, and making lignin depolymerization is liquid intermediate product-aromatics monomer mixture.The result is as shown in table 1.Can find out from this table: when temperature of reaction is being 550
oWhen C and electric current were 2A, aromatics monomer productive rate (pressing the actual aromatics monomer output that obtains and the ratio calculation of xylogen sample size) was 0.25 (kg monomer/kg xylogen); When temperature of reaction is being 550
oWhen C and electric current were 4A, aromatics monomer productive rate was 0.29 (kg monomer/kg xylogen).
Also done the situation of no current enhancement in the present embodiment process, promptly closed connection power supply wiry, making and feeding electric current wiry is 0, and only the power through conditioned reaction device externally heated oven comes the temperature in the conditioned reaction device inner chamber.Measure the growing amount of xylogen sample size and lignin depolymerization product then respectively; And calculate in the aromatics monomer productive rate table 1; The result shows; Under identical temperature of reaction, utilize the efficient of the xylogen catalytic depolymerization of electric current enhancement can be higher than the efficient of the xylogen catalytic depolymerization of no current enhancement.
Table 1 (data are the MV of three experiments in the table)
Embodiment 2Make the aromatics monomer set to being converted into benzene
In the present embodiment process, reactant feed adopts among the embodiment 1 600
oC and electric current are the aromatics monomer mixture that the xylogen catalytic degradation produces under the 0A condition.Catalyzer adopts 10 wt %Re/Y type rhenium-containing zeolite catalysts.Said Preparation of catalysts step is: weighing 16g nitric acid rhenium, add the 100mL deionized water, and be configured to nitric acid rhenium solution; Be that 5 HY zeolite powder 20g adds in the nitric acid rhenium solution that configures with the weighing silica alumina ratio then; Shake the powder that makes solution not have the HY zeolite; Leave standstill dipping after 24 hours; Moisture in 80 degree water-baths in the evaporate to dryness solution, in baking oven after the 120 degree dryings, 550 degree sintering are 6 hours in retort furnace then.Again 10wt %Re/Y type zeolite catalyst and the sticker (kaolin or field essence powder) of preparation carried out mixed grinding by a certain percentage and obtain mixed powder; Wherein sticker accounts for 20 wt. % of total mixed powder quality, with behind the above-mentioned mixed powder compressing tablet in temperature 110
oDrying is 8 hours under the condition of C, and sieving and obtaining particle diameter is 40-80 purpose particle, promptly is used for the catalyzer 10wt %Re/Y finished product of aromatics conversion of monomer.
The aromatics monomer catalytic conversion reactor of selecting for use is a tubular fixed bed catalytic reactor that has indirect heating and thermal insulation layer, and its both ends are connected with reactant (aromatics monomer liquid mixture) and carrier gas (N
2Gas) feed pipeline and reaction product output channel; The aromatics monomer stores to irritate and links to each other with the liquid infusion pump; Carrier gas is connected with feeding pipeline respectively, and is respectively equipped with gas control valve and reactant flow amount controller, and the outer wall that feeds pipeline is provided with the outer heating unit that is used for preheating; On the reaction product output channel, be connected with in turn and comprise double-condenser, product liquid scoop and exhaust collection device; The Ni-Cu wire that in the inner chamber of barrel reactor, is provided with ceramic insulating layer and is communicated with external source, power wiry is selected by desired reaction temperature and reactor volume.Open the valve of carrier gas nitrogen steel cylinder, connect the power supply wiry that is used to provide thermoelectron and internal heating again, make feeding electric current wiry be separately positioned on 0; 2; 4A is constant, through the power of conditioned reaction device externally heated oven, makes temperature in the reactor drum inner chamber at 550-650
oRegulate in the C scope.
The aromatics monomer set is to transforming system benzene method: at first will the above-mentioned 10wt.%Re/Y catalyzer finished product that is used for the aromatics conversion of monomer be filled in the built-in metal silk on every side and with the wire surface uniform contact.Catalyst levels is by the per hour inlet amount decision of reaction raw materials, and catalyst levels is 8g in the present embodiment, and the flow of regulating carrier gas is 1000ml/min, and after the air in the question response device was discharged from, the flow of regulating carrier gas was 150 ml/min.Connect preheating zone heat tape power supply then, the temperature that makes the preheating zone is at 180-200
oIn the C; Connection is used to provide the power supply wiry of thermoelectron and internal heating, makes to feed electric current wiry and be separately positioned on 0,2, and 4A is constant, through the power of conditioned reaction device externally heated oven, makes temperature in the reactor drum inner chamber at 550-650
oRegulate in the C scope.Open sampling pump and the valve of carrier gas on the outlet pipe that links to each other with aromatics raw material monomer hold-up vessel at last; Conditioned reaction raw material sample size; Aromatics monomer mixture after preheating and carrier gas feed pipeline through reactant and get into aromatics conversion of monomer reactor drum, make the aromatics monomer mixture under the synergy of thermoelectron and catalyzer, be converted into title product-benzene.In the present embodiment, aromatics raw material monomer feed rate is 50g/h, and flow rate of carrier gas is 150 ml/min.Then, under different electric currents and temperature conditions, measure the growing amount of reactant (being the aromatics monomer liquid mixture of lignin depolymerization preparation) and benzene, and calculate the productive rate and the selectivity of benzene, the result who records is as shown in table 2.
Can find out from table 2: when temperature of reaction 550
oWhen C and electric current were 2A, benzene productive rate (pressing the actual benzene yield that obtains and the ratio calculation of starting raw material xylogen usage quantity) and benzene selective (pressing the benzene yield of actual acquisition and the ratio calculation of all liquid product quality) were respectively 0.09 (kg benzene/kg xylogen) and 82.5 wt %; When temperature of reaction 550
oWhen C and electric current were 4A, benzene productive rate and benzene selective were increased to 0.13 (kg benzene/kg xylogen) and 95.5 wt % respectively.
Also done the Comparative Examples of the aromatics monomer catalyzed conversion that does not have under the electric current enhancement in the present embodiment process.Promptly close and connect Ni-Cu power supply wiry, making and feeding Ni-Cu electric current wiry is 0, through the power of conditioned reaction device externally heated oven, makes temperature in the reactor drum inner chamber at 550-650
oRegulate in the C scope.When Ni-Cu electric current wiry be 0 with temperature of reaction 550
oDuring C, benzene productive rate and benzene selective are respectively 0.06 (kg benzene/kg xylogen) and 71.6 wt%.In addition, when not having the electric current enhancement, increase productive rate and selectivity that temperature helps improving benzene, as temperature is increased to 650
oDuring C, benzene productive rate and benzene selective are increased to 0.10 (kg benzene/kg xylogen) and 96.0 wt% respectively.
Table 2 (the benzene productive rate in the table, benzene selective data are the MV of three experiments)
Embodiment 3With lignin depolymerization and aromatics monomer set to the coupling process that is converted into benzene
In the present embodiment process, the xylogen sample of xylogen raw material sources Lan Xu Bioisystech Co., Ltd in Hefei, principal element consists of carbon, hydrogen and oxygen element (element ratio is C:H:O=62.55:5.13:32.30) in the xylogen raw material.The lignin depolymerization catalyzer is that commercial silica alumina ratio is 100 HZSM-5 zeolite, and aromatics conversion of monomer catalyzer is 16% a commercial ReY catalyzer.With the mixed of these two kinds of catalyzer according to 1:1, the kaolin that adds 10wt% is as sticker.Promptly obtain having lignin depolymerization and monomer set to the dual-function catalyst finished product that is converted into benzene.
The catalytic conversion reactor that uses is the tubular fixed bed catalytic reactor that has indirect heating and thermal insulation layer.Its both ends are connected with reactant (xylogen) and carrier gas (N
2Gas) reactant feeds pipeline and reaction product output channel; The xylogen hold-up vessel links to each other with feeder; Carrier gas channel and reactant feed pipeline and connect, and are respectively equipped with gas control valve and reactant flow amount controller, on the access tube pipeline outer wall, are provided with the outer heating unit that is used for preheating; On the reaction product output channel, be connected with in turn and comprise double-condenser, product liquid scoop, solid product scoop and exhaust collection device; The wire that in the inner chamber of barrel reactor, is provided with ceramic insulating layer and is communicated with external source, power wiry is selected by desired reaction temperature and reactor volume, and adopting the built-in metal silk in the present embodiment process is the Fe-Cr-Al wire.
The xylogen system benzene method of PROCESS COUPLING: at first the dual-function catalyst finished product is filled in around the reactor drum built-in metal silk and with the wire surface uniform contact; Catalyst levels is by per hour lignin feed amount decision; Catalyst levels is 25g in the present embodiment; Connect preheating zone heat tape power supply then, the temperature that makes the preheating zone is 200
oC; Connection is used to provide the power supply wiry of thermoelectron and internal heating, makes to feed electric current wiry to be respectively 0 A, 2 A and 5A constant, and through the power of conditioned reaction device externally heated oven, making the temperature in the reactor drum inner chamber is 550-650
oC regulates.Open at last with xylogen raw material storage tanks outlet pipe on the sampling pump that links to each other and the valve of carrier gas; Regulate the flow of xylogen sample size and carrier gas; Xylogen after preheating and carrier gas feed pipeline through reactant and get into reactor drum, make xylogen depolymerization reaction and aromatics monomer set take place simultaneously to the catalyzed reaction that is converted into benzene under the synergy of thermoelectron and catalyzer.Collect the product liquid that contains a large amount of benzene with drainer.In the present embodiment, xylogen flow 100g/h, carrier gas flux 220 ml/min.
When temperature of reaction is 550
oWhen C and electric current were 2A, benzene productive rate (by the ratio calculation of actual benzene yield that obtains and the plain usage quantity of raw material wood) and benzene selective (pressing the actual benzene yield that obtains and the ratio calculation of all liquid product quality) were respectively 0.07 (kg benzene/kg xylogen) and 77.5wt%; When temperature of reaction is 550
oC, when electric current was increased to 5A, benzene productive rate and benzene selective were respectively 0.08 (kg benzene/kg xylogen) and 93.0 wt%.It is thus clear that increase electric current optionally improving of benzene in the product there is very big effect.
Also tested the situation of the aromatics monomer catalyzed conversion when not having the electric current enhancement in the present embodiment process.Promptly close and connect Fe-Cr-Al power supply wiry, making and feeding Fe-Cr-Al electric current wiry is 0, and the power through conditioned reaction device externally heated oven, makes temperature in the reactor drum inner chamber at 550-650
oRegulate in the C scope.Under the differing temps situation, compare the growing amount of xylogen sample size and benzene then, and calculate the productive rate and the selectivity of benzene, the result is as shown in table 3.Can find out by this table: when adopting the catalysis conversion method of no current effect, in same reaction temperature 550
oUnder the C situation, benzene productive rate and benzene selective all are lower than the situation that galvanic action is arranged; When increasing temperature of reaction to 650
oC, the productive rate of benzene all can increase with selecting thereupon.It can also be seen that from present embodiment, adopt method of the present invention, no matter have or not the feeding electric current, the selectivity of benzene all is higher than far away and adopts that lignin conversion is the selectivity (generally being lower than 20%) of benzene in the prior art.
Table 3 (benzene productive rate in the table and selective data are the MV of three experiments)
Embodiment 4Lignin depolymerization and aromatics monomer set is integrated to two reactors in series that are converted into benzene
Present embodiment is intended to estimate and adopts lignin depolymerization and aromatics monomer set to the series connection integrated approach that is converted into benzene, promptly carries out continuously in that lignin depolymerization reaction and aromatics conversion of monomer are reacted to be connected in two reactor drums.
In the present embodiment process, the xylogen sample of xylogen raw material sources Lan Xu Bioisystech Co., Ltd in Hefei, principal element consists of carbon, hydrogen and oxygen element (element ratio is C:H:O=62.55:5.13:32.30) in the xylogen raw material.The lignin depolymerization catalyzer is that commercial silica alumina ratio is 100 HZSM-5 zeolite, and aromatics conversion of monomer catalyzer is 16% a commercial ReY catalyzer.With first reactor drum as the lignin depolymerization reactor drum; Second reactor drum be as aromatics conversion of monomer reactor drum, the inside 16% ReY catalyzer of packing into.The reactor drum that uses is the tubular fixed bed catalytic reactor that has indirect heating and thermal insulation layer.Its both ends are connected with reactant (xylogen) and carrier gas (N
2Gas) reactant feeds pipeline and reaction product output channel; The xylogen hold-up vessel links to each other with feeder; Carrier gas channel and reactant feed pipeline and connect, and are respectively equipped with gas control valve and reactant flow amount controller, on the access tube pipeline outer wall, are provided with the outer heating unit that is used for preheating; On the reaction product output channel, be connected with in turn and comprise double-condenser, product liquid scoop, solid product scoop and exhaust collection device; The wire that in the inner chamber of barrel reactor, is provided with ceramic insulating layer and is communicated with external source, power wiry is selected by desired reaction temperature and reactor volume, and adopting the built-in metal silk in the present embodiment process is the Fe-Cr wire.
Two the xylogen system that reactors in series is integrated benzene methods: at first 16% ReY catalyzer is filled in first reactor drum (lignin depolymerization reactor drum), consumption is 5g.The HZSM-5 catalyzer is filled in second reactor drum (aromatics conversion of monomer reactor drum), and consumption is 10g.Connect the power supply wiry that is used to provide thermoelectron and internal heating then; Make and feed that electric current wiry is respectively 0A and 4.0A is constant; Through the power of conditioned reaction device externally heated oven, make the temperature in first reactor drum and second the reactor drum inner chamber be respectively 550
oC.Open at last with xylogen raw material storage tanks outlet pipe on the sampling pump that links to each other and the valve of carrier gas; Regulate the flow of xylogen sample size and carrier gas; Xylogen after preheating and carrier gas feed pipeline through reactant and get into first reactor drum; Make xylogen under the synergy of thermoelectron and catalyzer, depolymerization reaction take place, the aromatics monomer mixture of exporting from first reactor drum directly gets into second reactor drum through pipeline, under the synergy of thermoelectron and catalyzer, is converted into benzene.Collect the product liquid that contains a large amount of benzene with drainer.In the present embodiment, xylogen flow 100g/h, carrier gas flux 220 ml/min.When temperature of reaction is 550
oWhen C and electric current were 4.0 A, benzene productive rate (by the ratio calculation of actual benzene yield that obtains and the plain usage quantity of raw material wood) and benzene selective (pressing the actual benzene yield that obtains and the ratio calculation of all liquid product quality) were respectively 0.08 (kg benzene/kg xylogen) and 83.0 wt%.
Also tested the conversion situation when not having the electric current enhancement in the present embodiment process.Promptly close connection Fe-Cr power supply wiry, making and feeding Fe-Cr electric current wiry is 0, and through the power of conditioned reaction device externally heated oven, making the temperature in the reactor drum inner chamber is 550
oC.Measure the growing amount of xylogen sample size and benzene then, and calculate the productive rate and the selectivity of benzene, the result is as shown in table 4.Can be found out by this table: when adopting the catalysis conversion method of no current effect, benzene productive rate and benzene selective all are lower than the situation when the electric current enhancement is arranged.
Table 4 (benzene productive rate in the table and selective data are the MV of three experiments)
Can find out from embodiment 3 and embodiment 4; During the xylogen system of utilization benzene; Can lignin depolymerization conversion and aromatics monomer set be carried out in a reactor drum to transforming these two PROCESS COUPLING of system benzene, also can above-mentioned two preparation processes be connected in two reactor drums successively and carry out continuously.
Claims (3)
1. one kind is utilized the directed method for preparing benzene of xylogen; Comprise the reactor drum of selecting for use the tubular fixed bed catalytic reactor that is provided with conductive wire in the chamber to be prepared as benzene as xylogen; Said powder catalyst is filled in around the built-in metal silk and the wire surface uniform contact, starts reactor drum then and connect the external source of conductive wire, make to feed raw material generation conversion reaction; Described conductive wire is Ni-Cu or Ni-Cr, or a kind of among the Fe-Cr-Al; On the feed pipe of reactor drum and catalyticreactor, be provided with heating unit; It is characterized in that; Said conversion reaction be divided into two the step carry out: the first step utilizes the tubular fixed bed catalytic reactor that the xylogen catalytic degradation is converted into the aromatics monomer; The feeding raw material is an xylogen; Catalyst system therefor is pulverous zeolite catalyst or the modified zeolite catalyst that contains the transition metal nickel element, and its usage quantity is that to make the weight ratio of catalyzer hourly and xylogen be 0.3-10, and the product that obtains is an aromatic liquid class monomer mixture; Reaction conditions is: under inert gas atmosphere, temperature is at 450-650 in the reactor cavity
oIn the C scope, the feeding electric current of conductive wire is between the 0A-5A; Second step was to utilize the tubular fixed bed catalytic reactor to make aromatics monomer mixture orientation be converted into benzene, fed raw material for being preheating to 200-250
oThe aromatics monomer mixture of C; Catalyst system therefor is the zeolite catalyst of the pulverous Re of containing element; It is 0.2-15 that its usage quantity per hour makes aromatics monomer mixture and the weight ratio that contains the zeolite catalyst of Re element; Reaction conditions is: under inert gas atmosphere, temperature is at 450-650 in the reactor cavity
oIn the C scope, the feeding electric current of conductive wire is 0A-5A; The product that finally obtains is to be main mixing liquid with benzene.
2. the directed method for preparing benzene of xylogen of utilizing as claimed in claim 1; It is characterized in that; Said conversion reaction is to use two tubular fixed bed catalytic reactors; With the reactor drum that is used for lignin depolymerization of the first step and the aromatics monomer set in second step to the integrated production line of the reactors in series that is converted into benzene; That is: the xylogen of feeding changes into the aromatics monomer mixture at first reactor drum that is used for lignin depolymerization, and it directly gets into second aromatics monomer set to the reactor drum that is converted into benzene from this reactor drum output back, and accomplishing therein that conversion reaction obtains with benzene is main mixing liquid.
3. the directed method for preparing benzene of xylogen of utilizing as claimed in claim 1; It is characterized in that; Said conversion reaction is that described xylogen catalytic degradation and aromatics monomer set are carried out in a catalytic bed reactor to the two step PROCESS COUPLING that are converted into benzene simultaneously, that is:
Earlier with zeolite catalyst or contain the transition metal nickel element modified zeolite catalyst, mix according to mass ratio 1:10-5:1 with the zeolite catalyst of rhenium-containing element; And add sticker and mix and obtain having lignin depolymerization and the bifunctional mixed catalyst of aromatics conversion of monomer, wherein the mass content of sticker accounts for the 2-40wt% of total difunctional mixed catalyst quality; Again said difunctional mixed catalyst is filled in the tubular fixed bed catalytic reactor around the wire and with the wire surface uniform contact; Start reactor drum then and connect the external source of conductive wire, make in the reactor drum under inert gas atmosphere, temperature is at 450-650
oIn the C scope, the feeding electric current of conductive wire is 0-5.0A, will be preheating to 200-250
oThe xylogen powder stock of C is passed in the reactor drum; Its feeding amount is to make that the weight ratio of catalyzer and xylogen is 0.3-10; Make xylogen that lignin depolymerization reaction and the conversion reaction of aromatics monomer set to preparation benzene take place in the one-part form catalytic bed reactor simultaneously, obtaining with benzene is the mixing liquid of leading.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104387223A (en) * | 2014-10-29 | 2015-03-04 | 华东师范大学 | Method for catalytically converting lignin into aromatic hydrocarbon by using two-step process |
| US10308877B2 (en) | 2014-12-29 | 2019-06-04 | Shell Oil Company | Process for production of aromatics via pyrolysis of lignin-comprising material |
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| US20030100807A1 (en) * | 2001-10-05 | 2003-05-29 | Shabtai Joseph S | Process for converting lignins into a high octane additive |
| CN101824330A (en) * | 2010-04-30 | 2010-09-08 | 中国科学技术大学 | Catalytic thermal cracking method for lignin |
| CN101965323A (en) * | 2008-03-19 | 2011-02-02 | 东丽株式会社 | Method of converting ethylbenzene and process for producing p-xylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030100807A1 (en) * | 2001-10-05 | 2003-05-29 | Shabtai Joseph S | Process for converting lignins into a high octane additive |
| CN101965323A (en) * | 2008-03-19 | 2011-02-02 | 东丽株式会社 | Method of converting ethylbenzene and process for producing p-xylene |
| CN101824330A (en) * | 2010-04-30 | 2010-09-08 | 中国科学技术大学 | Catalytic thermal cracking method for lignin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104387223A (en) * | 2014-10-29 | 2015-03-04 | 华东师范大学 | Method for catalytically converting lignin into aromatic hydrocarbon by using two-step process |
| CN104387223B (en) * | 2014-10-29 | 2016-08-24 | 华东师范大学 | It is the method for aromatic hydrocarbons by two-step method catalyzed conversion lignin |
| US10308877B2 (en) | 2014-12-29 | 2019-06-04 | Shell Oil Company | Process for production of aromatics via pyrolysis of lignin-comprising material |
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