CN102701898B - 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 generating in coal coking process contains a certain amount of benzene.From 1 ton of coal, can extract approximately 1 kilogram of benzene.Global most benzene derives from non-renewable fossil feedstock now, and producing at present the most important three kinds of techniques of benzene is oil catalytic reforming, toluene hydrodealkylation and steam cracking.Along with a large amount of consumption of coal and oil traditional resource and the attention of environment protection, in the urgent need to developing reproducible green alternative materials.
The biomass total amount being generated by photosynthesis every year on the earth exceedes 2,000 hundred million tons, 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 with the speed regeneration of annual 50000000000 tons of left and right, the xylogen byproduct that only paper-making industry produces just reaches 5,000 ten thousand tons/year, and xylogen is also the large byproduct during the s-generation alcohol fuel 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 mainly comprises that xylogen hydrogenating reduction, catalyzed oxidation, thermo-cracking, bio oil are concise, xylogen gasification and biochemical conversion etc.For example document: (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).Xylogen catalytic hydrogenating reduction is by high-pressure hydrogenation, forms main containing compounds such as phenols, alkyl benzene and alkanes.Xylogen catalyzed oxidation is (as O at oxygenant
2/ H
2o
2) and catalyst action under, obtain comprising the mix products such as aldehyde, acid, aromatic alcohol and quinones.In addition, xylogen is at 400-600
othe organic liquid producing by thermo-cracking under gentle oxygen free condition in C, is called 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.).Xylogen catalytic pyrolysis is under the effect of catalyzer, obtains the 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, for heat and generating power, 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 prior art, that has reported mainly contains two kinds of technique approach from xylogen benzene processed: one is to adopt xylogen catalytic hydrogenation method, the product obtaining is the aromatics of the compositions such as phenols, benzene class and alkanes, the selectivity of benzene is generally lower than 10%, and this technique need to be used outside hydrogen source and react under condition of high voltage.Another kind of xylogen benzene process processed is xylogen Deep Catalytic Cracking process, the method is to utilize xylogen on the zeolite catalysts such as ZSM-5 molecular sieve, to carry out catalytic pyrolysis, the product forming mainly contains the material compositions such as toluene, dimethylbenzene, naphthalene, methylnaphthalene, benzene and phenols, and in the aromatic product obtaining, the selectivity of benzene is generally no more than 20%.Can find out, the products distribution that in existing technique, xylogen benzene processed obtains is very wide, and the selectivity of target product-benzene is very low, cannot reach the object 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.Utilize xylogen benzene processed that an important flat molecule of basic chemical industry raw material and the high-end chemical of development can be provided for petrochemical industry, still, it is not yet seen the relevant report of the controlled transformation technology of xylogen taking directional preparation benzene as target.
Summary of the invention
The object of the invention is to, controllably produce the technical barrier of benzene for the xylogen orientation that waits to solve in prior art, provide the one can be under without external hydrogen source, middle normal temperature and pressure and green gentle reaction environment, make the method for xylogen directional preparation benzene.
Object of the present invention is achieved through the following technical solutions.
The method of utilizing xylogen directional preparation benzene of the present invention, comprise the reactor of selecting the tubular fixed bed catalytic reactor that is provided with conductive wire in chamber to be prepared as benzene as xylogen, by described powder catalyst be filled in built-in metal silk around with wire surface uniform contact, then start reactor and connect the external source of conductive wire, make to pass into raw material generation conversion reaction, described conductive wire is Ni-Cu or Ni-Cr, or one in Fe-Cr-Al; On the feed pipe of reactor and catalyticreactor, be provided with heating unit; It is characterized in that, described conversion reaction is divided into two steps and carries out: the first step utilizes tubular fixed bed catalytic reactor that xylogen catalytic degradation is converted into aromatics monomer, passing into raw material is xylogen, used catalyst is pulverous zeolite catalyst or the modified zeolite catalyst containing transition metal nickel element, its usage quantity is that to make the weight ratio of catalyzer hourly and xylogen be 0.3-10, the product obtaining is aromatic liquid class monomer mixture, and reaction conditions is: the inherent rare gas element of reactor cavity is (as N
2gas) under atmosphere, temperature is at 450-650
owithin the scope of C, the electric current that passes into of conductive wire is between 0A-5A; Second step is to utilize tubular fixed bed catalytic reactor to make aromatics monomer mixture orientation be converted into benzene, passes into raw material for being preheating to 200-250
othe aromatics monomer mixture of C, used catalyst is pulverous zeolite catalyst containing Re element, it is 0.2-15 that its usage quantity makes aromatics monomer mixture per hour and the weight ratio of the zeolite catalyst containing Re element, and reaction conditions is: the inherent rare gas element of reactor cavity is (as N
2gas) under atmosphere, temperature is at 450-650
owithin the scope of C, the electric current that passes into of conductive wire is 0A-5A; The product finally obtaining is taking benzene as main mixing liquid.
In actual applications, produce for realizing serialization, can use two tubular fixed bed catalytic reactors, by the aromatics monomer set of the reactor for lignin depolymerization of the first step and second step to the integrated production line of the reactors in series that is converted into benzene, that is: at first, the reactor for lignin depolymerization changes into aromatics monomer mixture to the xylogen passing into, it directly enters second aromatics monomer set to the reactor that is converted into benzene from this reactor output, completes therein conversion reaction and obtains taking benzene as main mixing liquid.
In actual applications, be the flow process that simplifies the operation, also described xylogen catalytic degradation and aromatics monomer set can be carried out in a catalytic bed reactor to the two step PROCESS COUPLING that are converted into benzene simultaneously, that is:
First by zeolite catalyst or containing the modified zeolite catalyst of transition metal nickel element, mix according to mass ratio 1:10-5:1 with the zeolite catalyst of rhenium-containing (Re) element, and add binding agent to mix to obtain having lignin depolymerization and the bifunctional mixed catalyst of aromatics conversion of monomer, wherein the mass content of binding agent accounts for the 2-40wt% of total difunctional mixed catalyst quality; Again described difunctional mixed catalyst is filled in tubular fixed bed catalytic reactor to wire around and with wire surface uniform contact; Then start reactor and connect the external source of conductive wire, make the inherent rare gas element of reactor (as N
2gas) under atmosphere, temperature is at 450-650
owithin the scope of C, the electric current that passes into of conductive wire is 0-5.0A, will be preheating to 200-250
othe lignin powder powder stock of C is passed in reactor, its intake is that to make the weight ratio of catalyzer and xylogen be 0.3-10, make xylogen that the conversion reaction of lignin depolymerization reaction and aromatics monomer directional preparation benzene occur in one-part form catalytic bed reactor simultaneously, obtain taking benzene as main mixing liquid.
Zeolite catalyst, the modified zeolite catalyst that contains transiting metal nickel using in above process and the zeolite catalyst that contains Re element all can directly be buied from market, also can be prepared by following methods:
Preparation contains the zeolite catalyst of transition metal nickel element: the nickelous nitrate that compound concentration is 0.05-0.5mol/L or the solution of nickel acetate; The active ingredient zeolite of selecting is impregnated in above solution, and then drying, sintering obtain the zeolite catalyst through transition metal modification, and wherein the mass content of transition metal is the 0-40 wt% of zeolite catalyst quality; Described active ingredient zeolite is one or more mixture of ZSM-5 series zeolite, β zeolite, HY zeolite, overtemperature Y zeolite; Be powder by described modified zeolite catalyst and binding agent mixed grinding, wherein the mass content of binding agent accounts for the 2-35wt% of total mixed powder quality, and described binding agent is kaolin or field fine powder; By above-mentioned mixed powder compressing tablet, dry, then fragmentation sieves that to obtain particle diameter be 40-80 object fine-particle powder, is the zeolite catalyst finished product containing transition metal nickel element.
Preparation contains the element modified zeolite catalyst of Re: the nitric acid rhenium solution that compound concentration is 0.05-0.5mol/L; The active ingredient zeolite of selecting is impregnated in above solution, then drying, sintering obtain the zeolite catalyst element modified through Re, wherein the content of Re is 0-20 wt%, and described active ingredient zeolite is one or more mixture of ZSM-5 series zeolite, β zeolite, HY zeolite, overtemperature Y zeolite; Be powder by above-mentioned modified zeolite catalyst and binding agent mixed grinding, wherein the content of binding agent accounts for the 2-35wt% of total mixed powder quality, and described binding agent is kaolin or field fine powder; By above-mentioned mixed powder compressing tablet, dry, then fragmentation sieves that to obtain particle diameter be 40-80 object fine-particle powder, containing the zeolite catalyst finished product of Re element.
In the inventive method, the electric current that passes into of described conductive wire is 0-5.0A, and this expression can have the external source of connection or disconnect two kinds of situations of external source.In the time passing into electric current wiry and be zero, the aromatics monomer set of described lignin depolymerization aromatics monomer processed process and second step is only all to carry out under catalyst action to the process that is converted into benzene; When passing into electric current wiry when non-vanishing, according to the thermal electron emission principle of metallic surface, energising wire provides a large amount of thermoelectrons for catalyst surface, and the aromatics monomer set of lignin depolymerization aromatics monomer processed process and second step is all to carry out under the synergy of thermoelectron and catalyzer to the process that is converted into benzene.Compare two kinds of situations, the transformation efficiency while passing into electric current is apparently higher than disconnecting external source situation.This be because, in xylogen containing be difficult to resolve in a large number from aromatics polymer, the synergy of thermoelectron and catalyzer can promote ehter bond and carbon-to-carbon rupture and induction free radical chain chemical reaction in xylogen; Also can be for the feature of the aromatics monomer mixture of multi-component complex and a small amount of oligomer, promote functional group's fracture and regrouping process in aromatics monomer, thereby realizing and making the efficient depolymerization of xylogen is aromatics monomer, makes aromatics monomer efficiently and directionally be converted into target product-benzene.
Actual measurement shows, as taking 15 wt% Ni/HZSM-5 (load the HZSM-5 zeolite catalyst of weight content as 15% nickel) as lignin depolymerization catalyzer, under the condition of 600 DEG C 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 DEG C 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).During for use aromatics monomer catalytic cracking benzene, as taking 10 wt% Re/Y type zeolites (load the y-type zeolite catalyzer of weight content as 10% rhenium) as aromatics conversion of monomer catalyzer, the aromatics monomer obtaining with xylogen catalytic pyrolysis is as raw material, under the condition of 650 DEG C of temperature of reaction and electric current 0A, the productive rate of target product-benzene is 0.10 (kg benzene/kg xylogen), and the selectivity of benzene is 96.0%; Under the condition of 550 DEG C of temperature of reaction and electric current 4A, the productive rate of target 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 one-part form catalytic bed reactor to the two step PROCESS COUPLING that are converted into benzene, when using 15 wt% Ni/HZSM-5 as lignin depolymerization catalyzer, with the dual-function catalyst that is mixed to get in mass ratio lignin depolymerization-aromatics conversion of monomer taking 10wt % Re/Y type zeolite as aromatics conversion of monomer catalyzer as 2:1, using xylogen as starting raw material, under the condition of 650 DEG C of temperature of reaction and electric current 0A, the productive rate of target product-benzene is 0.07 (kg benzene/kg xylogen), the selectivity of benzene reaches 90.0wt%, under the condition of 550 DEG C 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%.As can be seen here, adopt the xylogen catalysis benzene processed (electric current is zero) of no current effect and have the xylogen catalysis benzene processed (electric current is non-vanishing) of galvanic action to operate, all can realize the object of xylogen directional preparation benzene; But adopt while passing into electric current, can be at benzene productive rate and the benzene selective higher compared with acquisition under low reaction temperatures.
Method of the present invention can be by xylogen without external hydrogen source, middle normal temperature and pressure becomes benzene with directed Efficient Conversion under green gentle reaction environment, and all raw materials that use are various reproducible biomass, for example, can use wood chip, stalk, the xylogen that the separation such as rice husk obtains or derive from the various xylogen of the pulping process of paper industry, its raw material has aboundresources, the advantage of environmental friendliness and the aspect such as renewable, xylogen benzene processed can be petrochemical industry basic chemical industry raw material is provided, also be an important flat molecule of the high-end chemical of development, be conducive to the recycle of the sustainability that realizes resource-environmental integration.
Embodiment
Be described further by the following examples.
embodiment 1making lignin depolymerization is aromatics monomer
In the present embodiment process, xylogen raw material is purchased from Lan Xu bio tech ltd of Hefei City.In xylogen raw material, principal element consists of carbon, hydrogen and oxygen element (element ratio is C:H:O=62.55:5.83:31.62).Lignin depolymerization catalyzer is 15 wt%Ni/HZSM-5 modified zeolite catalysts.The preparation process of this catalyzer is: weigh 37.5 g Nickelous nitrate hexahydrates, add 100mL deionized water, be configured to nickel nitrate solution; Then add in upper nickel nitrate solution weighing the HZSM-5 zeolite powder 20g that silica alumina ratio is 25, shake makes solution not there be the powder of ZSM-5, leave standstill dipping moisture in evaporate to dryness solution in 80 degree water-baths again after 24 hours, then after in baking oven, 120 degree are dried, 550 degree sintering 6 hours in retort furnace.Again 15 wt%Ni/HZSM-5 catalyzer of preparation and binding agent (kaolin or field fine powder) are carried out to mixed grinding and obtain mixed powder, wherein binding agent accounts for 10 wt% of total mixed powder quality, by after above-mentioned mixed powder compressing tablet in temperature 110
ounder the condition of C dry 8 hours, sieving and obtaining particle diameter was 40-80 object microparticle, for the modified zeolite catalyst 15 wt%Ni/HZSM-5 finished products containing transition metal nickel element of lignin depolymerization.
Lignin depolymerization catalyticreactor used is a tubular fixed bed catalytic reactor with indirect heating and thermal insulation layer, what be connected with reaction raw materials (xylogen) and carrier gas at its two ends passes into pipeline and reaction product output channel, xylogen hold-up vessel is connected with feeder, carrier gas channel and reactant pass into pipeline and connect, and being respectively equipped with gas control valve and reactant flow amount controller, access tube pipeline outer wall is provided with the external heating device for preheating; On reaction product output channel, be connected with in turn and comprise double-condenser, product liquid collector, solid product collector and exhaust collection device; The wire that is provided with ceramic insulating layer and is communicated with external source in the inner chamber of barrel reactor, power wiry is selected by desired reaction temperature and reactor volume, and described built-in metal silk is Ni-Cu wire.
In the present embodiment, first by be filled in the built-in wire of reactor for 15 wt%Ni/HZSM-5 zeolite catalysts of lignin depolymerization around and with wire surface uniform contact, catalyst levels is 10g, open the valve of carrier gas nitrogen steel cylinder, regulating the flow of carrier gas is 1000ml/min, after air in question response device is discharged from, regulating the flow of carrier gas is 450 ml/min.Connect for the power supply wiry of thermoelectron and interior heating is provided, making to pass into electric current wiry, to be separately positioned on 0,2,4A constant again, by regulating the power of reactor externally heated oven, makes temperature in reactor inner chamber at 450-650
owithin the scope of C, regulate.After temperature-stable in reactor, open the valve of the feeder on xylogen raw material storage tanks outlet pipe, lignin feed amount is 10g, and xylogen and carrier gas enter catalyticreactor inner chamber through passing into pipeline, and making lignin depolymerization is liquid intermediate product-aromatics monomer mixture.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 are 2A, aromatics monomer productive rate (the aromatics monomer output obtaining by reality and the ratio calculation of xylogen sample size) is 0.25 (kg monomer/kg xylogen); When temperature of reaction is being 550
owhen C and electric current are 4A, aromatics monomer productive rate is 0.29 (kg monomer/kg xylogen).
In the present embodiment process, also done the situation of no current enhancement, closed the power supply of connection metal silk, making to pass into electric current wiry is 0, only regulates the temperature in reactor inner chamber by the power that regulates reactor externally heated oven.Then measure respectively the growing amount of xylogen sample size and lignin depolymerization product, and calculate in aromatics monomer productive rate table 1, result shows, under identical temperature of reaction, utilize the efficiency of the xylogen catalytic depolymerization of intensifying current effect can be higher than the efficiency of the xylogen catalytic depolymerization of no current enhancement.
Table 1 (in table, data are the mean value of three experiments)
embodiment 2make aromatics monomer set to being converted into benzene
In the present embodiment process, reactant feed adopts in embodiment 1 600
oc and electric current are the aromatics monomer mixture that under 0A condition, xylogen catalytic degradation produces.Catalyzer adopts 10 wt %Re/Y type rhenium-containing zeolite catalysts.The preparation process of described catalyzer is: weigh 16g nitric acid rhenium, add 100mL deionized water, be configured to nitric acid rhenium solution; Then add in the nitric acid rhenium solution configuring weighing the HY zeolite powder 20g that silica alumina ratio is 5, shake makes solution not there be the powder of HY zeolite, leave standstill dipping after 24 hours, moisture in 80 degree water-baths in evaporate to dryness solution, then after in baking oven, 120 degree are dried, 550 degree sintering 6 hours in retort furnace.Again the 10wt %Re/Y type zeolite catalyst of preparation and binding agent (kaolin or field fine powder) are carried out by a certain percentage to mixed grinding and obtain mixed powder, wherein binding agent accounts for 20 wt. % of total mixed powder quality, by after above-mentioned mixed powder compressing tablet in temperature 110
ounder the condition of C dry 8 hours, sieving and obtaining particle diameter was 40-80 object particle, for the catalyzer 10wt %Re/Y finished product of aromatics conversion of monomer.
The aromatics monomer catalytic conversion reactor of selecting is a tubular fixed bed catalytic reactor with indirect heating and thermal insulation layer, and its both ends are connected with reactant (aromatics monomer liquid mixture) and carrier gas (N
2gas) pass into pipeline and reaction product output channel, aromatics monomer stores to fill with and is connected with liquid infusion pump, carrier gas is connected with passing into pipeline respectively, and is respectively equipped with gas control valve and reactant flow amount controller, and the outer wall that passes into pipeline is provided with the external heating device for preheating; On reaction product output channel, be connected with in turn and comprise double-condenser, product liquid collector and exhaust collection device; The Ni-Cu wire that is provided with ceramic insulating layer and is communicated with external source in the inner chamber of barrel reactor, power wiry is selected by desired reaction temperature and reactor volume.Open the valve of carrier gas nitrogen steel cylinder, then connect the power supply wiry for thermoelectron and interior heating are provided, make to pass into electric current wiry and be separately positioned on 0,2,4A is constant, by regulating the power of reactor externally heated oven, makes temperature in reactor inner chamber at 550-650
owithin the scope of C, regulate.
Aromatics monomer set is to transforming benzene method processed: first the above-mentioned 10wt.%Re/Y catalyzer finished product for aromatics conversion of monomer is filled in around built-in metal silk and with wire surface uniform contact.Catalyst levels determines by the inlet amount of reaction raw materials per hour, and in the present embodiment, catalyst levels is 8g, and regulating the flow of carrier gas is 1000ml/min, and after the air in question response device is discharged from, regulating the flow of carrier gas is 150 ml/min.Then connect preheating zone heat tape power supply, make the temperature of preheating zone at 180-200
oin C; Connect for the power supply wiry of thermoelectron and interior heating is provided, making to pass into electric current wiry, to be separately positioned on 0,2,4A constant, by regulating the power of reactor externally heated oven, makes temperature in reactor inner chamber at 550-650
owithin the scope of C, regulate.Finally open sampling pump on the outlet pipe being connected with aromatics raw material monomer hold-up vessel and the valve of carrier gas, regulate reaction raw materials sample size, aromatics monomer mixture after preheating and carrier gas pass into pipeline through reactant and enter aromatics conversion of monomer reactor, make aromatics monomer mixture be converted into target product-benzene under the synergy of thermoelectron and catalyzer.In the present embodiment, aromatics raw material monomer feed rate is 50g/h, and flow rate of carrier gas is 150 ml/min.Then, measure the growing amount of reactant (being aromatics monomer liquid mixture prepared by lignin depolymerization) and benzene under different electric currents and temperature conditions, and calculate productive rate and the selectivity of benzene, the result recording is as shown in table 2.
As can be seen from Table 2: when temperature of reaction is 550
owhen C and electric current are 2A, benzene productive rate (benzene yield obtaining by reality and the ratio calculation of starting raw material xylogen usage quantity) and benzene selective (benzene yield obtaining by reality and the ratio calculation of all liquid product quality) are respectively 0.09 (kg benzene/kg xylogen) and 82.5 wt %; When temperature of reaction is 550
owhen C and electric current are 4A, benzene productive rate and benzene selective are increased to respectively 0.13 (kg benzene/kg xylogen) and 95.5 wt %.
In the present embodiment process, also do the comparative example of the aromatics monomer catalyzed conversion not having under intensifying current effect.Close and connect Ni-Cu power supply wiry, making to pass into Ni-Cu electric current wiry is 0, by regulating the power of reactor externally heated oven, makes temperature in reactor inner chamber at 550-650
owithin the scope of C, regulate.When Ni-Cu electric current wiry is 0 and temperature of reaction 550
owhen C, benzene productive rate and benzene selective are respectively 0.06 (kg benzene/kg xylogen) and 71.6 wt%.In addition, do not having intensifying current to do the used time, increasing productive rate and selectivity that temperature is conducive to improve benzene, as temperature is increased to 650
owhen C, benzene productive rate and benzene selective are increased to respectively 0.10 (kg benzene/kg xylogen) and 96.0 wt%.
Table 2 (the benzene productive rate in table, benzene selective data are the mean value of three experiments)
embodiment 3by lignin depolymerization and aromatics monomer set to the coupling process that is converted into benzene
In the present embodiment process, xylogen raw material sources are in the xylogen sample of Hefei Lan Xu Bioisystech Co., Ltd, and in xylogen raw material, principal element consists of carbon, hydrogen and oxygen element (element ratio is C:H:O=62.55:5.13:32.30).Lignin depolymerization catalyzer is the HZSM-5 zeolite that commercial silica alumina ratio is 100, and aromatics conversion of monomer catalyzer is 16% commercial ReY catalyzer.These two kinds of catalyzer are mixed according to the ratio of 1:1, add the kaolin of 10wt% as binding agent.Obtain having lignin depolymerization and monomer set to the dual-function catalyst finished product that is converted into benzene.
The catalytic conversion reactor using is the tubular fixed bed catalytic reactor with indirect heating and thermal insulation layer.Its both ends are connected with reactant (xylogen) and carrier gas (N
2gas) reactant passes into pipeline and reaction product output channel, xylogen hold-up vessel is connected with feeder, carrier gas channel and reactant pass into pipeline and connect, and are respectively equipped with gas control valve and reactant flow amount controller, are provided with the external heating device for preheating on access tube pipeline outer wall; On reaction product output channel, be connected with in turn and comprise double-condenser, product liquid collector, solid product collector and exhaust collection device; The wire that is provided with ceramic insulating layer and is communicated with external source in the inner chamber of barrel reactor, power wiry is selected by desired reaction temperature and reactor volume, and in the present embodiment process, adopting built-in metal silk is Fe-Cr-Al wire.
The xylogen benzene method processed of PROCESS COUPLING: first dual-function catalyst finished product is filled in to reactor built-in metal silk around and with wire surface uniform contact, catalyst levels is determined by lignin feed amount per hour, in the present embodiment, catalyst levels is 25g, then connect preheating zone heat tape power supply, the temperature that makes preheating zone is 200
oc; Connect for the power supply wiry of thermoelectron and interior heating is provided, make to pass into that electric current wiry is respectively 0 A, 2 A and 5A is constant, by regulating the power of reactor externally heated oven, making the temperature in reactor inner chamber is 550-650
oc regulates.Finally open and the sampling pump being connected on xylogen raw material storage tanks outlet pipe and the valve of carrier gas, regulate the flow of xylogen sample size and carrier gas, xylogen after preheating and carrier gas pass into pipeline through reactant and enter reactor, make xylogen depolymerization reaction and aromatics monomer set occur under the synergy of thermoelectron and catalyzer simultaneously to the catalyzed reaction that 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 are 2A, benzene productive rate (by the ratio calculation of the actual benzene yield obtaining and raw material wood element usage quantity) and benzene selective (pressing the actual benzene yield obtaining and the ratio calculation of all liquid product quality) are respectively 0.07 (kg benzene/kg xylogen) and 77.5wt%; When temperature of reaction is 550
oc, when electric current is increased to 5A, benzene productive rate and benzene selective are respectively 0.08 (kg benzene/kg xylogen) and 93.0 wt%.Visible increase electric current optionally improves and has very large effect benzene in product.
In the present embodiment process, also test and do not had intensifying current to make the situation of the aromatics monomer catalyzed conversion of used time.Close and connect Fe-Cr-Al power supply wiry, making to pass into Fe-Cr-Al electric current wiry is 0, and by regulating the power of reactor externally heated oven, makes temperature in reactor inner chamber at 550-650
owithin the scope of C, regulate.Then in differing temps situation, compare the growing amount of xylogen sample size and benzene, and calculate productive rate and the selectivity of benzene, result is as shown in table 3.Can be found out by this table: in the time adopting the catalysis conversion method of no current effect, in same reaction temperature 550
ounder C situation, benzene productive rate and benzene selective are all lower than the situation that has galvanic action; When increasing temperature of reaction to 650
oc, the productive rate of benzene and selection all can increase thereupon.It can also be seen that from the present embodiment, adopt method of the present invention, no matter have or not and pass into electric current, the selectivity of benzene is all far away higher than adopting the selectivity (generally lower than 20%) that in prior art, lignin conversion is benzene.
Table 3 (the benzene productive rate in table and selective data are the mean value of three experiments)
embodiment 4by integrated to two reactors in series that are converted into benzene to lignin depolymerization and aromatics monomer set
The present embodiment is intended to evaluate and adopts lignin depolymerization and aromatics monomer set to the series connection integrated approach that is converted into benzene, carries out continuously lignin depolymerization reaction and aromatics conversion of monomer being reacted in being connected on two reactors.
In the present embodiment process, xylogen raw material sources are in the xylogen sample of Hefei Lan Xu Bioisystech Co., Ltd, and in xylogen raw material, principal element consists of carbon, hydrogen and oxygen element (element ratio is C:H:O=62.55:5.13:32.30).Lignin depolymerization catalyzer is the HZSM-5 zeolite that commercial silica alumina ratio is 100, and aromatics conversion of monomer catalyzer is 16% commercial ReY catalyzer.Using first reactor as lignin depolymerization reactor; Second reactor is as aromatics conversion of monomer reactor, and the inside packs 16% ReY catalyzer into.The reactor using is the tubular fixed bed catalytic reactor with indirect heating and thermal insulation layer.Its both ends are connected with reactant (xylogen) and carrier gas (N
2gas) reactant passes into pipeline and reaction product output channel, xylogen hold-up vessel is connected with feeder, carrier gas channel and reactant pass into pipeline and connect, and are respectively equipped with gas control valve and reactant flow amount controller, are provided with the external heating device for preheating on access tube pipeline outer wall; On reaction product output channel, be connected with in turn and comprise double-condenser, product liquid collector, solid product collector and exhaust collection device; The wire that is provided with ceramic insulating layer and is communicated with external source in the inner chamber of barrel reactor, power wiry is selected by desired reaction temperature and reactor volume, and in the present embodiment process, adopting built-in metal silk is Fe-Cr wire.
Two xylogen benzene methods processed that reactors in series is integrated: first 16% ReY catalyzer is filled in first reactor (lignin depolymerization reactor), consumption is 5g.HZSM-5 catalyzer is filled in second reactor (aromatics conversion of monomer reactor), and consumption is 10g.Then connect the power supply wiry for thermoelectron and interior heating are provided, make to pass into that electric current wiry is respectively 0A and 4.0A is constant, by regulating the power of reactor externally heated oven, make the temperature in first reactor and second reactor inner chamber be respectively 550
oc.Finally open and the sampling pump being connected on xylogen raw material storage tanks outlet pipe and the valve of carrier gas, regulate the flow of xylogen sample size and carrier gas, xylogen after preheating and carrier gas pass into pipeline through reactant and enter first reactor, make xylogen, under the synergy of thermoelectron and catalyzer, depolymerization reaction occur, directly enter second reactor by pipeline from the aromatics monomer mixture of first reactor output, under the synergy of thermoelectron and catalyzer, be 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 are 4.0 A, benzene productive rate (by the ratio calculation of the actual benzene yield obtaining and raw material wood element usage quantity) and benzene selective (pressing the actual benzene yield obtaining and the ratio calculation of all liquid product quality) are respectively 0.08 (kg benzene/kg xylogen) and 83.0 wt%.
In the present embodiment process, also test and do not had intensifying current to make the conversion situation of used time.Close and connect Fe-Cr power supply wiry, making to pass into Fe-Cr electric current wiry is 0, and by regulating the power of reactor externally heated oven, making the temperature in reactor inner chamber is 550
oc.Then measure the growing amount of xylogen sample size and benzene, and calculate productive rate and the selectivity of benzene, result is as shown in table 4.Can be found out by this table: in the time adopting the catalysis conversion method of no current effect, benzene productive rate and benzene selective are all lower than there being intensifying current to make the situation of used time.
Table 4 (the benzene productive rate in table and selective data are the mean value of three experiments)
Can find out from embodiment 3 and embodiment 4, while utilizing xylogen benzene processed, lignin depolymerization conversion and aromatics monomer set can be carried out in a reactor to transforming these two PROCESS COUPLING of benzene processed, also above-mentioned two preparation process can be connected on successively in two reactors and carry out continuously.
Claims (3)
1. one kind is utilized the method for xylogen directional preparation benzene, comprise the reactor of selecting the tubular fixed bed catalytic reactor that is provided with conductive wire in chamber to be prepared as benzene as xylogen, by powder catalyst be filled in built-in metal silk around with wire surface uniform contact, then start reactor and connect the external source of conductive wire, make to pass into raw material generation conversion reaction, described conductive wire is Ni-Cu or Ni-Cr, or one in Fe-Cr-Al; On the feed pipe of reactor and catalyticreactor, be provided with heating unit; It is characterized in that, described conversion reaction is divided into two steps and carries out: the first step utilizes tubular fixed bed catalytic reactor that xylogen catalytic degradation is converted into aromatics monomer, passing into raw material is xylogen, used catalyst is pulverous zeolite catalyst or the modified zeolite catalyst containing transition metal nickel element, its usage quantity is that to make the weight ratio of catalyzer hourly and xylogen be 0.3-10, the product obtaining is aromatic liquid class monomer mixture, reaction conditions is: in reactor cavity, under inert gas atmosphere, temperature is at 450-650
owithin the scope of C, the electric current that passes into of conductive wire is between 0A-5A; Second step is to utilize tubular fixed bed catalytic reactor to make aromatics monomer mixture orientation be converted into benzene, passes into raw material for being preheating to 200-250
othe aromatics monomer mixture of C, used catalyst is pulverous zeolite catalyst containing Re element, it is 0.2-15 that its usage quantity makes aromatics monomer mixture per hour and the weight ratio of the zeolite catalyst containing Re element, reaction conditions is: in reactor cavity, under inert gas atmosphere, temperature is at 450-650
owithin the scope of C, the electric current that passes into of conductive wire is 0A-5A; The product finally obtaining is taking benzene as main mixing liquid; The described zeolite catalyst containing Re element obtains by following preparation method: the nitric acid rhenium solution that compound concentration is 0.05-0.5mol/L; The active ingredient zeolite of selecting is impregnated in above solution, then drying, sintering obtain the zeolite catalyst element modified through Re, wherein the content of Re is 0-20wt%, and is not 0, the mixture of one or more that described active ingredient zeolite is HY zeolite, overstable gamma zeolite; Be powder by above-mentioned modified zeolite catalyst and binding agent mixed grinding, wherein the content of binding agent accounts for the 2-35wt% of total mixed powder quality, and described binding agent is kaolin or field fine powder; By above-mentioned mixed powder compressing tablet, dry, then fragmentation sieves that to obtain particle diameter be 40-80 object fine-particle powder, containing the zeolite catalyst finished product of Re element.
2. the method for utilizing xylogen directional preparation benzene as claimed in claim 1, it is characterized in that, described conversion reaction is to use two tubular fixed bed catalytic reactors, by the aromatics monomer set of the reactor for lignin depolymerization of the first step and second step to the integrated production line of the reactors in series that is converted into benzene, that is: at first, the reactor for lignin depolymerization changes into aromatics monomer mixture to the xylogen passing into, it directly enters second aromatics monomer set to the reactor that is converted into benzene from this reactor output, completing therein conversion reaction obtains taking benzene as main mixing liquid.
3. the method for utilizing xylogen directional preparation benzene as claimed in claim 1, it is characterized in that, described 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:
First by zeolite catalyst or containing the modified zeolite catalyst of transition metal nickel element, mix according to mass ratio 1:10-5:1 with the zeolite catalyst that contains Re element, and add binding agent to mix to obtain having lignin depolymerization and the bifunctional mixed catalyst of aromatics conversion of monomer, wherein the mass content of binding agent accounts for the 2-40wt% of total difunctional mixed catalyst quality; Again described difunctional mixed catalyst is filled in tubular fixed bed catalytic reactor to wire around and with wire surface uniform contact; Then start reactor and connect the external source of conductive wire, make in reactor under inert gas atmosphere, temperature is at 450-650
owithin the scope of C, the electric current that passes into of conductive wire is 0-5.0A, will be preheating to 200-250
othe lignin powder powder stock of C is passed in reactor, its intake is that to make the weight ratio of catalyzer and xylogen be 0.3-10, make xylogen that the conversion reaction of lignin depolymerization reaction and aromatics monomer directional preparation benzene occur in one-part form catalytic bed reactor simultaneously, obtain taking benzene as main mixing liquid.
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