CN104971775A - Solid acid catalyst and application thereof to synthesis of reproducible diesel oil or aviation kerosene - Google Patents
Solid acid catalyst and application thereof to synthesis of reproducible diesel oil or aviation kerosene Download PDFInfo
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Abstract
The invention relates to preparation of a solid acid catalyst and application of the solid acid catalyst to an alkylation reaction between lignocellulose-based platform compounds. The preparation method of a sodium lignin sulfonate derived phenolic aldehyde resin solid acid catalyst, provided by the invention is commonly divided into two steps: (1) adding a carbonyl compound into a sodium lignin sulfonate water solution to be used as a cross-linking agent; adding a phenol functional group in acid catalyzed sodium lignin sulfonate and carbonyl compound into the mixture to be subjected to a phenolic aldehyde condensation reaction to obtain a high-molecular polymer difficultly dissolved in water; and (2) carrying out ion exchange on a condensation product generated by the step 1 to obtain an acidic resin material containing sulfonate groups. According to the catalyst, the raw materials are cheap and easily obtained and the preparation process is simple; and the catalyst has very high catalytic activity and selectivity on the alkylation reaction between a lignocellulose-based furan compound and the carbonyl compound without solvents. An alkylated product obtained by the reaction is hydrogenated and deoxygenized to obtain the diesel oil or the aviation kerosene. The cheap and efficient solid acid catalyst, which is used for synthesizing a diesel oil or aviation kerosene precursor, by the lignocellulose-based platform compounds is provided by the invention.
Description
Technical field
The present invention relates to preparation method and the application of alkylated reaction between lignocellulosic base furan compound and carbonyls thereof of the acidic resins solid acid catalyst that a kind of sodium lignin sulfonate derives.Specifically comprise two steps: 1) in lignin sulfonic acid sodium water solution, add carbonyls and make crosslinking agent, in this mixture, then add the reaction of acid solution catalysis phenol formaldehyde condensation; 2) condensation product by generating step 1 carries out ion-exchange and obtains the acidic resins material containing sulfonate radical.Compared with currently reported solid acid catalyst, catalyst raw material of the present invention is cheap and easy to get, catalyst preparation process is simple, has higher activity and selectivity to the alkylated reaction under condition of no solvent between lignocellulosic base furan compound and carbonyls.The alkylate obtained by this reaction can obtain diesel oil or aviation kerosine alkane after hydrogenation deoxidation.The invention provides a kind of a kind of Cheap highly effective catalyst by lignocellulosic based platform compou nd synthesis diesel oil or aviation kerosine precursor.
Background technology
The environmental problems such as a large amount of rows of minimizing and the greenhouse gases caused that burnt by fossil energy day by day of fossil resource become increasingly conspicuous, in addition the social required quantity of the energy is also continuing to increase, oil price rises steadily, develop the new forms of energy of alternative fossil resource, open up renewable fuel oil supply new channel imperative.Living beings are applied in the production of material with carbon element, fuel and chemicals as a kind of reproducible organic carbon source becomes current hot research.
Diesel oil is one of main transport fuel, its composition mainly comprise carbon number 9 ~ 18 chain hydrocarbon, cyclic hydrocarbon, aromatic hydrocarbon composition.As national strategic goods and materials, the international demand amount of aviation kerosine is also increasing day by day.Aviation kerosine is generally made up of the alkane of carbon number between 6 ~ 16.Common are Jet-A and JP-8 two profiles number at present, wherein JP-8's is composed as follows: carbon number be 8 ~ 15 linear paraffin account for 35%, carbon number be 8 ~ 15 branched paraffin account for 35%, carbon number be 7 ~ 10 aromatic hydrocarbon account for 18%, carbon number be 6 ~ 10 cycloalkane account for 7%.From the viewpoint of protection of the environment, national energy security and potential economic worth three, greatly develop biodiesel and aviation kerosine technology has far-reaching strategic importance.
Lignocellulosic is the main component of agriculture and forestry organic waste material, is biomass resource the most rich and easy to get.Take lignocellulosic as raw material, by chemistry or biochemical method its depolymerization generated the Small molecular platform chemicals of a series of high reaction activity.These platform chemicals are obtained by C-C coupling reaction there is the oxygen-containing organic compound intermediate of diesel oil or aviation kerosine chain length range, then by the alkane of these intermediate hydrogenation deoxidations acquisition diesel oil or aviation kerosine scope be current international bio matter converting field one important research direction.Compared with the biodiesel obtained with additive method or aviation kerosine, lignocellulosic base diesel oil or aviation kerosine have low in raw material price, wide material sources, do not strive grain with people, do not strive with grain etc. advantage.
Alkylated reaction is a kind of important C-C coupling reaction by lignocellulosic based platform compou nd synthesis diesel oil or aviation kerosine precursor.At document (Angew.Chem.Int.Ed.2011,50,2375 – 2378, Energy & Environmental Science.2012, 5, 6328) in, with sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid, Amberlyst-15, MCM-41, the delamination zeolite ITQ-2 of modification is catalyst, by 2-methylfuran and acetaldehyde, propionic aldehyde, hutanal, valeral, 5 hydroxymethyl furfural, 5 methyl furfural, acetone, pentanone, isopropylidene acetone, and alkylated reaction has successfully synthesized the oxygen-containing organic compound intermediate that a series of carbon number with branched structure is 8 ~ 16 between 2-methylfuran hydrolysate (levulic aldehyde), and a series of branched paraffin with diesel oil and aviation kerosine chain length range has been synthesized to these oxygen-containing organic compound intermediate hydrogenation deoxidations.Relative to homogeneous catalysis, the catalyst used in heterogeneous catalysis is easy to reclaim, poor to equipment corrosion, more environmental protection.(Chinese patent: application number: 201110346501.1 in the work in this seminar early stage; 201210169817.2; 20121043947.9 with document ChemSusChem.2012,5,1958 – 1966; Bioresource Technology.2013,134,66 – 72; Chem.Commun., 2013,49,5727 ~ 5729), a series of oxygen-containing organic compound with diesel oil and aviation kerosine carbon number range is obtained by the alkylated reaction between the 2-methylfuran of a series of solid acid catalysis and lignocellulosic base carbonyls (furfural, ethyl levulinate, butyraldehyde, acetone, hydroxypropanone-, cyclopentanone, Mesityl oxide etc.) or aldol reaction, and by having synthesized to the hydrogenation deoxidation of alkylate the branched paraffin that some have diesel oil or aviation kerosine scope.Best by the acidity and selective discovery Nafion-212 catalytic activity that contrast different solid acid.But Nafion-212 catalyst is expensive.Therefore, from practical standpoint, need to develop some and there is greater activity and solid acid catalyst cheap and easy to get to alkylated reaction between lignocellulosic base furan compound and carbonyls.
Lignosulfonates are (as sodium lignin sulfonate, calcium lignosulfonate) be that a kind of important accessory substance of current slurrying and paper industry is mainly used in macromolecular material, cement water reducing agent, Surfactants Used for Oil field, dispersant, flocculant, corrosion inhibiting and descaling agent, agricultural chemicals, industry adhesive etc., there is vast potential for future development.In this patent, we find that the acidic resins that sodium lignin sulfonate derives can be used as solid acid for the alkylated reaction between lignocellulosic base furan compound and carbonyls, and have showed good activity and stability in these reactions.Can obtain by these reactions the oxygen-containing organic compound that a series of carbon number is 8 ~ 16, these compounds obtain the branched paraffin meeting diesel oil and aviation kerosine structural requirement by hydrogenation deoxidation.
Summary of the invention
The object of the invention is to provide a kind of preparation method that can be used for the high-performance solid acid catalyst of alkylated reaction between lignocellulosic base furan compound and carbonyls.
The present invention is achieved by the following technical solutions:
1) being raw material with sodium lignin sulfonate, take carbonyls as crosslinking agent, adds the carrying out of acid catalysis phenol formaldehyde condensation reaction after both being mixed.Sodium lignin sulfonate is soluble in water, and controlling its mass concentration is 10 ~ 40%.Then in lignin sulfonic acid sodium solution, dropwise crosslinking agent is added and the amount ratio controlling crosslinking agent and sodium lignin sulfonate is 5 ~ 30mmol
crosslinking agent/ g
sodium lignin sulfonate.Carbonyls as crosslinking agent is one or more in formaldehyde, formic acid, acetaldehyde, butyraldehyde, furfural, glucose, levulic acid, preferred formaldehyde.After the two being mixed, in this mixture, dropwise add acid solution, controlling hydrogen ion concentration in final mixture is 1 ~ 5mol/L.Inorganic acid is one or more in sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, phosphotungstic acid, phosphomolybdic acid; Organic acid is one or more in TFMS, trifluoroacetic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, acetic acid, monoxone.In condensation reaction mixture, the concentration of acid is 0.1 ~ 5mol/L.Condensation reaction is carried out in round-bottomed flask, and reaction temperature is 50 ~ 120 DEG C, and the reaction time is 1 ~ 12 hour;
2) gained condensation product carries out ion-exchange with certain density acid solution and makes it change into the acidic resins of proton type by ionic after suction filtration, drying, grinding, then this resin suction filtration, washing is just obtained required high-performance solid acid catalyst to neutral, dry.Ion exchange reagent used is one or more the mixed solution in inorganic acid or aqueous solutions of organic acids, the preferably sulfuric acid aqueous solution.Sulfuric acid concentration used is 0.1 ~ 5mol/L.In addition, the ratio of condensation product and acid solution controls as 5g
condensation product/ 50 ~ 500mL
acid solution.Ion exchange conditions is ion-exchange 1 ~ 12 hour at 20 ~ 80 DEG C.
The derivative acidic resins solid acid catalyst of the sodium lignin sulfonate of this patent synthesis to can be used between lignocellulosic base furan compound and carbonyls in alkylated reaction.Lignocellulosic base furan compound is one or both the mixture in furans, 2-methylfuran, hydroxymethylfurans, preferred 2-methylfuran; Lignocellulosic base carbonyls is formaldehyde, formic acid, hutanal, furfural, acetone, hydroxypropanone-, one or more the mixture in ethyl levulinate.Successively add in round-bottomed flask by reaction substrate, the molar ratio controlling furan compound and carbonyls is 0.25 ~ 4.Alkylated reaction temperature is 0 ~ 80 DEG C, and catalyst amount and furan compound ratio control to be 0.015 ~ 0.3g
catalyst/ 40mmol
furan compound, the reaction time is 0.5 ~ 12 hour, preferably 1.5 ~ 8 hours.Alkylation reaction product is the oxygenatedchemicals of carbon number between 8 ~ 16, and these oxygenatedchemicals make diesel oil or aviation kerosine alkane through hydrogenation deoxidation.
Formula 1 is typical 2-methylfuran and formaldehyde (a), formic acid (b), furfural (c), hydroxypropanone-(d), acetone (e), hutanal (f), ethyl levulinate (g), the reaction scheme of Reactive Synthesis diesel oil, aviation kerosine presoma.By these alkylated reactions can in solvent-free mild reaction conditions and in the shorter reaction time, high yield obtains carbon chain lengths is the oxygen-containing organic compound of 8 ~ 16, these compounds can be used as the presoma synthesizing renewable diesel or aviation kerosine scope branched paraffin.The present invention with lignocellulosic based platform compound for raw material, be there is the oxygen-containing organic compound presoma of diesel oil or aviation kerosine carbon-chain structure, for the production of biodiesel and aviation kerosine provides a kind of new sustainable approach to development by alkylated reaction preparation.
The alkylated reaction route of formula 1.2-methylfuran and multiple lignocellulosic base carbonyls
Tool of the present invention has the following advantages:
The acidic resins that sodium lignin sulfonate provided by the present invention derives can be used for the alkylated reaction between multiple lignocellulosic based platform compound, having the advantages that cheaper starting materials is easy to get, synthetic method simple, substrate universality is high, is a kind of solid acid catalyst having much development prospect.Directly can make by hydrogenation deoxidation the branched paraffin meeting diesel oil and aviation kerosine carbon number and freezing point and require with the alkylate become with this catalyst.
Detailed description of the invention
Embodiment 1 ~ 84
Resin precursor is made by condensation reaction
Sodium lignin sulfonate is soluble in water, and controlling its mass concentration is 10 ~ 40%.Then in lignin sulfonic acid sodium solution, dropwise crosslinking agent is added and the amount ratio controlling crosslinking agent and sodium lignin sulfonate is 5 ~ 30mmol
crosslinking agent/ g
sodium lignin sulfonate.Carbonyls as crosslinking agent is one or more in formaldehyde, formic acid, acetaldehyde, butyraldehyde, furfural, glucose, levulic acid.After the two being mixed, in this mixture, dropwise add acid solution, controlling hydrogen ion concentration in final mixture is 1 ~ 5mol/L.Inorganic acid is one or more in sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, phosphotungstic acid, phosphomolybdic acid; Organic acid is one or more in TFMS, trifluoroacetic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, acetic acid, monoxone.In condensation reaction mixture, the concentration of acid is 0.1 ~ 5mol/L.Condensation reaction is carried out in round-bottomed flask, and reaction temperature is 50 ~ 120 DEG C, and the reaction time is 1 ~ 12 hour;
Gained condensation product carries out ion-exchange with certain density acid solution after suction filtration, drying, grinding makes it change into the acidic resins of proton type by ionic, then this resin suction filtration, washing is just obtained required high-performance solid acid catalyst to neutral, dry.Ion exchange reagent used is inorganic acid or the organic acid aqueous solution, the preferably sulfuric acid aqueous solution, and concentration is 0.1 ~ 5mol/L.Ion-exchange temperature is 20 ~ 80 DEG C, and ion-exchange time is 1 ~ 12 hour.
In the active testing of catalyst synthesized by under differential responses condition, with the alkylated reaction between 2-methylfuran and furfural for model reaction.Alkylated reaction carries out in the round-bottomed flask being furnished with condensation reflux unit.In the round-bottomed flask of 50mL, add 0.15 gram of catalyst, 3.28 grams of 2-methylfurans (40mmol) and 1.92 grams of furfurals (20mmol), stir 2 hours under water bath with thermostatic control.By high performance liquid chromatography (HPLC), quantitative analysis is carried out to product.
Table 1. sodium lignin sulfonate (wooden sodium) concentration is on the impact of synthesized catalytic activity
Note: in embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of different quality, the mass concentration controlling sodium lignin sulfonate is 10% ~ 40%, then in lignin sulfonic acid sodium solution, add the formalin of a certain amount of 37%, the amount ratio controlling formaldehyde/sodium lignin sulfonate is 15mmol/g.Then in this mixture, add the carrying out of a certain amount of concentrated hydrochloric acid catalyzing and condensing reaction, the concentration controlling hydrochloric acid in final mixture is 3mol/L.Condensation reaction condition is react 6 hours at 90 DEG C.Each embodiment gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, 120 degrees Celsius of dryings, grinding.After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, 120 degrees Celsius of dryings.
As seen from Table 1, along with the raising of lignin sulfonic acid na concn, the catalytic activity of the acidic resins of final synthesis first improves and is tending towards constant afterwards.This may be due to lignin sulfonic acid na concn lower time, the haptoreaction probability of reactant molecule reduces, so cause the degree of cross linking of final catalyst not enough, sulfonate radical quantity reduces, and then causes catalytic activity to decline.
The relative concentration of table 2. formaldehyde and sodium lignin sulfonate is on the impact of synthesized catalytic activity
Note: in embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, add the formalin of a certain amount of 37%, the amount ratio controlling formaldehyde/sodium lignin sulfonate is 5 ~ 30mmol/g.Then in this mixture, adding a certain amount of concentrated hydrochloric acid, (the carrying out of catalyzing and condensing reaction, the concentration controlling hydrochloric acid in final mixture is 3mol/L.Condensation reaction condition is react 6 hours at 90 DEG C.Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of same concentrations after suction filtration, 120 degrees Celsius of dryings, grinding.After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, 120 degrees Celsius of dryings.
As can be seen from Table 2, along with the increase of formaldehyde consumption, the degree of cross linking increases, and the sulfonate radical quantity on unit mass catalyst is increased, thus improves its catalytic activity.
The different crosslinking agent of table 3. is on the impact of synthesized catalytic activity
Note: in embodiment 14, formaldehyde used is the formalin of 37%.In embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, adds a certain amount of crosslinking agent, and the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g.Then in this mixture, add the carrying out of a certain amount of concentrated hydrochloric acid catalyzing and condensing reaction, the concentration controlling hydrochloric acid in final mixture is 3mol/L.Condensation reaction condition is react 6 hours at 90 DEG C.Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of same concentrations after suction filtration, 120 degrees Celsius of dryings, grinding.After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, 120 degrees Celsius of dryings.
As seen from Table 3, the catalytic activity impact of different crosslinking agent on final synthetic acidic resin is little, but different crosslinking agent is different with the reactivity of phenolic hydroxyl group on sodium lignin sulfonate, thus causes the productive rate of final acidic resins different.
Table 4. catalyzing and condensing reacts the type of acid used to the impact of synthesized catalyst activity
Note: in embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, adds a certain amount of crosslinking agent, and the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g.Then in this mixture, add the carrying out of a certain amount of acid catalyzed condensation reaction.Controlling the concentration of acid in condensation reaction mixture is 3mol/L.Condensation reaction condition is react 6 hours at 90 DEG C.Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of same concentrations after suction filtration, 120 degrees Celsius of dryings, grinding.After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, 120 degrees Celsius of dryings.
As can be seen from Table 4, the product of different acid catalyzed condensation reaction presents the catalytic activity be not quite similar after ion-exchange, and the resin catalysis activity wherein formed under strong acid catalyst is higher, best with hydrochloric acid.
Table 5. catalyzing and condensing reacts the concentration of acid used to the impact of synthesized catalyst activity
Note: in embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, adds a certain amount of crosslinking agent, and the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g.Then in this mixture, add the carrying out of a certain amount of concentrated hydrochloric acid catalyzing and condensing reaction.Controlling the concentration of acid in condensation reaction mixture is 0.1 ~ 5mol/L.Condensation reaction condition is react 6 hours at 90 DEG C.Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of same concentrations after suction filtration, 120 degrees Celsius of dryings, grinding.After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, 120 degrees Celsius of dryings.
As can be seen from Table 5, in condensation reaction, the catalytic activity impact of concentration on synthesized acidic resins of acid is little, but finds in experimentation, the productive rate of catalyst can be caused when the use quantity not sufficient of acid to decline, reduce effective utilization of catalyst synthesis material.
Table 6. setting-up point is on the impact of synthesized catalyst activity
Note: in embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, adds a certain amount of crosslinking agent, and the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g.Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction.Controlling the concentration of acid in condensation reaction mixture is 3mol/L.Setting-up point is 50-120 DEG C, and the reaction time is 6 hours.Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of same concentrations after suction filtration, 120 degrees Celsius of dryings, grinding.After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, 120 degrees Celsius of dryings.
Find in experimentation, setting-up point is little to the activity influence of synthesized catalyst, but reaction temperature directly affects the reactivity of condensation reaction, and reaction temperature reduction causes the yield of catalyst to decline.
Table 7. condensation reaction time is on the impact of synthesized catalyst activity
Note: in embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, adds a certain amount of crosslinking agent, and the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g.Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction.Controlling the concentration of acid in condensation reaction mixture is 3mol/L.Setting-up point is 90 DEG C, and the reaction time is 1-12 hour.Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of same concentrations after suction filtration, 120 degrees Celsius of dryings, grinding.After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, 120 degrees Celsius of dryings.
Similar with the activity influence of setting-up point to synthesized catalyst, the catalytic activity impact of catalyst obtained under the differential responses time on alkylated reaction is little, but the reaction time directly can affect the yield of gained catalyst after condensation reaction.
Table 8. for the solution concentration of ion-exchange on the impact of synthesized catalyst activity
Note: in embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, adds a certain amount of crosslinking agent, and the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g.Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction.Controlling the concentration of acid in condensation reaction mixture is 3mol/L.Setting-up point is 90 DEG C, and the reaction time is 6 hours.Gained condensation product carries out ion-exchange with certain density aqueous sulfuric acid after suction filtration, 120 degrees Celsius of dryings, grinding.After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, 120 degrees Celsius of dryings.
As can be seen from Table 8, along with the increase of sulfuric acid concentration, ion-exchange degree improves, and adds the quantity of sulfonate radical, so the activity of catalyst constantly increases.After sulfuric acid concentration is greater than 2mol/L, the catalytic activity impact of raising on synthesized acidic resins of sulfuric acid concentration is little, thus shows that the most sodium groups in condensation product have been replaced into the sulfonate radical of proton type.
Table 9. ion-exchange temperature is on the impact of synthesized catalyst activity
Note: in embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, adds a certain amount of crosslinking agent, and the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g.Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction.Controlling the concentration of acid in condensation reaction mixture is 3mol/L.Setting-up point is 90 DEG C, and the reaction time is 6 hours.Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, 120 degrees Celsius of dryings, grinding.Ion-exchange temperature is 20 ~ 80 DEG C, and ion-exchange time is 2 hours.After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, 120 degrees Celsius of dryings.
As can be seen from Table 9, along with the rising of ion-exchange temperature, ion-exchange degree constantly increases, thus improves the catalytic activity of catalyst.
Table 10. ion-exchange time is on the impact of synthesized catalyst activity
Note: in embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, adds a certain amount of crosslinking agent, and the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g.Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction.Controlling the concentration of acid in condensation reaction mixture is 3mol/L.Setting-up point is 90 DEG C, and the reaction time is 6 hours.Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, 120 degrees Celsius of dryings, grinding.Ion-exchange time is 1 ~ 12 hour.After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, 120 degrees Celsius of dryings.
As can be seen from Table 10, along with the prolongation of ion-exchange time, ion-exchange degree constantly increases, thus causes improving constantly of catalyst activity.
Embodiment 85-102
2-methylfuran and formolite reaction activity rating
Evaluating catalyst of the present invention carries out in the round-bottomed flask being furnished with condensation reflux unit, and temperature is controlled by water bath with thermostatic control.Experimentation is as follows: in the round-bottomed flask of 50mL, add the acid resin catalyst of certain mass and 3.28 grams of 2-methylfurans (40mmol), 0.6 gram of formaldehyde (20mmol), react certain hour at a certain temperature.By high performance liquid chromatography (HPLC), quantitative analysis is carried out to product.
In embodiments, use the synthesis condition of acid resin catalyst to be: the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, add a certain amount of formaldehyde crosslinking agent, the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g; Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction; Controlling the concentration of acid in condensation reaction mixture is 3mol/L; Setting-up point is 90 DEG C, and the reaction time is 6 hours; Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, drying, grinding, and room-temperature ion exchanges 2 hours; After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, drying.
1) impact on acidic resin catalyst activity of alkylated reaction temperature, reaction result is in table 11.
Table 11. differential responses temperature is on the impact of catalytic activity
Note: in embodiment, catalyst amount is 0.15 gram, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 0.6 gram of formaldehyde (20mmol), and the reaction time is 2 hours.
The experimental result of table 11 shows, along with the rising of reaction temperature, the activity of catalyst increases gradually; When temperature is increased to after 60 DEG C, increase trend slows down.But formaldehyde used is the formalin of 37%, the existence of water affects the alkylation activity of formaldehyde and 2-methylfuran.
2) catalyst amount is on the impact of catalytic activity, and reaction result is in table 12.
Table 12. catalyst amount is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 0.6 gram of formaldehyde (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 12, along with the increase of catalyst amount, 2-methylfuran and butyraldehyde alkylation productive rate improve constantly.But optimal catalyst/substrate ratio is 0.15 gram/40mmol2-methylfuran.
3) reaction time is on the impact of catalytic result, and reaction result is in table 13.
Table 13. catalyst amount is on the impact of catalytic activity
Note: in embodiment, catalyst amount is 0.15 gram, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 0.6 gram of formaldehyde (20mmol), and reaction temperature is 50 DEG C.
As can be seen from Table 13, along with the prolongation in reaction time, the yield of target product increases gradually; But after the time extends to 24 hours, conversion ratio increases, and productive rate does not have significant change.This shows that the long reaction time result in the carrying out of side reaction, as formaldehyde self-polymerization, 2-methylfuran trimerization reaction.
2-methylfuran and formic acid reactivity are evaluated
Evaluating catalyst of the present invention carries out in the round-bottomed flask being furnished with condensation reflux unit, and reaction temperature is controlled by water bath with thermostatic control.Experimentation is as follows: in the round-bottomed flask of 50mL, add the catalyst of certain mass and 3.28 grams of 2-methylfurans (40mmol), 0.92 gram of formic acid (20mmol), react certain hour at a certain temperature.Finally product is carried out quantitative analysis by high performance liquid chromatography (HPLC).Shown in the reaction scheme (b) in 1, in the reaction of 2-methylfuran and formic acid, in liquid chromatogram, detect one poly-, dimerization and trimerization product simultaneously.
In embodiments, use the synthesis condition of acid resin catalyst to be: the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, add a certain amount of formaldehyde crosslinking agent, the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g; Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction; Controlling the concentration of acid in condensation reaction mixture is 3mol/L; Setting-up point is 90 DEG C, and the reaction time is 6 hours; Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, drying, grinding, and room-temperature ion exchanges 2 hours; After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, drying.
Embodiment 103 ~ 120
1) the activity contrast of differential responses temperature, Activity evaluation is in table 14.
Table 14. differential responses temperature is on the impact of catalytic activity
Note: in embodiment, catalyst amount is 0.15 gram, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 0.92 gram of formic acid (20mmol), and the reaction time is 2 hours.
The experimental result of table 14 shows, along with the rising of reaction temperature, the activity of catalyst increases gradually, but in this reaction, side reaction is more, one poly-, dimerization, trimerization alkylate selective all not high.
2) catalyst amount is on the impact of catalytic activity, and reaction result is in table 15.
Table 15. catalyst amount is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 0.92 gram of formic acid (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 7, along with the increase of catalyst amount, productive rate improves constantly.Meanwhile, too much catalyst can cause the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2-methylfuran.
3) the differential responses time is on the impact of catalytic activity, and reaction result is in table 16.
Table 16. reaction time is on the impact of catalytic activity
Note: in embodiment, catalyst amount is 0.15 gram, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 0.92 gram of formic acid (20mmol), and reaction temperature is 50 DEG C.
As can be seen from Table 16, along with the prolongation in reaction time, the yield of target product increases gradually; But after the time extends to 24 hours, conversion ratio increases, and the yield of target product does not have significant change.This shows that the long reaction time result in the carrying out of side reaction, as methylfuran trimerization reaction.
Embodiment 121 ~ 138
2-methylfuran and furfurol reaction activity rating
Evaluating catalyst of the present invention carries out in the round-bottomed flask being furnished with condensation reflux unit, and temperature is controlled by water bath with thermostatic control.Experimentation is as follows: in the round-bottomed flask of 50mL, add the catalyst of certain mass and 3.28 grams of 2-methylfurans (40mmol), 1.92 grams of furfurals (20mmol), react certain hour at a certain temperature.Finally product is carried out quantitative analysis by high performance liquid chromatography (HPLC).
In embodiments, use the synthesis condition of acid resin catalyst to be: the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, add a certain amount of formaldehyde crosslinking agent, the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g; Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction; Controlling the concentration of acid in condensation reaction mixture is 3mol/L; Setting-up point is 90 DEG C,
Reaction time is 6 hours; Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, drying, grinding, and room-temperature ion exchanges 2 hours; After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, drying.
1) the activity contrast of differential responses temperature, Activity evaluation is in table 17.
Table 17. differential responses temperature is on the impact of catalytic activity
Note: in embodiment, catalyst amount is 0.15 gram, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.92 grams of furfurals (20mmol), and the reaction time is 2 hours.
The experimental result of table 17 shows, along with the rising of reaction temperature, the activity of catalyst increases gradually; When temperature is increased to after 50 DEG C, increase trend slows down.
2) catalyst amount is on the impact of catalytic activity, and reaction result is in table 18.
Table 18. catalyst amount is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.92 grams of furfurals (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 18, along with the increase of catalyst amount, productive rate improves constantly.Meanwhile, too much catalyst can cause the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2-methylfuran.
3) the differential responses time is on the impact of catalytic activity, and reaction result is in table 19.
Table 19. reaction time is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.92 grams of furfurals (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 5, along with the prolongation in reaction time, the yield of target product increases gradually; But after the time extends to 24 hours, conversion ratio increases, and productive rate does not have significant change.This shows that the long reaction time result in the carrying out of side reaction, as methylfuran trimerization reaction.
Embodiment 139 ~ 156
2-methylfuran and hydroxypropanone-reactivity are evaluated
Evaluating catalyst of the present invention carries out in the round-bottomed flask being furnished with condensation reflux unit, and temperature is controlled by water bath with thermostatic control.Experimentation is as follows: in the round-bottomed flask of 50mL, add the catalyst of certain mass and 3.28 grams of 2-methylfurans (40mmol), 1.48 grams of hydroxypropanone-s (20mmol), react certain hour at a certain temperature.Finally product is carried out quantitative analysis by high performance liquid chromatography (HPLC).
In embodiments, use the synthesis condition of acid resin catalyst to be: the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, add a certain amount of formaldehyde crosslinking agent, the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g; Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction; Controlling the concentration of acid in condensation reaction mixture is 3mol/L; Setting-up point is 90 DEG C, and the reaction time is 6 hours; Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, drying, grinding, and room-temperature ion exchanges 2 hours; After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, drying.
1) the activity contrast of differential responses temperature, Activity evaluation is in table 20.
Table 20. differential responses temperature is on the impact of catalytic activity
Note: in embodiment, catalyst amount is 0.15 gram, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.48 grams of hydroxypropanone-s (20mmol), and the reaction time is 2 hours.
The experimental result of table 20 shows, along with the rising of reaction temperature, the activity of catalyst increases gradually; When temperature is increased to after 60 DEG C, increase trend slows down.
2) catalyst amount is on the impact of catalytic activity, and reaction result is in table 21.
Table 21. catalyst amount is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.48 grams of hydroxypropanone-s (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 21, along with the increase of catalyst amount, productive rate improves constantly.Meanwhile, too much catalyst can cause the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2-methylfuran.
3) the differential responses time is on the impact of catalytic activity, and reaction result is in table 22.
Table 22. reaction time is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.48 grams of hydroxypropanone-s (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 22, along with the prolongation in reaction time, the yield of target product increases gradually; But after the time extends to 24 hours, conversion ratio increases, and productive rate does not have significant change.This shows that the long reaction time result in the carrying out of side reaction, as methylfuran trimerization reaction.
Embodiment 157 ~ 174
2-methylfuran and acetone reactivity are evaluated
Evaluating catalyst of the present invention carries out in the round-bottomed flask being furnished with condensation reflux unit, and temperature is controlled by water bath with thermostatic control.Experimentation is as follows: in the round-bottomed flask of 50mL, add the catalyst of certain mass and 3.28 grams of 2-methylfurans (40mmol), 1.16 grams of acetone (20mmol), react certain hour at a certain temperature.Finally product is carried out quantitative analysis by high performance liquid chromatography (HPLC).
In embodiments, use the synthesis condition of acid resin catalyst to be: the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, add a certain amount of formaldehyde crosslinking agent, the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g; Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction; Controlling the concentration of acid in condensation reaction mixture is 3mol/L; Setting-up point is 90 DEG C, and the reaction time is 6 hours; Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, drying, grinding, and room-temperature ion exchanges 2 hours; After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, drying.
1) the activity contrast of differential responses temperature, Activity evaluation is in table 23.
Table 23. differential responses temperature is on the impact of catalytic activity
Note: in embodiment, catalyst amount is 0.15 gram, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.16 grams of acetone (20mmol), and the reaction time is 2 hours.
The experimental result of table 23 shows, along with the rising of reaction temperature, the activity of catalyst increases gradually; When temperature is increased to after 50 DEG C, increase trend slows down.
2) catalyst amount is on the impact of catalytic activity, and reaction result is in table 24.
Table 24. catalyst amount is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.16 grams of acetone (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 24, along with the increase of catalyst amount, productive rate improves constantly.Meanwhile, too much catalyst can cause the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2-methylfuran.
3) the differential responses time is on the impact of catalytic activity, and reaction result is in table 25.
Table 25. reaction time is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.16 grams of acetone (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 25, along with the prolongation in reaction time, the yield of target product increases gradually; But after the time extends to 24 hours, conversion ratio increases, and productive rate does not have significant change.This shows that the long reaction time result in the carrying out of side reaction, as methylfuran trimerization reaction.
Embodiment 175 ~ 192
2-methylfuran and hutanal reactivity are evaluated
Evaluating catalyst of the present invention carries out in the round-bottomed flask being furnished with condensation reflux unit, and temperature is controlled by water bath with thermostatic control.Experimentation is as follows: in the round-bottomed flask of 50mL, add the catalyst of certain mass and 3.28 grams of 2-methylfurans (40mmol), 1.44 grams of hutanals (20mmol), react certain hour at a certain temperature.Finally product is carried out quantitative analysis by high performance liquid chromatography (HPLC).
In embodiments, use the synthesis condition of acid resin catalyst to be: the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, add a certain amount of formaldehyde crosslinking agent, the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g; Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction; Controlling the concentration of acid in condensation reaction mixture is 3mol/L; Setting-up point is 90 DEG C, and the reaction time is 6 hours; Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, drying, grinding, and room-temperature ion exchanges 2 hours; After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, drying.
1) the activity contrast of differential responses temperature, Activity evaluation is in table 26.
Table 26. differential responses temperature is on the impact of catalytic activity
Note: in embodiment, catalyst amount is 0.15 gram, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.44 grams of hutanals (20mmol), and the reaction time is 2 hours.
The experimental result of table 26 shows, along with the rising of reaction temperature, the activity of catalyst increases gradually; When temperature is increased to after 50 DEG C, increase trend slows down.
2) catalyst amount is on the impact of catalytic activity, and reaction result is in table 27.
Table 27. catalyst amount is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.44 grams of hutanals (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 27, along with the increase of catalyst amount, productive rate improves constantly.Meanwhile, too much catalyst can cause the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2-methylfuran.
3) the differential responses time is on the impact of catalytic activity, and reaction result is in table 28.
Table 28. reaction time is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 1.44 grams of hutanals (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 28, along with the prolongation in reaction time, the yield of target product increases gradually; But after the time extends to 24 hours, conversion ratio increases, and productive rate does not have significant change.This shows that the long reaction time result in the carrying out of side reaction, as methylfuran trimerization reaction.
Embodiment 193 ~ 210
2-methylfuran and ethyl levulinate reactivity are evaluated
Evaluating catalyst of the present invention carries out in the round-bottomed flask being furnished with condensation reflux unit, and temperature is controlled by water bath with thermostatic control.Experimentation is as follows: in the round-bottomed flask of 50mL, add the catalyst of certain mass and 3.28 grams of 2-methylfurans (40mmol), 2.88 grams of ethyl levulinates (20mmol), react certain hour at a certain temperature.Finally product is carried out quantitative analysis by high performance liquid chromatography (HPLC).
In embodiments, use the synthesis condition of acid resin catalyst to be: the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, add a certain amount of formaldehyde crosslinking agent, the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g; Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction; Controlling the concentration of acid in condensation reaction mixture is 3mol/L; Setting-up point is 90 DEG C, and the reaction time is 6 hours; Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, drying, grinding, and room-temperature ion exchanges 2 hours; After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, drying.
1) the activity contrast of differential responses temperature, Activity evaluation is in table 29.
Table 29. differential responses temperature is on the impact of catalytic activity
Note: in embodiment, catalyst amount is 0.15 gram, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 2.88 grams of ethyl levulinates (20mmol), and the reaction time is 2 hours.
The experimental result of table 29 shows, along with the rising of reaction temperature, the activity of catalyst increases gradually; When temperature is increased to after 60 DEG C, increase trend slows down.
2) catalyst amount is on the impact of catalytic activity, and reaction result is in table 30.
Table 30. catalyst amount is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 2.88 grams of ethyl levulinates (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C
As can be seen from Table 30, along with the increase of catalyst amount, productive rate improves constantly.Meanwhile, too much catalyst can cause the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2-methylfuran.
3) the differential responses time is on the impact of catalytic activity, and reaction result is in table 31.
Table 31. reaction time is on the impact of catalytic activity
Note: in embodiment, reactant consumption is 3.28 grams of 2-methylfurans (40mmol), 2.88 grams of ethyl levulinates (20mmol), and the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from table 31, along with the prolongation in reaction time, the yield of target product increases gradually; But after the time extends to 24 hours, conversion ratio increases, and productive rate does not have significant change.This shows that the long reaction time result in the carrying out of side reaction, as methylfuran trimerization reaction.
Embodiment 211-222
The stability that recycles of acidic resins synthesized by the present invention and commercialization ion exchange resin (Amberlyst-15 and Amberlyst-36) contrasts
Each evaluating catalyst carries out in the round-bottomed flask being furnished with condensation reflux unit, and temperature is controlled by water bath with thermostatic control.Experimentation is as follows: in the round-bottomed flask of 50mL, add the catalyst of certain mass and 3.28 grams of 2-methylfurans (40mmol), 1.92 grams of furfurals (20mmol), react certain hour at a certain temperature.Finally product is carried out quantitative analysis by high performance liquid chromatography (HPLC).
In table 32, use the synthesis condition of acid resin catalyst to be: the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, the mass concentration controlling sodium lignin sulfonate is 35%, then in lignin sulfonic acid sodium solution, add a certain amount of formaldehyde crosslinking agent, the amount ratio controlling crosslinking agent/sodium lignin sulfonate is 15mmol/g; Then in this mixture, add the carrying out of a certain amount of hydrochloric acid catalysis condensation reaction; Controlling the concentration of acid in condensation reaction mixture is 3mol/L; Setting-up point is 90 DEG C, and the reaction time is 6 hours; Gained condensation product carries out ion-exchange with the aqueous sulfuric acid of 2mol/L after suction filtration, drying, grinding, and room-temperature ion exchanges 2 hours; After ion-exchange, gained acidic resins are required catalyst through suction filtration, washing after neutrality, drying.
In catalyst circulation stability test, used catalyst first uses washed with methanol, and removing reaction residue matter, is used further to after drying react next time.
Synthesized by table 32 the present invention, acidic resins recycles stability
That shows 33Amberlyst-15 resin recycles stability
That shows 34Amberlyst-36 resin recycles stability
Sum up: as can be seen from the comparing result of each embodiment, acidic resins synthesized by the present invention are at catalysis lignocellulosic base furan compound (preferred 2-methylfuran) and lignocellulosic base carbonyls (formaldehyde, formic acid, hutanal, furfural, hydroxypropanone-, acetone, ethyl levulinate) alkylated reaction in show excellent catalytic performance.And high catalytic activity and selective.In addition, the preparation technology of catalyst is simple, good cycling stability, raw material environmental friendliness, is cheaply easy to get, and makes it present the higher application advantage of the commercial ion exchanger resin higher than costs such as Amberlyst, Nafion.
Claims (9)
1. solid acid catalyst, is characterized in that:
1) take sodium lignin sulfonate as raw material, take carbonyls as crosslinking agent, add phenols functional group and the reaction of carbonyls generation phenol formaldehyde condensation in acid catalysis sodium lignin sulfonate after both being mixed, thus obtain a kind of high molecular polymer being insoluble in water;
Acid solution can be the aqueous solution of one or more the mixture in inorganic acid or organic acid; The temperature of condensation reaction is 50 ~ 120 DEG C, and the reaction time is 1 ~ 12 hour;
2) gained condensation product changes into the acidic resins material containing sulfonate radical after ion-exchange, is required catalyst;
Adopt acid solution to carry out ion-exchange to condensation product and change it into proton type by ionic, thus improve its acidity; Ion exchange reagent can be one or more the mixed solution in inorganic acid or organic acid.
2. catalyst according to claim 1, is characterized in that:
Be one or more in formaldehyde, formic acid, acetaldehyde, butyraldehyde, furfural, glucose sugar, levulic acid as the carbonyls of crosslinking agent.
3. catalyst according to claim 1, is characterized in that:
Add acid in the mixture of condensation reaction after, acid concentration is 0.1 ~ 5mol/L;
Inorganic acid is one or more the mixture in sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, phosphotungstic acid, phosphomolybdic acid;
Organic acid is one or more the mixture in TFMS, trifluoroacetic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, acetic acid, monoxone;
First, sodium lignin sulfonate is soluble in water, controlling its mass concentration is 10 ~ 40%; Then in lignin sulfonic acid sodium solution, dropwise crosslinking agent is added and the amount ratio controlling crosslinking agent and sodium lignin sulfonate is 5 ~ 30mmol
crosslinking agent/ g
sodium lignin sulfonate; After the two being mixed, in this mixture, dropwise add acid solution, controlling hydrogen ion concentration in final mixture is 0.1 ~ 5mol/L.
4. catalyst according to claim 1, is characterized in that:
The reaction temperature of condensation reaction is 50 ~ 120 DEG C, and the reaction time is 1 ~ 12 hour;
Gained condensation product carries out ion-exchange with acid solution after suction filtration, drying, grinding makes it change into the acidic resins of proton type by ionic;
Baking temperature is 60 ~ 120 DEG C, and drying time is 2-12 hour.
5. the catalyst according to claim 1 or 4, is characterized in that:
Be one or more in sulfuric acid, hydrochloric acid, phosphoric acid for carrying out the inorganic acid of ion-exchange to condensation product; Organic acid is one or more in benzene sulfonic acid, TFMS, p-methyl benzenesulfonic acid;
Condensation product is added in the acid solution of 0.1 ~ 5mol/L and carries out ion-exchange treatment and change it into proton type by ionic; The ratio of solid and acid solution controls as 5g
condensation product/ 50 ~ 500mL
acid solution; Ion exchange conditions is ion-exchange 1 ~ 12h at 20 ~ 80 DEG C.
6. an application for catalyst described in claim 1,2,3,4 or 5, is characterized in that: described solid acid catalyst to can be used between lignocellulosic base furan compound and carbonyls in alkylated reaction.
7. application according to claim 6, is characterized in that: lignocellulosic base furan compound is one or both the mixture in furans, 2-methylfuran, hydroxymethylfurans; Lignocellulosic base carbonyls is formaldehyde, formic acid, hutanal, furfural, acetone, hydroxypropanone-, one or more the mixture in cyclopentanone, ethyl levulinate;
Corresponding alkylation reaction product is: carbon number is the oxygenatedchemicals between 8 ~ 16, and these oxygenatedchemicals can make diesel oil or aviation kerosine alkane through hydrogenation deoxidation.
8. the method according to claim 6 or 7, is characterized in that: added respectively in reaction vessel by reaction substrate under condition of no solvent and carry out alkylated reaction, and the molar ratio controlling furan compound and carbonyls is 0.25 ~ 4.
9. the method according to claim 6,7 or 8, is characterized in that: alkylated reaction temperature is 0 ~ 80 DEG C, and catalyst amount and furan compound ratio control to be 0.015 ~ 0.3g
catalyst/ 40mmol
furans compound, the reaction time is 0.5 ~ 80 hour.
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| CN109134407A (en) * | 2018-09-30 | 2019-01-04 | 南京林业大学 | A kind of preparation method of aviation kerosine precursor |
| CN109134407B (en) * | 2018-09-30 | 2022-04-12 | 南京林业大学 | Preparation method of aviation kerosene precursor |
| CN109913200A (en) * | 2019-03-28 | 2019-06-21 | 汤新红 | A kind of nano material and preparation method thereof with magnetism and fluorescent dual function |
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