CN104971775B - Solid acid catalyst and its application in synthesis renewable diesel or aviation kerosine - Google Patents
Solid acid catalyst and its application in synthesis renewable diesel or aviation kerosine Download PDFInfo
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Abstract
The present invention relates to a kind of solid acid catalyst preparation and its between lignocellulosic based platform compound alkylated reaction application.Sodium lignin sulfonate of the present invention derives phenolic resinoid solid acid catalyst preparation method and is divided into two steps：1）Carbonyls is added into lignin sulfonic acid sodium water solution and makees crosslinking agent, phenols functional group and carbonyls in acid catalysis sodium lignin sulfonate is then added into the mixture, phenol formaldehyde condensation reaction occurs, to obtain a kind of high molecular polymer being insoluble in water；2）Ion exchange, which is carried out, by the condensation product generated to step 1 obtains the acidic resins material containing sulfonate radical.Catalyst raw material of the present invention is cheap and easy to get, and preparation process is simple, has very high catalytic activity and selectivity to the alkylated reaction under condition of no solvent between lignocellulosic base furan compound and carbonyls.It can get diesel oil or aviation kerosine alkane after the hydrogenated deoxidation of alkylate obtained by the reaction.The present invention provides a kind of by lignocellulosic based platform compound synthesis diesel oil or a kind of Cheap highly effective solid acid catalyst of aviation kerosine precursor.
Description
Technical field
The present invention relates to the preparation method of acidic resins solid acid catalyst derived from a kind of sodium lignin sulfonate and its
The application of alkylated reaction between lignocellulosic base furan compound and carbonyls.Specifically include two steps：1）To
Carbonyls is added in lignin sulfonic acid sodium water solution and makees crosslinking agent, acid solution is then added into the mixture is catalyzed phenolic aldehyde
Condensation reaction；2）Ion exchange, which is carried out, by the condensation product generated to step 1 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, and catalyst preparation process is simple,
There is higher work to the alkylated reaction under condition of no solvent between lignocellulosic base furan compound and carbonyls
Property and selectivity.It can get diesel oil or aviation kerosine alkane after the hydrogenated deoxidation of alkylate obtained by the reaction.This
Invention provides a kind of by lignocellulosic based platform compound synthesis diesel oil or a kind of Cheap highly effective of aviation kerosine precursor
Catalyst.
Background technology
Fossil resource is increasingly reduced and by environmental problems such as a large amount of rows of the caused greenhouse gases of fossil energy burning
It becomes increasingly conspicuous, the social required quantity of the energy is also continuing to increase in addition, and oil price rises steadily, and develops alternative fossil resource
New energy, open up renewable fuel supply new channel it is imperative.Biomass is answered as a kind of reproducible organic carbon source
For becoming current hot research in the production of carbon material, fuel and chemicals.
Diesel oil is one of main transport fuel, and composition mainly includes chain hydrocarbon, cyclic hydrocarbon, aromatic hydrocarbon of the carbon number 9~18
Composition.The international demand amount of the strategic goods and materials national as one, aviation kerosine is also increasingly increasing.Aviation kerosine is usually
It is made of alkane of the carbon number between 6~16.Two kinds of models of Jet-A and JP-8 are common are at present, the wherein composition of JP-8 is as follows：
The linear paraffin that carbon number is 8~15 accounts for 35%, and the branched paraffin that carbon number is 8~15 accounts for 35%, and the aromatic hydrocarbon that carbon number is 7~10 accounts for
18%, the cycloalkane that carbon number is 6~10 accounts for 7%.It is examined in terms of environmental protection, national energy security and potential economic value three
Consider, greatly developing 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.With wooden fibre
Dimension element is raw material, its depolymerization is generated to a series of small molecule platform chemical combination of high reaction activities by chemistry or biochemical method
Object.These platform chemicals are obtained by C-C coupling reaction oxygen-containing organic with diesel oil or aviation kerosine chain length range
Compound intermediate, then the alkane by the way that these intermediate hydrogenation deoxidations are obtained with diesel oil or aviation kerosine range is the current world
Biomass converts an important research direction in field.Compared with the biodiesel or aviation kerosine that other methods obtain,
Lignocellulosic base diesel oil or aviation kerosine have low in raw material price, derive from a wealth of sources, grain is not striven with people, do not strive with grain etc. it is excellent
Point.
Alkylated reaction is by a kind of heavy of lignocellulosic based platform compound synthesis diesel oil or aviation kerosine precursor
The C-C coupling reaction wanted.In 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, modified delamination zeolite ITQ-2 are catalyst, pass through 2- methylfurans and acetaldehyde, propionic aldehyde, n-butanal, valeral, 5- methylols
Furfural, 5 methyl furfural, acetone, pentanone, isopropylidene acetone and 2- methylfuran hydrolysates（Levulic aldehyde）Between alkyl
Change reaction and successfully synthesized a series of oxygen-containing organic compound intermediate that carbon numbers with branched structure are 8~16, and is right
These oxygen-containing organic compound intermediate hydrogenation deoxidations have synthesized a series of branches with diesel oil and aviation kerosine chain length range
Alkane.Relative to homogeneous catalysis, the catalyst used in heterogeneous catalysis is easily recycled, poor to equipment corrosion, more green
Environmental protection.In the work of this seminar early period（Chinese patent：Application number：201110346501.1；201210169817.2；
20121043947.9 with document ChemSusChem.2012,5,1958-1966；Bioresource Technology.2013,
134,66–72;Chem.Commun., 2013,49,5727~5729）, by the 2- methylfurans of solid acid catalysis a series of with
Lignocellulosic base carbonyls（Furfural, ethyl levulinate, butyraldehyde, acetone, hydroxypropanone-, cyclopentanone, isopropylidene third
Ketone etc.）Between alkylated reaction or aldol reaction obtain a series of containing with diesel oil and aviation kerosine carbon number range
Oxygen organic compound, and some branch with diesel oil or aviation kerosine range have been synthesized by the hydrogenation deoxidation to alkylate
Alkane.Find that Nafion-212 catalytic activity is best by the acidity and selectivity that compare different solid acids.But Nafion-
212 catalyst are expensive.Therefore, from practical standpoint, need to develop some to lignocellulosic base furan compound with
Alkylated reaction has greater activity and solid acid catalyst cheap and easy to get between carbonyls.
Lignosulfonates（Such as sodium lignin sulfonate, calcium lignosulfonate）It is that current slurrying and paper industry one kind are important
By-product be mainly used for high molecular material, cement water reducing agent, Surfactants Used for Oil field, dispersant, flocculant, inhibition resistance
Dirty agent, agricultural chemicals, industry adhesive etc. have vast potential for future development.We have found that sodium lignin sulfonate in this patent
Derivative acidic resins can be used as solid acid for the alkylation between lignocellulosic base furan compound and carbonyls
Reaction, and activity and stability well are demonstrated by these reactions.By these reaction can get a series of carbon numbers be 8~
16 oxygen-containing organic compound, these compounds can obtain the branch for meeting diesel oil and aviation kerosine structural requirement by hydrogenation deoxidation
Alkane.
Invention content
Present invention aims at provide one kind can be used for alkane between lignocellulosic base furan compound and carbonyls
The preparation method of the high-performance solid acid catalyst of glycosylation reaction.
The present invention is achieved by the following technical solutions：
1）Using sodium lignin sulfonate as raw material, using carbonyls as crosslinking agent, the two is added to acid after mixing and is urged
Change the progress of phenol formaldehyde condensation reaction.Sodium lignin sulfonate is soluble in water, and it is 10~40% to control its mass concentration.Then to wood
Crosslinking agent is added dropwise in quality sodium sulfonate solution and control the amount ratio of crosslinking agent and sodium lignin sulfonate be 5~
30mmolCrosslinking agent/gSodium lignin sulfonate.Carbonyls as crosslinking agent is formaldehyde, formic acid, acetaldehyde, butyraldehyde, furfural, glucose, second
One or more of acyl propionic acid, preferably formaldehyde.After mixing by the two, it is molten that acid is added dropwise into the mixture
Liquid, it is 1~5mol/L to control hydrogen ion concentration in final mixture.Inorganic acid be sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid,
One or more of phosphotungstic acid, phosphomolybdic acid；Organic acid be trifluoromethanesulfonic acid, trifluoroacetic acid, methanesulfonic acid, to toluene sulphur
One or more of acid, acetic acid, monoxone.In condensation reaction mixture, sour a concentration of 0.1~5mol/L.Contracting
It closes reaction to carry out in round-bottomed flask, reaction temperature is 50~120 DEG C, and the reaction time is 1~12 hour；
2）Gained condensation product carries out ion exchange after suction filtration, drying, grinding with certain density acid solution makes it
It is converted to the acidic resins of proton type by ionic, then filters the resin, washing to neutral, drying just obtains required height
Imitate solid acid catalyst.Ion exchange reagent used is the mixed of one or more of inorganic acid or aqueous solutions of organic acids
Close solution, preferably sulfuric acid aqueous solution.Sulfuric acid concentration used is 0.1~5mol/L.In addition, the ratio control of condensation product and acid solution
It is made as 5gCondensation product/ 50~500mLAcid solution.Ion exchange conditions are ion exchange 1~12 hour at 20~80 DEG C.
Acidic resins solid acid catalyst can be used for lignocellulosic base derived from the sodium lignin sulfonate of this patent synthesis
Between furan compound and carbonyls in alkylated reaction.Lignocellulosic base furan compound is furans, 2- methyl furans
It mutters, the mixture of one or both of hydroxymethylfurans, preferably 2- methylfurans；Lignocellulosic base carbonyls is first
Aldehyde, formic acid, n-butanal, furfural, acetone, hydroxypropanone-, the mixture of one or more of ethyl levulinate.It will be anti-
Substrate is answered successively to be added in round-bottomed flask, the molar ratio for controlling furan compound and carbonyls is 0.25~4.Alkylation
Reaction temperature is 0~80 DEG C, and catalyst amount and the control of furan compound ratio are 0.015~0.3gCatalyst/40mmolFuran compound,
Reaction time is 0.5~12 hour, preferably 1.5~8 hours.Alkylation reaction product is that carbon number contains oxidation between 8~16
Object is closed, diesel oil or aviation kerosine alkane is made in the hydrogenated deoxidation of these oxygenatedchemicals.
Formula 1 is typical 2- methylfurans and formaldehyde (a), formic acid (b), furfural (c), hydroxypropanone- (d), acetone (e), just
Butyraldehyde (f), ethyl levulinate (g) react the reaction route of combined diesel oil, aviation kerosine presoma.Pass through these alkylations
Reaction can be in solvent-free mild reaction conditions and high yield obtains carbon chain lengths in the shorter reaction time is 8~16 to contain
Oxygen organic compound, these compounds can be used as synthesizing the presoma of renewable diesel or aviation kerosine range branched paraffin.This
Using lignocellulosic based platform compound as raw material, being prepared by alkylated reaction has diesel oil or aviation kerosine carbochain knot for invention
The oxygen-containing organic compound presoma of structure provides a kind of new sustainable development way for the production of biodiesel and aviation kerosine
Diameter.
The alkylated reaction route of formula 1.2- methylfurans and a variety of lignocellulosic base carbonyls
The invention has the advantages that：
Acidic resins derived from sodium lignin sulfonate provided by the present invention can be used for a variety of lignocellulosic based platforms
The alkylated reaction between object is closed, has the characteristics that raw material is cheap and easy to get, synthetic method is simple, substrate universality is high, is a kind of
Have much the solid acid catalyst of development prospect.With the catalyst and at alkylate can symbol be directly made by hydrogenation deoxidation
Close the branched paraffin that diesel oil and aviation kerosine carbon number and solidification point require.
Specific implementation mode
Examples 1 to 84
Resin precursor is made by condensation reaction
Sodium lignin sulfonate is soluble in water, and it is 10~40% to control its mass concentration.Then to lignin sulfonic acid sodium solution
In crosslinking agent is added dropwise and controls the amount ratio of crosslinking agent and sodium lignin sulfonate is 5~30mmolCrosslinking agent/gSodium lignin sulfonate.As
The carbonyls of crosslinking agent be formaldehyde, formic acid, acetaldehyde, butyraldehyde, furfural, glucose, one or both of levulic acid with
On.After mixing by the two, acid solution is added dropwise into the mixture, it is 1 to control hydrogen ion concentration in final mixture
~5mol/L.Inorganic acid is one or more of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, phosphotungstic acid, phosphomolybdic acid；
Organic acid is one or more of trifluoromethanesulfonic acid, trifluoroacetic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, acetic acid, monoxone.
In condensation reaction mixture, sour a concentration of 0.1~5mol/L.Condensation reaction carries out in round-bottomed flask, and reaction temperature is
50~120 DEG C, the reaction time is 1~12 hour；
Gained condensation product after suction filtration, drying, grinding with certain density acid solution carry out ion exchange make its by
Ionic is converted to the acidic resins of proton type, then the resin is filtered, wash to it is neutral, dry just obtain it is required efficient
Solid acid catalyst.Ion exchange reagent used is the aqueous solution of inorganic acid or organic acid, and preferably sulfuric acid aqueous solution is a concentration of
0.1~5mol/L.Ion-exchange temperature is 20~80 DEG C, and ion-exchange time is 1~12 hour.
Under the conditions of differential responses in the active testing of synthesized catalyst, with the alkyl between 2- methylfurans and furfural
It is model reaction to change reaction.Alkylated reaction carries out in the round-bottomed flask equipped with condensation reflux unit.It is burnt to the round bottom of 50mL
0.15 gram of catalyst, 3.28 grams of 2- methylfurans are added in bottle（40mmol）With 1.92 grams of furfurals（20mmol）, in water bath with thermostatic control
Lower stirring 2 hours.Pass through high performance liquid chromatography（HPLC）Quantitative analysis is carried out to reaction product.
1. sodium lignin sulfonate of table（The wooden sodium）Influence of the concentration to synthesized catalytic activity
Note：In embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of different quality, controls lignin
The mass concentration of sodium sulfonate is 10%~40%, and a certain amount of 37% formalin is then added into lignin sulfonic acid sodium solution,
The amount ratio for controlling formaldehyde/sodium lignin sulfonate is 15mmol/g.Then a certain amount of concentrated hydrochloric acid is added into the mixture to urge
Change the progress of condensation reaction, controls a concentration of 3mol/L of hydrochloric acid in final mixture.Condensation reaction condition is to react 6 at 90 DEG C
Hour.Condensation product obtained by each embodiment is carried out through filtering, after 120 degrees Celsius of dryings, grindings with the aqueous sulfuric acid of 2mol/L
Ion exchange.Gained acidic resins are required after filtering, washing to neutral, 120 degrees Celsius of dryings to ion exchange later
Catalyst.
As seen from Table 1, with the raising of lignin sulfonic acid na concn, the catalytic activity of the acidic resins finally synthesized first carries
Tend to after height constant.When this may be relatively low due to lignin sulfonic acid na concn, the haptoreaction probability of reactant molecule reduces,
So causing the degree of cross linking of final catalyst insufficient, sulfonate radical quantity is reduced, and in turn results in catalytic activity decline.
Influence of the relative concentration of 2. formaldehyde of table and sodium lignin sulfonate to synthesized catalytic activity
Note：In embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, controls lignin
The mass concentration of sodium sulfonate is 35%, and a certain amount of 37% formalin is then added into lignin sulfonic acid sodium solution, is controlled
The amount ratio of formaldehyde/sodium lignin sulfonate processed is 5~30mmol/g.Then a certain amount of concentrated hydrochloric acid is added into the mixture
（The progress of catalyzing and condensing reaction, controls a concentration of 3mol/L of hydrochloric acid in final mixture.Condensation reaction condition is anti-at 90 DEG C
It answers 6 hours.Gained condensation product carries out ion through filtering, after 120 degrees Celsius of dryings, grindings with the aqueous sulfuric acid of same concentrations
It exchanges.Acidic resins obtained by after ion exchange are catalyzed needed for being after filtering, washing to neutral, 120 degrees Celsius of dryings
Agent.
From table 2 it can be seen that with the increase of formaldehyde dosage, the degree of cross linking increases so that the sulphur on unit mass catalyst
Acid group quantity increases, to improve its catalytic activity.
Influence of the different crosslinking agents of table 3. to synthesized catalytic activity
Note：The formalin that formaldehyde used is 37% in embodiment 14.In embodiments, by the wooden of certain mass
Plain sodium sulfonate is dissolved in the water of certain mass, and the mass concentration for controlling sodium lignin sulfonate is 35%, then to sodium lignin sulfonate
A certain amount of crosslinking agent is added in solution, the amount ratio of control crosslinking agent/sodium lignin sulfonate is 15mmol/g.Then mixed to this
The progress that a certain amount of concentrated hydrochloric acid catalyzing and condensing reaction is added in object is closed, a concentration of 3mol/ of hydrochloric acid in final mixture is controlled
L.Condensation reaction condition is to be reacted 6 hours at 90 DEG C.Gained condensation product is after suction filtration, 120 degrees Celsius of dryings, grindings with identical
The aqueous sulfuric acid of concentration carries out ion exchange.Gained acidic resins are taken the photograph through filtering, washing to neutrality, 120 after ion exchange
Catalyst needed for being after the drying of family name's degree.
As seen from Table 3, different crosslinking agents influence the catalytic activity for finally synthesizing acidic resins little, but different friendships
It is different with the reactivity of phenolic hydroxyl group on sodium lignin sulfonate to join agent, to cause the yield of final acidic resins different.
Influence of the type of 4. catalyzing and condensing of table reaction acid used to synthesized catalyst activity
Note：In embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, controls lignin
The mass concentration of sodium sulfonate is 35%, is then added a certain amount of crosslinking agent into lignin sulfonic acid sodium solution, control crosslinking agent/
The amount ratio of sodium lignin sulfonate is 15mmol/g.Then be added into the mixture reaction of a certain amount of acid catalyzed condensation into
Row.A concentration of 3mol/L of the control acid in condensation reaction mixture.Condensation reaction condition is to be reacted 6 hours at 90 DEG C.Gained
Condensation product carries out ion exchange through filtering, after 120 degrees Celsius of dryings, grindings with the aqueous sulfuric acid of same concentrations.Ion is handed over
Alternatively rear gained acidic resins are required catalyst after filtering, washing to neutral, 120 degrees Celsius of dryings.
As can be seen from Table 4, the products of different acid catalyzed condensation reactions is presented after ion exchange is not quite similar
Catalytic activity, the resin catalysis activity higher wherein formed under strong acid catalyst are best with hydrochloric acid.
Influence of the concentration of 5. catalyzing and condensing of table reaction acid used to synthesized catalyst activity
Note：In embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, controls lignin
The mass concentration of sodium sulfonate is 35%, is then added a certain amount of crosslinking agent into lignin sulfonic acid sodium solution, control crosslinking agent/
The amount ratio of sodium lignin sulfonate is 15mmol/g.Then a certain amount of concentrated hydrochloric acid catalyzing and condensing reaction is added into the mixture
Progress.A concentration of 0.1~5mol/L of the control acid in condensation reaction mixture.Condensation reaction condition is to react 6 at 90 DEG C
Hour.Gained condensation product carries out ion friendship through filtering, after 120 degrees Celsius of dryings, grindings with the aqueous sulfuric acid of same concentrations
It changes.Gained acidic resins are required catalyst after filtering, washing to neutral, 120 degrees Celsius of dryings to ion exchange later.
As can be seen from Table 5, in condensation reaction, catalytic activity shadow of the sour concentration to synthesized acidic resins
It rings less, but is found in experimentation, the yield of catalyst can be caused to decline when the dosage deficiency of acid, reduce catalyst and close
At efficiently using for raw material.
Influence of 6. setting-up point of table to synthesized catalyst activity
Note：In embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, controls lignin
The mass concentration of sodium sulfonate is 35%, is then added a certain amount of crosslinking agent into lignin sulfonic acid sodium solution, control crosslinking agent/
The amount ratio of sodium lignin sulfonate is 15mmol/g.Then a certain amount of hydrochloric acid catalysis condensation reaction is added into the mixture
It carries out.A concentration of 3mol/L of the control acid in condensation reaction mixture.Setting-up point is 50-120 DEG C, and the reaction time is
6 hours.Gained condensation product carries out ion friendship through filtering, after 120 degrees Celsius of dryings, grindings with the aqueous sulfuric acid of same concentrations
It changes.Gained acidic resins are required catalyst after filtering, washing to neutral, 120 degrees Celsius of dryings to ion exchange later.
It is found in experimentation, setting-up point is little to the activity influence of synthesized catalyst, but reaction temperature
The reactivity of condensation reaction is directly affected, reaction temperature reduction causes the yield of catalyst to decline.
Influence of 7. condensation reaction time of table to synthesized catalyst activity
Note：In embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, controls lignin
The mass concentration of sodium sulfonate is 35%, is then added a certain amount of crosslinking agent into lignin sulfonic acid sodium solution, control crosslinking agent/
The amount ratio of sodium lignin sulfonate is 15mmol/g.Then a certain amount of hydrochloric acid catalysis condensation reaction is added into the mixture
It carries out.A concentration of 3mol/L of the control acid in condensation reaction mixture.Setting-up point is 90 DEG C, reaction time 1-12
Hour.Gained condensation product carries out ion friendship through filtering, after 120 degrees Celsius of dryings, grindings with the aqueous sulfuric acid of same concentrations
It changes.Gained acidic resins are required catalyst after filtering, washing to neutral, 120 degrees Celsius of dryings to ion exchange later.
It is similar to the activity influence of synthesized catalyst with setting-up point, obtained catalysis under the differential responses time
Agent the catalytic activity of alkylated reaction is influenced it is little, but the reaction time will have a direct impact on gained catalyst after condensation reaction
Yield.
Table 8. is used for influence of the solution concentration of ion exchange to synthesized catalyst activity
Note：In embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, controls lignin
The mass concentration of sodium sulfonate is 35%, is then added a certain amount of crosslinking agent into lignin sulfonic acid sodium solution, control crosslinking agent/
The amount ratio of sodium lignin sulfonate is 15mmol/g.Then a certain amount of hydrochloric acid catalysis condensation reaction is added into the mixture
It carries out.A concentration of 3mol/L of the control acid in condensation reaction mixture.Setting-up point is 90 DEG C, and the reaction time is 6 small
When.Gained condensation product carries out ion exchange through filtering, after 120 degrees Celsius of dryings, grindings with certain density aqueous sulfuric acid.
Gained acidic resins are required catalyst after filtering, washing to neutral, 120 degrees Celsius of dryings to ion exchange later.
As can be seen from Table 8, as the increase of sulfuric acid concentration, ion exchange degree improve, the quantity of sulfonate radical is increased,
So the activity of catalyst is continuously increased.After sulfuric acid concentration is more than 2mol/L, the raising of sulfuric acid concentration is to synthesized acid tree
The catalytic activity of fat influences less, to show that most sodium groups in condensation product have been replaced into the sulfonic acid of proton type
Root.
Influence of 9. ion-exchange temperature of table to synthesized catalyst activity
Note：In embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, controls lignin
The mass concentration of sodium sulfonate is 35%, is then added a certain amount of crosslinking agent into lignin sulfonic acid sodium solution, control crosslinking agent/
The amount ratio of sodium lignin sulfonate is 15mmol/g.Then a certain amount of hydrochloric acid catalysis condensation reaction is added into the mixture
It carries out.A concentration of 3mol/L of the control acid in condensation reaction mixture.Setting-up point is 90 DEG C, and the reaction time is 6 small
When.Gained condensation product carries out ion exchange through filtering, after 120 degrees Celsius of dryings, grindings with the aqueous sulfuric acid of 2mol/L.From
Sub- exchange temperature is 20~80 DEG C, and ion-exchange time is 2 hours.Gained acidic resins are through filtering, washing after ion exchange
Catalyst needed for being after to neutral, 120 degrees Celsius of dryings.
As can be seen from Table 9, it as the raising of ion-exchange temperature, ion-exchange degree are continuously increased, is urged to improve
The catalytic activity of agent.
Influence of 10. ion-exchange time of table to synthesized catalyst activity
Note：In embodiments, the sodium lignin sulfonate of certain mass is dissolved in the water of certain mass, controls lignin
The mass concentration of sodium sulfonate is 35%, is then added a certain amount of crosslinking agent into lignin sulfonic acid sodium solution, control crosslinking agent/
The amount ratio of sodium lignin sulfonate is 15mmol/g.Then a certain amount of hydrochloric acid catalysis condensation reaction is added into the mixture
It carries out.A concentration of 3mol/L of the control acid in condensation reaction mixture.Setting-up point is 90 DEG C, and the reaction time is 6 small
When.Gained condensation product carries out ion exchange through filtering, after 120 degrees Celsius of dryings, grindings with the aqueous sulfuric acid of 2mol/L.From
Sub- swap time is 1~12 hour.Gained acidic resins are through filtering, washing to neutral, 120 degrees Celsius of dryings after ion exchange
Catalyst needed for being later.
As can be seen from Table 10, with the extension of ion-exchange time, ion-exchange degree is continuously increased, so as to cause catalysis
The active continuous improvement of agent.
Embodiment 85-102
2- methylfurans and the evaluation of formaldehyde reactivity
The evaluating catalyst of the present invention carries out in the round-bottomed flask equipped with condensation reflux unit, and temperature passes through water bath with thermostatic control
Control.Experimentation is as follows：The acid resin catalyst and 3.28 grams of 2- first of certain mass are added in the round-bottomed flask of 50mL
Base furans（40mmol）, 0.6 gram of formaldehyde（20mmol）, certain time is reacted at a certain temperature.Pass through high performance liquid chromatography
（HPLC）Quantitative analysis is carried out to reaction product.
In embodiments, the synthesis condition of used acid resin catalyst is：By the lignin sulfonic acid of certain mass
Sodium is dissolved in the water of certain mass, and the mass concentration for controlling sodium lignin sulfonate is 35%, then into lignin sulfonic acid sodium solution
A certain amount of formaldehyde crosslinking agent is added, the amount ratio of control crosslinking agent/sodium lignin sulfonate is 15mmol/g；Then to the mixing
The progress of a certain amount of hydrochloric acid catalysis condensation reaction is added in object；A concentration of 3mol/ of the control acid in condensation reaction mixture
L；Setting-up point is 90 DEG C, and the reaction time is 6 hours；Gained condensation product is after suction filtration, drying, grinding with 2mol/L's
Aqueous sulfuric acid carries out ion exchange, and room-temperature ion exchanges 2 hours；Gained acidic resins are through filtering, washing after ion exchange
To neutral, dry catalyst as required later.
1）Alkylated reaction temperature on the active influence of acidic resin catalyst, reaction result is shown in Table 11.
Influence of the 11. differential responses temperature of table to catalytic activity
Note：Catalyst amount is 0.15 gram in embodiment, and reactant dosage is 3.28 grams of 2- methylfurans（40mmol）、
0.6 gram of formaldehyde（20mmol）, the reaction time is 2 hours.
Table 11 the experimental results showed that, with the raising of reaction temperature, the activity of catalyst gradually increases；When temperature increases
To after 60 DEG C, increase trend slows down.But formaldehyde used is 37% formalin, the presence of water influences formaldehyde and 2-
The alkylation activity of methylfuran.
2）Influence of the catalyst amount to catalytic activity, reaction result are shown in Table 12.
Influence of 12. catalyst amount of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 0.6 gram of formaldehyde（20mmol）, instead
It is 2 hours between seasonable, reaction temperature is 50 DEG C.
As can be seen from Table 12, with the increase of catalyst amount, 2- methylfurans are constantly carried with butyraldehyde alkylation yield
It is high.But most suitable catalyst/substrate ratio is 0.15 gram/40mmol2- methylfurans.
3）Influence of the reaction time to catalytic result, reaction result are shown in Table 13.
Influence of 13. catalyst amount of table to catalytic activity
Note：Catalyst amount is 0.15 gram in embodiment, and reactant dosage is 3.28 grams of 2- methylfurans（40mmol）、
0.6 gram of formaldehyde（20mmol）, reaction temperature is 50 DEG C.
As can be seen from Table 13, with the extension in reaction time, the yield of target product gradually increases；But when the time prolongs
Length to conversion ratio after 24 hours increases, and yield does not have significant change.This shows that the long reaction time results in side reaction
It carries out, such as formaldehyde self-polymerization, 2- methylfuran trimerization reactions.
2- methylfurans and the evaluation of formic acid reactivity
The evaluating catalyst of the present invention carries out in the round-bottomed flask equipped with condensation reflux unit, and reaction temperature passes through constant temperature
Water-bath controls.Experimentation is as follows：The catalyst and 3.28 grams of 2- methyl furans of certain mass are added in the round-bottomed flask of 50mL
It mutters（40mmol）, 0.92 gram of formic acid（20mmol）, certain time is reacted at a certain temperature.Product is finally passed through into efficient liquid phase
Chromatography（HPLC）Carry out quantitative analysis.Such as the reaction route in formula 1（b）It is shown, in the reacting of 2- methylfurans and formic acid, liquid
A poly-, dimerization and trimerization product have been detected simultaneously by phase chromatography.
In embodiments, the synthesis condition of used acid resin catalyst is：By the lignin sulfonic acid of certain mass
Sodium is dissolved in the water of certain mass, and the mass concentration for controlling sodium lignin sulfonate is 35%, then into lignin sulfonic acid sodium solution
A certain amount of formaldehyde crosslinking agent is added, the amount ratio of control crosslinking agent/sodium lignin sulfonate is 15mmol/g；Then to the mixing
The progress of a certain amount of hydrochloric acid catalysis condensation reaction is added in object；A concentration of 3mol/ of the control acid in condensation reaction mixture
L；Setting-up point is 90 DEG C, and the reaction time is 6 hours；Gained condensation product is after suction filtration, drying, grinding with 2mol/L's
Aqueous sulfuric acid carries out ion exchange, and room-temperature ion exchanges 2 hours；Gained acidic resins are through filtering, washing after ion exchange
To neutral, dry catalyst as required later.
Embodiment 103~120
1）The activity comparison of differential responses temperature, Activity evaluation are shown in Table 14.
Influence of the 14. differential responses temperature of table to catalytic activity
Note：Catalyst amount is 0.15 gram in embodiment, and reactant dosage is 3.28 grams of 2- methylfurans（40mmol）、
0.92 gram of formic acid（20mmol）, the reaction time is 2 hours.
Table 14 the experimental results showed that, with the raising of reaction temperature, the activity of catalyst gradually increases, but the reaction
Middle side reaction is more, and one poly-, dimerization, the selectivity of trimerization alkylate be not high.
2）Influence of the catalyst amount to catalytic activity, reaction result are shown in Table 15.
Influence of 15. catalyst amount of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 0.92 gram of formic acid（20mmol）, instead
It is 2 hours between seasonable, reaction temperature is 50 DEG C.
As can be seen from Table 7, with the increase of catalyst amount, yield is continuously improved.Meanwhile excessive catalyst can be led
Cause the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2- methylfurans.
3）Influence of the differential responses time to catalytic activity, reaction result are shown in Table 16.
Influence of 16. reaction time of table to catalytic activity
Note：Catalyst amount is 0.15 gram in embodiment, and reactant dosage is 3.28 grams of 2- methylfurans（40mmol）、
0.92 gram of formic acid（20mmol）, reaction temperature is 50 DEG C.
As can be seen from Table 16, with the extension in reaction time, the yield of target product gradually increases；But when the time prolongs
Length to conversion ratio after 24 hours increases, and the yield of target product does not have significant change.This shows that the long reaction time causes
The progress of side reaction, such as methylfuran trimerization reaction.
Embodiment 121~138
2- methylfurans and furfurol reaction activity rating
The evaluating catalyst of the present invention carries out in the round-bottomed flask equipped with condensation reflux unit, and temperature passes through water bath with thermostatic control
Control.Experimentation is as follows：The catalyst and 3.28 grams of 2- methylfurans of certain mass are added in the round-bottomed flask of 50mL
（40mmol）, 1.92 grams of furfurals（20mmol）, certain time is reacted at a certain temperature.Product is finally passed through into high-efficient liquid phase color
Spectrum（HPLC）Carry out quantitative analysis.
In embodiments, the synthesis condition of used acid resin catalyst is：By the lignin sulfonic acid of certain mass
Sodium is dissolved in the water of certain mass, and the mass concentration for controlling sodium lignin sulfonate is 35%, then into lignin sulfonic acid sodium solution
A certain amount of formaldehyde crosslinking agent is added, the amount ratio of control crosslinking agent/sodium lignin sulfonate is 15mmol/g；Then to the mixing
The progress of a certain amount of hydrochloric acid catalysis condensation reaction is added in object；A concentration of 3mol/ of the control acid in condensation reaction mixture
L；Setting-up point is 90 DEG C,
Reaction time is 6 hours；Gained condensation product after suction filtration, drying, grinding with the aqueous sulfuric acid of 2mol/L into
Row ion exchange, room-temperature ion exchange 2 hours；Gained acidic resins are through filtering, washing to neutral, drying after ion exchange
Catalyst needed for being afterwards.
1）The activity comparison of differential responses temperature, Activity evaluation are shown in Table 17.
Influence of the 17. differential responses temperature of table to catalytic activity
Note：Catalyst amount is 0.15 gram in embodiment, and reactant dosage is 3.28 grams of 2- methylfurans（40mmol）、
1.92 gram furfural（20mmol）, the reaction time is 2 hours.
Table 17 the experimental results showed that, with the raising of reaction temperature, the activity of catalyst gradually increases；When temperature increases
To after 50 DEG C, increase trend slows down.
2）Influence of the catalyst amount to catalytic activity, reaction result are shown in Table 18.
Influence of 18. catalyst amount of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 1.92 grams of furfurals（20mmol）, instead
It is 2 hours between seasonable, reaction temperature is 50 DEG C.
As can be seen from Table 18, with the increase of catalyst amount, yield is continuously improved.Meanwhile excessive catalyst meeting
Lead to the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2- methylfurans.
3）Influence of the differential responses time to catalytic activity, reaction result are shown in Table 19.
Influence of 19. reaction time of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 1.92 grams of furfurals（20mmol）, instead
It is 2 hours between seasonable, reaction temperature is 50 DEG C.
As can be seen from Table 5, with the extension in reaction time, the yield of target product gradually increases；But when the time prolongs
Length to conversion ratio after 24 hours increases, and yield does not have significant change.This shows that the long reaction time results in side reaction
It carries out, such as methylfuran trimerization reaction.
Embodiment 139~156
2- methylfurans and the evaluation of hydroxypropanone- reactivity
The evaluating catalyst of the present invention carries out in the round-bottomed flask equipped with condensation reflux unit, and temperature passes through water bath with thermostatic control
Control.Experimentation is as follows：The catalyst and 3.28 grams of 2- methylfurans of certain mass are added in the round-bottomed flask of 50mL
（40mmol）, 1.48 grams of hydroxypropanone-s（20mmol）, certain time is reacted at a certain temperature.Product is finally passed through into efficient liquid
Phase chromatography（HPLC）Carry out quantitative analysis.
In embodiments, the synthesis condition of used acid resin catalyst is：By the lignin sulfonic acid of certain mass
Sodium is dissolved in the water of certain mass, and the mass concentration for controlling sodium lignin sulfonate is 35%, then into lignin sulfonic acid sodium solution
A certain amount of formaldehyde crosslinking agent is added, the amount ratio of control crosslinking agent/sodium lignin sulfonate is 15mmol/g；Then to the mixing
The progress of a certain amount of hydrochloric acid catalysis condensation reaction is added in object；A concentration of 3mol/ of the control acid in condensation reaction mixture
L；Setting-up point is 90 DEG C, and the reaction time is 6 hours；Gained condensation product is after suction filtration, drying, grinding with 2mol/L's
Aqueous sulfuric acid carries out ion exchange, and room-temperature ion exchanges 2 hours；Gained acidic resins are through filtering, washing after ion exchange
To neutral, dry catalyst as required later.
1）The activity comparison of differential responses temperature, Activity evaluation are shown in Table 20.
Influence of the 20. differential responses temperature of table to catalytic activity
Note：Catalyst amount is 0.15 gram in embodiment, and reactant dosage is 3.28 grams of 2- methylfurans（40mmol）、
1.48 gram hydroxypropanone-（20mmol）, the reaction time is 2 hours.
Table 20 the experimental results showed that, with the raising of reaction temperature, the activity of catalyst gradually increases；When temperature increases
To after 60 DEG C, increase trend slows down.
2）Influence of the catalyst amount to catalytic activity, reaction result are shown in Table 21.
Influence of 21. catalyst amount of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 1.48 grams of hydroxypropanone-s
（20mmol）, the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 21, with the increase of catalyst amount, yield is continuously improved.Meanwhile excessive catalyst meeting
Lead to the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2- methylfurans.
3）Influence of the differential responses time to catalytic activity, reaction result are shown in Table 22.
Influence of 22. reaction time of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 1.48 grams of hydroxypropanone-s
（20mmol）, the reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 22, with the extension in reaction time, the yield of target product gradually increases；But when the time prolongs
Length to conversion ratio after 24 hours increases, and yield does not have significant change.This shows that the long reaction time results in side reaction
It carries out, such as methylfuran trimerization reaction.
Embodiment 157~174
2- methylfurans and the evaluation of acetone reactivity
The evaluating catalyst of the present invention carries out in the round-bottomed flask equipped with condensation reflux unit, and temperature passes through water bath with thermostatic control
Control.Experimentation is as follows：The catalyst and 3.28 grams of 2- methylfurans of certain mass are added in the round-bottomed flask of 50mL
（40mmol）, 1.16 grams of acetone（20mmol）, certain time is reacted at a certain temperature.Product is finally passed through into high-efficient liquid phase color
Spectrum（HPLC）Carry out quantitative analysis.
In embodiments, the synthesis condition of used acid resin catalyst is：By the lignin sulfonic acid of certain mass
Sodium is dissolved in the water of certain mass, and the mass concentration for controlling sodium lignin sulfonate is 35%, then into lignin sulfonic acid sodium solution
A certain amount of formaldehyde crosslinking agent is added, the amount ratio of control crosslinking agent/sodium lignin sulfonate is 15mmol/g；Then to the mixing
The progress of a certain amount of hydrochloric acid catalysis condensation reaction is added in object；A concentration of 3mol/ of the control acid in condensation reaction mixture
L；Setting-up point is 90 DEG C, and the reaction time is 6 hours；Gained condensation product is after suction filtration, drying, grinding with 2mol/L's
Aqueous sulfuric acid carries out ion exchange, and room-temperature ion exchanges 2 hours；Gained acidic resins are through filtering, washing after ion exchange
To neutral, dry catalyst as required later.
1）The activity comparison of differential responses temperature, Activity evaluation are shown in Table 23.
Influence of the 23. differential responses temperature of table to catalytic activity
Note：Catalyst amount is 0.15 gram in embodiment, and reactant dosage is 3.28 grams of 2- methylfurans（40mmol）、
1.16 gram acetone（20mmol）, the reaction time is 2 hours.
Table 23 the experimental results showed that, with the raising of reaction temperature, the activity of catalyst gradually increases；When temperature increases
To after 50 DEG C, increase trend slows down.
2）Influence of the catalyst amount to catalytic activity, reaction result are shown in Table 24.
Influence of 24. catalyst amount of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 1.16 grams of acetone（20mmol）, instead
It is 2 hours between seasonable, reaction temperature is 50 DEG C.
As can be seen from Table 24, with the increase of catalyst amount, yield is continuously improved.Meanwhile excessive catalyst meeting
Lead to the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2- methylfurans.
3）Influence of the differential responses time to catalytic activity, reaction result are shown in Table 25.
Influence of 25. reaction time of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 1.16 grams of acetone（20mmol）, instead
It is 2 hours between seasonable, reaction temperature is 50 DEG C.
As can be seen from Table 25, with the extension in reaction time, the yield of target product gradually increases；But when the time prolongs
Length to conversion ratio after 24 hours increases, and yield does not have significant change.This shows that the long reaction time results in side reaction
It carries out, such as methylfuran trimerization reaction.
Embodiment 175~192
2- methylfurans and the evaluation of n-butanal reactivity
The evaluating catalyst of the present invention carries out in the round-bottomed flask equipped with condensation reflux unit, and temperature passes through water bath with thermostatic control
Control.Experimentation is as follows：The catalyst and 3.28 grams of 2- methylfurans of certain mass are added in the round-bottomed flask of 50mL
（40mmol）, 1.44 grams of n-butanals（20mmol）, certain time is reacted at a certain temperature.Product is finally passed through into efficient liquid phase
Chromatography（HPLC）Carry out quantitative analysis.
In embodiments, the synthesis condition of used acid resin catalyst is：By the lignin sulfonic acid of certain mass
Sodium is dissolved in the water of certain mass, and the mass concentration for controlling sodium lignin sulfonate is 35%, then into lignin sulfonic acid sodium solution
A certain amount of formaldehyde crosslinking agent is added, the amount ratio of control crosslinking agent/sodium lignin sulfonate is 15mmol/g；Then to the mixing
The progress of a certain amount of hydrochloric acid catalysis condensation reaction is added in object；A concentration of 3mol/ of the control acid in condensation reaction mixture
L；Setting-up point is 90 DEG C, and the reaction time is 6 hours；Gained condensation product is after suction filtration, drying, grinding with 2mol/L's
Aqueous sulfuric acid carries out ion exchange, and room-temperature ion exchanges 2 hours；Gained acidic resins are through filtering, washing after ion exchange
To neutral, dry catalyst as required later.
1）The activity comparison of differential responses temperature, Activity evaluation are shown in Table 26.
Influence of the 26. differential responses temperature of table to catalytic activity
Note：Catalyst amount is 0.15 gram in embodiment, and reactant dosage is 3.28 grams of 2- methylfurans（40mmol）、
1.44 gram n-butanal（20mmol）, the reaction time is 2 hours.
Table 26 the experimental results showed that, with the raising of reaction temperature, the activity of catalyst gradually increases；When temperature increases
To after 50 DEG C, increase trend slows down.
2）Influence of the catalyst amount to catalytic activity, reaction result are shown in Table 27.
Influence of 27. catalyst amount of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 1.44 grams of n-butanals（20mmol）,
Reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 27, with the increase of catalyst amount, yield is continuously improved.Meanwhile excessive catalyst meeting
Lead to the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2- methylfurans.
3）Influence of the differential responses time to catalytic activity, reaction result are shown in Table 28.
Influence of 28. reaction time of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 1.44 grams of n-butanals（20mmol）,
Reaction time is 2 hours, and reaction temperature is 50 DEG C.
As can be seen from Table 28, with the extension in reaction time, the yield of target product gradually increases；But when the time prolongs
Length to conversion ratio after 24 hours increases, and yield does not have significant change.This shows that the long reaction time results in side reaction
It carries out, such as methylfuran trimerization reaction.
Embodiment 193~210
2- methylfurans and the evaluation of ethyl levulinate reactivity
The evaluating catalyst of the present invention carries out in the round-bottomed flask equipped with condensation reflux unit, and temperature passes through water bath with thermostatic control
Control.Experimentation is as follows：The catalyst and 3.28 grams of 2- methylfurans of certain mass are added in the round-bottomed flask of 50mL
（40mmol）, 2.88 grams of ethyl levulinates（20mmol）, certain time is reacted at a certain temperature.Product is finally passed through into height
Effect liquid phase chromatogram（HPLC）Carry out quantitative analysis.
In embodiments, the synthesis condition of used acid resin catalyst is：By the lignin sulfonic acid of certain mass
Sodium is dissolved in the water of certain mass, and the mass concentration for controlling sodium lignin sulfonate is 35%, then into lignin sulfonic acid sodium solution
A certain amount of formaldehyde crosslinking agent is added, the amount ratio of control crosslinking agent/sodium lignin sulfonate is 15mmol/g；Then to the mixing
The progress of a certain amount of hydrochloric acid catalysis condensation reaction is added in object；A concentration of 3mol/ of the control acid in condensation reaction mixture
L；Setting-up point is 90 DEG C, and the reaction time is 6 hours；Gained condensation product is after suction filtration, drying, grinding with 2mol/L's
Aqueous sulfuric acid carries out ion exchange, and room-temperature ion exchanges 2 hours；Gained acidic resins are through filtering, washing after ion exchange
To neutral, dry catalyst as required later.
1）The activity comparison of differential responses temperature, Activity evaluation are shown in Table 29.
Influence of the 29. differential responses temperature of table to catalytic activity
Note：Catalyst amount is 0.15 gram in embodiment, and reactant dosage is 3.28 grams of 2- methylfurans（40mmol）、
2.88 gram ethyl levulinate（20mmol）, the reaction time is 2 hours.
Table 29 the experimental results showed that, with the raising of reaction temperature, the activity of catalyst gradually increases；When temperature increases
To after 60 DEG C, increase trend slows down.
2）Influence of the catalyst amount to catalytic activity, reaction result are shown in Table 30.
Influence of 30. catalyst amount of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 2.88 grams of ethyl levulinates
（20mmol）, the reaction time is 2 hours, and reaction temperature is 50 DEG C
As can be seen from Table 30, with the increase of catalyst amount, yield is continuously improved.Meanwhile excessive catalyst meeting
Lead to the generation of side reaction.So best catalyst/substrate ratio is 0.15 gram/40mmol2- methylfurans.
3）Influence of the differential responses time to catalytic activity, reaction result are shown in Table 31.
Influence of 31. reaction time of table to catalytic activity
Note：Reactant dosage is 3.28 grams of 2- methylfurans in embodiment（40mmol）, 2.88 grams of ethyl levulinates
（20mmol）, the reaction time is 2 hours, and reaction temperature is 50 DEG C.
The extension with the reaction time is can be seen that from table 31, the yield of target product gradually increases；But when the time prolongs
Length to conversion ratio after 24 hours increases, and yield does not have significant change.This shows that the long reaction time results in side reaction
It carries out, such as methylfuran trimerization reaction.
Embodiment 211-222
Acidic resins synthesized by the present invention and commercialization ion exchange resin（Amberlyst-15 and Amberlyst-36）
Recycling stability contrast
Each evaluating catalyst carries out in the round-bottomed flask equipped with condensation reflux unit, and temperature is controlled by water bath with thermostatic control.
Experimentation is as follows：The catalyst and 3.28 grams of 2- methylfurans of certain mass are added in the round-bottomed flask of 50mL
（40mmol）, 1.92 grams of furfurals（20mmol）, certain time is reacted at a certain temperature.Product is finally passed through into high-efficient liquid phase color
Spectrum（HPLC）Carry out quantitative analysis.
In table 32, the synthesis condition of used acid resin catalyst is：The sodium lignin sulfonate of certain mass is molten
In the water of certain mass, the mass concentration for controlling sodium lignin sulfonate is 35%, is then added into lignin sulfonic acid sodium solution
The amount ratio of a certain amount of formaldehyde crosslinking agent, control crosslinking agent/sodium lignin sulfonate is 15mmol/g；Then into the mixture
The progress of a certain amount of hydrochloric acid catalysis condensation reaction is added；A concentration of 3mol/L of the control acid in condensation reaction mixture；Contracting
It is 90 DEG C to close reaction temperature, and the reaction time is 6 hours；Gained condensation product uses the sulfuric acid of 2mol/L after suction filtration, drying, grinding
Aqueous solution carries out ion exchange, and room-temperature ion exchanges 2 hours；Gained acidic resins are through filtering, washing into after ion exchange
Property, it is dry after be needed for catalyst.
In catalyst circulation stability test, used catalyst is first cleaned with methanol, removes reaction residue matter,
It is used further to next secondary response after dry.
The recycling stability of acidic resins synthesized by 32 present invention of table
The recycling stability of table 33Amberlyst-15 resins
The recycling stability of table 34Amberlyst-36 resins
It summarizes：As can be seen that the acidic resins synthesized by the present invention are wooden in catalysis from the comparing result of each embodiment
Cellulose base furan compound（It is preferred that 2- methylfurans）With lignocellulosic base carbonyls（Formaldehyde, formic acid, n-butanal,
Furfural, hydroxypropanone-, acetone, ethyl levulinate）Alkylated reaction in show excellent catalytic performance.And high catalysis
Activity and selectivity.In addition, the preparation process of catalyst is simple, good cycling stability, raw material are environmental-friendly, cheap and easily-available,
Make it that the higher application advantage of commercial ion exchanger resin more higher than costs such as Amberlyst, Nafion be presented.
Claims (7)
1. preparing alkane between lignocellulosic base furan compound and lignocellulosic base carbonyls with solid acid catalyst
The method of glycosylation reaction product, it is characterised in that：
1）The preparation method of the solid acid catalyst is：
Using sodium lignin sulfonate as raw material, the carbonyls as crosslinking agent is added, acid is added in the two after mixing, is urged
Change phenols functional group and the carbonyls as crosslinking agent in sodium lignin sulfonate and phenol formaldehyde condensation reaction occurs, to obtain one
Kind is insoluble in the high molecular polymer of water；
The temperature of condensation reaction is 50 ~ 120 DEG C, and the reaction time is 1 ~ 12 hour；The acid is sulfuric acid, hydrochloric acid, nitric acid, high chlorine
One in acid, phosphoric acid, phosphotungstic acid, phosphomolybdic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, acetic acid, monoxone
Kind or two or more mixtures；
Ion exchange is carried out to the high molecular polymer that upper step obtains using acid solution, it is changed into proton type by ionic,
To improve its acidity, as required catalyst；
The acid solution be sulfuric acid, hydrochloric acid, phosphoric acid, benzene sulfonic acid, trifluoromethanesulfonic acid, one or both of p-methyl benzenesulfonic acid with
On；
2) by the catalyst for being alkylated between lignocellulosic base furan compound and lignocellulosic base carbonyls
In reaction；
Wherein：Lignocellulosic base furan compound is the mixed of one or both of furans, 2- methylfurans, hydroxymethylfurans
Close object；Lignocellulosic base carbonyls is formaldehyde, formic acid, n-butanal, furfural, acetone, hydroxypropanone-, cyclopentanone, acetyl
The mixture of one or more of ethyl propionate；
Corresponding alkylation reaction product is：Carbon number is the oxygenatedchemicals between 8 ~ 16, these oxygenatedchemicals can be hydrogenated
Diesel oil or aviation kerosine alkane is made in deoxidation.
2. according to the method described in claim 1, it is characterized in that：
Carbonyls as crosslinking agent is one kind in formaldehyde, formic acid, acetaldehyde, butyraldehyde, furfural, glucose sugar, levulic acid
Or it is two or more.
3. according to the method described in claim 1, it is characterized in that：
First, sodium lignin sulfonate is soluble in water, it is 10 ~ 40% to control its mass concentration；Then to lignin sulfonic acid sodium solution
In crosslinking agent is added dropwise and controls the amount ratio of crosslinking agent and sodium lignin sulfonate is 5 ~ 30 mmol crosslinking agents/g sulfomethylated lignins
Sour sodium；After mixing by the two, acid solution is added dropwise into the mixture, controlling hydrogen ion concentration in final mixture is
0.1~5 mol/L。
4. according to the method described in claim 1, it is characterized in that：
Gained condensation product carries out ion exchange after suction filtration, drying, grinding with acid solution makes it be converted to matter by ionic
The acidic resins of subtype；
Drying temperature is 60 ~ 120 DEG C, and drying time is 2-12 hours.
5. method according to claim 1 or 4, it is characterised in that：
Condensation product is added to progress ion-exchange treatment in the acid solution of 0.1 ~ 5mol/L, it is changed into proton by ionic
Type；The control of the ratio of solid and acid solution is 5 gCondensation product/50~500 mLAcid solution；Ion exchange conditions are ion at 20 ~ 80 DEG C
Exchange 1 ~ 12 h.
6. according to the method described in claim 1, it is characterized in that：
Lignocellulosic base furan compound and lignocellulosic base carbonyls are separately added into reaction under condition of no solvent
It is alkylated reaction in container, controls mole of lignocellulosic base furan compound and lignocellulosic base carbonyls
Ratio is 0.25 ~ 4.
7. according to the method described in claim 1, it is characterized in that：
Alkylated reaction temperature is 0 ~ 80 DEG C, the control of catalyst amount and lignocellulosic base furan compound ratio is 0.015 ~
The mmol furan compounds of 0.3g catalyst/40, reaction time are 0.5 ~ 80 hour.
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| CN108358876A (en) * | 2018-04-23 | 2018-08-03 | 南京工业大学 | Bio-based furan monomer and preparation method and application thereof |
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