CN108794434A - The method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether - Google Patents
The method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether Download PDFInfo
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
The invention discloses a kind of methods that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether, include the following steps：S1, micropore Si-Al molecular sieve is chosen；S2, addition acid or alkali are handled, and the multi-stage porous Si-Al molecular sieve of micropore and mesoporous is formed while having；S3, multi-stage porous Si-Al molecular sieve made from step S2 is loaded on fixed bed reactors；S4, it is passed through reaction raw materials liquid BHMF and alcohol progress etherification reaction, product is made.This hair prepares multi-stage porous Si-Al molecular sieve, in applying it to from 2,5-FDM to the etherification reaction of 2,5-FDM diether, for more common micropore Si-Al molecular sieve, the diffusion limitation for effectively improving reaction process, is greatly reduced the generation of by-product, and BRMF yields reach 85-99%, after simple distillation removes unreacted alcohol, without later separation, you can obtain two ether products of 2,5-FDM of 95% or more purity.
Description
Technical field
The present invention relates to a kind of preparation methods of furyl dimethyl carbinol diether more particularly to a kind of catalysis furyl dimethyl carbinol to be etherified
The method for preparing furyl dimethyl carbinol diether.
Background technology
With the fast development of global economy, conventional petroleum resource is increasingly reduced and the ever-increasing lance of fossil fuel demand
Shield is more and more prominent.Dependence to fossil fuel will effectively be reduced by preparing fuel with reproducible biomass resource, to
Above-mentioned contradiction is alleviated to a certain extent, therefore there is extremely important meaning.Using from photosynthetic direct production
It is current research and development both at home and abroad that object-carbohydrate (especially hexose carbohydrate), which prepares various biological base liquid fuels,
Emphasis direction, such as the alcohol fuel of industrialization and biofermentation prepare biological-based chemicals etc..By carbohydrate
(with cellulose, glucose and fructose etc. for representative) is converted into liquid fuel and is usually first put down carbohydrate-modifying to be various
Platform compound, then again by platform chemicals by adding the processes such as hydrogen, etherificate to be converted into liquid fuel.It is flat in numerous biology bases
In platform compound, 5 hydroxymethyl furfural (HMF) is most potential one kind, has become biomass conversion in recent years and grinds
The hot spot studied carefully.
There can be following methods from HMF liquid fuel was prepareds, first, hydrogen is added to directly generate 2,5- dimethyl furans
It mutters (2,5-DMF)；Second is that directly generating monoether (RMF) by etherification reaction with alcohol；Third, first hydrogenation selectivity generates 2,5-
Furyl dimethyl carbinol (BHMF) then generates 2,5-FDM diether (BRMF) with alcohol by etherification reaction again.2,5-DMF
Have the characteristics that high-energy density, high-octane rating, but it is only suitable for as gasoline component, and the conversion from HMF to 2,5-DMF
There is the loss of molecular weight close to 30% in the process, therefore Atom economy is poor.And the preparation process of RMF and BRMF almost without
Loss of molecular weight, Atom economy are preferable.But, it due to also retaining a relatively active aldehyde radical in the structure of RMF, is easy
Polymerisation occurs, therefore stability is short of.Comparatively, not only stability is more preferable by BRMF, but also the adjustable model of carbon number
Enclose it is wider, both can be used as gasoline component, can also be used as kerosene or diesel component.In addition, BRMF also have density it is big,
Low temperature flow is good, can be miscible with arbitrary proportion and petrol and diesel oil the features such as, therefore is a kind of very potential new bio base
Liquid fuel.
So far, the research that related BHMF etherificates prepare BRMF is also considerably less, and only several open source literatures report is such as
Under：Qingdao energy Suo Muxindong seminars of the Chinese Academy of Sciences are using commercial micropore ZSM-5 molecular sieve as catalyst, in 140 DEG C of reaction
In kettle, BHMF and methanol etherification are prepared into 2,5-FDM dimethyl ether, 70% or so (Applied of product yield
Catalysis A:General 481(2014)49–53).The A.T.Bell seminars of Univ California-Berkeley with
Amberlyst-15 resins are catalyst, and 2,5-FDM two has been synthesized with ethyl alcohol etherificate in 60 DEG C of sealing scintillation vial
Ether, product yield is less than 70% (Journal ofCatalysis 313 (2014) 70-79).Delaware, USA university
BHMF and propyl alcohol are etherified in 180 DEG C of reaction kettle, obtain using Sn-Beta molecular sieves as catalyst by R.F.Lobo seminars
80% or so dipropyl ether product (ChemCatChem 2014,6,508-513).As a whole, at present prepared by BHMF etherificates
The problem of process of BRMF is primarily present be：The yield of two ether products of target (BRMF) is not high, and this aspect, which increases, to be prepared into
This, it is often more important that, a large amount of by-products of generation have seriously affected the service life of catalyst, and are brought to the separation of subsequent product
Great difficulty.
Chinese patent 201110401610.9 discloses " a method of by sugar prepare furyl dimethyl carbinol dialkyl ether ",
Used micropore Si-Al molecular sieve as the catalyst of etherification reaction, due to microporous molecular sieve duct to a certain extent caused by
The diffusion of reactant or product limits, more so as to cause side reaction, and the yield of two ether products is universal relatively low (less than 50%),
It is subsequent isolate and purify it is difficult.
Invention content
The technical problem to be solved in the present invention is to provide a kind of catalysis furyl dimethyl carbinol etherificates to prepare furyl dimethyl carbinol diether
Method；This method prepares multi-stage porous (being provided simultaneously with micropore and mesoporous) sial by hydrothermal synthesis method and corresponding post-processing
Molecular sieve applies it in the etherification reaction that 2,5-FDM etherificate prepares 2,5-FDM diether, more commonly
Micropore Si-Al molecular sieve for, effectively improve reaction process diffusion limitation, the generation of by-product, BRMF is greatly reduced
Yield reaches 85-99%, after simple distillation removes unreacted alcohol, is not necessarily to later separation, you can the 2 of 95% or more purity are obtained,
Two ether products of 5- furyl dimethyl carbinols.
In the present invention, term " micropore " refers to aperture≤2nm, and term " mesoporous ", also referred to as " mesoporous ", refer to 2nm<Aperture≤
50nm。
In order to solve the above technical problems, a kind of catalysis furyl dimethyl carbinol etherificate of the present invention prepares the side of furyl dimethyl carbinol diether
Method includes the following steps：
S1, micropore Si-Al molecular sieve is chosen；
S2, addition acid or alkali are handled, and the multi-stage porous Si-Al molecular sieve of micropore and mesoporous is formed while having；
S3, multi-stage porous Si-Al molecular sieve made from step S2 is loaded on fixed bed reactors；
S4, it is passed through reaction raw materials liquid BHMF and alcohol progress etherification reaction, product is made.
As a further improvement on the present invention, the silicoaluminophosphate molecular screened from：ZSM-5,ZSM-22,ZSM-23,ZSM-48,
It is one or more in Beta, modenite；It is highly preferred that the silicoaluminophosphate molecular screened from：ZSM-5, ZSM-23 or Beta.This Shen
In technical solution please, above-mentioned molecular sieve is not used, the selectivity of reaction is very low, is less than 20%.
Preferably, in step S2, the acid is selected from HCl, HNO3、H2SO4In it is one or more.It is highly preferred that the acid
For HCl.Through experiment, handled using other acid very poor to the modification effect in duct, such as pore-size distribution is uncontrollable.
Preferably, in step S2, the alkali is selected from NaOH, Na2CO3, it is one or more in KOH；It is highly preferred that described
Alkali is NaOH.Handled using other alkali very poor to the modification effect in duct, such as pore-size distribution is uncontrollable.
Preferably, in step S2, a concentration of 0.1-2M of the acid or alkali；It is highly preferred that described sour or alkali dense
Degree is 0.5-1M.Through experiment, the concentration of acid or alkali is not within the above range, poor to the modification effect in duct, such as pore-size distribution
It is uncontrollable.
Preferably, in step S2, the acid or the solvent and solute weight ratio between alkali and molecular sieve are 5-100：1；It is highly preferred that
The acid or the solvent and solute weight ratio between alkali and molecular sieve are 10-30：1；Most preferably, between the acid or alkali and molecular sieve
Solvent and solute weight ratio is 15-20：1.
Preferably, in step S2,25-80 DEG C of the treatment temperature of acid or alkali, processing time 6-24h is added；It is highly preferred that plus
Enter 50-60 DEG C of the treatment temperature of acid or alkali, processing time 6-8h.
As a further improvement on the present invention, in step S3, the multi-stage porous Si-Al molecular sieve grain size is 40-60 mesh.
As a further improvement on the present invention, in step S4, reaction temperature is 30-80 DEG C；Flow rate of liquid 0.5-3.0h-1；
It is highly preferred that reaction temperature is 50-65 DEG C, flow rate of liquid 1-1.5h-1。
Preferably, in step S4, the molar ratio between the BHMF and alcohol is：1-3：8-20.
In step S4, the alcohol can be selected from conventional alkyl alcohols, such as methanol, ethyl alcohol, propyl alcohol, ethylene glycol, isopropanol
Deng.
In the present invention, temperature ranges and the place of acid or alkali is added in the concentration range of acid or alkali in step S2, step S2
The selection for managing the time obtains being suitable for the reasonably combined micropore and mesoporous that the present invention reacts；Reaction in matching step S4 again
Temperature range and flow rate of liquid range etc. constitute an organic whole, by the selection of these parameter areas, to reach
The effect (being promoted from existing 50% or less to 85% or more) that the application BRMF is increased substantially.
Product detects (chromatographiccondition see the table below 1) using HPLC, BRMF yields 85-99%.After reaction, through subtracting
After pressure distillation removes unreacted alcohol, you can obtain the BRMF products of purity 95-99%.
1 high performance liquid chromatography of table (HPLC) analysis condition
Use the set of the above-mentioned all preferred embodiments of the present invention：Product is detected using HPLC, and BRMF yields can reach
95-99%；After reaction, after vacuum distillation removes unreacted alcohol, you can obtain the BRMF products of purity 97-99%.
Any range recorded in the present invention includes any numerical value between end value and end value and end value or end value
Between the arbitrary subrange that is constituted of any number.
Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention
The conventional equipment in fields can be used or carried out with reference to the prior art of fields.
The present invention has the advantages that：
The present invention prepares suitable multi-stage porous Si-Al molecular sieve of arranging in pairs or groups by hydrothermal synthesis method and corresponding post-processing, will
During it is applied to from 2,5-FDM to the etherification reaction of 2,5-FDM diether, more common micropore silicoaluminophosphate molecular
For sieve, the diffusion limitation of reaction process being effectively improved, the generation of by-product is greatly reduced, BRMF yields reach 85-99%,
After simple distillation removes unreacted alcohol, it is not necessarily to later separation, you can obtain the 2,5-FDM two of 95% or more purity
Ether products.
Description of the drawings
Specific embodiments of the present invention will be described in further detail below in conjunction with the accompanying drawings
Fig. 1 is the BET test result figures of the HP-ZSM-5-1 samples of embodiment 1；
Fig. 2 is the product HPLC analysis result figures of embodiment 1.
Specific implementation mode
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection domain of invention.
Embodiment 1
A kind of preparation method of furyl dimethyl carbinol dimethyl ether, includes the following steps：
S1, take 15g hydrothermal synthesis micropore ZSM-5 molecular sieve (such as：Tianjin Nan Hua catalyst Co., Ltd produces)
(http://www.nkcatalyst.com/)；
S2, it is added in the HCl solution of 300ml 0.5M, 50 DEG C are stirred to react 6h, and filtering, deionized water washing, drying obtain
To multi-stage porous Si-Al molecular sieve (HP-ZSM-5-1)；
S3,5g HP-ZSM-5-1 are taken to be fitted into 10ml fixed bed reactors；
S4, fixed bed reactors are warming up to 65 DEG C, are passed through mixing liquid, and liquid group becomes：10mol%BHMF, 90mol%
Methanol, flow rate of liquid 1.0h-1, product detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 99%.
Fig. 1 gives the BET test results of HP-ZSM-5-1 samples, and Fig. 2 gives the analysis result collection of illustrative plates of HPLC.
Embodiment 2
A kind of preparation method of two ethyl methyl ether of furyl dimethyl carbinol, includes the following steps：
S1, the micropore ZSM-5 molecular sieve for taking 20g hydrothermal synthesis；
S2, it is added in the NaOH solution of 300ml 1M, 60 DEG C are stirred to react 8h, are filtered, washed, dry, obtain multi-stage porous
Si-Al molecular sieve (HP-ZSM-5-2).
S3,5g HP-ZSM-5-2 are taken to be fitted into 10ml fixed bed reactors,
S4, fixed bed reactors are warming up to 50 DEG C, are passed through mixing liquid, and liquid group becomes：10%BHMF, 90% ethyl alcohol,
Flow rate of liquid 0.5h-1, product detected using HPLC, furyl dimethyl carbinol diethyl ether (BEMF) yield 97%.
Embodiment 3
A kind of preparation method of furyl dimethyl carbinol dimethyl ether, includes the following steps：
S1, take 10g hydrothermal synthesis micropore Beta molecular sieves (such as：International catalyst Co. zeolyst
International is produced), http://www.zeolyst.com；
S2, it is added in the HCl solution of 300ml 0.5M, 60 DEG C are stirred to react 6h, are filtered, washed, dry, obtain multi-stage porous
Si-Al molecular sieve (HP-Beta-1).
S3,5g HP-Beta-1 are taken to be fitted into 10ml fixed bed reactors,
S4, fixed bed reactors are warming up to 60 DEG C, are passed through mixing liquid, and liquid group becomes：10%BHMF, 90% methanol,
Flow rate of liquid 1h-1, product detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 98%.
Embodiment 4
A kind of preparation method of furyl dimethyl carbinol dimethyl ether, includes the following steps：
S1, take 11g hydrothermal synthesis micropore ZSM-23 molecular screen (such as：International catalyst Co. zeolyst
International is produced), http://www.zeolyst.com；
S2, it is added in the HCl solution of 300ml 0.5M, 50 DEG C are stirred to react 6h, are filtered, washed, dry, obtain multi-stage porous
Si-Al molecular sieve (HP-ZSM-23-1).
S3,5g HP-ZSM-23-1 are taken to be fitted into 10ml fixed bed reactors,
S4, fixed bed reactors are warming up to 65 DEG C, are passed through mixing liquid, and liquid group becomes：10%BHMF, 90% methanol,
Flow rate of liquid 0.5h-1, product detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 97%.
Embodiment 5
A kind of preparation method of furyl dimethyl carbinol dimethyl ether, includes the following steps：
S1, the micropore ZSM-23 molecular screen for taking 15g hydrothermal synthesis；
S2, it is added in the NaOH solution of 300ml 0.8M, 50 DEG C are stirred to react 8h, are filtered, washed, dry, obtain multistage
Hole Si-Al molecular sieve (HP-ZSM-23-2).
S3,5g HP-ZSM-23-2 are taken to be fitted into 10ml fixed bed reactors,
S4, fixed bed reactors are warming up to 65 DEG C, are passed through mixing liquid, and liquid group becomes：10%BHMF, 90% propyl alcohol,
Flow rate of liquid 0.6h-1, product detected using HPLC, furyl dimethyl carbinol dipropyl ether (BPMF) yield 99%.
Comparative example 1
A kind of preparation method of furyl dimethyl carbinol dimethyl ether, includes the following steps：
S1 takes 5g micropore ZSM-5 molecular sieves to be fitted into 10ml fixed bed reactors；
S2, fixed bed reactors are warming up to 65 DEG C, are passed through mixing liquid, and liquid group becomes：10mol%BHMF, 90mol%
Methanol, flow rate of liquid 1.0h-1, product detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 45%.
Embodiment 6
A kind of preparation method of furyl dimethyl carbinol dimethyl ether, includes the following steps：
S1, the micropore ZSM-23 molecular screen for taking 10g hydrothermal synthesis；
S2, it is added in the HCl solution of 200ml 2M, 80 DEG C are stirred to react 10h, are filtered, washed, dry, obtain multi-stage porous
Si-Al molecular sieve (HP-ZSM-23-3).
S3,5g HP-ZSM-23-3 are taken to be fitted into 10ml fixed bed reactors,
S4, fixed bed reactors are warming up to 65 DEG C, are passed through mixing liquid, and liquid group becomes：10%BHMF, 90% methanol,
Flow rate of liquid 0.5h-1, product detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 78%.
Embodiment 7
A kind of preparation method of furyl dimethyl carbinol dimethyl ether, includes the following steps：
S1, the micropore ZSM-5 molecular sieve for taking 10g hydrothermal synthesis；
S2, the Na that 300ml 0.5M are added2CO3In solution, 50 DEG C are stirred to react 5h, are filtered, washed, dry, obtain multistage
Hole Si-Al molecular sieve (HP-ZSM-5-3).
S3,5g HP-ZSM-23-3 are taken to be fitted into 10ml fixed bed reactors,
S4, fixed bed reactors are warming up to 65 DEG C, are passed through mixing liquid, and liquid group becomes：10%BHMF, 90% methanol,
Flow rate of liquid 1h-1, product detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 85%.
Embodiment 8
A kind of preparation method of furyl dimethyl carbinol dimethyl ether, includes the following steps：
S1, take 15g hydrothermal synthesis micropore ZSM-5 molecular sieve (such as：Tianjin Nan Hua catalyst Co., Ltd produces)
(http://www.nkcatalyst.com/)；
S2, it is added in the HCl solution of 300ml 0.2M, 50 DEG C are stirred to react 6h, and filtering, deionized water washing, drying obtain
To multi-stage porous Si-Al molecular sieve (HP-ZSM-5-3)；
S3,5g HP-ZSM-5-3 are taken to be fitted into 10ml fixed bed reactors；
S4, fixed bed reactors are warming up to 50 DEG C, are passed through mixing liquid, and liquid group becomes：10mol%BHMF, 90mol%
Methanol, flow rate of liquid 0.5h-1, product detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 90%.
Embodiment 9
A kind of preparation method of furyl dimethyl carbinol dimethyl ether, includes the following steps：
S1, take 15g hydrothermal synthesis micropore ZSM-5 molecular sieve (such as：Tianjin Nan Hua catalyst Co., Ltd produces)
(http://www.nkcatalyst.com/)；
S2, it is added in the HCl solution of 300ml 2M, 80 DEG C are stirred to react for 24 hours, and filtering, deionized water washing, drying obtain
To multi-stage porous Si-Al molecular sieve (HP-ZSM-5-3)；
S3,5g HP-ZSM-5-3 are taken to be fitted into 10ml fixed bed reactors；
S4, fixed bed reactors are warming up to 80 DEG C, are passed through mixing liquid, and liquid group becomes：10mol%BHMF, 90mol%
Methanol, flow rate of liquid 3h-1, product detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 95%.
Comparative example 2
Repeat embodiment 1, difference only in：
In step S2, a concentration of 0.05M of HCl solution；
Product is detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 64%.
Comparative example 3
Repeat embodiment 1, difference only in：
In step S2, a concentration of 0.1M of HCl solution；
Product is detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 91%.
Comparative example 4
Repeat embodiment 1, difference only in：
In step S2, a concentration of 3M of HCl solution；
Product is detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 62%.
Comparative example 5
Repeat embodiment 1, difference only in：
In step S2, after HCl solution is added, 20 DEG C are stirred to react 30h；
Product is detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 71%.
Comparative example 6
Repeat embodiment 1, difference only in：
In step S2, after HCl solution is added, 30 DEG C are stirred to react 6h；
Product is detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 89%.
Comparative example 7
Repeat embodiment 1, difference only in：
In step S2, after HCl solution is added, 90 DEG C are stirred to react 5h；
Product is detected using HPLC, furyl dimethyl carbinol dimethyl ether (BMMF) yield 83%.
Comparative example 8
Repeat embodiment 1, difference only in：
In step S4, fixed bed reactors are warming up to 25 DEG C, flow rate of liquid 1.0h-1, product detected using HPLC, furans two
Methanol and dimethyl ether (BMMF) yield 31%.
Comparative example 9
Repeat embodiment 1, difference only in：
In step S4, fixed bed reactors are warming up to 50 DEG C, flow rate of liquid 1.0h-1, product detected using HPLC, furans two
Methanol and dimethyl ether (BMMF) yield 83%.
Comparative example 10
Repeat embodiment 1, difference only in：
In step S4, fixed bed reactors are warming up to 90 DEG C, flow rate of liquid 1.0h-1, product detected using HPLC, furans two
Methanol and dimethyl ether (BMMF) yield 73%.
Comparative example 11
Repeat embodiment 1, difference only in：
In step S4, fixed bed reactors are warming up to 50 DEG C, flow rate of liquid 0.4h-1, product detected using HPLC, furans two
Methanol and dimethyl ether (BMMF) yield 47%.
Comparative example 12
Repeat embodiment 1, difference only in：
In step S4, fixed bed reactors are warming up to 50 DEG C, flow rate of liquid 3.5h-1, product detected using HPLC, furans two
Methanol and dimethyl ether (BMMF) yield 43%.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is every to belong to this hair
Row of the obvious changes or variations that bright technical solution is extended out still in protection scope of the present invention.
Claims (10)
1. the method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether, which is characterized in that include the following steps：
S1, micropore Si-Al molecular sieve is chosen；
S2, addition acid or alkali are handled, and the multi-stage porous Si-Al molecular sieve of micropore and mesoporous is formed while having；
S3, multi-stage porous Si-Al molecular sieve made from step S2 is loaded on fixed bed reactors；
S4, it is passed through reaction raw materials liquid BHMF and alcohol progress etherification reaction, product is made.
2. the method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether according to claim 1, it is characterised in that：
The silicoaluminophosphate molecular screened from：It is one or more in ZSM-5, ZSM-22, ZSM-23, ZSM-48, Beta, modenite；It is preferred that
Ground, the silicoaluminophosphate molecular screened from：ZSM-5, ZSM-23 or Beta.
3. the method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether according to claim 1, it is characterised in that：
In step S2, the acid is selected from HCl, HNO3、H2SO4In it is one or more；Preferably, the acid is HCl.
4. the method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether according to claim 1, it is characterised in that：
Preferably, in step S2, the alkali is selected from NaOH, Na2CO3, it is one or more in KOH；It is highly preferred that the alkali is NaOH.
5. the method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether according to claim 1, it is characterised in that：
In step S2, a concentration of 0.1-2M of the acid or alkali；Preferably, a concentration of 0.5-1M of the acid or alkali.
6. the method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether according to claim 1, it is characterised in that：
Preferably, in step S2, the acid or the solvent and solute weight ratio between alkali and molecular sieve are 5-100：1；It is highly preferred that it is described acid or
Solvent and solute weight ratio between alkali and molecular sieve is 10-30：1；Most preferably, the acid or the liquid between alkali and molecular sieve consolidate weight
Than for 15-20：1.
7. the method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether according to claim 1, it is characterised in that：
In step S2,25-80 DEG C of the treatment temperature of acid or alkali, processing time 6-24h is added；Preferably, the processing temperature of acid or alkali is added
50-60 DEG C of degree, processing time 6-8h.
8. the method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether according to claim 1, it is characterised in that：
In step S3, the multi-stage porous Si-Al molecular sieve grain size is 40-60 mesh.
9. the method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether according to claim 1, it is characterised in that：
In step S4, reaction temperature is 30-80 DEG C；Flow rate of liquid 0.5-3.0h-1；Preferably, reaction temperature is 50-65 DEG C, liquid flow
Fast 1-1.5h-1。
10. the method that catalysis furyl dimethyl carbinol etherificate prepares furyl dimethyl carbinol diether according to claim 1, feature exist
In：In step S4, the molar ratio between the BHMF and alcohol is：1-3：8-20；The alcohol is selected from alkylol.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851597A (en) * | 2018-12-25 | 2019-06-07 | 东莞理工学院 | A kind of preparation method of 2,5- furyl dimethyl carbinol dialkyl ether |
| CN110343078A (en) * | 2018-04-04 | 2019-10-18 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of furans ether compound |
| CN111233799A (en) * | 2020-03-19 | 2020-06-05 | 浙江糖能科技有限公司 | Preparation method of bis- (5-formylfurfuryl) ether |
| CN111233798A (en) * | 2020-02-28 | 2020-06-05 | 浙江糖能科技有限公司 | Preparation method of bis- (5-formylfurfuryl) ether and polyamide material |
| CN113372306A (en) * | 2020-12-31 | 2021-09-10 | 浙江糖能科技有限公司 | Preparation method of 2, 5-furandimethanol di-tert-butyl ether |
| CN114685407A (en) * | 2020-12-29 | 2022-07-01 | 中国科学院宁波材料技术与工程研究所 | Method for preparing 2, 5-furan dimethanol dialkyl ether by etherification of 2, 5-furan dimethanol |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343078A (en) * | 2018-04-04 | 2019-10-18 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of furans ether compound |
| CN109851597A (en) * | 2018-12-25 | 2019-06-07 | 东莞理工学院 | A kind of preparation method of 2,5- furyl dimethyl carbinol dialkyl ether |
| CN111233798A (en) * | 2020-02-28 | 2020-06-05 | 浙江糖能科技有限公司 | Preparation method of bis- (5-formylfurfuryl) ether and polyamide material |
| CN111233799A (en) * | 2020-03-19 | 2020-06-05 | 浙江糖能科技有限公司 | Preparation method of bis- (5-formylfurfuryl) ether |
| CN111233799B (en) * | 2020-03-19 | 2022-03-22 | 浙江糖能科技有限公司 | Preparation method of bis- (5-formylfurfuryl) ether |
| CN114685407A (en) * | 2020-12-29 | 2022-07-01 | 中国科学院宁波材料技术与工程研究所 | Method for preparing 2, 5-furan dimethanol dialkyl ether by etherification of 2, 5-furan dimethanol |
| CN113372306A (en) * | 2020-12-31 | 2021-09-10 | 浙江糖能科技有限公司 | Preparation method of 2, 5-furandimethanol di-tert-butyl ether |
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