CN108794434B

CN108794434B - Method for preparing furan dimethanol diether by catalyzing furan dimethanol etherification

Info

Publication number: CN108794434B
Application number: CN201710287365.0A
Authority: CN
Inventors: 闫海生; 尹荃
Original assignee: Shenyang Kaichuang Lisi Technology Co ltd
Current assignee: Shenyang Kaichuang Lisi Technology Co ltd
Priority date: 2017-04-27
Filing date: 2017-04-27
Publication date: 2020-08-11
Anticipated expiration: 2037-04-27
Also published as: CN108794434A

Abstract

The invention discloses a method for preparing furan dimethanol diether by catalyzing furan dimethanol etherification, which comprises the following steps: s1, selecting a microporous silicon-aluminum molecular sieve; s2, adding acid or alkali for treatment to form a hierarchical pore silicon-aluminum molecular sieve with micropores and mesopores; s3, filling the hierarchical pore silicon-aluminum molecular sieve prepared in the step S2 on a fixed bed reactor; s4, introducing reaction raw material liquid BHMF and alcohol to carry out etherification reaction, and obtaining the product. Compared with the common microporous silicon-aluminum molecular sieve, the prepared hierarchical porous silicon-aluminum molecular sieve effectively improves the diffusion limitation of the reaction process, greatly reduces the generation of byproducts, achieves the BRMF yield of 85-99 percent, and can obtain the 2, 5-furandimethanol diether product with the purity of more than 95 percent without subsequent separation after the unreacted alcohol is removed by simple distillation.

Description

Method for preparing furan dimethanol diether by catalyzing furan dimethanol etherification

Technical Field

The invention relates to a preparation method of furan dimethanol diether, in particular to a method for preparing furan dimethanol diether by catalyzing furan dimethanol etherification.

Background

With the rapid development of global economy, the contradiction between the gradual reduction of traditional petroleum resources and the continuous increase of demand of petrochemical fuels is more and more prominent. The preparation of fuel by using renewable biomass resources can effectively reduce the dependence on petrochemical fuel, thereby relieving the contradiction to a certain extent, and having great significance. The preparation of various bio-based liquid fuels by using direct products from photosynthesis, namely carbohydrates (especially six-carbon sugar carbohydrates), is a key direction of current research and development at home and abroad, such as industrialized fuel ethanol and bio-based chemical preparation by biological fermentation. The conversion of carbohydrates (represented by cellulose, glucose, fructose, and the like) into liquid fuels generally involves converting the carbohydrates into various platform compounds, and then converting the platform compounds into liquid fuels through processes such as hydrogenation, etherification, and the like. Among the numerous bio-based platform compounds, 5-Hydroxymethylfurfural (HMF) is one of the most promising potential for development and has recently become a hotspot in biomass conversion research.

The liquid fuel prepared from HMF can be prepared by the following modes, namely, hydrogenation is directly carried out to generate 2, 5-dimethyl furan (2, 5-DMF); secondly, the alcohol and the alcohol directly generate monoether (RMF) through etherification reaction; thirdly, hydrogenation is carried out to selectively generate 2, 5-furan dimethanol (BHMF), and then the 2, 5-furan dimethanol diether (BRMF) is generated by etherification with alcohol. 2,5-DMF has the characteristics of high energy density, high octane number and the like, but is only suitable as a gasoline component, and the conversion process from HMF to 2,5-DMF has molecular weight loss close to 30 percent, so the atom economy is poor. The preparation processes of RMF and BRMF almost have no molecular weight loss, and the atom economy is better. However, the RMF has a relatively active aldehyde group remaining in the structure, and thus is susceptible to polymerization, resulting in a lack of stability. Relatively speaking, the BRMF has better stability and wider adjustable range of carbon number, and can be used as a gasoline component and a kerosene or diesel component. In addition, the BRMF has the characteristics of high density, good low-temperature fluidity, capability of being mixed and dissolved with gasoline and diesel oil in any proportion and the like, so that the BRMF is a novel potential bio-based liquid fuel.

So far, the research on preparing BRMF by etherifying BHMF is very few, and only a few publications are reported as follows: the Xindong project group of Qingdao energy institute of Chinese academy of sciences uses commercial microporous ZSM-5 molecular sieve as catalyst, and etherifies BHMF and methanol in a reaction kettle at 140 ℃ to prepare 2, 5-furan dimethanol dimethyl ether, and the product yield is about 70% (applied catalysis A: General 481(2014) 49-53). The group of subjects, a.t. bell, at berkeley division, university of california, used Amberlyst-15 resin as a catalyst and etherified with ethanol in a sealed scintillation vial at 60 ℃ to synthesize 2, 5-furandimethanol diethyl ether with a product yield of less than 70% (Journal of catalysis 313 (2014)) 70-79. The R.F. Lobo topic group of the university of Delaware in USA uses Sn-Beta molecular sieve as catalyst, and BHMF and propanol are etherified in a reaction kettle at 180 ℃ to obtain about 80% dipropyl ether product (ChemCatchem 2014,6, 508-. In summary, the main problems of the current processes for preparing BRMF by BHMF etherification are as follows: the yield of the target diether product (BRMF) is not high, which increases the preparation cost, and more importantly, the large amount of by-products generated seriously affects the service life of the catalyst and brings great difficulty to the subsequent product separation.

Chinese patent 201110401610.9 discloses a method for preparing furan dimethanol dialkyl ether from sugar, which uses microporous silicon-aluminum molecular sieve as catalyst for etherification reaction, because microporous pore channels of the molecular sieve cause diffusion limitation of reactants or products to a certain extent, side reactions are more, the yield of diether products is generally low (less than 50%), and the subsequent separation and purification difficulty is very large.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a method for preparing furan dimethanol diether by catalyzing furan dimethanol etherification; the method prepares the hierarchical pore (simultaneously provided with micropores and mesopores) silicon-aluminum molecular sieve by a hydrothermal synthesis method and corresponding post-treatment, applies the hierarchical pore (simultaneously provided with micropores and mesopores) silicon-aluminum molecular sieve to the etherification reaction for preparing the 2, 5-furandimethanol diether by etherification of the 2, 5-furandimethanol, effectively improves the diffusion limitation in the reaction process and greatly reduces the generation of byproducts compared with the common microporous silicon-aluminum molecular sieve, the yield of BRMF reaches 85-99%, and the 2, 5-furandimethanol diether product with the purity of more than 95 percent can be obtained without subsequent separation after the unreacted alcohol is removed by simple distillation.

In the present invention, the term "micropore" means a pore diameter of 2nm or less, and the term "mesopore", also referred to as "mesopore", means 2nm < a pore diameter of 50nm or less.

In order to solve the technical problem, the invention provides a method for preparing furan dimethanol diether by catalyzing furan dimethanol etherification, which comprises the following steps:

s1, selecting a microporous silicon-aluminum molecular sieve;

s2, adding acid or alkali for treatment to form a hierarchical pore silicon-aluminum molecular sieve with micropores and mesopores;

s3, filling the hierarchical pore silicon-aluminum molecular sieve prepared in the step S2 on a fixed bed reactor;

s4, introducing reaction raw material liquid BHMF and alcohol to carry out etherification reaction, and obtaining the product.

As a further improvement of the invention, the silicoaluminophosphate molecular sieve is selected from: one or more of ZSM-5, ZSM-22, ZSM-23, ZSM-48, Beta and mordenite; more preferably, the silicoaluminophosphate molecular sieve is selected from: ZSM-5, ZSM-23 or Beta. In the technical scheme of the application, the molecular sieve is not used, and the selectivity of the reaction is very low and is lower than 20%.

Preferably, in step S2, the acid is selected from HCl, HNO₃、H₂SO₄One or more of (a). More preferably, the acid is HCl. Tests show that the modification effect of the pore channel by using other acids is poor, such as uncontrollable pore size distribution.

Preferably, in step S2, the alkali is selected from NaOH and Na₂CO₃One or more of KOH and KOH; more preferably, the base is NaOH. The modification of the channels by treatment with other bases is poor, for example the pore size distribution is not controllable.

Preferably, in step S2, the concentration of the acid or base is 0.1-2M; more preferably, the concentration of the acid or base is 0.5-1M. Tests show that the concentration of the acid or the alkali is not in the above range, and the modification effect on the pore channel is poor, such as the pore size distribution is uncontrollable.

Preferably, in step S2, the liquid-solid weight ratio between the acid or base and the molecular sieve is 5-100: 1; more preferably, the liquid-solid weight ratio between the acid or base and the molecular sieve is from 10 to 30: 1; most preferably, the liquid-solid weight ratio between the acid or base and the molecular sieve is from 15 to 20: 1.

preferably, in the step S2, the treatment temperature of the added acid or alkali is 25-80 ℃, and the treatment time is 6-24 h; more preferably, the treatment temperature of adding acid or alkali is 50-60 ℃, and the treatment time is 6-8 h.

As a further improvement of the invention, in step S3, the particle size of the multi-stage pore silicon-aluminum molecular sieve is 40-60 meshes.

As a further improvement of the invention, in the step S4, the reaction temperature is 30-80 ℃; the liquid flow rate is 0.5-3.0h^-1(ii) a More preferably, the reaction temperature is 50-65 ℃ and the liquid flow rate is 1-1.5h^-1。

Preferably, in step S4, the molar ratio between the BHMF and the alcohol is: 1-3: 8-20.

In step S4, the alcohol may be selected from conventional alkyl alcohols, such as methanol, ethanol, propanol, ethylene glycol, isopropanol, and the like.

In the present invention, the concentration range of the acid or base in step S2, the treatment temperature range of the acid or base added in step S2, and the treatment time are selected to obtain micropores and mesopores with reasonable arrangement suitable for the reaction of the present invention; and the reaction temperature range, the liquid flow rate range and the like in the step S4 are matched to form an organic whole, and the BRMF greatly improved effect (improved from the existing 50% to more than 85%) is achieved through the selection of the parameter ranges.

The product was checked by HPLC (chromatographic conditions see Table 1 below) and the BRMF was produced in 85-99% yield. After the reaction is finished, removing unreacted alcohol by reduced pressure distillation to obtain the BRMF product with the purity of 95-99%.

TABLE 1 High Performance Liquid Chromatography (HPLC) analysis conditions

Using the set of all the above preferred embodiments of the invention: the BRMF yield can reach 95-99% by using HPLC detection on a product; after the reaction is finished, removing unreacted alcohol through reduced pressure distillation, and obtaining the BRMF product with the purity of 97-99%.

Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.

The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.

The invention has the following beneficial effects:

the invention prepares the appropriate multi-stage pore silicon aluminum molecular sieve by hydrothermal synthesis and corresponding post-treatment, applies the multi-stage pore silicon aluminum molecular sieve to the etherification reaction from 2, 5-furandimethanol to 2, 5-furandimethanol diether, effectively improves the diffusion limitation of the reaction process compared with the common microporous silicon aluminum molecular sieve, greatly reduces the generation of byproducts, achieves the BRMF yield of 85-99 percent, and can obtain the 2, 5-furandimethanol diether product with the purity of more than 95 percent without subsequent separation after the unreacted alcohol is removed by simple distillation.

Drawings

The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings

FIG. 1 is a graphical representation of the BET test results for the HP-ZSM-5-1 sample of example 1;

FIG. 2 is a graph showing the results of HPLC analysis of the product of example 1.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

Example 1

A preparation method of furan dimethanol dimethyl ether comprises the following steps:

s1, taking 15g of a microporous ZSM-5 molecular sieve (such as a microporous ZSM-5 molecular sieve produced by Tianjin south chemical catalyst Co., Ltd.) (http:// www.nkcatalyst.com /);

s2, adding 300ml of 0.5M HCl solution, stirring and reacting for 6 hours at 50 ℃, filtering, washing with deionized water, and drying to obtain a hierarchical pore silica-alumina molecular sieve (HP-ZSM-5-1);

s3, 5g of HP-ZSM-5-1 is taken and put into a 10ml fixed bed reactor;

s4, heating the fixed bed reactor to 65 ℃, and introducing mixed liquid, wherein the liquid comprises the following components: 10 mol% BHMF, 90 mol% methanol, liquid flow rate 1.0h^-1The product was tested by HPLC and furan dimethanol dimethyl ether (BMMF) was produced in 99% yield.

The BET test results of the HP-ZSM-5-1 sample are shown in FIG. 1, and the HPLC analysis results are shown in FIG. 2.

Example 2

s1, taking 20g of a microporous ZSM-5 molecular sieve synthesized by a hydrothermal method;

s2, adding 300ml of 1M NaOH solution, stirring and reacting for 8h at 60 ℃, filtering, washing and drying to obtain the hierarchical porous silica-alumina molecular sieve (HP-ZSM-5-2).

S3, 5g of HP-ZSM-5-2 is taken and put into a 10ml fixed bed reactor,

s4, heating the fixed bed reactor to 50 ℃, and introducing mixed liquid, wherein the liquid comprises the following components: 10% BHMF, 90% ethanol, liquid flow rate 0.5h^-1The product was checked by HPLC, furan dimethanol diethyl ether (BEMF) yield 97%.

Example 3

s1, taking 10g of a hydrothermally synthesized microporous Beta molecular sieve (for example, produced by Zeolystatin International of International catalyst corporation), http:// www.zeolyst.com;

s2, adding 300ml of 0.5M HCl solution, stirring and reacting for 6h at 60 ℃, filtering, washing and drying to obtain the hierarchical porous silica-alumina molecular sieve (HP-Beta-1).

S3, 5g of HP-Beta-1 is taken and put into a 10ml fixed bed reactor,

s4, heating the fixed bed reactor to 60 ℃, and introducing mixed liquid, wherein the liquid comprises the following components: 10% BHMF, 90% methanol, liquid flow rate 1h^-1The product was determined by HPLC and was 98% in yield of furan dimethanol dimethyl ether (BMMF).

Example 4

s1, taking 11g of a microporous ZSM-23 molecular sieve (such as that produced by Zeolystatin International of International catalyst corporation) synthesized by a hydrothermal method, http:// www.zeolyst.com;

s2, adding 300ml of 0.5M HCl solution, stirring and reacting for 6h at 50 ℃, filtering, washing and drying to obtain the hierarchical pore silica-alumina molecular sieve (HP-ZSM-23-1).

S3, 5g of HP-ZSM-23-1 is taken and put into a 10ml fixed bed reactor,

s4, heating the fixed bed reactor to 65 DEG CIntroducing mixed liquid, wherein the liquid comprises the following components: 10% BHMF, 90% methanol, liquid flow rate 0.5h^-1The product was checked by HPLC and the yield of furan dimethanol dimethyl ether (BMMF) was 97%.

Example 5

s1, taking 15g of a microporous ZSM-23 molecular sieve synthesized by a hydrothermal method;

s2, adding 300ml of 0.8M NaOH solution, stirring and reacting for 8h at 50 ℃, filtering, washing and drying to obtain the hierarchical pore silica-alumina molecular sieve (HP-ZSM-23-2).

S3, 5g of HP-ZSM-23-2 is taken and put into a 10ml fixed bed reactor,

s4, heating the fixed bed reactor to 65 ℃, and introducing mixed liquid, wherein the liquid comprises the following components: 10% BHMF, 90% propanol, liquid flow rate 0.6h^-1The product was detected by HPLC with 99% yield of furandimethanol dipropyl ether (BPMF).

Comparative example 1

s1 filling 5g of microporous ZSM-5 molecular sieve into a 10ml fixed bed reactor;

s2, heating the fixed bed reactor to 65 ℃, and introducing mixed liquid, wherein the liquid comprises the following components: 10 mol% BHMF, 90 mol% methanol, liquid flow rate 1.0h^-1Product was checked by HPLC with a yield of furandimethanol dimethyl ether (BMMF) of 45%.

Example 6

s1, taking 10g of a microporous ZSM-23 molecular sieve synthesized by a hydro-thermal method;

s2, adding 200ml of 2M HCl solution, stirring and reacting for 10 hours at 80 ℃, filtering, washing and drying to obtain the hierarchical pore silica-alumina molecular sieve (HP-ZSM-23-3).

S3, 5g of HP-ZSM-23-3 is taken and put into a 10ml fixed bed reactor,

s4, heating the fixed bed reactor to 65 ℃, and introducing mixed liquid, wherein the liquid comprises the following components: 10% BHMF, 90% methanol, liquidThe volume flow rate is 0.5h^-1The product was tested by HPLC and furan dimethanol dimethyl ether (BMMF) yield was 78%.

Example 7

s1, taking 10g of a microporous ZSM-5 molecular sieve synthesized by a hydrothermal method;

s2, adding 300ml of 0.5M Na₂CO₃And (3) stirring and reacting the solution for 5 hours at 50 ℃, filtering, washing and drying to obtain the hierarchical porous silica-alumina molecular sieve (HP-ZSM-5-3).

S3, 5g of HP-ZSM-23-3 is taken and put into a 10ml fixed bed reactor,

s4, heating the fixed bed reactor to 65 ℃, and introducing mixed liquid, wherein the liquid comprises the following components: 10% BHMF, 90% methanol, liquid flow rate 1h^-1The product was checked by HPLC and yield of furandimethanol dimethyl ether (BMMF) was 85%.

Example 8

s2, adding 300ml of 0.2M HCl solution, stirring and reacting for 6 hours at 50 ℃, filtering, washing with deionized water, and drying to obtain a hierarchical pore silicon-aluminum molecular sieve (HP-ZSM-5-3);

s3, 5g of HP-ZSM-5-3 is taken and put into a 10ml fixed bed reactor;

s4, heating the fixed bed reactor to 50 ℃, and introducing mixed liquid, wherein the liquid comprises the following components: 10mol percent BHMF, 90mol percent methanol and liquid flow rate of 0.5h^-1The product was checked by HPLC with 90% yield of furan dimethanol dimethyl ether (BMMF).

Example 9

s2, adding the mixture into 300ml of 2M HCl solution, stirring and reacting for 24 hours at 80 ℃, filtering, washing with deionized water, and drying to obtain a hierarchical pore silica-alumina molecular sieve (HP-ZSM-5-3);

s3, 5g of HP-ZSM-5-3 is taken and put into a 10ml fixed bed reactor;

s4, heating the fixed bed reactor to 80 ℃, and introducing mixed liquid, wherein the liquid comprises the following components: 10mol percent BHMF, 90mol percent methanol and a liquid flow rate of 3 hours^-1Product was checked by HPLC with 95% yield of furan dimethanol dimethyl ether (BMMF).

Comparative example 2

Example 1 was repeated with the difference that:

in step S2, the HCl solution concentration is 0.05M;

the product was checked by HPLC and furan dimethanol dimethyl ether (BMMF) yield was 64%.

Comparative example 3

Example 1 was repeated with the difference that:

in step S2, the HCl solution concentration is 0.1M;

the product was checked by HPLC and was 91% yield of furandimethanol dimethyl ether (BMMF).

Comparative example 4

Example 1 was repeated with the difference that:

in step S2, the HCl solution concentration is 3M;

the product was checked by HPLC and gave 62% yield of furan dimethanol dimethyl ether (BMMF).

Comparative example 5

Example 1 was repeated with the difference that:

in the step S2, adding HCl solution, stirring and reacting for 30h at 20 ℃;

the product was checked by HPLC and was found to be 71% yield of furan dimethanol dimethyl ether (BMMF).

Comparative example 6

Example 1 was repeated with the difference that:

in the step S2, adding HCl solution, stirring and reacting for 6h at 30 ℃;

the product was checked by HPLC and furan dimethanol dimethyl ether (BMMF) yield was 89%.

Comparative example 7

Example 1 was repeated with the difference that:

in the step S2, adding HCl solution, stirring and reacting for 5h at 90 ℃;

the product was checked by HPLC and was 83% yield of furan dimethanol dimethyl ether (BMMF).

Comparative example 8

Example 1 was repeated with the difference that:

in step S4, the temperature of the fixed bed reactor is raised to 25 ℃, and the liquid flow rate is 1.0h^-1Product was checked by HPLC with 31% yield of furan dimethanol dimethyl ether (BMMF).

Comparative example 9

Example 1 was repeated with the difference that:

in step S4, the temperature of the fixed bed reactor is raised to 50 ℃, and the liquid flow rate is 1.0h^-1The product was checked by HPLC and was 83% yield of furan dimethanol dimethyl ether (BMMF).

Comparative example 10

Example 1 was repeated with the difference that:

in step S4, the temperature of the fixed bed reactor is raised to 90 ℃, and the liquid flow rate is 1.0h^-1The product was checked by HPLC and was found to be 73% furan dimethanol dimethyl ether (BMMF) in yield.

Comparative example 11

Example 1 was repeated with the difference that:

in step S4, the temperature of the fixed bed reactor is raised to 50 ℃, and the liquid flow rate is 0.4h^-1The product was tested by HPLC and gave 47% yield of furan dimethanol dimethyl ether (BMMF).

Comparative example 12

Example 1 was repeated with the difference that:

in step S4, the temperature of the fixed bed reactor is raised to 50 ℃, and the liquid flow rate is 3.5h^-1Product was checked by HPLC with 43% yield of furan dimethanol dimethyl ether (BMMF).

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.

Claims

1. The method for preparing furan dimethanol diether by catalyzing furan dimethanol etherification is characterized by comprising the following steps:

s1, selecting a microporous silicon-aluminum molecular sieve;

s4, introducing reaction raw material liquid BHMF and alcohol to carry out etherification reaction to obtain a product;

the silicoaluminophosphate molecular sieve is selected from: one or more of ZSM-5, ZSM-22, ZSM-23, ZSM-48, Beta and mordenite;

in step S2, the acid is selected from HCl and HNO₃、H₂SO₄One or more of;

in step S2, the alkali is selected from NaOH and Na₂CO₃One or more of KOH and KOH;

in step S2, the concentration of the acid or alkali is 0.1-2M;

in the step S2, adding acid or alkali at the treatment temperature of 25-80 ℃ for 6-24 h;

in step S4, the reaction temperature is 30-80 ℃; the liquid flow rate is 0.5-3.0h^-1。

2. The process for the catalytic etherification of furan dimethanol according to claim 1 to produce furan dimethanol diethers, characterized in that: the concentration of the acid or the alkali is 0.5-1M.

3. The process for the catalytic etherification of furan dimethanol according to claim 1 to produce furan dimethanol diethers, characterized in that: in step S2, the liquid-solid weight ratio between the acid or base and the molecular sieve is 5 to 100: 1.

4. the process for the catalytic etherification of furan dimethanol according to claim 3, wherein: the liquid-solid weight ratio between the acid or alkali and the molecular sieve is 10-30: 1.

5. the process of claim 4 for the catalytic etherification of furan dimethanol to produce furan dimethanol diethers, wherein: the liquid-solid weight ratio between the acid or alkali and the molecular sieve is 15-20: 1.

6. the process for the catalytic etherification of furan dimethanol according to claim 1 to produce furan dimethanol diethers, characterized in that: in step S2, acid or alkali is added for 6-8h at 50-60 deg.C.

7. The process for the catalytic etherification of furan dimethanol according to claim 1 to produce furan dimethanol diethers, characterized in that: in step S3, the particle size of the hierarchical porous silica-alumina molecular sieve is 40-60 meshes.

8. The process for the catalytic etherification of furan dimethanol according to claim 1 to produce furan dimethanol diethers, characterized in that: in step S4, the reaction temperature is 50-65 ℃, and the liquid flow rate is 1-1.5h^-1。

9. The process for the catalytic etherification of furan dimethanol according to claim 1 to produce furan dimethanol diethers, characterized in that: in step S4, the molar ratio between the BHMF and the alcohol is: 1-3: 8-20 parts of; the alcohol is selected from alkyl alcohols.