Bi-phasic continuous-flow tubular reactor and heterogeneous catalysts preparation method for production of 5-hydroxymethyl furfural

A reactor system for production of 5-hydroxymethyl furfural (5-HMF) from feedstock containing any one or combination of simple C6-based sugars, industrial-grade sugar syrups and sugars derived from starch and/or cellulosic biomass, comprising:

• an elongate bi-phasic continuous-flow tubular reactor having located therein a packed-bed column of heterogeneous solid catalyst containing any one or combination of Brønsted acid sites and Lewis acid sites, said packed-bed column extending along a preselected length of said elongate tubular reactor, said packed-bed column of heterogeneous solid catalyst having first and second opposed ends located within the tubular reactor;
• temperature sensors positioned to sense the temperature at each of said opposed ends of said packed-bed column of heterogeneous solid catalyst;
• a heat conducting element enveloping the said elongate tubular reactor, a heat generator surface inside a column heater attached to said heat conductor envelope, a temperature controller coupled to said column heater for controlling an maintaining a preselected temperature in said elongate tubular reactor and programmed to maintain the temperatures of the first and second opposed ends to within about 10° C. of each other during operation;
• a feedstock container and a first liquid pump for pumping aqueous liquid from said feedstock container;
• an extracting solvent container and a second liquid pump for pumping extracting organic solvent from said extracting solvent container;
• the first and second pumps being in flow communication with a reactor input passageway for flowing a bi-phasic mixture of aqueous feedstock and extracting organic solvent through said elongate tubular reactor and said packed-bed column of heterogeneous solid catalyst located therein;
• a back-pressure regulator valve for regulating and controlling an internal pressure of the continuous-flow reactor, a pressure gauge for measuring the internal pressure;
• and
• an output conduit leading from an output port on said elongate tubular reactor to a product container, and an in-line filter located on said output conduit to filter the bi-phasic liquid product of the reaction.

A method for production of 5-hydroxymethyl furfural (5-HMF) from feedstock containing any one or combination of simple C6-based sugars, industrial-grade sugar syrups and sugars derived from starch and/or cellulosic biomass, comprising:

• continuously flowing a bi-phasic reaction medium including water, an organic solvent and the feedstock through an elongate tubular reactor having located therein a packed-bed column of heterogeneous solid catalyst containing any one or combination of Brønsted acid sites and Lewis acid sites and being any one or combination of a metal phosphate, a metal oxide modified with an acid group and a heteropoly acid, wherein the heteropoly acid is any one of H3PW12O40, H4SiW12O40 and H3PMo12O40, the packed-bed column extending along a preselected length of the said elongate tubular reactor, the packed-bed column of heterogeneous solid catalyst having first and second opposed ends located within the tubular reactor;
• heating the elongate tubular reactor to a preselected temperature suitable for inducing reaction between a particular feedstock and a particular heterogenous solid catalyst;
• monitoring temperatures of the first and second opposed ends of the packed-bed column and controlling and maintaining the temperature of the elongate tubular reactor such that the temperatures of the first and second opposed ends are within about 10° C. of each other;
• operating the elongate tubular reactor at a pressure sufficiently high to prevent boiling of the water and the organic solvent at the preselected temperature such that the feedstock undergoes reaction to form 5-hydroxymethyl furfural in aqueous phase;
• and
• continuously and in-situ extracting the produced 5-hydroxymethyl furfural (HMF) from the aqueous phase to the organic phase/solvent as soon as produced while flowing through the tubular reactor.

A reactor system for production of 5-hydroxymethyl furfural (5-HMF) from feedstock containing any one or combination of simple C6-based sugars, industrial-grade sugar syrups and sugars derived from starch and/or cellulosic biomass, comprising:

• an elongate bi-phasic continuous-flow tubular reactor having located therein a packed-bed column of heterogeneous solid catalyst containing any one or combination of Brønsted acid sites and Lewis acid sites and being any one or combination of a metal phosphate, a metal oxide modified with an acid group and a heteropoly acid, wherein the heteropoly acid is any one of H3PW12O40, H4SiW12O40 and H3PMo12O40, said packed-bed column extending along a preselected length of said elongate tubular reactor, said packed-bed column of heterogeneous solid catalyst having first and second opposed ends located within the tubular reactor;
• temperature sensors positioned to sense the temperature at each of said opposed ends of said packed-bed column of heterogeneous solid catalyst;
• a heat conducting element enveloping the said elongate tubular reactor, a heat generator surface inside a column heater attached to said heat conductor envelope, a temperature controller coupled to said column heater for controlling an maintaining a preselected temperature in said elongate tubular reactor and programmed to maintain the temperatures of the first and second opposed ends to within about 10° C. of each other during operation;
• a feedstock container and a first liquid pump for pumping aqueous liquid from said feedstock container;
• an extracting solvent container and a second liquid pump for pumping extracting organic solvent from said extracting solvent container;
• the first and second pumps being in flow communication with a reactor input passageway for flowing a bi-phasic mixture of aqueous feedstock and extracting organic solvent through said elongate tubular reactor and said packed-bed column of heterogeneous solid catalyst located therein;
• a back-pressure regulator valve for regulating and controlling an internal pressure of the continuous-flow reactor, a pressure gauge for measuring the internal pressure;
• and
• an output conduit leading from an output port on said elongate tubular reactor to a product container, and an in-line filter located on said output conduit to filter the bi-phasic liquid product of the reaction.

A method for production of 5-hydroxymethyl furfural (5-HMF) from feedstock containing fructose, comprising:

• continuously flowing a bi-phasic reaction medium including water, methyl isobutyl ketone (MIBK) or tetrahydrofuran (THF) organic solvent and the fructose feedstock through an elongate tubular reactor having located therein a packed-bed column of heterogeneous solid catalyst Amberlyst 36 (Amb. 36), the packed-bed column extending along a preselected length of the said elongate tubular reactor, the packed-bed column of heterogeneous solid catalyst having first and second opposed ends located within the tubular reactor;
• heating the elongate tubular reactor to a preselected temperature in a range from about 110° C. to about 150° C. suitable for inducing reaction between a particular feedstock and a particular heterogenous solid catalyst;
• monitoring temperatures of the first and second opposed ends of the packed-bed column and controlling and maintaining the temperature of the elongate tubular reactor such that the temperatures of the first and second opposed ends are within about 10° C. of each other;
• operating the elongate tubular reactor at a pressure sufficiently high to prevent boiling of the water and the organic solvent at the preselected temperature such that the feedstock undergoes reaction to form 5-hydroxymethyl furfural in aqueous phase;
• and
• continuously and in-situ extracting the produced 5-hydroxymethyl furfural (HMF) from the aqueous phase to the organic phase/solvent as soon as produced while flowing through the tubular reactor.