CN101130532A - System and method for producing furol by using agricultural and forestry castoff - Google Patents
System and method for producing furol by using agricultural and forestry castoff Download PDFInfo
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- CN101130532A CN101130532A CNA2007101519646A CN200710151964A CN101130532A CN 101130532 A CN101130532 A CN 101130532A CN A2007101519646 A CNA2007101519646 A CN A2007101519646A CN 200710151964 A CN200710151964 A CN 200710151964A CN 101130532 A CN101130532 A CN 101130532A
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Abstract
The invention discloses a system and method to produce furfural with agricultural wastes, which is characterized by the following: choosing two-step method; comprising hydrolysis system and dehydration distilling system; setting the hydrolysis system as N grade hydrolysis autoclave with end-to-end; proceeding continuous hydrolysis for the agricultural wastes; generating pentose solution; setting the dehydration distilling system as dehydration distilling unit and dehydration reclaiming unit; dewatering and distilling for the pentose solution with the dehydration distilling unit; getting furfural steam; setting the dehydration reclaiming unit as at least one grade dewatering reactor; further-dewatering; generating furfural steam; sending into dehydration distilling tower; distilling continuously; sending the waste water from the dehydration reclaiming unit back to dehydration system; realizing zero discharge for waste water. This invention possesses high productivity, low energy consumption and warm reacting condition, which can be used as raw material to produce alcohol.
Description
Technical field
The invention belongs to furfural production preparation field, relate in particular to a kind of system and method that utilizes agriculture and forestry organic waste material to produce furfural.
Background technology
Furfural, have another name called furtural, it has two two keys and an aldehyde radical on the furan nucleus, this unique chemical structure, can make it that reactions such as oxidation, hydrogenation, chlorination, nitrated and condensation take place, generate a lot of Chemicals, so be widely used in a plurality of production fields such as agricultural chemicals, medicine, petrochemical industry, foodstuff additive, casting.
Furfural is to be rich in the vegetable fibre of piperylene, as corn cob, and bagasse, straw, corn stalk, cotton seed hull, rice husk etc. are raw material production, and its principle is that piperylene at first is hydrolyzed into pentose in the vegetable fibre, and the pentose dehydration generates furfural then, promptly
The piperylene pentose
The pentose furfural
The producing and manufacturing technique of furfural mainly is divided into single stage method and two step method in the world at present.Single stage method is that pentosan hydralysis and pentose dehydration generation furfural two-step reaction are once finished in same reactor; The main drawback that single stage method exists is that steam consumption is big, and furaldehyde yield low (≤55%) produces a large amount of many shortcomings such as liquid and waste slag produced.Two-step approach is that the process that the pentosan hydralysis in the raw material becomes pentose (wood sugar) and pentose dehydration to generate furfural is to finish at least two different reactors; Than single stage method, two-step approach has overcome difficult problems such as existing furfural raw materials for production transformation efficiency is low, the generation processing wastewater is difficult to administer, the furfural dregs utility value is low.Along with the development of furfurol industry, and the raising of raw material requirements of comprehensive utilization, development two-step approach furfural production technology, Mierocrystalline cellulose in the separate raw materials and hemicellulose also are used respectively, are the inevitable development trend of furfurol industry.But often technical process relative complex of two step method has high input in advance, and the dewatering process condition is very unripe, popularizes at present to have many difficulties.
English Patent GB850367 discloses a kind of treatment process of vegetable matter, after filling raw material in the filler basket on the hydrolysis kettle inwall, feeding steam heats hydrolysis kettle, spray acid solution by shower to raw material then, the mixed solution that contains pentose, furfural that hydrolysis produces enters distillation tower through collector, evaporation unit, and wherein the part pentose solution enters retort from evaporation unit, distillation tower bottom by the intermediate collector; The aqueous solution, chaff aldehyde, the spent acid solution that contain pentose in distillation tower are discharged from the different positions of described distillation tower through separating respectively, the wherein said aqueous solution and the spent acid solution that contains pentose enters in the collector through corresponding receiver, by sending into the shower in the described reactor after adjustment concentration and the pH value, spray by shower participates in hydrolysis reaction, and the chaff aldehyde that produces in described chaff aldehyde and the retort enters Furfural Treating Process after merging.Disclosed treatment vegetable material is produced the method for furfural in this patent, from be seen as two-step approach in form, be that the hydrolysis of vegetable matter and the dehydration of pentose are carried out in different reactors, but in fact when the first step hydrolysis, produced more furfural, temperature and pressure height when this just means the vegetable matter hydrolysis, therefore hydrolysis degree is dark, has destroyed Mierocrystalline cellulose in the solid material and xylogen after the hydrolysis, is unfavorable for its next step comprehensive utilization.In addition, also there is following shortcoming in disclosed technical scheme in this patent:
(1) only adopt a retort to carry out the dehydration reaction of pentose, pentose transforms not exclusively;
(2) acid solution in the furfural production process and the aqueous solution that contains pentose is after overregulating pH value and concentration, returned to participate in reaction in the hydrolysis kettle, prove absolutely thus through also having unreacted pentose after the steps such as hydrolysis, dehydration, so pentose transforms insufficient;
(3) disclosing catalyzer in this patent documentation is the circulation of VFA, yet the just circulation of acid in the vegetable matter hydrolytic process of described organic acid circulation, but having added new mineral acid in the pentose dehydration is the catalyzer of sulfuric acid as dehydration reaction, in this patent documentation, the processing of reacting back sulfuric acid and waste water is not mentioned, so be not that all acid and waste water all obtain recycle in this patent.
Summary of the invention
For this reason, primary technical problem to be solved by this invention is to propose the method and system that the high two step method of a kind of furfural productive rate is produced furfural.
Secondly, technical problem to be solved by this invention is to propose the method and system that two step method that a kind of catalyzer and waste water can recycle is produced furfural.
Once more, technical problem to be solved by this invention is to propose the method and system of the two step method production furfural that a kind of energy consumption is low, reaction conditions is gentle.
For achieving the above object, a kind of system that utilizes agriculture and forestry organic waste material to produce furfural of the present invention, described system comprises:
Hydrolysis system comprises the mutual placed in-line hydrolysis unit of N level, is used for agriculture and forestry organic waste material is carried out continuous hydrolysis, generates pentose solution; And
The dehydration Distallation systm comprising dehydration distillation unit, and described dehydration distillation unit comprises a dehydration reaction distillation tower at least, is used for the distillation of dewatering of described pentose solution is obtained furfural steam;
Wherein, N is the integer more than or equal to 2.
Described each grade hydrolysis unit comprises a placed in-line hydrolysis device and an equipment for separating liquid from solid mutually respectively, described agriculture and forestry organic waste material is hydrolyzed and the solidliquid mixture after the hydrolysis is carried out solid-liquid separation generates hydrolysis acid solution and the solids contain pentose, and wherein the hydrolysis unit of each grade comprises at least:
A solid inlet is positioned on the described hydrolysis device, accepts the described solids that the upper level hydrolysis unit is sent here, and wherein the solid inlet of first step hydrolysis unit is accepted described agriculture and forestry organic waste material;
A liquid inlet is positioned on the described hydrolysis device, accepts the hydrolysis acid solution that the next stage hydrolysis unit is sent here, and wherein the outside hydrolysis acid solution that adds is accepted in the liquid inlet of last step hydrolysis unit;
A liquid exit, be positioned on the described equipment for separating liquid from solid, discharge the described unitary liquid inlet of the supreme one-stage hydrolysis of hydrolysis acid solution of containing pentose, wherein the hydrolysis acid solution of the liquid exit of first step hydrolysis unit discharge is the hydrolysis acid solution that contains pentose that described hydrolysis system generates;
A solid outlet is positioned on the described equipment for separating liquid from solid, discharges the solid inlet of described solids to the next stage hydrolysis unit, and wherein the solids of last step hydrolysis unit discharge is the Mierocrystalline cellulose slag.
Described dehydration Distallation systm also comprises the dewatering and recovery unit, be connected with described dehydration reaction distillation tower, described dewatering and recovery unit comprises at least one grade of dehydration reactor, the waste water that contains pentose of discharging at the bottom of the described dehydration reaction distillation Tata is further carried out dehydration reaction, and the furfural steam that generates returns to described dehydration reaction distillation tower.
The top of the described dehydration reactor of each grade is provided with a pentose solution inlet, an aldehyde vapor outlet, a steam-in at least, the bottom is provided with a waste liquid outlet at least, and the waste liquid outlet of upper level dehydration reactor is connected with the aldehyde vapor outlet with the pentose solution inlet of next stage dehydration reactor respectively with the steam-in; The pentose solution inlet of described first step dehydration reactor connects at the bottom of the described dehydration reaction distillation Tata.
The waste liquid outlet of described last step dehydration reactor is connected to the last step hydrolysis unit of described hydrolysis system, sends the waste water that contains catalyzer of described dehydration Distallation systm generation back to described hydrolysis system and does the catalyzer use.
Described dewatering and recovery unit also comprises the heating unit that is connected with described last step dehydration reactor, be used for to the heat supply of described last step dehydration reactor, and deliver to the described dehydration reactor of each grade with heat is up step by step, and finally give described dehydration reaction distillation tower by the furfural steam that produces in the one-level dehydration reactor in the end.
Described dehydration reactor is the still kettle of band heating jacket and whipping appts; Described heating unit is a dehydration reboiler, and the part of the waste water that the last step dehydration reactor is discharged is heated to be steam, and sends described last step dehydration reactor back to.
Be provided with potential difference between described dehydration reaction distillation tower and the described first step dehydration reactor, be provided with potential difference between described every adjacent secondary dehydration reactor, described dehydration reaction distillation tower position is the highest, and described last step dehydration reactor position is minimum.
The waste liquid outlet of described dehydration reaction distillation tower is higher than the pentose solution inlet of described first step dehydration reactor, and the waste liquid outlet of upper level is higher than the pentose solution inlet of next stage in described every adjacent secondary dehydration reactor.
Described dehydration distillation unit also comprises a condenser and low pressure phase splitter that is connected with described dehydration reaction distillation tower cat head, the aldehyde vapour that described dehydration reaction distillation tower produces is transported to described condenser, the thick aldehyde that described condenser condenses obtains is transported to and is separated into aldehyde in the described low pressure phase splitter and reaches water mutually, and described water turns back to described dehydration reaction distillation tower and continues distillation.
The pressure of described low pressure phase splitter is identical with pressure in the described dehydration reaction distillation tower.
Described dehydration Distallation systm back also connects distillation system, the isolated aldehyde of described low pressure phase splitter is further made with extra care mutually generated furfural; The waste liquid outlet of described distillation system is connected to the liquid inlet of described last step hydrolysis unit, sends waste liquid the thinner use of described hydrolysis system as hydrolyst back to.
The mutual placed in-line hydrolysis unit of 2-5 level is set in hydrolysis system, the mutual placed in-line dehydration reactor of 2-5 level is set in described dewatering and recovery unit.
Described hydrolysis device is for having heating and adding sour device and can carry out solid-liquid blended mechanical means.
Described hydrolysis device is hydrolysis cylinder, rotary spherical digester or spiral screw feeder.
The sour device that adds of described hydrolysis cylinder is an at least one shower.
Be between described hydrolysis cylinder and the horizontal plane and tilt to place, the angle of inclination is less than 20 degree.
Between the described hydrolysis cylinder potential difference that sets gradually is arranged, the described hydrolysis cylinder of the first step is the highest, and the described hydrolysis cylinder of last step is minimum.
Do not have potential difference between the described hydrolysis cylinder, carry out the conveying of material by e Foerderanlage between the described hydrolysis cylinders at different levels.
Described equipment for separating liquid from solid is three-roll press machine, plate-and-frame filter press, whizzer, hydraulic squeezing press or filter plant.
Temperature is 130-200 ℃ in the described last step dehydration reactor, along with reducing of described dehydration reactor progression, temperature reduces in the described dehydration reactor, and the temperature difference is 3-15 ℃, and temperature is than the high 3-15 of temperature in the described dehydration reaction distillation tower ℃ in the described first step dehydration reactor.
The oven dry weight of agriculture and forestry organic waste material is 1 with the ratio of the weight of hydrolysis acid solution in the hydrolysis system: 3-1: 15.
Described agriculture and forestry organic waste material comprises one or more of following material: wheat straw, rice straw, corn cob, bagasse, sunflower seed shell, cotton bavin, cotton seed hulls, straw, rice husk, pourous wood.
The make a living Mierocrystalline cellulose slag of producing and ethanol of the solids that described last step hydrolysis unit is discharged.
A kind of method of utilizing agriculture and forestry organic waste material to produce furfural may further comprise the steps:
A. hydrolysing step: described agriculture and forestry organic waste material is hydrolyzed in the mutual placed in-line hydrolysis unit of N level, obtains containing the hydrolysis acid solution of pentose;
B. distilation steps dewaters: the described hydrolysis acid solution that contains pentose is dewatered to distill in described dehydration reaction distillation tower generates furfural steam;
Wherein, N is the integer more than or equal to 2.
Described step a further comprises:
The solids that n-1 level hydrolysis unit is generated is sent in the hydrolysis device of n level hydrolysis unit and is continued hydrolysis, makes it the hydrolysis acid solution thorough mixing hydrolysis of sending here with n+1 level hydrolysis unit; Solidliquid mixture after the hydrolysis of n level is carried out solid-liquid separation generate n level hydrolysis acid solution and n level solids; Described n level hydrolysis acid solution is delivered to n-1 level hydrolysis unit; Described n level solids is delivered to n+1 level hydrolysis unit; Wherein, 2≤n≤N and n are integer;
Wherein, initiate solids is described agriculture and forestry organic waste material in the hydrolysis device of first step hydrolysis unit, and the hydrolysis acid solution that the first step is discharged is the hydrolysis acid solution that contains pentose that described hydrolysing step generates; The hydrolysis acid solution of last step hydrolysis unit comes from the outside initiate hydrolysis acid solution that contains catalyzer, and the solids that the last step hydrolysis unit is discharged is the Mierocrystalline cellulose slag.
Described method also comprises the dewatering and recovery step after step b:
The solution of discharging at the bottom of the described dehydration distillation Tata is delivered to described dewatering and recovery unit, carry out wherein pentose at least that the dehydration reaction of one-level generates furfural steam, return to described dehydration reaction distillation tower then and continue to participate in distillation.
Described dewatering and recovery step further comprises:
Descending step by step described solution after finishing distillation is carried out one-level dehydration reaction at least, the waste liquid that the upper level dehydration reactor produces is delivered to the next stage dehydration reactor, and the furfural steam that the next stage dehydration reactor produces is delivered to the upper level dehydration reactor, and the furfural steam that described first step dehydration reactor produces returns to described dehydration reaction distillation tower and continues to participate in the dehydration distillation.
Described dewatering and recovery step also comprises a heating steps, only the described dehydration reactor of last step is carried out heat supply, by up step by step described furfural steam heat is delivered to the described dehydration reactor of each grade step by step, and finally give described dehydration reaction distillation tower.
Described step b also comprises a waste water reclamation step, and the waste liquid of described last step dehydration reactor is returned to described hydrolysis system as catalyzer or complex acid component, realizes the wastewater zero discharge of described furfural preparation system.
Described step b also comprises:
The furfural steam that described dehydration distillation generates being discharged from the distillation tower top, be condensed into thick aldehyde then, is that aldehyde reaches water mutually with the phase-splitting of described thick aldehyde low pressure again, and described water turns back to described dehydration reaction distillation tower and continues distillation.
The pressure of described low pressure phase-splitting is identical with pressure in the dehydration reaction distillation tower.
Described dehydration distilation steps back also comprises rectification step, described aldehyde is further made with extra care mutually generated furfural; The waste liquid that rectifying produces sends back to the thinner use of described hydrolysis system as hydrolyst.
The hydrolysis temperature of the described hydrolysis device of each grade is 80-100 ℃, and hydrolysis time is 1-5 hour.
Described last step dehydration reactor is heated to 130-200 ℃, along with reducing of described dehydration reactor progression, temperature reduces in the described dehydration reactor, and the temperature difference is 3-15 ℃, and temperature is than the high 3-15 of temperature in the described dehydration reaction distillation tower ℃ in the described first step dehydration reactor.
Before described hydrolysing step, also comprise the step that described agriculture and forestry organic waste material is cut and cleans.
The waste residue of discharging in the hydrolysis device of described last step hydrolysis unit is for making the alcoholic acid raw material.
The method and system of utilizing agriculture and forestry organic waste material to produce furfural of the present invention compared with prior art have the following advantages:
(1) the present invention proposes the method and system that perfect two step method is produced furfural.Realize separating fully of hydrolysing step and dehydrating step, thereby reduced the reaction conditions of hydrolysis reaction and dehydration reaction, and improved the productive rate of furfural.
(2) pentose transformation efficiency, furfural yield height.In dehydration Distallation systm of the present invention, pentose solution dewaters in dehydration distillation unit and dewatering and recovery unit respectively, can make unreacted completely pentose solution fully react, improved the concentration of furfural in the first step dehydration reactor, thereby improved the productive rate of furfural; Simultaneously, the water that contains furfural that phase-splitting obtains through low pressure in dehydration distillation unit returns to once more in the dehydration distillation tower and separates, guaranteed that the furfural that generates farthest is separated, furfural productivity ratio tradition furfural production technology of the present invention has improved nearly 20-40%, can be up to 65-85%.
(3) diluent that is sent back in the hydrolysis system as catalyzer or catalyzer of the waste water that produces in dehydration Distallation systm of the present invention and the refining system uses, reach the zero release of waste water, thoroughly solved the external exhaust emission problem of environment of waste water that furfural production produces.
(4) energy consumption is low, and save energy reduces cost.Because this invention can be only needs a heating plant just can reach the higher aldehyde rate that goes out, as adopts this invention technology, greatly degree reduces production costs; As the method that adopts the used heat in the furfural condensation of gas process of distillation tower of the present invention top to utilize again, the usage quantity that can save steam had again greatly both reduced production cost, had also reached the purpose of energy-conserving and environment-protective simultaneously.
(5) in addition, in hydrolysis device of the present invention, (hydrolysis temperature is 80-100 ℃ to the reaction conditions gentleness, pressure is normal pressure), therefore Mierocrystalline cellulose and xylogen are not destroyed substantially in the waste residue that obtains after the hydrolysis end, can carry out next step comprehensive utilization, not needing to carry out pre-treatment as waste residue when the fermentative production alcohol just can be directly and the cellulase preparation saccharification of fermenting, and greatly reduces the cost of Alcohol Production.
Description of drawings
For the easier quilt of content of the present invention is clearly understood, below according to a particular embodiment of the invention and in conjunction with the accompanying drawings, the present invention is further detailed explanation, wherein is the schema that agriculture and forestry organic waste material of the present invention prepares furfural;
Fig. 1 is the schema of hydrolysis system of the present invention;
Fig. 2 is the device synoptic diagram of one embodiment of the invention, is specially the device synoptic diagram of an embodiment of the hydrolysis system in the furfural production;
Fig. 3 is the device synoptic diagram of one embodiment of the invention, is specially the device synoptic diagram of an embodiment of the dehydration Distallation systm in the furfural production.
Embodiment
The invention will be further described below in conjunction with drawings and Examples, but should be noted that these embodiment only are used to method and apparatus of the present invention is described, and scope of the present invention can not be confined to this.
Be the schema that agriculture and forestry organic waste material of the present invention prepares furfural as shown in Figure 1, wherein solid line partly represents to contain the hydrolysis acid solution of pentose or the flow direction of furfural generative process, and dotted portion represents to produce in the system flow direction of liquid and waste slag produced process.As can be seen from Figure 1, whole big system is divided into two systems of dehydration Distallation systm that agriculture and forestry organic waste material prepares the hydrolysis system and the manufacturing furol with pentose solution of pentose solution, whole big system has only two to advance scene 2, what advance is respectively agriculture and forestry organic waste material and additional catalyzer and water, all advances from hydrolysis system; What go out is Mierocrystalline cellulose slag and thick aldehyde, and wherein the Mierocrystalline cellulose slag goes out from hydrolysis system, and thick aldehyde escapes and enter refining system from the dehydration Distallation systm and finally obtains the furfural finished product.The waste water that dehydration distilation steps and purification step produce all turns back to the thinner use of hydrolysing step as hydrolyst and/or hydrolyst, and (processing of these waste water is described in detail afterwards, and this does not give unnecessary details) be not so total system is externally discharged any waste water.For no other reason than that the Mierocrystalline cellulose slag of discharging will be taken away a part of catalytic solution, so need to replenish a spot of catalyzer and water at hydrolysis system.
Below whole big system of the present invention being divided into hydrolysis system discusses respectively principle of the present invention with the dehydration Distallation systm:
The first step is introduced the principle of hydrolysis system.
As shown in Figure 1, hydrolysis system of the present invention and method principle are summarized as follows: multistage mutual placed in-line hydrolysis unit is set, each grade hydrolysis unit all comprises a hydrolysis device and a placed in-line with it equipment for separating liquid from solid successively, corresponding each grade hydrolysis reaction all comprises first hydrolysis, two steps of back solid-liquid separation, earlier agriculture and forestry organic waste material is hydrolyzed, then the solidliquid mixture after the hydrolysis is carried out solid-liquid separation and generate hydrolysis acid solution and the solids that contains pentose, wherein the raw material of first step hydrolysis reaction is an agriculture and forestry organic waste material, concerning each grade hydrolysis reaction except that the first step, its raw material is to come from the slag (being the solids that obtains after the solid-liquid separation) that the upper level hydrolysis reaction finally obtains, concerning each grade hydrolysis reaction except that last step, its hydrolysis acid solution is to come from the solution (being the solution that contains pentose that obtains after the solid-liquid separation) that finally obtains behind the next stage hydrolysis reaction, wherein the hydrolysis acid solution of last step comes from the outside hydrolysis acid solution that adds, waste water that the Distallation systm that promptly dewaters returns and/or the new catalyst solution that replenishes.The solid materials that obtains after the solid-liquid separation is from circulate successively downwards to the end one-stage hydrolysis device and from the output of last step hydrolysis device of first step hydrolysis device like this, and output is the Mierocrystalline cellulose slag.
The solution that obtains after the solid-liquid separation is from upwards circulate the successively hydrolysis device of previous stage of last step hydrolysis unit, and finally from the output of first step hydrolysis device, obtains the final pentose solution of high density.
That is to say, the hydrolysis unit of each grade of the present invention all comprises two outlets and two inlets respectively at least, be respectively: a solid inlet, be positioned on the hydrolysis device at the corresponding levels, accept the described solids that the upper level hydrolysis unit is sent here, wherein the solid inlet of first step hydrolysis device is accepted described agriculture and forestry organic waste material; A liquid inlet is positioned on the hydrolysis device at the corresponding levels, accepts the hydrolysis acid solution that the next stage hydrolysis unit is sent here, and wherein the outside hydrolysis acid solution that adds is accepted in the liquid inlet of last step hydrolysis device; A liquid exit is positioned on the described equipment for separating liquid from solid, discharges the liquid inlet of the supreme one-stage hydrolysis device of hydrolysis acid solution that contains pentose, and wherein the hydrolysis acid solution of the liquid exit of first step equipment for separating liquid from solid discharge is final pentose solution; A solid outlet, be positioned on the equipment for separating liquid from solid at the corresponding levels, discharge through equipment for separating liquid from solid at the corresponding levels and carry out the solids that obtains after the solid-liquid separation solid inlet to the next stage hydrolysis device, wherein the last step equipment for separating liquid from solid solids of discharging is the Mierocrystalline cellulose slag of producing ethanol or being used for other purposes.
Because the present invention do not need agriculture and forestry organic waste material is carried out pyroprocessing, do not destroy the Mierocrystalline cellulose in the agriculture and forestry organic waste material, so main component is a Mierocrystalline cellulose in the solids that finally obtains, can be used for preparing ethanol, help environmental protection.And each grade hydrolysis finishes and all passes through squeezing, makes material meticulousr, helps next step utilization.
Second step, the principle of introduction dehydration Distallation systm.
The cardinal principle of this system is exactly by dehydration still-process and dewatering and recovery process the pentose solution that contains catalyzer that hydrolysis system among the present invention produces to be prepared into furfural.Specifically be summarized as follows:
From the furfural among the present invention produce pentose solution in the hydrolysis system be introduced into the cyclodehydration reaction takes place in the dehydration reaction distillation tower after, the furfural of generation is discharged from cat head with the form of aldehyde vapour and is carried out condensation, phase process; The unreacted that produces pentose solution is completely then sent into the multistage dehydration reactor successively from tower bottom, make pentose further be converted into furfural, and with the form of aldehyde vapour get back to proceed in the described dehydration reaction distillation tower distillation, can be only in the dehydration Distallation systm in second step in the end the one-level dehydration reactor heating unit is set, by up step by step aldehyde vapour dehydration reactors at different levels and dehydration reaction distillation tower are heated.Certainly, the present invention also can adopt traditional heating mode, repeats no more.
Below be core with the dehydration reaction distillation tower, the treatment process that material is discharged in dehydration reaction distillation tower top and bottom is simply introduced respectively:
1) after the aldehyde vapour process condensation of dehydration reaction distillation tower top discharge, the phase-splitting, the aldehyde that obtains is delivered to the furfural treatment system mutually and is carried out further making with extra care, and inorganic directly being returned to mutually in the described dehydration reaction distillation tower continues to participate in distilling so that raising furfural productive rate.
2) the dehydration reaction distillation tower bottom unreacted of discharging completely pentose solution in the multistage dehydration reactor of serial connection, react, make unreacted completely pentose react once more and generate aldehyde vapour, send back at last and proceed distillation in the dehydration reaction distillation tower.Compared to prior art, multistage dehydration reactor is provided with the transformation efficiency that can improve pentose greatly.Type of heating in one of them preferred embodiment can be only in the end the one-level dehydration reactor heating unit is set, for the whole series dehydration Distallation systm provides heat, the aldehyde vapour concentration that obtains from the last step dehydration reactor to first step dehydration reactor increases gradually like this, finally sends into the dehydration reaction distillation tower after first step dehydration reactor is discharged.In the up step by step process of aldehyde vapour, aldehyde vapour wherein can play two effects simultaneously, the one, wherein furfural is upwards sent step by step with aldehyde vapour form, increased furfural concentration step by step, the 2nd, can simultaneously the heat that contains be sent into dehydration reactors at different levels and finally send into the dehydration reaction distillation tower with aldehyde vapour.Therefore, compared to prior art, the present invention can cut down the consumption of energy greatly, has saved the furfural production cost.In addition, be provided with potential difference between the two-stage dehydration reactor that is connected in series, can make solution flow into the next stage dehydration reactor automatically and need not additionaling power, this point will describe in detail below.
3) waste water that mainly contains catalyzer of last step dehydration reactor bottom discharge, the thinner that is used as the hydrolysis acid solution and is hydrolyst or complex acid component and be hydrolyst returns to furfural among described the present invention and produces in the hydrolysis system and participate in hydrolysis reaction, compared to prior art, technology of the present invention does not need separately furfural production waste water to be handled again, not only can reduce production costs, and can cause any pollution to environment hardly.
More than be ultimate principle of the present invention, describe below by more detailed embodiment:
Being the device synoptic diagram that furfural is produced an embodiment of hydrolysis system among the present invention as shown in Figure 2, is the device synoptic diagram of an embodiment of furfural production dehydration Distallation systm among the present invention as shown in Figure 3.Below hydrolysis system and dehydration Distallation systm are described in detail respectively.
The first step utilizes agriculture and forestry organic waste material to prepare the detailed description of the hydrolysis system of pentose solution.
As shown in Figure 2, be example so that three grades of hydrolysis devices to be set, and hydrolysis device wherein use is the hydrolysis cylinder, what equipment for separating liquid from solid was used is three-roll press machine.The hydrolysis cylinder is horizontal by tilting to place, the angle that tilts is 20 degree or littler, be convenient to moving forward of reactant in the hydrolysis cylinder like this, between hydrolysis systems at different levels one poor location is arranged preferably simultaneously, the solid materials that this potential difference should make squeezing at the corresponding levels obtain can directly enter the hydrolysis cylinder of next stage by the effect of gravity.In another embodiment of the present invention, also can between cylinders at different levels potential difference be set, promptly the angle of Qing Xieing is 0 degree, carries out the transportation of material by e Foerderanlage.The hydrolysis cylinder of certain present embodiment and the type product that three-roll press machine also can be other substitute, as long as can realize the object of the invention, all should be the contents that technical scheme of the present invention comprises.
With wherein second stage hydrolysis device is example, and it comprises hydrolysis cylinder 210 and three-roll press machine 220.Hydrolysis cylinder 210 1 ends are provided with a solids inlet 211 and a liquid-inlet 212, the other end is provided with an outlet 213, from Fig. 3, can know and find out, solids inlet 211 is connected with the solid outlet 122 of upper level, liquid-inlet 212 is connected with the liquid exit 323 of next stage, exports 213 and is connected with the import 221 of three-roll press machine 220; Cylinder inside is provided with and makes the spiral stirrer plate that material at the uniform velocity pushes ahead and the shower of hydrolyzation catalysis agent solution, and shower is one in present embodiment, can be many in other embodiment; Cylinder also is provided with heating unit outward in addition, and by being mainly: the external energy such as steam, electricity, thermal oil and other thermal medium provide heat for hydrolysis reaction at the corresponding levels.This hydrolysis cylinder 210 is mechanical tourelle, and velocity of rotation adopts variable frequency adjustment.The pressing device that device 220 is used for press for extracting juice sugarcane commonly used is pressed in described three roll-ins.One end of three-roll press machine 220 is provided with an import 221, and this import 221 interconnects with the outlet 213 of hydrolysis cylinder 210, and the other end of three-roll press machine 220 is provided with a solid outlet 222 and a liquid exit 223.
Described first step hydrolysis device comprises hydrolysis cylinder 110 and three-roll press machine 120, is provided with solid inlet 111, liquid inlet 112 at hydrolysis cylinder 110 1 ends, is provided with the outlet 113 of solidliquid mixture at the other end; Three-roll press machine 120 is provided with solidliquid mixture import 121, liquid exit 122 and solid outlet 123.
Described third stage hydrolysis device comprises hydrolysis cylinder 310 and three-roll press machine 320, is provided with solid inlet 311, liquid inlet 312 at hydrolysis cylinder 310 1 ends, is provided with the outlet 313 of solidliquid mixture at the other end; Three-roll press machine 320 is provided with solidliquid mixture import 321, liquid exit 322 and solid outlet 323.
Hydrolysis cylinder of the present invention and three roll-ins are pressed the device roller and are used austenitic stainless steel or carbon steel lining stainless steel and other metal or the nonmetal corrosion-resistant material of minimum standard as SUS304 (0Cr18Ni9) with the material of material contact part.
Below introduce the concrete steps that the first step of the present invention prepares pentose solution from the angle of method:
At first, carry out pre-treatment, raw material is cut into stalk section less than 50mm, then this stalk section is carried out scrubbing dust collection according to raw material condition.
Then, to send into the import 111 of first step hydrolysis cylinder 110 through simple pretreated stalk section continuously, the acid solution shower 112 that simultaneously solution that obtains after 220 squeezings of the second stage three roll-ins press for extracting juice device is passed through first step hydrolysis cylinder 110 tops adds, and start heating system simultaneously and heat, reaction 1.5 hours is hydrolyzed under 95 ℃ of temperature, first step hydrolysis finishes in the first step hydrolysis cylinder, reacted solidliquid mixture is sent into 120 squeezings of the first step three roll-ins press for extracting juice device by solidliquid mixture outlet 113 carry out solid-liquid separation, separate the liquid that obtains and be pentose solution, this solution is transported to the dehydration Distallation systm and is used for preparing furfural.
Then, the solids that first step separation obtains is transported in the second stage hydrolysis cylinder 210 continuously as the material of second stage hydrolysis reaction, simultaneously the third stage three roll-ins are pressed device 320 and squeeze the acid solution shower adding that the solution that obtains passes through second stage hydrolysis cylinder 210 tops, and start heating system simultaneously and heat, under 95 ℃ of temperature, carry out 2 hours hydrolysis reaction.Second stage hydrolysis finishes, and the mixture after the hydrolysis is sent into 220 squeezings of the second stage three roll-ins press for extracting juice device carry out solid-liquid separation.
Then, the material that the solids that second stage separation obtains is used as third stage hydrolysis reaction is transported to third stage hydrolysis cylinder 310 continuously, the make-up catalyst solution that will dewater the waste water of Distallation systm and catalyzer simultaneously and newly join adds by the acid solution shower of cylinder reactor top, and start heating system simultaneously and heat, reaction 2.5 hours is hydrolyzed under 95 ℃ of temperature.Third stage hydrolysis reaction finishes, and the mixture behind the hydrolysis reaction is sent into the third stage three roll-ins press device 320 squeezings and carry out solid-liquid separation, and separating the solids that obtains promptly is the ethanol raw material Mierocrystalline cellulose, is used for producing ethanol or as other purposes.The solution that the squeezing separation obtains turns back to second stage hydrolysis reactor and uses as the hydrolysis acid solution.
According to above-mentioned technical process, hydrolysis reaction and squeezing are carried out continuously, and it is pentose solution that the isolated solution of device 120 squeezings is pressed in the first step three roll-ins.The third stage three roll-ins are pressed the isolated solids in device 320 squeezing backs and are preparation alcoholic acid raw cellulose.
In the above-described embodiments, the oven dry weight of all solids material is 1: 3 to 1: 15 with the ratio of the weight of hydrolysis acid solution in the described whole hydrolysis system, is preferable over 1: 5 to 1: 10.
Certainly the present invention also can carry out under 100 ℃ of temperature, and at this moment the reaction times of each grade can shorten accordingly, such as being followed successively by 1,1.5,2 hour.Obvious raw material of the present invention also can be any agriculture and forestry organic waste material, such as corn cob, bagasse, sunflower seed shell, cotton bavin, straw, rice husk, pourous wood etc.
In addition, also need to prove, the foregoing description is one of embodiments of the invention, can also comprise in the present invention such as secondary, level Four or more multistage hydrolysis device, hydrolysis device wherein also is not limited only to the hydrolysis cylinder, it can also be paper industry rotary spherical digester commonly used, or spiral screw feeder etc. has heating unit and can carry out solid-liquid blended mechanical means, and the also available miscellaneous equipment of three-roll press machine substitutes such as the mechanical means that plate-and-frame filter press, whizzer, hydraulic squeezing press, filter plant etc. carry out solid-liquid separation.
Second step, the detailed description of the dehydration Distallation systm of manufacturing furol with pentose solution.
As shown in Figure 3, in existing furfural production technology, shortcomings such as the pentose turnover ratio is low, steam consumption is big, furfural production waste water is difficult, the invention provides a kind of system and method for manufacturing furol with pentose solution, below respectively the effect and the technological operation of each equipment among Fig. 3 be explained as follows:
Dehydration reaction distillation tower 400:
Acting as of dehydration reaction distillation tower 400: the cyclodehydration reaction takes place in pentose in dehydration reaction distillation tower 400, and through still-process, the furfural vapour that generates is steamed from cat head.Dehydration reaction distillation tower 400 tops are connected with low pressure phase splitter 800 with condenser 700, and the furfural steam that is used for distillation tower 400 is distilled out is handled; And the bottom of distillation tower 400 is connected with first and second grade dehydration reactor 510,520, is used for reclaiming the furfural composition that distills the waste water that produces.Owing to have the temperature difference in the dehydration reaction distillation tower 400, tower inside is along with the increase temperature of height decreases.Furfural that generates and water form azeotropic mixture, the constant boiling point of azeotropic mixture is lower than the boiling point with water under the condition, therefore the furfural that generates concentrates on top of tower, and pentose solution mainly is present in tower bottom, and pentose is converted into the process of furfural also mainly to carry out in the tower bottom.The technological operation flow process of dehydration reaction distillation tower 400 is: after the pentose solution that contains catalyzer that obtains in the furfural production hydrolysis system enters dehydration reaction distillation tower 400, in temperature of reaction is 130-200 ℃, reaction pressure is under the condition of 0.3-1.5MPa, the reaction of pentose generation cyclodehydration, and the catalyzer that reacts required can directly utilize the catalyzer that contains in the pentose solution itself, and promptly this process does not need to add in addition catalyzer.
Next the aldehyde vapour that distillation tower 400 generates further will be purified, the present invention adopts with lower device:
Condenser 700:
The effect of condenser 700 is that the aldehyde vapour of will discharge from dehydration reaction distillation tower 400 tops is condensed into liquid.Condensed fluid temperature is 90-110 ℃, and the aldehyde liquid of process condensation is sent to and carries out phase-splitting in the low pressure phase splitter 800.
Certainly, can reach other heat exchangers of the purpose of cooling aldehyde vapour all can instead of condensor 700.In a preferred embodiment, aldehyde vapour also can pass through heat exchange earlier before entering condenser 700, heat in the condensation process is fully recycled, and offer the heat that reclaims in the system of the present invention or other links of furfural production in need the part that heats, strengthened the energy-conservation effect of the present invention.
Low pressure phase splitter 800:
800 effects of low pressure phase splitter are that condenser 700 condensed aldehyde liquid are carried out phase-splitting, and aldehyde is delivered to the furfural rectifying device mutually, and inorganic returning mutually proceeded distillation in the dehydration reaction distillation tower 400.
In the pure process of above-mentioned aldehyde stripping, there is a partial circulation, by the top of distillation tower 400, condenser 700, and low pressure phase splitter 800 constitute, as shown in Figure 3, aldehyde vapour is come out to enter in the condenser 700 by the top of distillation tower 400, the furfural liquid that obtains is sent into from the top of low pressure phase splitter 800 and is carried out phase-splitting, obtain inorganic phase and aldehyde mutually, aldehyde mutually will be further by refining.Need to prove, upper solution is inorganic phase after the phase-splitting, therefore the inorganic outlet mutually with low pressure phase splitter 800 sidewalls middle part is connected with the reflux inlet of distillation tower 400 side wall upper part, in one embodiment, low pressure phase splitter 800 inorganic exports particular location mutually in the position from top meter 1/5-1/2, and the position of the reflux inlet of distillation tower 400 is from the several 3-5 piece of cat head column plate; So just finished partial working cycle.In this circulation, need make the pressure in the low pressure phase splitter 800 identical with pressure in the dehydration reaction distillation tower 400, flow into smoothly in the low pressure phase splitter 800 with the liquid that guarantees the process condensation, specifically an equilibration tube can be set at low pressure phase splitter 800 tops, owing to be not to be emphasis of the present invention, herein so do not give unnecessary details.
Dehydration reactor 510,520, dehydration reboiler 600:
Acting as of dehydration reactor 510,520: every grade of dehydration reactor 510,520 provides the certain reaction temperature and pressure, and unreacted pentose solution further reaction in dehydration reactor 510,520 completely that dehydration reaction distillation tower 400 bottoms are discharged generates furfural; Dehydration the acting as of reboiler 600: the liquid heat vaporization that is used for the part that discharge last step dehydration reactor 520 bottoms is contained catalyzer forms steam, the steam that forms returns in the last step dehydration reactor 520, heat exchange is carried out in the direct contact of pentose solution completely to the unreacted in the dehydration reactor 520, provide heat for pentose further reacts the generation furfural, the aldehyde vapour of generation continues the thermal source as the upper level dehydration reactor.Wherein, dehydration reactor 510,520 can be the reactor of band heating jacket and whipping appts, volume size with material charging and material the residence time in still relevant, concrete relation is as follows:
V＝Q×t/80％，
V-reactor volume, unit are m
3The inlet amount of Q-material, unit is m
3/ h; The residence time of t-material in still, unit is h; The packing factor of 80%-material in reactor.
The inlet amount of material depends on the Design of device production capacity; The residence time of material in still depended on the quantity of dehydration reactor, and generalized case total residence time in dehydration reactor is 1-3 hour.Stir preferred disc turbine formula in the dehydration reactor 510,520, help steam like this and in time discharge in the reactor, connect into steam-pipe at the bottom of the still, promptly advance steam-pipe below agitator with the furfural that fully contacting of material is more conducive to generate.Vary in size according to reactor volume, can adopt double-deck at least the stirring or the multilayer stirring.
Dehydration reactor 510,520 mode of connection is: first step dehydration reactor 510 tops are provided with a pentose solution inlet 511, the inlet 513 of aldehyde vapor outlet 512 and steam, the bottom is provided with waste liquid outlet 514, can clearly be seen that from the device synoptic diagram, aldehyde vapor outlet 512 links to each other with dehydration reaction distillation tower 400 bottoms, pentose solution inlet 511 is accepted the unreacted of discharging dehydration reaction distillation tower 400 bottoms pentose solution completely, the steam that contains furfural that dehydration reactor 520 aldehyde vapor outlets 522 in the second stage are sent here is accepted in steam-in 513, and the waste liquid that will still contain pentose after waste liquid outlet 514 will react is transported in the second stage dehydration reactor 520 by pentose solution inlet 521.Dehydration reactor 520 tops in the second stage are provided with an aldehyde vapor outlet 522, pentose solution inlet 521 and steam-in 523, the bottom is provided with waste liquid outlet 524, the pentose solution of discharging from the outlet 514 of first step dehydration reactor 510 flows into the second stage dehydration reactor 520 by pentose solution inlet 521, the heat of heating unit dehydration reboiler 600 523 enters second stage dehydration reactor 520 from the steam-in, pentose solution is heated to be the steam that contains furfural and is sent to first step dehydration reactor 510 from aldehyde vapor outlet 522, this steam can play two kinds of effects, the one, furfural is wherein sent in the first step dehydration reactor 510, make furfural concentration increase, the 2nd, the heat that contains is also sent in the first step dehydration reactor 510 with steam, and pentose solution wherein heated, thereby reduced energy consumption of the present invention.The hydrolysis system that described vegetable fibre is hydrolyzed into pentose solution is discharged and delivered to the waste liquid of finishing after the dehydration from exporting 524, so because its most of composition uses for the remaining catalyst solution in reaction back still can be used as catalyzer; So just realized wastewater zero discharge.
Dehydration reactor 510,520 and the technological operation flow process of dehydration reboiler 600 be: because there are potential difference in dehydration reaction distillation tower 400 and 510 of dehydration reactors, the unreacted that discharge dehydration reaction distillation tower 400 bottoms pentose solution completely can flow automatically in the dehydration reactor 510, in temperature of reaction is 130-200 ℃, reaction pressure is under the condition of 0.3-1.5MPa, pentose further is converted into furfural, the aldehyde vapour that generates is sent into the dehydration reaction distillation tower 400 from the vapour outlet 512 at dehydration reactor 510 tops, pentose solution in the dehydration reaction distillation tower 400 is heated, for the pentose reaction provides heat and pressure, the pentose reaction generates furfural, and furfural concentration increases and discharges from cat head with the form of aldehyde vapour; Again because there are potential difference in dehydration reactor 510 and 520 of dehydration reactors, remaining unreacted pentose solution completely can be discharged the back from flowing into the dehydration reactor 520 from the waste liquid outlet 514 of dehydration reactor 510 bottoms, in temperature of reaction is 130-200 ℃, reaction pressure is under the condition of 0.3-1.5MPa, pentose further reacts the generation furfural, aldehyde vapour is discharged from the aldehyde vapor outlet 522 at dehydration reactor 520 tops, and enter in the dehydration reactor 510, to the unreacted in the dehydration reactor 510 completely pentose solution heat, for further reacting, pentose provides heat and pressure, the pentose reaction generates furfural, and furfural concentration increases and discharges from dehydration reactor 510 tops with the form of aldehyde vapour; After the waste water that contains catalyzer that the entire reaction Distallation systm produces is discharged from the waste liquid outlet 524 of last step dehydration reactor 520 bottoms, a part is sent into the formation steam of vaporizing in the dehydration reboiler 600, the vapor temperature that produces is 130-200 ℃, saturated vapor pressure is 0.3-1.5MPa, this steam is sent back to the dehydration reactor 520 from dehydration reboiler 600 tops, with unreacted in the dehydration reactor 520 completely pentose solution directly contact and carry out heat exchange, for further reacting, pentose provides heat and pressure, the pentose reaction generates furfural, the aldehyde vapour that generates is discharged from dehydration reactor 520 tops, the hydrolysis system that the remaining waste water that contains catalyzer of another part returns furfural production is the hydrolysis system participation hydrolysis reaction that vegetable fibre is hydrolyzed into pentose solution, there be not of the discharging of any furfural production waste water, and realized the recycle of furfural production waste water and catalyzer to the external world.Wherein, there are difference in adjacent two-stage dehydration reactor temperature of reaction and pressure, after the aldehyde vapour that the next stage dehydration reactor produces enters aldehyde vapour that upper level dehydration reactor or first step dehydration reactor 510 produce and enters dehydration reaction distillation tower 400, temperature reduces 3-15 ℃, and saturated vapor pressure reduces 0.03-0.2MPa.
Certainly, dehydration reaction distillation tower 400 can only connect a dehydration reactor among the present invention, just can realize with unreacted completely pentose solution continue to be converted into the purpose of furfural, a plurality of dehydration reactors of also can connecting as required, make pentose fully react the purpose that generates furfural to reach, preferred 2-5, behind employing the present invention, the transformation efficiency of pentose is significantly improved.Dehydration reboiler 600 can change other heating plant into, provides heat by the external energy, and the external energy is mainly: steam, electricity, thermal oil and the heating of other thermal medium, to reach the purpose of gasifying liquid; Can be as required, except last step dehydration reactor 520, other every grade dehydration reactor bottom can connect a heating plant that high temperature and high pressure steam is provided.Among the present invention, the material of dehydration reactor and dehydration reaction distillation tower 525 is that minimum standard is SUS304 (0Cr18Ni9) austenitic stainless steel, and certainly, aforesaid device also can adopt other kind model, as long as can realize purpose of the present invention, all should be within the scope of the present invention.
The transformation efficiency that uses pentose dehydration of the present invention to generate furfural can reach 55～85% (the actual furfural that obtains accounts for the per-cent that the pentose dehydration generates the furfural theoretical amount).What list in the following table 1 is the reaction parameter (pressure all is meant gauge pressure in the table) of embodiments of the invention 1-5.
Table 1
| Reaction conditions | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Hydrolysis temperature (℃) | 85 | 80 | 95 | 90 | 100 | |
| Hydrolysis pressure (Mpa) | Normal pressure | |||||
| The weight ratio of hydrolyzed solution and over dry corn cob | 3∶1 | 15∶1 | 12∶1 | 9∶1 | 6∶1 | |
| First step hydrolysis time (hour) | 2 | 2.5 | 3.5 | 5 | 1 | |
| Second stage hydrolysis time (hour) | 2 | 2.5 | 3.5 | 5 | 1 | |
| Third stage hydrolysis time (hour) | 2 | 2.5 | 3.5 | 5 | 1 | |
| In the first step dehydration reactor | Temperature/℃ | 143 | 150 | 170 | 180 | 200 |
| Pressure/MPa | 0.3 | 0.38 | 0.7 | 0.9 | 1.45 | |
| In the dehydration reactor of the second stage | Temperature/℃ | 140 | 145 | 164 | 173 | 185 |
| Pressure/MPa | 0.26 | 0.32 | 0.58 | 0.75 | 1.02 | |
| The dehydration reaction distillation tower | Temperature/℃ | 130 | 137 | 159 | 168 | 183 |
| Pressure/MPa | 0.17 | 0.23 | 0.50 | 0.65 | 0.97 | |
| Furfural transformation efficiency/% | 55 | 65 | 85 | 80 | 75 | |
Need to prove in above embodiment, after the raw material hydrolysis is finished, the raw material waste residue of discharging from described hydrolysis system can be taken away a part of catalyzer, therefore described catalyzer is in recycling process, also need make-up catalyst, the amount of the catalyzer that is replenished is 0.1～2.5 times of over dry raw material weight.
What need further specify is, the present invention also connects a refining system after the dehydration Distallation systm, and soon isolated chaff aldehyde is made with extra care from low pressure phase splitter 800.Be that with the prior art difference waste water that refining system of the present invention produces is sent back to the thinner of hydrolysis system as catalyzer and used, to realize wastewater zero discharge of the present invention.
Catalyzer among the present invention, main component is: monocalcium phosphate, nitric acid, phosphoric acid, sal epsom, potassium primary phosphate, water; Also can be monocalcium phosphate, nitric acid, phosphoric acid, potassium primary phosphate, water; Also can be monocalcium phosphate, nitric acid, phosphoric acid, sal epsom, water; Also can be monocalcium phosphate, nitric acid, phosphoric acid, water; Perhaps can only contain monocalcium phosphate, nitric acid, water; Perhaps can only contain monocalcium phosphate, phosphoric acid, water.
In sum, the present invention proposes the method and system that perfect two step method is produced furfural.Realize separating fully of hydrolysing step and dehydrating step, thereby reduced the reaction conditions of hydrolysis reaction and dehydration reaction, and improved the productive rate of furfural.
In dehydration Distallation systm of the present invention, pentose solution dewaters in dehydration distillation unit and dewatering and recovery unit respectively, can make unreacted completely pentose solution fully react, improved the concentration of furfural in the first step dehydration reactor, thereby improved the productive rate of furfural; Simultaneously, the water that contains furfural that phase-splitting obtains through low pressure in dehydration distillation unit returns to once more in the dehydration distillation tower and separates, guaranteed that the furfural that generates farthest is separated, furfural productivity ratio tradition furfural production technology of the present invention has improved nearly 20-40%, can be up to 65-85%.
The diluent that the waste water that produces in dehydration Distallation systm of the present invention and the refining system is sent back in the hydrolysis system as catalyzer or catalyzer uses, reach the zero release of waste water, thoroughly solved the external exhaust emission problem of environment of waste water that furfural production produces.
Because this invention can be only needs a heating plant just can reach the higher aldehyde rate that goes out, as adopts this invention technology, greatly degree reduces production costs; As the method that adopts the used heat in this invention to utilize again, the usage quantity that can save steam has greatly not only reduced production cost, has also reached the purpose of energy-conserving and environment-protective simultaneously.
In addition, in hydrolysis device of the present invention, (hydrolysis temperature is 80-100 ℃ to the reaction conditions gentleness, pressure is normal pressure), therefore Mierocrystalline cellulose and xylogen are not destroyed substantially in the waste residue that obtains after the hydrolysis end, can carry out next step comprehensive utilization, not needing to carry out pre-treatment as waste residue when the fermentative production alcohol just can be directly and the cellulase preparation saccharification of fermenting, and greatly reduces the cost of Alcohol Production.
Obviously, the foregoing description only is for example clearly is described, and is not the qualification to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of being extended out thus or change still are among the protection domain of the invention.
Claims (37)
1. system that utilizes agriculture and forestry organic waste material to produce furfural, it is characterized in that: described system comprises:
Hydrolysis system comprises the mutual placed in-line hydrolysis unit of N level, is used for agriculture and forestry organic waste material is carried out continuous hydrolysis, generates pentose solution; And
The dehydration Distallation systm comprising dehydration distillation unit, and described dehydration distillation unit comprises a dehydration reaction distillation tower at least, is used for the distillation of dewatering of described pentose solution is obtained furfural steam;
Wherein, N is the integer more than or equal to 2.
2. the system as claimed in claim 1, it is characterized in that: described each grade hydrolysis unit comprises a placed in-line hydrolysis device and an equipment for separating liquid from solid mutually respectively, described agriculture and forestry organic waste material is hydrolyzed and the solidliquid mixture after the hydrolysis is carried out solid-liquid separation generates hydrolysis acid solution and the solids contain pentose, and wherein the hydrolysis unit of each grade comprises at least:
A solid inlet is positioned on the described hydrolysis device, accepts the described solids that the upper level hydrolysis unit is sent here, and wherein the solid inlet of first step hydrolysis unit is accepted described agriculture and forestry organic waste material;
A liquid inlet is positioned on the described hydrolysis device, accepts the hydrolysis acid solution that the next stage hydrolysis unit is sent here, and wherein the outside hydrolysis acid solution that adds is accepted in the liquid inlet of last step hydrolysis unit;
A liquid exit, be positioned on the described equipment for separating liquid from solid, discharge the described unitary liquid inlet of the supreme one-stage hydrolysis of hydrolysis acid solution of containing pentose, wherein the hydrolysis acid solution of the liquid exit of first step hydrolysis unit discharge is the hydrolysis acid solution that contains pentose that described hydrolysis system generates;
A solid outlet is positioned on the described equipment for separating liquid from solid, discharges the solid inlet of described solids to the next stage hydrolysis unit, and wherein the solids of last step hydrolysis unit discharge is the Mierocrystalline cellulose slag.
3. system as claimed in claim 1 or 2, it is characterized in that: described dehydration Distallation systm also comprises the dewatering and recovery unit, be connected with described dehydration reaction distillation tower, described dewatering and recovery unit comprises at least one grade of dehydration reactor, the waste water that contains pentose of discharging at the bottom of the described dehydration reaction distillation Tata is further carried out dehydration reaction, and the furfural steam that generates returns to described dehydration reaction distillation tower.
4. system as claimed in claim 3, it is characterized in that: the top of the described dehydration reactor of each grade is provided with a pentose solution inlet, an aldehyde vapor outlet, a steam-in at least, the bottom is provided with a waste liquid outlet at least, and the waste liquid outlet of upper level dehydration reactor is connected with the aldehyde vapor outlet with the pentose solution inlet of next stage dehydration reactor respectively with the steam-in; The pentose solution inlet of described first step dehydration reactor connects at the bottom of the described dehydration reaction distillation Tata.
5. system as claimed in claim 4, it is characterized in that: the waste liquid outlet of described last step dehydration reactor is connected to the last step hydrolysis unit of described hydrolysis system, sends the waste water that contains catalyzer of described dehydration Distallation systm generation back to described hydrolysis system and does the catalyzer use.
6. as claim 3,4 or 5 described systems, it is characterized in that: described dewatering and recovery unit also comprises the heating unit that is connected with described last step dehydration reactor, be used for to the heat supply of described last step dehydration reactor, and deliver to the described dehydration reactor of each grade with heat is up step by step, and finally give described dehydration reaction distillation tower by the furfural steam that produces in the one-level dehydration reactor in the end.
7. system as claimed in claim 6 is characterized in that: described dehydration reactor is the still kettle of band heating jacket and whipping appts; Described heating unit is a dehydration reboiler, and the part of the waste water that the last step dehydration reactor is discharged is heated to be steam, and sends described last step dehydration reactor back to.
8. as the arbitrary described system of claim 3-7, it is characterized in that: be provided with potential difference between described dehydration reaction distillation tower and the described first step dehydration reactor, be provided with potential difference between described every adjacent secondary dehydration reactor, described dehydration reaction distillation tower position is the highest, and described last step dehydration reactor position is minimum.
9. system as claimed in claim 8, it is characterized in that: the waste liquid outlet of described dehydration reaction distillation tower is higher than the pentose solution inlet of described first step dehydration reactor, and the waste liquid outlet of upper level is higher than the pentose solution inlet of next stage in described every adjacent secondary dehydration reactor.
10. as any described system of claim 1-9, it is characterized in that: described dehydration distillation unit also comprises a condenser and low pressure phase splitter that is connected with described dehydration reaction distillation tower cat head, the aldehyde vapour that described dehydration reaction distillation tower produces is transported to described condenser, the thick aldehyde that described condenser condenses obtains is transported to and is separated into aldehyde in the described low pressure phase splitter and reaches water mutually, and described water turns back to described dehydration reaction distillation tower and continues distillation.
11. system as claimed in claim 10 is characterized in that: the pressure of described low pressure phase splitter is identical with pressure in the described dehydration reaction distillation tower.
12. as any described system of claim 1-11, it is characterized in that: described dehydration Distallation systm back also connects distillation system, the isolated aldehyde of described low pressure phase splitter is further made with extra care mutually generated furfural; The waste liquid outlet of described distillation system is connected to the liquid inlet of described last step hydrolysis unit, sends waste liquid the thinner use of described hydrolysis system as hydrolyst back to.
13., it is characterized in that: the mutual placed in-line hydrolysis unit of 2-5 level is set in hydrolysis system, the mutual placed in-line dehydration reactor of 2-5 level is set in described dewatering and recovery unit as any described system of claim 1-12.
14. as any described system of claim 2-11, it is characterized in that: described hydrolysis device is for having heating and adding sour device and can carry out solid-liquid blended mechanical means.
15. system as claimed in claim 14 is characterized in that: described hydrolysis device is hydrolysis cylinder, rotary spherical digester or spiral screw feeder.
16. system as claimed in claim 15 is characterized in that: the sour device that adds of described hydrolysis cylinder is an at least one shower.
17. system as claimed in claim 16 is characterized in that: be between described hydrolysis cylinder and the horizontal plane and tilt to place, the angle of inclination is less than 20 degree.
18. as claim 16 or 17 described systems, it is characterized in that: between the described hydrolysis cylinder potential difference that sets gradually is arranged, the described hydrolysis cylinder of the first step is the highest, and the described hydrolysis cylinder of last step is minimum.
19., it is characterized in that: do not have potential difference between the described hydrolysis cylinder, carry out the conveying of material by e Foerderanlage between the described hydrolysis cylinders at different levels as claim 16 or 17 described systems.
20. as any described system of claim 2-19, it is characterized in that: described equipment for separating liquid from solid is three-roll press machine, plate-and-frame filter press, whizzer, hydraulic squeezing press or filter plant.
21. as any described system of claim 3-20, it is characterized in that: temperature is 130-200 ℃ in the described last step dehydration reactor, along with reducing of described dehydration reactor progression, temperature reduces in the described dehydration reactor, the temperature difference is 3-15 ℃, and temperature is than the high 3-15 of temperature in the described dehydration reaction distillation tower ℃ in the described first step dehydration reactor.
22. as any described system of claim 1-21, it is characterized in that: the oven dry weight of agriculture and forestry organic waste material is 1 with the ratio of the weight of hydrolysis acid solution in the hydrolysis system: 3-1: 15.
23. as any described system of claim 1-22, it is characterized in that: described agriculture and forestry organic waste material comprises one or more of following material: wheat straw, rice straw, corn cob, bagasse, sunflower seed shell, cotton bavin, cotton seed hulls, straw, rice husk, pourous wood.
24., it is characterized in that: the make a living Mierocrystalline cellulose slag of producing and ethanol of the solids that described last step hydrolysis unit is discharged as any described system of claim 2-23.
25. a method of utilizing agriculture and forestry organic waste material to produce furfural adopts the system as claim 1-24, it is characterized in that: said method comprising the steps of:
A. hydrolysing step: described agriculture and forestry organic waste material is hydrolyzed in the mutual placed in-line hydrolysis unit of N level, obtains containing the hydrolysis acid solution of pentose;
B. distilation steps dewaters: the described hydrolysis acid solution that contains pentose is dewatered to distill in described dehydration reaction distillation tower generates furfural steam;
Wherein, N is the integer more than or equal to 2.
26. method as claimed in claim 25 is characterized in that: described step a further comprises:
The solids that n-1 level hydrolysis unit is generated is sent in the hydrolysis device of n level hydrolysis unit and is continued hydrolysis, makes it the hydrolysis acid solution thorough mixing hydrolysis of sending here with n+1 level hydrolysis unit; Solidliquid mixture after the hydrolysis of n level is carried out solid-liquid separation generate n level hydrolysis acid solution and n level solids; Described n level hydrolysis acid solution is delivered to n-1 level hydrolysis unit; Described n level solids is delivered to n+1 level hydrolysis unit; Wherein, 2≤n≤N and n are integer;
Wherein, initiate solids is described agriculture and forestry organic waste material in the hydrolysis device of first step hydrolysis unit, and the hydrolysis acid solution that the first step is discharged is the hydrolysis acid solution that contains pentose that described hydrolysing step generates; The hydrolysis acid solution of last step hydrolysis unit comes from the outside initiate hydrolysis acid solution that contains catalyzer, and the solids that the last step hydrolysis unit is discharged is the Mierocrystalline cellulose slag.
27. as claim 25 or 26 described methods, it is characterized in that: described method also comprises the dewatering and recovery step after step b:
The solution of discharging at the bottom of the described dehydration distillation Tata is delivered to described dewatering and recovery unit, carry out wherein pentose at least that the dehydration reaction of one-level generates furfural steam, return to described dehydration reaction distillation tower then and continue to participate in distillation.
28. method as claimed in claim 27 is characterized in that: described dewatering and recovery step further comprises:
Descending step by step described solution after finishing distillation is carried out one-level dehydration reaction at least, the waste liquid that the upper level dehydration reactor produces is delivered to the next stage dehydration reactor, and the furfural steam that the next stage dehydration reactor produces is delivered to the upper level dehydration reactor, and the furfural steam that described first step dehydration reactor produces returns to described dehydration reaction distillation tower and continues to participate in the dehydration distillation.
29. method as claimed in claim 28, it is characterized in that: described dewatering and recovery step also comprises a heating steps, only the described dehydration reactor of last step is carried out heat supply, by up step by step described furfural steam heat is delivered to the described dehydration reactor of each grade step by step, and finally give described dehydration reaction distillation tower.
30. as any described method of claim 25-29, it is characterized in that: described step b also comprises a waste water reclamation step, the waste liquid of described last step dehydration reactor is returned to described hydrolysis system as catalyzer or complex acid component, realize the wastewater zero discharge of described furfural preparation system.
31. as any described method of claim 25-30, it is characterized in that: described step b also comprises:
The furfural steam that described dehydration distillation generates being discharged from the distillation tower top, be condensed into thick aldehyde then, is that aldehyde reaches water mutually with the phase-splitting of described thick aldehyde low pressure again, and described water turns back to described dehydration reaction distillation tower and continues distillation.
32. method as claimed in claim 31 is characterized in that: the pressure of described low pressure phase-splitting is identical with pressure in the dehydration reaction distillation tower.
33. as each described method of claim 25-32, it is characterized in that: described dehydration distilation steps back also comprises rectification step, described aldehyde is further made with extra care mutually generated furfural; The waste liquid that rectifying produces sends back to the thinner use of described hydrolysis system as hydrolyst.
34. as any described method of claim 25-33, it is characterized in that: the hydrolysis temperature of the described hydrolysis device of each grade is 80-100 ℃, hydrolysis time is 1-5 hour.
35. as any described method of claim 25-34, it is characterized in that: described last step dehydration reactor is heated to 130-200 ℃, along with reducing of described dehydration reactor progression, temperature reduces in the described dehydration reactor, the temperature difference is 3-15 ℃, and temperature is than the high 3-15 of temperature in the described dehydration reaction distillation tower ℃ in the described first step dehydration reactor.
36., it is characterized in that: before described hydrolysing step, also comprise the step that described agriculture and forestry organic waste material is cut and cleans as any described method of claim 25-35.
37. as any described method of claim 25-36, it is characterized in that: the waste residue of discharging in the hydrolysis device of described last step hydrolysis unit is for making the alcoholic acid raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101519646A CN101130532B (en) | 2007-09-24 | 2007-09-24 | System and method for producing furol by using agricultural and forestry castoff |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130756A (en) * | 2011-11-22 | 2013-06-05 | 济南圣泉集团股份有限公司 | Process for producing furfural by lignocellulose biomass |
| US20130172585A1 (en) * | 2011-12-28 | 2013-07-04 | E I Du Pont De Nemours And Company | Process for the production of furfural |
| CN103193737A (en) * | 2013-03-29 | 2013-07-10 | 山东龙力生物科技股份有限公司 | Method for preparing furfural and co-producing lignin and cellulosic ethanol via plant material |
| CN107827847A (en) * | 2017-12-06 | 2018-03-23 | 易高环保能源研究院有限公司 | The system and method for furfural is continuously prepared using lignocellulose raw material |
| CN111848557A (en) * | 2020-07-17 | 2020-10-30 | 青岛科技大学 | Preparation process of furfural |
| EP3733655A4 (en) * | 2017-12-06 | 2021-06-09 | Eco Environmental Energy Research Institute Limited | System and method for continuously preparing furfural using lignocellulosic raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2462433A1 (en) * | 1979-08-03 | 1981-02-13 | Bertin & Cie | IMPROVEMENTS IN PROCESSES AND EQUIPMENT FOR OBTAINING FURFURAL FROM PLANT MATERIALS |
| US4533743A (en) * | 1983-12-16 | 1985-08-06 | Atlantic Richfield Company | Furfural process |
| AT387247B (en) * | 1987-05-12 | 1988-12-27 | Voest Alpine Ind Anlagen | COMBINED PROCESS FOR THE THERMAL AND CHEMICAL TREATMENT OF BIOMASS CONTAINING LIGNOCELLULOSE AND FOR THE EXTRACTION OF FURFURAL |
| CN1062910C (en) * | 1995-12-19 | 2001-03-07 | 于是今 | Method for production of xylose by continuous hydrolysis of corncob or bagasse |
| CN1872726A (en) * | 2006-06-07 | 2006-12-06 | 济南圣泉集团股份有限公司 | Method for treating wastewater from furfural production |
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| CN103130756A (en) * | 2011-11-22 | 2013-06-05 | 济南圣泉集团股份有限公司 | Process for producing furfural by lignocellulose biomass |
| CN103130756B (en) * | 2011-11-22 | 2016-01-20 | 济南圣泉集团股份有限公司 | A kind of technique of being produced furfural by lignocellulose biomass |
| US20130172585A1 (en) * | 2011-12-28 | 2013-07-04 | E I Du Pont De Nemours And Company | Process for the production of furfural |
| CN103193737A (en) * | 2013-03-29 | 2013-07-10 | 山东龙力生物科技股份有限公司 | Method for preparing furfural and co-producing lignin and cellulosic ethanol via plant material |
| CN103193737B (en) * | 2013-03-29 | 2015-01-28 | 山东龙力生物科技股份有限公司 | Method for preparing furfural and co-producing lignin and cellulosic ethanol via plant material |
| CN107827847A (en) * | 2017-12-06 | 2018-03-23 | 易高环保能源研究院有限公司 | The system and method for furfural is continuously prepared using lignocellulose raw material |
| CN107827847B (en) * | 2017-12-06 | 2021-05-28 | 易高环保能源研究院有限公司 | System and method for continuously preparing furfural by utilizing lignocellulose raw material |
| EP3733655A4 (en) * | 2017-12-06 | 2021-06-09 | Eco Environmental Energy Research Institute Limited | System and method for continuously preparing furfural using lignocellulosic raw material |
| US11767304B2 (en) | 2017-12-06 | 2023-09-26 | Eco Environmental Energy Research Institute Limited | System and method for continuously preparing furfural using lignocellulosic raw material |
| CN111848557A (en) * | 2020-07-17 | 2020-10-30 | 青岛科技大学 | Preparation process of furfural |
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| CN101130532B (en) | 2010-11-24 |
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Denomination of invention: System and method for producing furol by using agricultural and forestry castoff Effective date of registration: 20160302 Granted publication date: 20101124 Pledgee: Industrial Commercial Bank of China Ltd Zhangqiu branch Pledgor: Shengquan Group Co., Ltd., Ji'nan City Registration number: 2016990000130 |
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