CN111747998B - Method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography - Google Patents
Method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography Download PDFInfo
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Abstract
The invention discloses a method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography, belonging to the technical field of separation and extraction. The method comprises the following steps: (1) pretreating xylose hydrolysate; (2) and removing inorganic acid and acetic acid in the xylose hydrolysate by using intermittent simulated moving bed chromatography. The method not only can efficiently and continuously separate the inorganic acid from the xylose hydrolysate, avoid the problems of 'three wastes' and the like caused by the fact that the acid for catalysis cannot be recovered and neutralized for acid removal, but also solves the problem of inhibiting subsequent fermentation by the main byproduct acetic acid in the xylose hydrolysate, and can simultaneously separate the inorganic acid and the acetic acid to realize comprehensive utilization.
Description
Technical Field
The invention belongs to the technical field of separation and extraction, and relates to a method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography.
Background
The saccharides refer to polyhydroxy aldehydes or ketones, are the most abundant biomolecules in nature and are widely distributed. The functional sugar with special effects has the special effects of low calorie, providing nutrition, promoting improvement of human physiological functions and the like, is initially applied to the nutritional health care and food industry, and then gradually develops into the non-food fields of chemical industry, pharmacy and the like, so that the application of the functional sugar in the commercial market is increasingly concerned.
Xylose is one of the major products in functional sugars. In industry, the primary sugar liquid is obtained by catalytic hydrolysis of agricultural and sideline products such as corncobs, straws, bagasse and the like through dilute inorganic acid, and then the xylose is prepared through refining, concentration and crystallization. In this respect, it is first necessary to remove the acid used for the catalytic hydrolysis and to reduce the amount of organic acid by-products produced during the hydrolysis, supplying the downstream sections with a pure xylose solution. The acid for catalytic hydrolysis comprises sulfuric acid, hydrochloric acid and the like, the byproduct organic acid comprises formic acid, acetic acid, levulinic acid and the like, and the acetic acid has relatively high content in the hydrolysate.
In the prior art, methods for removing inorganic acids and organic acids from xylose hydrolysate include ion exclusion chromatography (Chinese patent publication No. CN108220486A, etc.), alkali neutralization (Chinese patent publication No. CN110564899A, etc.), ion exchange (Chinese patent publication Nos. CN110564897A, CN109908977A, CN110368817A, etc.), distillation (new energy development, 2019,7(6): 505-. However, among the separation methods, the reported ion exclusion chromatography methods suffer from some disadvantages, such as intermittent single-column or dual-column alternating operation, low efficiency, high eluent consumption; the conventional four-zone (as shown in figure 1) or sequential (as shown in figure 2) simulated moving bed can only separate two components, but can not separate more than three components; five zones (as shown in figure 3) and above simulated moving beds have more control points, the system is too complex and the investment is large. The alkali neutralization method produces a large amount of three wastes, the loss rate of saccharides is high, and additional treatment is needed to remove residual anions and cations. In addition, the ion exchange method generates a large amount of acid-base wastewater, and the resin has high operation load and short service life. Distillation coupled with esterification can be used for organic acid removal, but has limited effect on dilute mineral acid separation.
Therefore, in order to effectively separate and recover the inorganic acid in the xylose hydrolysate and the organic acid generated in the hydrolysis process, simplify the downstream separation process and the operation load, and control the recovery cost, the method is a first concern of resource utilization of biomass in the functional sugar industry.
Chinese patent CN105669419A discloses a sequential simulated moving method for separating sugar acid in corn straw acid hydrolysis, which separates sulfuric acid and sugar solution in straw acid hydrolysis solution by using an eight-column three-substep mode. Chinese patent CN108220486A discloses a method for separating sugar from acid by using acid-retarded resin, in the chlorine type
Separating the saccharides and the inorganic acid on a single column of A-32Fine mesh resin with the height-diameter ratio of 15: 1-25: 1. Chinese patent CN1066325525A discloses a method for separating sulfuric acid from glucose xylose, which separates sulfuric acid from glucose xylose in a single-column mode without involving the separation of byproducts. Chinese patent CN102600640A discloses a process for separating sugars, acids and salts in lignocellulose hydrolysis, which refers to the separation of fast (acids and salts) and slow (sugars and acetic acid) components by a rotating disk simulated moving bed, the slow components are concentrated by evaporation under reduced pressure, and the acetic acid in the solution is removed by anion exchange resin, said process does not separate acetic acid from sugars simultaneously. Li Xun, etc. in single-column mode [ solar bulletin, 2005,26(4):529-]And a simulated movement pattern [ solar journal, 2005,29(6):747-]The ion exclusion chromatography of the four-zone simulated moving bed is used for separating sugar and sulfuric acid in the wood hydrolysate, so that the time for separating substances is short, the efficiency is low, the cost is high and the like.
A batch simulated moving bed is a new chromatographic separation process, as shown in fig. 4, with the ports arranged in a similar fashion to a conventional four-zone simulated moving bed architecture. The four-zone batch simulated moving bed is separated from zone I to zone III in the first time interval and zone IV in the second time interval, and the raffinate is inevitably diluted. The method for exploring the chromatographic separation of the novel four-zone intermittent simulated moving bed can overcome the problems of the conventional chromatographic separation methods of four-zone, sequential, five-zone and above simulated moving beds and the like.
Disclosure of Invention
In order to solve the problems, the invention provides a method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography, which can continuously separate and remove the inorganic acid and the acetic acid in the xylose hydrolysate.
The technical scheme of the invention is as follows:
a method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography comprises the following steps:
(1) pretreatment of xylose hydrolysate: filtering the xylose hydrolysate to remove colloid and solid matters, removing color matters in the xylose hydrolysate by using active carbon or resin, and evaporating and concentrating to obtain a raw material;
(2) and (3) intermittent simulated moving bed chromatographic separation: separating the raw material obtained in the step (1) by intermittent simulated moving bed chromatography to remove inorganic acid and acetic acid; the intermittent simulated moving bed chromatography takes H-type strong acid cation resin as stationary phase resin and deionized water as an eluent, and the working temperature is 40-65 ℃; the intermittent simulated moving bed chromatogram comprises a No. 1 chromatographic column, a No. 2 chromatographic column, a No. 3 chromatographic column, a No. 4 chromatographic column, a No. 5 chromatographic column and a No. 6 chromatographic column which are sequentially connected in series, and comprises a zone I, a zone II, a zone III and a zone IV, wherein the zone I, the zone II and the zone III respectively contain 2 chromatographic columns which are sequentially connected in series, and the zone IV contains 6 chromatographic columns which are sequentially connected in series; the zone I is positioned between an eluent inlet and a raw material inlet; the zone II is positioned between the raw material inlet and the inorganic acid component outlet; the III zone is between the inorganic acid component outlet and the acetic acid component outlet, and the IV zone is between the eluent inlet and the saccharide component outlet.
Furthermore, corncob, bagasse, straw, eucalyptus or birch of the agricultural and forestry waste are subjected to crushing, water washing and hot water leaching treatment, and then hydrolyzed by 0.5-2.0% of inorganic acid to obtain xylose hydrolysate; filtering to remove colloid and solid, removing color and luster substances by using activated carbon or resin, and evaporating and concentrating at 55-65 ℃ to obtain a raw material; in the raw materials, the concentration of saccharides is 50-70 mg/mL, the concentration of inorganic acid is 10-20 mg/mL, and the concentration of acetic acid is 5-10 mg/L.
Further, the stationary phase resin is any one of Dowex 99 or 50W H type, JK 006H type, XAD 4H type, D001H type or LS001H type, and the particle size of the resin is 120-320 mu m; the aspect ratio of the chromatographic stationary phase is as follows: 15: 1-30: 1.
Further, the chromatographic column is insulated by circulating water through a concentric jacket, and the temperature is 40-65 ℃; the front and the back of each chromatographic column are provided with a distributed electromagnetic valve bank, the eluent inlet, the raw material inlet, the saccharide outlet, the inorganic acid outlet and the acetic acid outlet are respectively provided with an eluent valve, a raw material valve, a saccharide component valve, an inorganic acid component valve and an acetic acid component valve, and the electromagnetic valve banks are controlled to be opened or closed by a PLC program to realize the simulated movement of raw materials or elution water, saccharides or acid components flowing out and a chromatographic stationary phase column; the adjacent chromatographic columns are connected by pipelines, and one-way valves are arranged in the pipelines.
Further, the step (2) specifically comprises the following steps:
(a) opening an eluent valve before the No. 1 chromatographic column to inject eluent, opening a raw material valve before the No. 3 chromatographic column to inject raw materials, and controlling the ratio of the raw materials to the water to be 1: 1.5-1: 2.5; the inorganic acid component outlet at the end of the No. 4 chromatographic column flows out the inorganic acid with the weak retention component; the acetic acid component outlet at the end of the No. 6 chromatographic column flows out the strong reserved component acetic acid of the last period; the carbohydrate of the intermediate retention component is retained in the chromatographic zone between column No. 3 and column No. 4;
(b) after the step (a) is finished, closing a front raw material valve of a No. 3 chromatographic column and a tail inorganic acid component valve of a No. 4 chromatographic column, forming an independent chromatographic separation area from the No. 1 chromatographic column to the No. 6 chromatographic column, enabling eluent to flow in the direction from the No. 1 chromatographic column to the No. 6 chromatographic column, enabling medium reserved components and strong reserved components to flow into a chromatographic system under the pushing of the eluent, and enabling medium reserved component saccharides to flow into a saccharide component valve at the tail of the No. 6 chromatographic column;
(c) after the step (b) is finished, switching an eluent inlet from the front end of the No. 1 chromatographic column to the front end of the No. 2 chromatographic column; the raw material inlet is switched from the front end of the No. 3 chromatographic column to the front end of the No. 4 chromatographic column; the inorganic acid component outlet is switched from the tail end of the No. 4 chromatographic column to the tail end of the No. 5 chromatographic column; the acetic acid component outlet or the saccharide component outlet is switched from the end of the No. 6 chromatographic column to the end of the No. 1 chromatographic column.
(d) After the step (c) is switched, repeating the step (a) and the step (b) for operation; after running each period, the position of each port is moved forward by one chromatographic column along the flowing direction of the eluent, and the initial position is recovered after 6 cycles are completed.
Further, the flow rate of the eluent is 4-6 mL/min, the flow rate of the raw material is 2-3 mL/min, the flow rate of the inorganic acid component is 3-4 mL/min, the flow rate of the acetic acid component is 4-5 mL/min, the flow rate of the saccharide component is 5-6 mL/min, the time of the step (a) is 4-7 min, and the time of the step (b) is 8-12 min.
The working mechanism of the invention is as follows: the H-type strong acid cation resin chromatographic stationary phase has high charge density, and according to the Tao-nan repulsion principle, strong electrolyte components are repelled when passing through the stationary phase and cannot enter resin micropores without retention; the non-dissociative component is not repelled and permeates into the micropores of the resin to be reserved; thereby causing a partitioning phenomenon between the components in the spaces between the resin particles and the components in the resin pores. The extent to which the dissociated electrolyte components are repelled is related to the strength of the acid and the electrolyte dissociation. The saccharide is neutral molecule, the sulfuric acid or hydrochloric acid is strong electrolyte, the acetic acid is weak electrolyte, and the three are respectively retained, non-retained and strongly retained (partial hydrogen bond action) on the H-type strong acid cation resin chromatographic stationary phase. When the three components of the saccharide, the sulfuric acid or the hydrochloric acid and the acetic acid in the xylose hydrolysate pass through the stationary phase, the sulfuric acid or the hydrochloric acid firstly flows out, the saccharide then flows out, and the acetic acid finally flows out. Six columns form an intermittent port reset simulated moving bed four-zone open-loop chromatographic system, and can realize continuous flow of xylose hydrolysate, a raffinate port in the first substep collects weak retention component sulfuric acid or hydrochloric acid, an extraction port collects strong retention component acetic acid in the last period, and an extraction port in the second substep collects medium retention component saccharides. And then switching ports along the flowing direction of the eluent to simulate the stationary phase movement of the chromatographic column, and continuously and simultaneously removing the inorganic acid and the acetic acid in the xylose hydrolysate by using the intermittent simulated moving bed chromatography.
The invention has the beneficial effects that:
(1) the method can continuously separate and remove the inorganic acid and the acetic acid in the xylose hydrolysate, and has higher acid yield, sugar yield, acid purity and sugar solution purity;
(2) the invention can prevent the concentration of the extraction solution from being diluted, the recovered inorganic acid can be used for hydrolysis again after the concentration is adjusted, the concentration of the component outlet is higher than that of a four-zone or five-zone or a sequential simulated moving bed, and the subsequent concentration cost is reduced;
(3) the invention reduces the resin dosage and the number of chromatographic columns, and reduces the equipment investment and the production loss; the back mixing of the feed liquid is reduced, and the purity and the yield of the product are improved;
(4) the purity of the three components of the sugar, the inorganic acid and the acetic acid which are continuously recovered by the method reaches more than 90 percent.
Drawings
FIG. 1 is a schematic diagram of a four-zone simulated moving bed chromatography.
FIG. 2 is a schematic diagram of sequential simulated moving bed chromatography.
FIG. 3 is a schematic diagram of a five-zone simulated moving bed chromatography.
FIG. 4 is a schematic diagram of four-zone batch simulated moving bed chromatography; fig. 4a and 4b show port configurations in a first time interval and a second time interval, respectively.
FIG. 5 is a schematic diagram of a four-zone port rearrangement batch simulated moving bed chromatography.
Detailed Description
The batch simulated moving bed chromatography described in the following examples is shown in fig. 5, and comprises a No. 1 chromatographic column, a No. 2 chromatographic column, a No. 3 chromatographic column, a No. 4 chromatographic column, a No. 5 chromatographic column and a No. 6 chromatographic column which are sequentially connected in series, and comprises a zone I, a zone II, a zone III and a zone IV, wherein the zone I, the zone II and the zone III respectively contain 2 chromatographic columns which are sequentially connected in series, and the zone IV contains 6 chromatographic columns which are sequentially connected in series; the zone I is positioned between an eluent inlet and a raw material inlet; the zone II is positioned between the raw material inlet and the inorganic acid component outlet; the III zone is between the inorganic acid component outlet and the acetic acid component outlet, and the IV zone is between the eluent inlet and the saccharide component outlet. The chromatographic column is insulated by circulating water through a concentric jacket, and the temperature is 40-65 ℃; the front and the back of each chromatographic column are provided with a distributed electromagnetic valve bank, the eluent inlet, the raw material inlet, the saccharide outlet, the inorganic acid outlet and the acetic acid outlet are respectively provided with an eluent valve, a raw material valve, a saccharide component valve, an inorganic acid component valve and an acetic acid component valve, and the electromagnetic valve banks are controlled to be opened or closed by a PLC program to realize the simulated movement of raw materials or elution water, saccharides or acid components flowing out and a chromatographic stationary phase column; the adjacent chromatographic columns are connected by pipelines, and one-way valves are arranged in the pipelines.
The method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography in the following embodiment comprises the following steps:
(a) opening an eluent valve before the No. 1 chromatographic column to inject eluent, opening a raw material valve before the No. 3 chromatographic column to inject raw materials, and controlling the ratio of the raw materials to the water to be 1: 1.5-1: 2.5; the inorganic acid component outlet at the end of the No. 4 chromatographic column flows out the inorganic acid with the weak retention component; the acetic acid component outlet at the end of the No. 6 chromatographic column flows out the strong reserved component acetic acid of the last period; the carbohydrate of the intermediate retention component is retained in the chromatographic zone between column No. 3 and column No. 4;
(b) after the step (a) is finished, closing a front raw material valve of a No. 3 chromatographic column and a tail inorganic acid component valve of a No. 4 chromatographic column, forming an independent chromatographic separation area from the No. 1 chromatographic column to the No. 6 chromatographic column, enabling eluent to flow in the direction from the No. 1 chromatographic column to the No. 6 chromatographic column, enabling medium reserved components and strong reserved components to flow into a chromatographic system under the pushing of the eluent, and enabling medium reserved component saccharides to flow into a saccharide component valve at the tail of the No. 6 chromatographic column;
(c) after the step (b) is finished, switching an eluent inlet from the front end of the No. 1 chromatographic column to the front end of the No. 2 chromatographic column; the raw material inlet is switched from the front end of the No. 3 chromatographic column to the front end of the No. 4 chromatographic column; the inorganic acid component outlet is switched from the tail end of the No. 4 chromatographic column to the tail end of the No. 5 chromatographic column; the acetic acid component outlet or the saccharide component outlet is switched from the end of the No. 6 chromatographic column to the end of the No. 1 chromatographic column.
(d) After the step (c) is switched, repeating the step (a) and the step (b) for operation; after running in each period, the position of each port is moved backwards by one chromatographic column along the flowing direction of the eluent, and the initial position is recovered after 6 cycles are completed.
The "about" ranges mentioned in the examples below are given as concentration values. + -. 1 mg/mL.
Example 1
A method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography comprises the following steps.
(1) Preparing raw materials: performing precise filtration on the xylose hydrolysate to remove colloids and solid matters, removing color matters in the xylose hydrolysate by using active carbon or resin to obtain faint yellow xylose hydrolysate, and performing evaporation concentration (55-65 ℃) by using a rotary evaporator until the total sugar content, the sulfuric acid concentration and the acetic acid concentration in the solution are about 59.2mg/mL, 13.5mg/mL and 8.8mg/L respectively.
(2) And (3) removing sulfuric acid and acetic acid by using intermittent simulated moving bed chromatography: the raw material is subjected to ion exclusion chromatographic separation on batch simulated moving bed chromatography, the stationary phase resin is Dowex 99H type, and the eluent is deionized water at 40 ℃. Before separating the acid, deionized hot water at 40 ℃ was previously fed to the eluent inlet, and the flow rate was maintained at 2mL/min while the raw material valve, the saccharide component valve, the inorganic acid component valve, and the acetic acid component valve were closed, and no air was trapped in the column. After completion of the run, the eluent was increased to a target value of 5mL/min, a feed flow of 2.47mL/min, a sulfuric acid component flow of 3.22mL/min, an acetic acid component flow of 4.25mL/min, a saccharide component flow of 5mL/min, a single cycle time of 15min, wherein step (a) was 6.5min and step (b) was 8.5 min.
In a single cycle, the sub-steps are divided into two, and the port distribution sequence is changed along with the change of the sub-steps. Step (a): injecting eluent at 40 ℃ into an eluent inlet before the No. 1 chromatographic column and injecting raw materials into a raw material inlet before the No. 3 chromatographic column, collecting sulfuric acid components flowing out of an inorganic acid outlet at the end of the No. 4 chromatographic column and collecting acetic acid components flowing out of an acetic acid component outlet at the end of the No. 6 chromatographic column; step (b): injecting eluent at 40 deg.C into eluent inlet before No. 1 chromatographic column, and collecting saccharide component flowing out from saccharide component outlet at end of No. 6 chromatographic column.
After running in each period, the position of each port is moved backwards by one chromatographic column along the flowing direction of the eluent, and the initial position is recovered after 6 cycles are completed.
Based on the above separation procedure, the total sugar yield was 98.2%, the purity was 96.6%, the sulfuric acid yield was 93.2%, the purity was 94.5%, the acetic acid yield was 92.2%, and the purity was 92.6%.
Example 2
A method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography comprises the following steps:
(1) preparing raw materials: performing precise filtration on the xylose hydrolysate to remove colloids and solid matters, removing color matters in the xylose hydrolysate by using active carbon or resin to obtain faint yellow xylose hydrolysate, and performing evaporation concentration (55-65 ℃) by using a rotary evaporator until the total sugar, the hydrochloric acid and the acetic acid in the solution are about 65.2mg/mL, about 12.5mg/mL and about 7.7mg/L respectively.
(2) Removing hydrochloric acid and acetic acid by using intermittent simulated moving bed chromatography: the raw material is subjected to ion exclusion chromatographic separation by intermittent simulated moving bed chromatography, the stationary phase resin is JK 006H type, and the eluent is deionized water at 50 ℃. Before separating the acid, 50 ℃ deionized hot water eluent was previously injected into the eluent inlet, and the flow rate was maintained at 2.5mL/min while the raw material valve, the saccharide component valve, the inorganic acid component valve, and the acetic acid component valve were closed, and no air was trapped in the column. After completion of the run, the eluent was increased to a target value of 5.8mL/min, a feed flow of 2.9mL/min, a sulfuric acid component flow of 3.85mL/min, an acetic acid component flow of 4.85mL/min, a saccharide component flow of 5.8mL/min, a single cycle time of 17min, wherein step (a) was 5.7min, and step (b) was 11.3 min.
In a single cycle, the sub-steps are divided into two, and the port distribution sequence is changed along with the change of the sub-steps. Step (a): injecting eluent at 50 ℃ into an eluent inlet before the No. 1 chromatographic column and injecting raw materials into a raw material inlet before the No. 3 chromatographic column, collecting sulfuric acid components flowing out of an inorganic acid outlet at the end of the No. 4 chromatographic column and collecting acetic acid components flowing out of an acetic acid component outlet at the end of the No. 6 chromatographic column; step (b): injecting eluent at 50 ℃ into an eluent inlet before the No. 1 chromatographic column, and collecting saccharide components flowing out of a saccharide component outlet at the end of the No. 6 chromatographic column.
After running in each period, the position of each port is moved backwards by one chromatographic column along the flowing direction of the eluent, and the initial position is recovered after 6 cycles are completed.
Based on the above separation procedure, the total sugar yield was 97.6%, the purity was 97.3%, the hydrochloric acid yield was 92.2%, the purity was 96.1%, the acetic acid yield was 94.3%, and the purity was 93.5%.
Example 3
A method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography comprises the following steps:
(1) preparing raw materials: performing precise filtration on the xylose hydrolysate to remove colloids and solid matters, removing color matters in the xylose hydrolysate by using active carbon or resin to obtain faint yellow xylose hydrolysate, and performing evaporation concentration (55-65 ℃) by using a rotary evaporator until the total sugar content, the sulfuric acid concentration and the acetic acid concentration in the solution are about 59.2mg/mL, 13.5mg/mL and 8.8mg/L respectively.
(2) And (3) removing sulfuric acid and acetic acid by using intermittent simulated moving bed chromatography: the raw material is subjected to ion exclusion chromatographic separation by intermittent simulated moving bed chromatography, the stationary phase resin is XAD 4H type, and the eluent is deionized water at 60 ℃. Before separating the acid, 60 ℃ deionized hot water eluent was injected into the eluent inlet in advance, and the flow rate was maintained at 2mL/min while the raw material valve, the saccharide component valve, the inorganic acid component valve, and the acetic acid component valve were closed, and no air was trapped in the column. After completion of the run, the eluent was increased to a target value of 5mL/min, a feed flow of 2.67mL/min, a sulfuric acid component flow of 3.15mL/min, an acetic acid component flow of 4.25mL/min, a saccharide component flow of 5mL/min, a single cycle time of 16min, wherein step (a) was 5.5min and step (b) was 10.5 min.
In a single cycle, the sub-steps are divided into two, and the port distribution sequence is changed along with the change of the sub-steps. Step (a): injecting eluent at 60 ℃ into an eluent inlet before the No. 1 chromatographic column and injecting raw materials into a raw material inlet before the No. 3 chromatographic column, collecting sulfuric acid components flowing out of an inorganic acid outlet at the end of the No. 4 chromatographic column and collecting acetic acid components flowing out of an acetic acid component outlet at the end of the No. 6 chromatographic column; step (b): injecting eluent at 60 ℃ into an eluent inlet before the No. 1 chromatographic column, and collecting saccharide components flowing out of a saccharide component outlet at the end of the No. 6 chromatographic column.
After running in each period, the position of each port is moved backwards by one chromatographic column along the flowing direction of the eluent, and the initial position is recovered after 6 cycles are completed.
Based on the above separation procedure, the total sugar yield was 97.6%, the purity 98.3%, the sulfuric acid yield 92.2%, the purity 95.7%, the acetic acid yield 92.8%, and the purity 93.5% were obtained.
Example 4
A method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography comprises the following steps:
(1) preparing raw materials: performing precise filtration on the xylose hydrolysate to remove colloids and solid matters, removing color matters in the xylose hydrolysate by using active carbon or resin to obtain faint yellow xylose hydrolysate, and performing evaporation concentration (55-65 ℃) by using a rotary evaporator until the total sugar, the hydrochloric acid and the acetic acid in the solution are about 65.2mg/mL, about 12.5mg/mL and about 7.7mg/L respectively.
(2) Removing hydrochloric acid and acetic acid by using intermittent simulated moving bed chromatography: and carrying out ion exclusion chromatography separation on the xylose concentrated solution in an intermittent simulated moving bed, wherein the stationary phase resin is D001H type, and the eluent is deionized water at 55 ℃. Before separating the acid, 50 ℃ deionized hot water eluent was previously injected into the eluent inlet, and the flow rate was maintained at 2.2mL/min while the raw material valve, the saccharide component valve, the inorganic acid component valve, and the acetic acid component valve were closed, and no air was trapped in the column. After completion of the run, the eluent was increased to a target value of 5.8mL/min, a feed flow of 2.5mL/min, a sulfuric acid component flow of 3.65mL/min, an acetic acid component flow of 4.65mL/min, a saccharide component flow of 5.8mL/min, a single cycle time of 14min, wherein step (a) was 4.7min, and step (b) was 9.3 min.
In a single cycle, the sub-steps are divided into two, and the port distribution sequence is changed along with the change of the sub-steps. Step (a): injecting 55 ℃ eluent into an eluent inlet before the No. 1 chromatographic column and injecting raw materials into a raw material inlet before the No. 3 chromatographic column, collecting sulfuric acid components flowing out of an inorganic acid outlet at the end of the No. 4 chromatographic column and collecting acetic acid components flowing out of an acetic acid component outlet at the end of the No. 6 chromatographic column; step (b): injecting eluent at 55 deg.C into eluent inlet before No. 1 chromatographic column, and collecting saccharide component flowing out from saccharide component outlet at end of No. 6 chromatographic column.
After running in each period, the position of each port is moved backwards by one chromatographic column along the flowing direction of the eluent, and the initial position is recovered after 6 cycles are completed.
Based on the above separation procedure, the total sugar yield was 98.6%, the purity was 92.3%, the hydrochloric acid yield was 93.2%, the purity was 95.2%, the acetic acid yield was 92.1%, and the purity was 95.5%.
Comparative example
In the method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography, in order to search for a proper ion exclusion chromatography stationary phase, a resin functional group and coordination ions are evaluated experimentally, and the method specifically comprises the following steps:
(1) crushing, washing and leaching agricultural and forestry waste corncobs with hot water, and then carrying out catalytic hydrolysis on the corncobs by using 1.5% dilute sulfuric acid at the temperature of 113-115 ℃ and under the pressure of 0.15-0.18 MPa for 1.5 hours; removing colloid and solid substance by precision filtration; vacuum rotary evaporation and concentration (60-65 ℃) until the total sugar is about 59mg/mL, the sulfuric acid is about 13mg/mL, the acetic acid is about 8mg/, and active carbon or resin is used for removing color materials to obtain the raw material.
(2) The strong acid group or the resin coordinated with the strong acid group has larger polarity, and is favorable for generating southeast rejection when being used as a chromatographic stationary phase, and on the resin, the non-ionic solute has smaller southeast rejection than the ionic solute and shows long retention time. Strong acid hydrogen type cation resin, strong alkali sulfate radical type anion resin and strong alkali chlorine type anion resin are selected for experiments. Respectively taking 25g of the raw material solution, filling the raw material solution into a single column according to the height-diameter ratio of 20:1, performing dynamic experiments, loading 10mL of the raw material solution, eluting the raw material solution by using hot water at 50 ℃ at 1.5mL/min, collecting eluent, analyzing and calculating the yield and purity of saccharides, the purity and yield of sulfuric acid and the yield and purity of acetic acid in the sample, and obtaining a better effect of separating the three components by using the strong acid hydrogen type cationic resin.
(3) Macroporous and gel type strongly acidic hydrogen type cation resins HD-8, JK-006, HZ-016, D001, 002SC, HS001, 001 × 7, 001 × 8, LS001, Dowex 99 or 50W, XAD4, 15Wet and 252Na are selected. 25g of the raw material liquid is loaded into a single column according to the height-diameter ratio of 20:1 and is subjected to dynamic experiment, 10mL of the raw material liquid is loaded, then the raw material liquid is eluted by hot water at 50 ℃ at 1.5mL/min, eluent is collected and analyzed to calculate the yield and purity of saccharides, the purity and yield of sulfuric acid and the yield and purity of acetic acid in the sample, and the separation performance of the resin is evaluated. The results show that the separation effect of Dowex 99 or 50W, JK006, XAD4, D001 and LS001 is relatively better, therefore, the five resins are selected as the chromatographic stationary phases for removing the inorganic acid and the acetic acid in the xylose hydrolysate by the simulated moving bed.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography, which is characterized by comprising the following steps:
(1) pretreatment of xylose hydrolysate: filtering the xylose hydrolysate to remove colloid and solid matters, removing color matters in the xylose hydrolysate by using active carbon or resin, and evaporating and concentrating to obtain a raw material;
(2) and (3) intermittent simulated moving bed chromatographic separation: separating the raw material obtained in the step (1) by intermittent simulated moving bed chromatography to remove inorganic acid and acetic acid;
the intermittent simulated moving bed chromatography takes H-type strong acid cation resin as stationary phase resin and deionized water as an eluent, and the working temperature is 40-65 ℃; the intermittent simulated moving bed chromatogram comprises a No. 1 chromatographic column, a No. 2 chromatographic column, a No. 3 chromatographic column, a No. 4 chromatographic column, a No. 5 chromatographic column and a No. 6 chromatographic column which are sequentially connected in series, and comprises a zone I, a zone II, a zone III and a zone IV, wherein the zone I, the zone II and the zone III respectively contain 2 chromatographic columns which are sequentially connected in series, and the zone IV contains 6 chromatographic columns which are sequentially connected in series; the zone I is positioned between an eluent inlet and a raw material inlet; the zone II is positioned between the raw material inlet and the inorganic acid component outlet; the III zone is positioned between the inorganic acid component outlet and the acetic acid component outlet, and the IV zone is positioned between the eluent inlet and the saccharide component outlet;
the stationary phase resin is any one of Dowex 50W H type, JK 006H type, XAD 4H type, D001H type or LS001H type, and the particle size of the resin is 120-320 mu m; the aspect ratio of the chromatographic stationary phase is as follows: 15: 1-30: 1;
the step (2) specifically comprises the following steps:
(a) opening an eluent valve before the No. 1 chromatographic column to inject eluent, opening a raw material valve before the No. 3 chromatographic column to inject raw materials, and controlling the ratio of the raw materials to the water to be 1: 1.5-1: 2.5; the inorganic acid component outlet at the end of the No. 4 chromatographic column flows out the inorganic acid with the weak retention component; the acetic acid component outlet at the end of the No. 6 chromatographic column flows out the strong reserved component acetic acid of the last period; the carbohydrate of the intermediate retention component is retained in the chromatographic zone between column No. 3 and column No. 4;
(b) after the step (a) is finished, closing a front raw material valve of a No. 3 chromatographic column and a tail inorganic acid component valve of a No. 4 chromatographic column, forming an independent chromatographic separation area from the No. 1 chromatographic column to the No. 6 chromatographic column, enabling eluent to flow in the direction from the No. 1 chromatographic column to the No. 6 chromatographic column, enabling medium reserved components and strong reserved components to flow into a chromatographic system under the pushing of the eluent, and enabling medium reserved component saccharides to flow into a saccharide component valve at the tail of the No. 6 chromatographic column;
(c) after the step (b) is finished, switching an eluent inlet from the front end of the No. 1 chromatographic column to the front end of the No. 2 chromatographic column; the raw material inlet is switched from the front end of the No. 3 chromatographic column to the front end of the No. 4 chromatographic column; the inorganic acid component outlet is switched from the tail end of the No. 4 chromatographic column to the tail end of the No. 5 chromatographic column; the acetic acid component outlet or the saccharide component outlet is switched from the tail end of the No. 6 chromatographic column to the tail end of the No. 1 chromatographic column;
(d) after the step (c) is switched, repeating the step (a) and the step (b) for operation; after running each period, the position of each port is moved forward by one chromatographic column along the flowing direction of the eluent, and the initial position is recovered after 6 cycles are completed.
2. The method as claimed in claim 1, wherein the corn cob, bagasse, straw, eucalyptus wood or birch wood of the agricultural and forestry waste is subjected to crushing, water washing and hot water leaching, and then hydrolyzed by 0.5-2.0% of inorganic acid to obtain xylose hydrolysate; filtering to remove colloid and solid, removing color substances by using activated carbon or resin, and evaporating and concentrating at 55-65 ℃ to obtain a raw material; in the raw materials, the concentration of saccharides is 50-70 mg/mL, the concentration of inorganic acid is 10-20 mg/mL, and the concentration of acetic acid is 5-10 mg/L.
3. The method according to claim 1, wherein the chromatographic column is insulated by circulating water with a concentric jacket at a temperature of 40-65 ℃; the front and the back of each chromatographic column are provided with a distributed electromagnetic valve bank, the eluent inlet, the raw material inlet, the saccharide outlet, the inorganic acid outlet and the acetic acid outlet are respectively provided with an eluent valve, a raw material valve, a saccharide component valve, an inorganic acid component valve and an acetic acid component valve, and the electromagnetic valve banks are controlled to be opened or closed by a PLC program to realize the simulated movement of raw materials or elution water, saccharides or acid components flowing out and a chromatographic stationary phase column; the adjacent chromatographic columns are connected by pipelines, and one-way valves are arranged in the pipelines.
4. The method according to claim 1, wherein the eluent has a flow rate of 4 to 6mL/min, the raw material has a flow rate of 2 to 3mL/min, the inorganic acid component has a flow rate of 3 to 4mL/min, the acetic acid component has a flow rate of 4 to 5mL/min, the saccharide component has a flow rate of 5 to 6mL/min, the time of step (a) is 4 to 7min, and the time of step (b) is 8 to 12 min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101516821A (en) * | 2006-08-18 | 2009-08-26 | 艾欧基能源公司 | Process for obtaining an organic salt or organic acid from an aqueous sugar stream |
| CN106632525A (en) * | 2016-12-27 | 2017-05-10 | 厦门欣赛科技有限公司 | Method for separating sulfuric acid from a glucose-xylose solution |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101516821A (en) * | 2006-08-18 | 2009-08-26 | 艾欧基能源公司 | Process for obtaining an organic salt or organic acid from an aqueous sugar stream |
| CN106632525A (en) * | 2016-12-27 | 2017-05-10 | 厦门欣赛科技有限公司 | Method for separating sulfuric acid from a glucose-xylose solution |
Non-Patent Citations (4)
| Title |
|---|
| Improving performance of a tandem simulated moving bed process for sugar separation by making a difference in the adsorbents and the column lengths of the two subordinate simulated moving bed units;Sungyong Mun;《J. Chromatogr. A》;20130105;第1277卷;第48-57页 * |
| Standing-Wave Design of Tandem SMB for linear Multicomponent Systems;Benjamin J. Hritzko et al.;《AIChE Journal》;20021231;第48卷(第12期);第2769-2787 * |
| 木糖水解液糖酸色谱分离技术基础研究;朱程旭;《中国优秀硕士学位论文全文数据库（电子期刊）》;20200115(第01期);第B014-1373页 * |
| 间歇模拟移动床色谱分离过程的建模与优化;杨永辉 等;《化学世界》;20171231(第3期);第182-189页 * |
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