CN111302892B - Method for preparing xylitol by using citrus peel - Google Patents
Method for preparing xylitol by using citrus peel Download PDFInfo
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- CN111302892B CN111302892B CN202010123603.6A CN202010123603A CN111302892B CN 111302892 B CN111302892 B CN 111302892B CN 202010123603 A CN202010123603 A CN 202010123603A CN 111302892 B CN111302892 B CN 111302892B
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- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 title claims abstract description 61
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000811 xylitol Substances 0.000 title claims abstract description 60
- 235000010447 xylitol Nutrition 0.000 title claims abstract description 60
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 title claims abstract description 60
- 229960002675 xylitol Drugs 0.000 title claims abstract description 60
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- 241000207199 Citrus Species 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005342 ion exchange Methods 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 10
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- 229920005989 resin Polymers 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
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- 150000001450 anions Chemical class 0.000 claims description 12
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- 150000001768 cations Chemical class 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
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- 230000003472 neutralizing effect Effects 0.000 claims description 6
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 5
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000003028 elevating effect Effects 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 208000002064 Dental Plaque Diseases 0.000 description 1
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- 229920002527 Glycogen Polymers 0.000 description 1
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- 241001093501 Rutaceae Species 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing xylitol by using citrus peel, which comprises the following steps: (1) hydrolysis; (2) neutralization; (3) decoloring; (4) ion exchange; (5) hydrogenation; (6) concentrating, crystallizing and separating. The invention provides a method for preparing xylitol, which has novel raw materials, mild reaction conditions, low production cost, less equipment investment and easy realization of industrialization.
Description
Technical Field
The invention relates to a preparation method of xylitol, in particular to a method for producing xylitol by utilizing agricultural waste citrus peel.
Background
Citrus plants of the Rutaceae subfamily are the prop industry in Zhejiang rural areas, and the citrus incomes in the main producing areas become important for peasant incomes. The citrus fruit serving as the traditional fruit in Zhejiang has a planting area of about 12 ten thousand hectares, the yield of the citrus fruit in full province exceeds 200 ten thousand tons, the citrus fruit accounts for 20% of the total amount of domestic wide-skin citrus fruits, and the citrus fruit can reach 10% of the total amount of world wide-skin citrus fruits, and 60% of the world orange can come from Zhejiang. For many years, citrus production in Zhejiang province was the first three nationally, and single production was the first nationally. Along with the rapid increase of the yield of citrus fruit in China, the citrus fruit is in a state of being supplied and demanded, and the Zhejiang citrus fruit industry faces a great challenge. At present, the research on oranges has the problems of single product and shorter industrial chain, but the orange peel residues accounting for more than 30% of the total amount of the oranges are not fully utilized, so that the resources are wasted greatly, and the environment is polluted seriously.
Xylitol is an intermediate of human body carbohydrate metabolism, can be absorbed and utilized by tissues through cell membranes without insulin promotion under the condition of lacking insulin to influence carbohydrate metabolism in vivo, is supplied to cells for nutrition and energy, does not cause the rise of blood sugar value, eliminates three or more symptoms after being taken by diabetics, and is a nutritional sugar substitute most suitable for diabetics to eat; xylitol can promote synthesis of hepatic glycogen, blood sugar will not rise, and has effects of improving liver function and resisting fatty liver for liver disease patients; the caries preventing property of xylitol is best among all sweeteners, it is not fermented by caries-producing bacteria in the oral cavity, and it can inhibit the growth of streptococcus and the production of acid, prevent caries and reduce the production of dental plaque. The global sales of xylitol have grown by 500% since the 90 s of the last century. At present, the annual demand of the international market is 20 ten thousand tons, but the annual output is only about 7 ten thousand tons. The domestic market capacity is about 2.5 ten thousand tons/year, and in recent years, along with the increase of contradiction between supply and demand, the price of xylitol has been continuously increased.
Disclosure of Invention
In order to obtain xylitol with high quality and low cost, the invention provides a preparation method of xylitol, which has the advantages of novel raw materials, mild reaction conditions, low production cost and less equipment investment, and is easy to realize industrialization.
The invention adopts the following technical scheme:
a method for preparing xylitol by using citrus peel, which comprises the following steps:
(1) Hydrolysis: cleaning raw material citrus peel, drying, crushing, placing in a hydrolysis kettle, adding water with the mass of 3-5 times of that of the raw material citrus peel, boiling for 80-120 min, draining, adding sulfuric acid with the mass of 0.5-0.8 wt% of that of the raw material citrus peel, and hydrolyzing for 3-5 h at the temperature of 120-130 ℃ and under the pressure of 0.1-0.15 MPa to obtain hydrolysate;
(2) And (3) neutralization: heating the hydrolysate obtained in the step (1) to 75-80 ℃, and adding CaCO (CaCO) while stirring 3 Neutralizing the emulsion until the pH value is 3.5-4.0, preserving the temperature for 60-90 min, and filtering to remove residues to obtain a sugar solution;
(3) Decoloring: concentrating the sugar solution obtained in the step (2) under reduced pressure to 1/5-1/7 of the original volume, filtering out precipitated solid, wherein the solid is CaSO 4 Heating to 75-80 ℃, regulating the pH to 2.5-3.5, adding active carbon while stirring for decoloring, and filtering the active carbon after decoloring to obtain decolored sugar solution;
(4) Ion exchange: carrying out ion exchange treatment on the decolorized sugar solution obtained in the step (3), and carrying out cross ion exchange treatment by adopting 001 x 7 strong acid cation resin and D296R or D201 strong base porous anion resin, wherein the cross ion exchange treatment method comprises the following steps: firstly, carrying out ion exchange by using the cation resin, then carrying out ion exchange by using the anion resin, and repeating the ion exchange for 2-3 times with the ion exchange as a period to obtain sugar solution after ion exchange;
(5) Hydrogenation: adding a catalyst into the sugar solution obtained in the step (4) after ion exchange, heating to 110-125 ℃, adjusting the pH to 7.5-8.5, introducing hydrogen/nitrogen with the hydrogen volume concentration of 10-12% for hydrogenation reaction, and controlling the reaction pressure to 65-85 kg/cm 2 The reaction time is 50-70 h, and after the reaction is finished, the catalyst is filtered out to obtain hydrogenated sugar solution; wherein the catalyst is selected from nickel or ruthenium carbon catalyst, the loading capacity of the ruthenium carbon catalyst is 5%, and the mass dosage of the catalyst is 2.5% -5.5% of the mass of the sugar solution;
(6) Concentrating, crystallizing and separating: evaporating and concentrating the hydrogenated sugar solution obtained in the step (5), wherein the evaporating and concentrating steps are as follows: the method comprises the steps of firstly concentrating sugar solution to a xylitol content of 48-52 wt% under the condition that the vacuum degree is 690-710 mm Hg and the temperature is 48-55 ℃, secondly, adopting an elevating film evaporator to increase the vacuum degree to 650-680 mm Hg and the temperature to 70-75 ℃, discharging when the sugar solution is concentrated to a xylitol content of 85-90 wt%, pressing into a crystallizer, adding xylitol as seed crystal when the temperature is reduced to 60-70 ℃, slowly stirring for crystallization, cooling to the room temperature at a cooling rate of 0.8-1.2 ℃/h, and filtering and separating to obtain xylitol and mother liquor.
In the step (1), the citrus peel is dried and crushed until the granularity is 2-5 mm.
Still further, in the step (2), caCO was added because the hydrolysate still contained residual sulfuric acid and had a pH of about 2.5 3 Neutralization of the emulsion, preferably said CaCO 3 The Baume degree of the emulsion is 15-17 degrees.
Further, in the step (3), since the concentrated sugar solution has a darker color, the activated carbon is used for the decoloring treatment, and preferably the mass amount of the activated carbon is 8% to 12% of the mass of the sugar solution, and the transparency (refractive index) of the decolored sugar solution is usually 30% to 40%.
Preferably, in the step (4), the sugar solution is further purified by ion exchange treatment, so that the transparency (refraction) of the sugar solution can reach 93% -97%, and the sugar solution is colorless and transparent.
In the step (5), the carbonyl group of xylose contained in the sugar solution is converted into a hydroxyl group by hydrogenation.
In the step (6), when the sugar solution is concentrated, the xylitol content in the sugar solution is determined by ultraviolet spectrophotometry.
In the step (6), the obtained mother liquor is a byproduct of crystallization separation of finished xylitol, and 1t of mother liquor containing 70wt% of xylitol can be obtained per 1t of finished product, and the mother liquor contains more impurities and has low purity and brown yellow color, wherein the mother liquor contains a small amount of arabitol, sorbitol, mannitol and other miscellaneous alcohols besides most xylitol, and has certain economic value. Thus, it is recommended to recover the mother liquor obtained by: the mother liquor is decolorized by active carbon, then is subjected to cross ion exchange treatment by 001 x 7 strong acid cation resin and D296R strong base porous anion resin, and finally is concentrated, crystallized (crystal growing time is prolonged, crystal grains are thinned), filtered and separated out, so that the xylitol remained in the mother liquor can be recovered, the purity of the obtained xylitol meets the standard, and the recovery rate is 30-40 wt% of the mother liquor.
In the present invention, the inventors tried to produce xylitol using citrus produced in Zhejiang province as a raw material, so as to meet the increasing demands of xylitol market. The traditional raw materials for producing xylitol use corncob, which is unfavorable for the production of south enterprises in China, and the corncob pigment content is high, which is unfavorable for the decolorization treatment. In order to reduce the cost, the invention adopts citrus peel as a raw material to produce xylitol.
Compared with the prior art, the invention has the beneficial effects that:
1) The citrus peel is used as a raw material, and related reports and applications are not found at home and abroad;
2) The raw material pigment content is low, the traditional xylitol production raw material multi-purpose corncob has the advantages that the pigment content difference enables the decoloring process to be simple, the using amount of a decoloring agent is reduced, the burden is reduced for subsequent process purification, the decoloring cost in the xylitol production is about 50% of the whole cost, and the cost is greatly reduced;
3) The specific surface area of the citrus peel is far greater than that of the corncob, and the specific surface area of the corncob is about 1300m 2 The specific surface area of the citrus peel per gram is about 1500m 2 And/g, the citrus peel has large specific surface area and is easy to hydrolyze, and when the citrus peel acts with a catalyst, the mass transfer and heat transfer effects are obvious, the catalysis time can be shortened, and the catalysis effect can be improved.
Description of the embodiments
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
example 1
A method for preparing xylitol by using citrus peel, which takes citrus peel as a raw material, comprising the following steps:
(1) Hydrolysis
Cleaning the selected citrus peel with a cleaning machine, drying and crushing, putting 100g of crushed citrus peel (with granularity of 2 mm) into a hydrolysis kettle, adding 300g of water, heating to 100 ℃, boiling for 90min, draining, adding 500g of sulfuric acid with 0.6wt% again, heating to 121 ℃, and hydrolyzing for 3h under the pressure condition of 0.12MPa to obtain hydrolysate;
(2) Neutralization
The obtained hydrolysate still contains residual sulfuric acid, and has pH of about 2.5, and CaCO with Baume degree of 15 degrees is added 3 The emulsion is neutralized, and the specific steps are as follows: adding the hydrolysate into a neutralization tank, heating to 75 ℃, and adding the CaCO while stirring 3 Regulating the pH of the emulsion to 3.5, fully precipitating, neutralizing, preserving heat for 60 minutes, and filtering to remove residues to obtain a sugar solution;
(3) Decoloring (decoloring)
Evaporating the deslagged sugar solution under reduced pressure, concentrating to the original volume1/6, and precipitating CaSO 4 Filtering;
the concentrated sugar solution has darker color, and is decolorized by using 8g of activated carbon: heating the sugar solution to 75 ℃, regulating the pH value to 2.5, adding active carbon while stirring for decoloring, and filtering the active carbon after decoloring to obtain decolored sugar solution with transparency (refractive index) of 35%;
(4) Ion exchange
In order to further purify sugar solution, ion exchange is carried out, 001X 7 type strong acid cation resin and D296R type strong base porous anion resin are selected for cross ion exchange treatment, the diameter of a chromatographic column is 4cm, the height of a column bed is 42cm, and the flow rate of xylitol liquid is controlled to be 1.5mL/cm 2 Min. The method for the cross ion exchange treatment comprises the following steps: firstly, carrying out ion exchange by using the cation resin, then carrying out ion exchange by using the anion resin, and repeating the ion exchange for 2 times in a period, so that the transparency (refraction) of the sugar solution reaches about 95%, and the sugar solution is colorless and transparent;
(5) Hydrogenation
Adding 3g nickel catalyst (CAS No. 7440-02-0, model: HRKJ4-RTH-311, western-style instrument (Beijing) technology Co., ltd.) into 100g sugar solution subjected to ion exchange treatment, heating to 110deg.C, adjusting pH to 7.5, introducing hydrogen/nitrogen with hydrogen volume concentration of 10% for hydrogenation reaction, and controlling reaction pressure at 70kg/cm 2 The reaction time is 60min, so that the carbonyl of xylose is changed into hydroxyl, and after the reaction is finished, the catalyst is filtered out, so that hydrogenated sugar solution is obtained;
(6) Concentrating, crystallizing and separating
Evaporating and concentrating the obtained hydrogenated sugar solution, wherein the evaporating and concentrating steps are as follows: concentrating the sugar solution to the xylitol content of 50wt% under the condition of the vacuum degree of 700mm Hg and the temperature of 50 ℃, secondly, adopting an elevating film evaporator to increase the vacuum degree to 660mm Hg, heating to 70 ℃, discharging when the xylitol content is 85wt% in the sugar solution, pressing into a crystallizer, adding 1g of xylitol as seed crystal when the temperature is reduced to 65 ℃, slowly stirring for crystallization, reducing the temperature to room temperature at the cooling rate of 1 ℃/h, filtering and separating to obtain a product, and measuring the xylitol to 18.27g and the mother liquor to 20mL by adopting an ultraviolet-visible spectrophotometry;
the mother liquor is recovered, and the recovery method comprises the following steps: the mother liquor is decolorized by using 2g of active carbon, then is subjected to cross ion exchange treatment by using 001 x 7 type strong acid cationic resin and D296R type strong base porous anion resin, and finally is concentrated, crystallized, filtered and collected to separate out crystals, thus 1.23g of xylitol remained in the mother liquor can be recovered.
Example 2
A method for preparing xylitol by using citrus peel, which takes citrus peel as a raw material, comprising the following steps:
(1) Hydrolysis
Cleaning selected citrus peel with a cleaning machine, drying, crushing, putting 100g of crushed citrus peel (with granularity of 4 mm) into a hydrolysis kettle, adding 400g of water, heating to 100 ℃ and boiling for 100min, draining, adding 550g of 0.80wt% sulfuric acid, heating to 125 ℃, and hydrolyzing for 4h under the pressure condition of 0.1MPa to obtain hydrolysate;
(2) Neutralization
The obtained hydrolysate still contains residual sulfuric acid, and has pH of about 2.5, and therefore CaCO with Baume degree of 16 degrees is added 3 The emulsion is neutralized, and the specific steps are as follows: adding the hydrolysate into a neutralization tank, heating to 78 ℃, and adding the CaCO while stirring 3 Regulating the pH of the emulsion to 3.8, fully precipitating, neutralizing, preserving heat for 70 minutes, and filtering to remove residues to obtain a sugar solution;
(3) Decoloring (decoloring)
Evaporating the deslagged sugar solution under reduced pressure, concentrating to 1/5 of the original volume, and separating out CaSO 4 Filtering;
the concentrated sugar solution has darker color, and is decolorized by using 8.5g of activated carbon: heating the sugar solution to 78 ℃, regulating the pH value to 3, adding active carbon while stirring for decoloring, and filtering the active carbon after decoloring to obtain decolored sugar solution with the transparency (refractive index) of 38%;
(4) Ion exchange
Ion exchange is required to further purify the sugar solutionSelecting 001 x 7 strong acid cation resin and D296R strong alkali porous anion resin for cross ion exchange treatment, wherein the diameter of a chromatographic column is 4cm, the height of a column bed is 42cm, and the flow rate of xylitol liquid is controlled to be 1.5mL/cm 2 Min. The method for the cross ion exchange treatment comprises the following steps: firstly, carrying out ion exchange by using the cation resin, then carrying out ion exchange by using the anion resin, and repeating the ion exchange for 3 times in a period, so that the transparency (refraction) of the sugar solution reaches 96%, and the sugar solution is colorless and transparent;
(5) Hydrogenation
Adding 2.5g ruthenium-carbon catalyst (CAS No.:7440-18-8, product No. 1007433, gray Seiya chemical technology Co., ltd.) with 5% load into 100g sugar solution subjected to ion exchange treatment, heating to 118 deg.C, adjusting pH to 7.7, introducing hydrogen/nitrogen with 11% hydrogen volume concentration for hydrogenation reaction, and controlling reaction pressure at 65kg/cm 2 The reaction time is 70min, so that the carbonyl of xylose is changed into hydroxyl, and after the reaction is finished, the catalyst is filtered out, so that hydrogenated sugar solution is obtained;
(6) Concentrating, crystallizing and separating
Evaporating and concentrating the obtained hydrogenated sugar solution, wherein the evaporating and concentrating steps are as follows: concentrating the sugar solution to 48wt% of xylitol at a temperature of 48 ℃ under a vacuum degree of 690mm Hg, and then, adopting an elevating film evaporator to raise the vacuum degree to 650mm Hg, raising the temperature to 75 ℃, discharging when the sugar solution is concentrated to 88wt% of xylitol, pressing into a crystallizer, adding 1g of xylitol as seed crystal when the temperature is lowered to 60 ℃, slowly stirring for crystallization, cooling to room temperature at a cooling rate of 1.2 ℃/h, filtering and separating to obtain a product, and measuring 16.9g of xylitol and 20mL of mother liquor by adopting an ultraviolet-visible spectrophotometry;
the mother liquor was recovered in the same manner as in example 1 to obtain 1.36g of xylitol remaining in the mother liquor.
Example 3
A method for preparing xylitol by using citrus peel, which takes citrus peel as a raw material, comprising the following steps:
(1) Hydrolysis
Cleaning selected citrus peel with a cleaning machine, drying, crushing, putting 100g of crushed citrus peel (with granularity of 5 mm) into a hydrolysis kettle, adding 500g of water, heating to 100 ℃ and boiling for 120min, draining, adding 600g of 1wt% sulfuric acid, heating to 130 ℃, and hydrolyzing for 5h under the pressure condition of 0.15MPa to obtain hydrolysate;
(2) Neutralization
The obtained hydrolysate still contains residual sulfuric acid, and has pH of about 2.5, and CaCO with Baume degree of 15 degrees is added 3 The emulsion is neutralized, and the specific steps are as follows: adding the hydrolysate into a neutralization tank, heating to 80 ℃, and adding the CaCO while stirring 3 Regulating the pH of the emulsion to 4.0, fully precipitating, neutralizing, preserving heat for 90 minutes, and filtering to remove residues to obtain a sugar solution;
(3) Decoloring (decoloring)
Evaporating the deslagged sugar solution under reduced pressure, concentrating to 1/7 of the original volume, and separating out CaSO 4 Filtering;
the concentrated sugar solution has darker color, and is decolorized by using 8.0g of activated carbon: heating the sugar solution to 80 ℃, regulating the pH value to 3.5, adding active carbon while stirring for decoloring, and filtering the active carbon after decoloring to obtain decolored sugar solution with the transparency (refractive index) of 37%;
(4) Ion exchange
In order to further purify sugar solution, ion exchange is carried out, 001X 7 type strong acid cation resin and D296R type strong base porous anion resin are selected for cross ion exchange treatment, the diameter of a chromatographic column is 4cm, the height of a column bed is 42cm, and the flow rate of xylitol liquid is controlled to be 1.5mL/cm 2 Min. The method for the cross ion exchange treatment comprises the following steps: firstly, carrying out ion exchange by using the cation resin, then carrying out ion exchange by using the anion resin, and repeating the ion exchange for 3 times in a period, so that the transparency (refraction) of the sugar solution reaches 96%, and the sugar solution is colorless and transparent;
(5) Hydrogenation
5.5g of nickel catalyst (CAS No.:7440-02-0, model: HRKJ4-RTH-311, western instrument) was added to 100g of the ion-exchanged sugar solutionBeijing) science and technology Co., ltd.) is heated to 125 ℃, the pH value is adjusted to 8.5, hydrogen/nitrogen with the volume concentration of 12% is introduced to carry out hydrogenation reaction, and the reaction pressure is controlled at 85kg/cm 2 The reaction time is 50min, so that the carbonyl of xylose is changed into hydroxyl, and after the reaction is finished, the catalyst is filtered out, so that hydrogenated sugar solution is obtained;
(6) Concentrating, crystallizing and separating
Evaporating and concentrating the obtained hydrogenated sugar solution: the evaporation concentration is divided into two steps: concentrating the sugar solution to the xylitol content of 52% under the condition of the vacuum degree of 710mm Hg and the temperature of 55 ℃, in the second step, adopting an elevating film evaporator, increasing the vacuum degree to 680mm Hg, increasing the temperature to 74 ℃, discharging when the sugar solution is concentrated to the xylitol content of 90%, pressing into a crystallizer, adding 1g of xylitol as seed crystals when the temperature is reduced to 70 ℃, slowly stirring for crystallization, reducing the temperature to room temperature at the cooling rate of 0.21 ℃/h, filtering and separating to obtain a product, and measuring 18.72g of xylitol and 20mL of mother liquor by adopting an ultraviolet-visible spectrophotometry;
the mother liquor was recovered in the same manner as in example 1 to obtain 0.94g of xylitol remaining in the mother liquor.
Claims (1)
1. A method for preparing xylitol by using citrus peel, which is characterized by comprising the following steps:
(1) Hydrolysis: cleaning raw material citrus peel, drying, crushing, placing in a hydrolysis kettle, adding water with the mass of 3-5 times of that of the raw material citrus peel, boiling for 80-120 min, draining, adding sulfuric acid with the mass of 0.5-0.8 wt% of that of the raw material citrus peel, and hydrolyzing for 3-5 h at the temperature of 120-130 ℃ and under the pressure of 0.1-0.15 MPa to obtain hydrolysate;
(2) And (3) neutralization: heating the hydrolysate obtained in the step (1) to 75-80 ℃, and adding CaCO (CaCO) while stirring 3 Neutralizing the emulsion until the pH value is 3.5-4.0, preserving the temperature for 60-90 min, and filtering to remove residues to obtain a sugar solution;
(3) Decoloring: concentrating the sugar solution obtained in the step (2) under reduced pressure to 1/5-1/7 of the original volume, filtering out precipitated solid, wherein the solid is CaSO 4 Heating to 75-80 ℃, adjusting the pH to 2.5-3.5, stirringAdding activated carbon while stirring for decoloring, and filtering the activated carbon after decoloring to obtain decolored sugar solution;
(4) Ion exchange: carrying out ion exchange treatment on the decolorized sugar solution obtained in the step (3), and carrying out cross ion exchange treatment by adopting 001 x 7 type strong acid cation resin and D296R type strong base porous anion resin, wherein the cross ion exchange treatment method comprises the following steps: firstly, carrying out ion exchange by using the cation resin, then carrying out ion exchange by using the anion resin, and repeating the ion exchange for 2-3 times with the ion exchange as a period to obtain sugar solution after ion exchange;
(5) Hydrogenation: adding a catalyst into the sugar solution obtained in the step (4) after ion exchange, heating to 110-125 ℃, adjusting the pH to 7.5-8.5, introducing hydrogen/nitrogen with the hydrogen volume concentration of 10-12% for hydrogenation reaction, and controlling the reaction pressure to 65-85 kg/cm 2 The reaction time is 50-70 h, and after the reaction is finished, the catalyst is filtered out to obtain hydrogenated sugar solution; wherein the catalyst is selected from nickel or ruthenium carbon catalyst, the loading capacity of the ruthenium carbon catalyst is 5%, and the mass dosage of the catalyst is 2.5% -5.5% of the mass of the sugar solution;
(6) Concentrating, crystallizing and separating: evaporating and concentrating the hydrogenated sugar solution obtained in the step (5), wherein the evaporating and concentrating steps are as follows: concentrating the sugar solution to a xylitol content of 48-52 wt% under the condition that the vacuum degree is 690-710 mm Hg and the temperature is 48-55 ℃, adopting an elevating film evaporator to increase the vacuum degree to 650-680 mm Hg, heating to 70-75 ℃, discharging when the sugar solution is concentrated to a xylitol content of 85-90 wt%, pressing into a crystallizer, adding xylitol as seed crystal when the temperature is reduced to 60-70 ℃, slowly stirring for crystallization, cooling to room temperature at a cooling rate of 0.8-1.2 ℃/h, and filtering and separating to obtain xylitol and mother liquor;
in the step (1), the citrus peel is dried and then crushed until the granularity is 2-5 mm;
in the step (2), caCO is added 3 Neutralizing the emulsion, wherein the CaCO 3 The Baume degree of the emulsion is 15-17 ℃;
in the step (3), activated carbon is used for decoloring, the mass consumption of the activated carbon is 8% -12% of the mass of the sugar solution, and the transparency of the decolored sugar solution is 30% -40%;
in the step (4), the sugar solution is further purified through ion exchange treatment, so that the transparency of the sugar solution can reach 93% -97%, and the sugar solution is colorless and transparent;
in the step (5), the carbonyl group of xylose contained in the sugar solution is changed into a hydroxyl group through hydrogenation reaction;
in the step (6), when the sugar solution is concentrated, the xylitol content in the sugar solution is measured by an ultraviolet spectrophotometry;
in the step (6), the obtained mother liquor is a byproduct after crystallization and separation of finished xylitol, and the obtained mother liquor is recovered, and the recovery method comprises the following steps: the method comprises the steps of decoloring mother liquor by using active carbon, carrying out cross ion exchange treatment on the mother liquor by using 001 x 7 type strong acid cationic resin and D296R type strong alkali porous anionic resin, concentrating, crystallizing, filtering, collecting precipitated crystals, and recovering the residual xylitol in the mother liquor, wherein the purity of the obtained xylitol meets the standard, and the recovery rate is 30-40 wt% of the mother liquor.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4066711A (en) * | 1976-03-15 | 1978-01-03 | Suomen Sokeri Osakeyhtio (Finnish Sugar Company) | Method for recovering xylitol |
| CN103608450A (en) * | 2011-05-06 | 2014-02-26 | 索拉兹米公司 | Genetically engineered microorganisms that metabolize xylose |
| CN104761432A (en) * | 2015-03-09 | 2015-07-08 | 浙江工业大学 | Method for preparing xylitol by utilizing winter bamboo shoot shells |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4066711A (en) * | 1976-03-15 | 1978-01-03 | Suomen Sokeri Osakeyhtio (Finnish Sugar Company) | Method for recovering xylitol |
| CN103608450A (en) * | 2011-05-06 | 2014-02-26 | 索拉兹米公司 | Genetically engineered microorganisms that metabolize xylose |
| CN104761432A (en) * | 2015-03-09 | 2015-07-08 | 浙江工业大学 | Method for preparing xylitol by utilizing winter bamboo shoot shells |
Non-Patent Citations (1)
| Title |
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| 吴春霞.柑橘皮渣发酵生产木糖醇的研究.《中国优秀硕士学位论文全文数据库（工程科技I辑）》.2008,(第9期),B024-77. * |
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