CN111302892A - Method for preparing xylitol by using citrus peel - Google Patents
Method for preparing xylitol by using citrus peel Download PDFInfo
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- CN111302892A CN111302892A CN202010123603.6A CN202010123603A CN111302892A CN 111302892 A CN111302892 A CN 111302892A CN 202010123603 A CN202010123603 A CN 202010123603A CN 111302892 A CN111302892 A CN 111302892A
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- sugar solution
- xylitol
- ion exchange
- mother liquor
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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 68
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000811 xylitol Substances 0.000 title claims abstract description 67
- 235000010447 xylitol Nutrition 0.000 title claims abstract description 67
- 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 67
- 229960002675 xylitol Drugs 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 25
- 241000207199 Citrus Species 0.000 title claims description 38
- 235000020971 citrus fruits Nutrition 0.000 title claims description 37
- 238000005342 ion exchange Methods 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 239000012452 mother liquor Substances 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 25
- 238000010438 heat treatment 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 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000413 hydrolysate Substances 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 12
- 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 10
- 239000013078 crystal Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000004042 decolorization Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 229910052925 anhydrite Inorganic materials 0.000 claims description 5
- 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
- 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
- 238000001816 cooling Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000002798 spectrophotometry method Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 102000004877 Insulin Human genes 0.000 description 2
- 108090001061 Insulin Proteins 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 230000023852 carbohydrate metabolic process Effects 0.000 description 2
- 235000021256 carbohydrate metabolism Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 208000002925 dental caries Diseases 0.000 description 2
- 206010012601 diabetes mellitus Diseases 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940125396 insulin Drugs 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 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
- 208000004930 Fatty Liver Diseases 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- 206010019708 Hepatic steatosis Diseases 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 241001093501 Rutaceae Species 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000000675 anti-caries Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 210000000887 face Anatomy 0.000 description 1
- 208000010706 fatty liver disease Diseases 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 231100000240 steatosis hepatitis Toxicity 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
Abstract
A method for preparing xylitol by using orange peels comprises the following steps: (1) hydrolyzing; (2) neutralizing; (3) decoloring; (4) ion exchange; (5) hydrogenation; (6) concentrating, crystallizing and separating. The invention provides the method for preparing the xylitol, which has the advantages of 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 using agricultural waste citrus peel.
Background
Citrus plants of Rutaceae of Citrus are the industry of support columns in Zhejiang countryside, and the income of oranges in the main production area becomes an important income for farmers. The citrus is used as the traditional fruit in Zhejiang, the planting area is about 12 million hectares, the citrus yield in the whole province exceeds 200 million tons, the citrus yield accounts for 20 percent of the total amount of the citrus with broad peel in China, 10 percent of the total amount of the citrus with broad peel in the world can be achieved, and 60 percent of the citrus can in the world comes from Zhejiang. For many years, the citrus yield in Zhejiang province is the first three nationwide, and the yield per unit is the first nationwide. With the rapid increase of citrus production in China, citrus is gradually in a state of being over-supplied and over-demand, and Zhejiang citrus industry faces huge challenges. At present, the problems of single product and short industrial chain exist in the research of oranges, and the orange peel residues accounting for more than 30 percent of the total amount of the oranges are not fully utilized, so that the great waste of resources is caused, and the environment is seriously polluted. Currently, China is in a new historical stage for promoting socialist new rural construction, Zhejiang agriculture has a large population, and the development of citrus industry is beneficial to improving the income of farmers, providing a large number of employment posts and promoting new rural construction.
Xylitol is an intermediate of carbohydrate metabolism of a human body, can permeate cell membranes without being promoted by insulin under the condition that the carbohydrate metabolism is influenced by the lack of the insulin in the body, is absorbed and utilized by tissues, provides nutrition and energy for cells, does not cause the rise of blood sugar value, eliminates more than three symptoms after being taken by a diabetic patient, and is a nutritional sugar substitute which is most suitable for the diabetic patient to eat; xylitol can promote synthesis of glycogen, blood sugar can not rise, and liver function and fatty liver resistance of patients with liver diseases can be improved; the anti-caries properties of xylitol are most effective in all sweeteners, are not utilized by the bacteria responsible for caries in the oral cavity, and are capable of inhibiting streptococcal growth and acid production, preventing caries and reducing plaque production. The global sales of xylitol has increased by 500% in whole since the last 90 s. 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 production capacity of the domestic market is about 2.5 ten thousand tons per year, and in recent years, the price of the xylitol is continuously increased along with the increase of the contradiction between supply and demand.
Disclosure of Invention
In order to obtain xylitol with high quality and low cost, the invention provides the xylitol preparation method which has novel raw materials, mild reaction conditions, low production cost, less equipment investment and easy realization of industrialization.
The invention adopts the following technical scheme:
a method for preparing xylitol by using orange peels comprises the following steps:
(1) hydrolysis: cleaning raw material orange peel, drying, crushing, placing in a hydrolysis kettle, adding water which is 3-5 times of the mass of the raw material orange peel, boiling for 80-120 min, draining, adding 0.5-0.8 wt% sulfuric acid which is 5-6 times of the mass of the raw material orange peel, and hydrolyzing for 3-5 h at 120-130 ℃ under the condition of 0.1-0.15 MPa to obtain hydrolysate;
(2) neutralizing: heating the hydrolysate obtained in the step (1) to 75-80 ℃, and adding CaCO while stirring3Neutralizing the emulsion until the pH is 3.5-4.0, preserving the temperature for 60-90 min, and filtering and removing slag to obtain sugar liquid;
(3) and (3) decoloring: concentrating the sugar solution obtained in the step (2) under reduced pressure to 1/5-1/7 times of the original volume, and filtering out precipitated solid which is CaSO4Heating to 75-80 ℃, adjusting the pH to 2.5-3.5, adding activated carbon while stirring for decoloring, and filtering the activated carbon after decoloring to obtain a decolored sugar solution;
(4) ion exchange: performing ion exchange treatment on the decolorized sugar solution obtained in the step (3), and performing cross ion exchange treatment by using 001 × 7 type strong acid cation resin and D296R or D201 type strong base porous anion resin, wherein the cross ion exchange treatment method comprises the following steps: 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 by taking the ion exchange as a period to obtain sugar liquor after ion exchange;
(5) hydrogenation: adding a catalyst into the sugar solution obtained after the ion exchange in the step (4), 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/cm2The reaction time is 50-70 h, and after the reaction is finished, filtering out the catalyst to obtain hydrogenated sugar solution; wherein the catalyst is selected from a nickel or ruthenium-carbon catalyst, the loading amount of the ruthenium-carbon catalyst is 5%, and the mass usage amount of the catalyst is 2.5-5.5% of the mass of the sugar solution;
(6) concentration, crystallization and separation: and (3) carrying out evaporation concentration on the hydrogenated sugar solution obtained in the step (5), wherein the evaporation concentration comprises two steps: firstly, under the conditions that the vacuum degree is 690-710 mm Hg and the temperature is 48-55 ℃, concentrating the sugar solution until the content of xylitol is 48-52 wt%, secondly, adopting a lifting film evaporator to increase the vacuum degree to 650-680 mm Hg, increasing the temperature to 70-75 ℃, concentrating the sugar solution until the content of xylitol is 85-90 wt%, discharging, pressing into a crystallizer, adding xylitol as seed crystal when the temperature is reduced to 60-70 ℃, slowly stirring for crystallization, reducing the temperature to room temperature at the cooling rate of 0.8-1.2 ℃/h, filtering and separating to obtain xylitol and mother liquor.
Further, in the step (1), the orange peel is dried and then crushed until the particle size is 2-5 mm.
Still further, in the step (2), because the hydrolysate still contains residual sulfuric acid and the pH value is about 2.5, CaCO is added3Neutralizing the emulsion, preferably with CaCO3The Baume degree of the emulsion is 15-17 degrees.
Furthermore, in the step (3), since the concentrated sugar solution has a dark color, activated carbon is used for decoloring, 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 sugar solution after decoloring is usually 30 to 40%.
Preferably, in the step (4), the sugar solution is further purified by ion exchange treatment, so that the transparency (refractive index) of the sugar solution is 93 to 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 a hydrogenation reaction.
In the step (6), when the sugar solution is concentrated, the content of xylitol in the sugar solution is measured by an ultraviolet spectrophotometry.
In the step (6), the obtained mother liquor is a byproduct obtained after crystallization and separation of the finished product xylitol, 1t of mother liquor containing 70 wt% of xylitol can be obtained when 1t of the finished product is prepared, the mother liquor contains more impurities, has low purity and is brown yellow, and contains a small amount of arabitol, sorbitol, mannitol and other fusel besides most of xylitol, but still has a certain economic value. Therefore, it is recommended to recover the mother liquor obtained by the following method: firstly, decoloring the mother liquor by using activated carbon, then carrying out cross ion exchange treatment on the mother liquor by using 001-7 type strong acid cation resin and D296R strong base porous anion resin, finally concentrating, crystallizing (the crystal growing time is prolonged, the crystal grains become thin), filtering, collecting and separating out crystals, namely 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.
In the invention, the inventor tries to produce xylitol by taking citrus produced in Taizhou Zhejiang as a raw material so as to meet the increasing demand of the xylitol market. Corncobs are used as raw materials for producing xylitol in the prior art, which is not beneficial to the production of enterprises in south China, and the corncobs have high pigment content and are not beneficial to decoloring treatment. In order to reduce the cost, the invention adopts the citrus peel as the raw material to produce the xylitol.
Compared with the prior art, the invention has the beneficial effects that:
1) the citrus peel is used as a raw material, and no relevant report and application are found at home and abroad;
2) the pigment content of the raw material is low, the traditional xylitol production raw material is multi-purpose corncobs, the pigment content difference between the raw material and the corncobs ensures that the decoloring process is simple, the consumption of a decoloring agent is reduced, the burden of subsequent process purification is reduced, the decoloring cost in the xylitol production approximately accounts for 50 percent of the whole cost, and the cost is greatly reduced;
3) the specific surface area of the citrus peel is far larger than that of the corncob, and the specific surface area of the corncob is about 1300m2Per g, the specific surface area of the orange peel is about 1500m2The citrus peel has large specific surface area, is easy to hydrolyze, has obvious mass and heat transfer effects when being used with a catalyst, and can shorten the catalysis time and improve the catalysis effect.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1
A method for preparing xylitol by using citrus peels, which selects the citrus peels as raw materials, comprises the following steps:
(1) hydrolysis
Cleaning selected citrus peel by using a cleaning machine, drying and crushing, putting 100g of crushed citrus peel (the granularity is 2mm) into a hydrolysis kettle, adding 300g of water, heating to 100 ℃, boiling for 90min, draining, adding 500g of 0.6 wt% sulfuric acid, 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 a pH value of about 2.5, so that CaCO with a Baume degree of 15 degrees is added3Neutralizing the emulsion, and specifically comprising the following steps: adding the hydrolysate into a neutralization tank, heating to 75 ℃, and adding the CaCO while stirring3Regulating pH to 3.5 to obtain emulsion, precipitating, neutralizing, maintaining for 60min, filtering, and removing residue to obtain sugar solution;
(3) decolorization of
Evaporating the sugar solution after deslagging under reduced pressure, concentrating to 1/6 of the original volume, and separating out CaSO4Filtering;
the concentrated sugar solution is darker in color, and 8g of active carbon is used for decolorization: heating the sugar solution to 75 ℃, regulating the pH value to 2.5, adding activated carbon while stirring for decoloring, and filtering the activated carbon after decoloring to obtain the decolored sugar solution with the transparency (refractivity) of 35%;
(4) ion exchange
Ion exchange is carried out to further purify the sugar solution, and a 001 × 7 type strong acid cation resin and a D296R type strong base porous anion resin are selected for carrying out cross ion exchange treatment, the diameter of a chromatographic column is 4cm, the height of the column bed is 42cm, and the flow rate of the xylitol solution is controlled to be 1.5mL/cm2Min. The method for the cross ion exchange treatment comprises the following steps: firstly, the cation resin is used for ion exchange, then the anion resin is used for ion exchange, and the ion exchange is repeated for 2 times with the cycle as a period, so that the transparency (refractive index) of the sugar solution reaches about 95 percent, and the sugar solution is colorless and transparent;
(5) hydrogenation of
Adding 3g nickel catalyst (CAS No. 7440-02-0, model: HRKJ4-RTH-311, Seiko instruments (Beijing) science and technology Co., Ltd.) into 100g sugar solution subjected to ion exchange treatment, heating to 110 deg.C, adjusting pH to 7.5, introducing hydrogen/nitrogen with 10% hydrogen volume concentration for hydrogenation reaction, and controlling reaction pressure at 70kg/cm2The reaction time is 60min, so that the carbonyl group of the xylose is changed into hydroxyl, and after the reaction is finished, the catalyst is filtered to obtain hydrogenated sugar solution;
(6) concentrating, crystallizing, and separating
And (3) carrying out evaporation concentration on the obtained hydrogenated sugar solution, wherein the evaporation concentration comprises two steps: step one, under the conditions of a vacuum degree of 700mm Hg and a temperature of 50 ℃, concentrating the sugar solution until the content of xylitol is 50 wt%, and step two, adopting a lifting film evaporator, increasing the vacuum degree to 660mm Hg, increasing the temperature to 70 ℃, concentrating the sugar solution until the content of xylitol is 85 wt%, discharging, 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 a cooling rate of 1 ℃/h, filtering and separating to obtain a product, and measuring the content of xylitol to be 18.27g and the volume of mother liquor to be 20mL by adopting an ultraviolet-visible spectrophotometry;
recovering the obtained mother liquor, wherein the recovery method comprises the following steps: firstly, 2g of activated carbon is used for decoloring the mother liquor, then 001 × 7 type strong acid cation resin and D296R type strong base porous anion resin are used for carrying out cross ion exchange treatment on the mother liquor, and finally, 1.23g of xylitol remained in the mother liquor can be recovered by concentrating, crystallizing, filtering and collecting precipitated crystals.
Example 2
A method for preparing xylitol by using citrus peels, which selects the citrus peels as raw materials, comprises the following steps:
(1) hydrolysis
Cleaning selected citrus peel by using a cleaning machine, drying and crushing, putting 100g of crushed citrus peel (the granularity is 4mm) into a hydrolysis kettle, adding 400g of water, heating to 100 ℃, boiling for 100min, draining, adding 550g of 0.80 wt% 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 a pH value of about 2.5, so that CaCO with a Baume degree of 16 degrees is added3Neutralizing the emulsion, and specifically comprising the following steps: adding the hydrolysate into a neutralization tank, heating to 78 ℃, and adding the CaCO while stirring3Regulating pH to 3.8 to obtain emulsion, precipitating, neutralizing, maintaining the temperature for 70min, and filtering to remove residue to obtain sugar solution;
(3) decolorization of
Evaporating the sugar solution after deslagging under reduced pressure, concentrating to 1/5 of the original volume, and separating out CaSO4Filtering;
the concentrated sugar solution is darker in color, and 8.5g of activated carbon is used for decolorization: heating the sugar solution to 78 ℃, regulating the pH value to 3, adding activated carbon while stirring for decoloring, filtering the activated carbon after decoloring, wherein the transparency (refractive index) of the decolored sugar solution is 38%;
(4) ion exchange
Ion exchange is carried out to further purify the sugar solution, and a 001 × 7 type strong acid cation resin and a D296R type strong base porous anion resin are selected for carrying out cross ion exchange treatment, the diameter of a chromatographic column is 4cm, the height of the column bed is 42cm, and the flow rate of the xylitol solution is controlled to be 1.5mL/cm2Min. The method for the cross ion exchange treatment comprises the following steps: firstly, the cation resin is used for ion exchange, then the anion resin is used for ion exchange, and the ion exchange is repeated for 3 times with the cycle as a cycle, so that the transparency (refractive index) of the sugar solution can reach 96 percent, and the sugar solution is colorless and transparent;
(5) hydrogenation of
Adding 2.5g of ruthenium-carbon catalyst (CASNO. 7440-18-8, product number: 1007433, Golay chemical technology Co., Ltd.) with the loading of 5% into 100g of sugar solution subjected to ion exchange treatment, heating to 118 ℃, adjusting the pH value to 7.7, introducing hydrogen/nitrogen with the hydrogen volume concentration of 11% for hydrogenation reaction, and controlling the reaction pressure to be 65kg/cm2The reaction time is 70min, so that the carbonyl group of the xylose is changed into hydroxyl, and after the reaction is finished, the catalyst is filtered to obtain hydrogenated sugar solution;
(6) concentrating, crystallizing, and separating
And (3) carrying out evaporation concentration on the obtained hydrogenated sugar solution, wherein the evaporation concentration comprises two steps: step one, under the conditions that the vacuum degree is 690mm Hg and the temperature is 48 ℃, concentrating the sugar solution until the content of xylitol is 48 wt%, and step two, adopting a lifting film evaporator, increasing the vacuum degree to 650mm Hg, increasing the temperature to 75 ℃, concentrating the sugar solution until the content of xylitol is 88 wt%, discharging, pressing into a crystallizer, adding 1g of xylitol as seed crystal when the temperature is reduced to 60 ℃, slowly stirring for crystallization, reducing the temperature to room temperature at the rate of 1.2 ℃/h, filtering and separating to obtain a product, and measuring the content of xylitol to be 16.9g and the volume of mother liquor to be 20mL 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 peels, which selects the citrus peels as raw materials, comprises the following steps:
(1) hydrolysis
Cleaning selected citrus peel by using a cleaning machine, drying and crushing, putting 100g of crushed citrus peel (the granularity is 5mm) into a hydrolysis kettle, adding 500g of water, heating to 100 ℃, boiling for 120min, draining, adding 600g of 1 wt% 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 a pH value of about 2.5, so that CaCO with a Baume degree of 15 degrees is added3Neutralizing the emulsion, and specifically comprising the following steps: adding the hydrolysate into a neutralization tank, heating to 80 ℃, and adding the CaCO while stirring3Regulating pH to 4.0 to obtain emulsion, precipitating, neutralizing, maintaining for 90min, and filtering to remove residue to obtain sugar solution;
(3) decolorization of
Evaporating the sugar solution after removing residues under reduced pressure, concentrating to 1/7 of original volume, and separating out CaSO4Filtering;
the concentrated sugar solution is darker in color, and 8.0g of activated carbon is used for decolorization: heating the sugar solution to 80 ℃, regulating and controlling the pH value to be 3.5, adding activated carbon while stirring for decoloring, and filtering the activated carbon after decoloring to obtain the decolored sugar solution with the transparency (refractivity) of 37%;
(4) ion exchange
Ion exchange is carried out to further purify the sugar solution, and a 001 × 7 type strong acid cation resin and a D296R type strong base porous anion resin are selected for carrying out cross ion exchange treatment, the diameter of a chromatographic column is 4cm, the height of the column bed is 42cm, and the flow rate of the xylitol solution is controlled to be 1.5mL/cm2Min. The method for the cross ion exchange treatment comprises the following steps: firstly, the cation resin is used for ion exchange, then the anion resin is used for ion exchange, and the ion exchange is repeated for 3 times with the cycle as a cycle, so that the transparency (refractive index) of the sugar solution can reach 96 percent, and the sugar solution is colorless and transparent;
(5) hydrogenation of
Adding 5.5g nickel catalyst (CAS No. 7440-02-0, model: HRKJ4-RTH-311, Seiko instruments (Beijing) science and technology Co., Ltd.) into 100g sugar solution subjected to ion exchange treatment, heating to 125 deg.C, adjusting pH to 8.5, introducing hydrogen/nitrogen with 12% hydrogen volume concentration for hydrogenation reaction, and controlling reaction pressure at 85kg/cm2The reaction time is 50min, so that the carbonyl group of the xylose is changed into hydroxyl, and after the reaction is finished, the catalyst is filtered to obtain hydrogenated sugar solution;
(6) concentrating, crystallizing, and separating
And (3) evaporating and concentrating the obtained hydrogenated sugar solution: the evaporation concentration is divided into two steps: firstly, concentrating the sugar solution until the content of xylitol is 52% under the conditions of a vacuum degree of 710mm Hg and a temperature of 55 ℃, secondly, adopting a lifting film evaporator, increasing the vacuum degree to 680mm Hg, increasing the temperature to 74 ℃, concentrating the sugar solution until the content of xylitol is 90%, discharging, pressing into a crystallizer, adding 1g of xylitol as seed crystal when the temperature is reduced to 70 ℃, slowly stirring for crystallization, reducing the temperature to room temperature at a 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 (8)
1. A method for preparing xylitol by using orange peels is characterized by comprising the following steps:
(1) hydrolysis: cleaning raw material orange peel, drying, crushing, placing in a hydrolysis kettle, adding water which is 3-5 times of the mass of the raw material orange peel, boiling for 80-120 min, draining, adding 0.5-0.8 wt% sulfuric acid which is 5-6 times of the mass of the raw material orange peel, and hydrolyzing for 3-5 h at 120-130 ℃ under the condition of 0.1-0.15 MPa to obtain hydrolysate;
(2) neutralizing: heating the hydrolysate obtained in the step (1) to 75-80 ℃, and adding CaCO while stirring3Neutralizing the emulsion until the pH is 3.5-4.0, preserving the temperature for 60-90 min, and filtering and removing slag to obtain sugar liquid;
(3) and (3) decoloring: concentrating the sugar solution obtained in the step (2) under reduced pressure to 1/5-1/7 times of the original volume, and filtering out precipitated solid which is CaSO4Heating to 75-80 ℃, adjusting the pH to 2.5-3.5, adding activated carbon while stirring for decoloring, and filtering the activated carbon after decoloring to obtain a decolored sugar solution;
(4) ion exchange: performing ion exchange treatment on the decolorized sugar solution obtained in the step (3), and performing cross ion exchange treatment by using 001 × 7 type strong acid cation resin and D296R or D201 type strong base porous anion resin, wherein the cross ion exchange treatment method comprises the following steps: 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 by taking the ion exchange as a period to obtain sugar liquor after ion exchange;
(5) hydrogenation: adding a catalyst into the sugar solution obtained after the ion exchange in the step (4), 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/cm2The reaction time is 50-70 h, and after the reaction is finished, filtering out the catalyst to obtain hydrogenated sugar solution; wherein the catalyst is selected from nickel or ruthenium carbon catalyst, the loading amount of the ruthenium carbon catalyst is 5 percent, and the mass usage amount of the catalystThe mass of the sugar solution is 2.5-5.5%;
(6) concentration, crystallization and separation: and (3) carrying out evaporation concentration on the hydrogenated sugar solution obtained in the step (5), wherein the evaporation concentration comprises two steps: firstly, under the conditions that the vacuum degree is 690-710 mm Hg and the temperature is 48-55 ℃, concentrating the sugar solution until the content of xylitol is 48-52 wt%, secondly, adopting a lifting film evaporator to increase the vacuum degree to 650-680 mm Hg, increasing the temperature to 70-75 ℃, concentrating the sugar solution until the content of xylitol is 85-90 wt%, discharging, pressing into a crystallizer, adding xylitol as seed crystal when the temperature is reduced to 60-70 ℃, slowly stirring for crystallization, reducing the temperature to room temperature at the cooling rate of 0.8-1.2 ℃/h, filtering and separating to obtain xylitol and mother liquor.
2. The method for preparing xylitol by using citrus peel as claimed in claim 1, wherein in the step (1), the citrus peel is dried and then crushed to have a particle size of 2-5 mm.
3. The method for preparing xylitol by using citrus peel as claimed in claim 1 or 2, wherein CaCO is added in the step (2)3Neutralizing the emulsion with CaCO3The Baume degree of the emulsion is 15-17 degrees.
4. The method for preparing xylitol by using citrus peels as claimed in claim 1 or 2, wherein in the step (3), activated carbon is used for decolorization, the mass amount of the activated carbon is 8-12% of the mass of the sugar solution, and the transparency of the sugar solution after decolorization is 30-40%.
5. The method for preparing xylitol according to claim 1 or 2, wherein in the step (4), the sugar solution is further purified by ion exchange treatment, so that the transparency of the sugar solution is 93-97%, and the sugar solution is colorless and transparent.
6. The method for producing xylitol according to claim 1 or 2, wherein in step (5), the carbonyl group of xylose contained in the sugar solution is changed to a hydroxyl group by hydrogenation.
7. The method for preparing xylitol according to claim 1 or 2, wherein in the step (6), when the sugar solution is concentrated, the content of xylitol in the sugar solution is measured by ultraviolet spectrophotometry.
8. The method for preparing xylitol by using citrus peels as claimed in claim 1 or 2, wherein in the step (6), the obtained mother liquor is a byproduct after the finished product xylitol is separated by crystallization, and the obtained mother liquor is recovered by a method comprising the following steps: firstly, decoloring the mother liquor by using activated carbon, then carrying out cross ion exchange treatment on the mother liquor by using 001-7 type strong acid cation resin and D296R strong base porous anion resin, finally concentrating, crystallizing, filtering and collecting precipitated crystals, thus 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 | A method of preparing xylitol by utilization of 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 | A method of preparing xylitol by utilization of winter bamboo shoot shells |
Non-Patent Citations (1)
| Title |
|---|
| 吴春霞: "柑橘皮渣发酵生产木糖醇的研究" * |
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