CN1236768A - Process for preparing D-sorbitol - Google Patents
Process for preparing D-sorbitol Download PDFInfo
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- CN1236768A CN1236768A CN98111312.5A CN98111312A CN1236768A CN 1236768 A CN1236768 A CN 1236768A CN 98111312 A CN98111312 A CN 98111312A CN 1236768 A CN1236768 A CN 1236768A
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- catalyst
- sorbitol
- glucose
- nickel
- prepared
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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 title claims abstract description 20
- 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 title claims abstract description 20
- 229960002920 sorbitol Drugs 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 16
- 239000008103 glucose Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000521 B alloy Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VFYPSWGDJSPEQI-UHFFFAOYSA-N [B].[P].[Ni] Chemical compound [B].[P].[Ni] VFYPSWGDJSPEQI-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- DTNVUQFDRPOYFY-UHFFFAOYSA-L nickel(2+);diacetate;hexahydrate Chemical class O.O.O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O DTNVUQFDRPOYFY-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A process for preparing D-sorbitol features that the D-sorbitol is prepared from glucose through catalytic hydrogenation in solvent by means of Ni-base non-crystal alloy catalyst. Its advantages are no self-burning of catalyst, easy preparing, no environmental pollution, and high conversion rate (up to 90% or more) and selectivity (88% or more) of glucose.
Description
The invention relates to preparation of D-sorbitol, in particular to preparation of D-sorbitol by catalytic hydrogenation of glucose.
D-sorbitol is a raw material for preparing vitamin C, sorbose, propylene glycol, synthetic resin and the like, is a bulk product and has a large demand. Currently, D-sorbitol is industrially produced by the liquid phase hydrogenation of glucose in the presence of a skeletal nickel catalyst. Wherein the application of the skeletal nickel catalyst is the technical key of the whole production process. Because the skeleton nickel catalyst is very active and unstable and can quickly spontaneously combust in the air, the catalyst is generally prepared into a semi-finished product firstly, namely the preparation process of the aluminum nickel catalyst with certain components is complicated,and the influence of operation factors on the activity of the catalyst is variable. In particular, it is necessary to use a large amount of strong alkali caustic soda in the alkali dissolution treatment, and the post-treatment process is difficult, and environmental pollution and public nuisance are likely to occur.
The invention aims to provide a method for preparing D-sorbitol by hydrogenating glucose in the presence of a catalyst, wherein the catalyst is easy to prepare, does not spontaneously combust and does not pollute the environment.
The purpose of the invention is realized by the following technical scheme.
The nickel-boron superfine amorphous alloy can be prepared by reducing nickel ions with potassium borohydride. The reaction equation is: depending on the manner in which the reaction solution is mixed, the salt solution and the potassium borohydride solution may be mixed and reacted by passing them co-currently through a y-tube mixing reaction [ see l.yiping et al j.magn.mater, 79(321)1989.]Alternatively, the salt solution is dropped into a potassium borohydride solution [ see D.S.Xue et al, J.Mater.Sci.Lett,9(1990)506.]Alternatively, a solution of potassium borohydride is dropped into a salt solution [ see S.Well et al, J.Phys. (c),1(1989)8199, and A, Inoue et al, Metal. trans. A,19A (1988)2315]. Catalysts of different boron content can be prepared by selection and control of the preparation conditions [ see j.van Wonterghem et al, Nature,322(1986)622, and z.hu et al, j.appl.phys.,70(1991)436.]. Vannin et al chemically prepared nickel-boron amorphous alloys have a boron content of 32 atom% or 33 atom% [ see Y.Fan et al, J.Mater.Sci.Lett, 12(1993)596 and Y.Fan et al, Chinese Sci.Bull.,40(1995)1.]. Shi Yi, similarly prepared Ni-B amorphous alloy has a boron content of 35 atom% [see Shi Yi, report on inorganic chemistry, 11(1995)1.]. In addition to boron-containing elements, amorphous alloys containing two types of metallic elements, such as nickel-phosphorus-boron, may be prepared. The relative amounts of boron and phosphorus can be varied by controlling the reaction conditions [ see J.Shen et al, J.appl.Phys.,71(1992)5217.]. The amorphous alloy of Van-Se-B is Ni73P11B11[ see fang-ning et al, proceedings of higher school chemistry, 15(1994)117.]。
Amorphous alloys have the characteristic of long-range disorder and short-range order. The material has the characteristics of amorphous alloy and ultrafine particles, so the material has good catalytic performance. For example, nickel-boron amorphous alloys can be used for hydrogenation of 1, 3-butadiene [ see Y.Okamoto et al, J.Catal.,74(1982)173], hydrogenation of cycloolefins [ see Y.Okamoto et al, J.Catal.,64(1980)397]), and hydrogenation of other olefins [ see J.Deng et al, appl.Catal.,37(1988)339], as well as for carbon monoxide hydrogenation [ see Y.Fan et al, in "Proc.8th China-Japan-USA Symposium on Catalysis",1993, Beijing, China].
The invention uses nickel-base amorphous alloy as catalyst to hydrogenate glucose to prepare D-sorbierite. The specific technical scheme is as follows:
a process for preparing D-sorbitol features that the glucose is hydrogenated in solvent in the presence of catalyst, which is non-crystalline Ni-B alloy or non-crystalline Ni-P-B alloy. The amount of the catalyst is 4-10% of the weight of the glucose.
The solvent for the above hydrogenation process may be water, ethanol or a water-ethanol mixed solvent. The reaction can be carried out at 90-150 ℃, and the hydrogen pressure of hydrogenation is 0.5-2.5 MPa.
By adopting the preparation method of the invention, the nickel-boron or nickel-phosphorus-boron amorphous alloy catalyst is easy to prepare, does not spontaneously combust, is safe, does not need strong alkali in the preparation process, and does not pollute the environment.
The invention is further illustrated by the following examples.
Example 1.
1.1 catalyst preparation
Preparing a series of nickel acetate hexahydrate solutions with the concentrations of 0.075M,0.125M,0.25M and 0.375M and potassium borohydride solutions with the concentrations of 0.75M and 2.5M respectively, and adding 60ml of the potassium borohydride solution with the concentration of 0.75M into 600ml of nickel salt solutions with different concentrations or adding 60ml of the potassium borohydride solution with the concentrations of 0.75M and 2.5M into 600ml of the nickel salt solution with the concentration of 0.125M under vigorous stirring. The preparation method comprises standing, removing supernatant by decantation, washing with distilled water for several times, washing with anhydrous ethanol for two times, and storing in anhydrous ethanol. The ICP detection result shows that the nickel content in the nickel-boron amorphous alloy is 68 atom%, and the boron content is 32 atom%.
Care should be taken throughout the preparation to avoid oxidation of the catalyst formed by air.
1.2 catalytic reaction Process
Prepared at a concentration of400ml of 10% (w/w) glucose solution, water of solvent: the ethanol ratio was 1: 1, 1.6g of nickel-boron catalyst (Ni) was added68B32). The glucose solution and the catalyst were added to the autoclave. Replacing air in the kettle with high-purity nitrogen for 4-5 times, then filling hydrogen to 1.8MPa, stirring at 450 rpm, heating to 120 deg.C from room temperature, maintaining at120 deg.C, repeatedly filling hydrogen after hydrogen pressure is reduced, and no hydrogen is absorbed after 2 hr. The reaction was then stopped. Cooling, opening the kettle and taking out the reactant. Filtering to remove catalyst, and evaporating to remove solvent to obtain D-sorbitol. The conversion of glucose was 97% using benidiy reagent, the selectivity was 90% as determined by multiple recrystallizations in ethanol combined with melting point measurements, and the yield was 87%.
Example 2.
D-sorbitol was prepared as described in example 1, but the solvent was changed to water/ethanol at 1: 3. The catalyst amount was 4g, and the hydrogen pressure was changed to 1.5MPa, and D-sorbitol was also obtained at a conversion of 90%, a selectivity of 90% and a yield of 81%.
Example 3.
D-sorbitol was prepared by the procedure described in example 1, except that the amount of catalyst was 4g, the reaction temperature was changed to 150 ℃ and the reaction was completed for 1 hour, and D-sorbitol was also prepared with a conversion of 90%, a selectivity of 90% and a yield of 81%.
Example 4.
4.1 catalyst preparation
200ml of 10.4M NiCl was prepared2,200ml 10.8M NaH2PO4The solution was mixed and shaken in ultrasound for 20 minutes, 200ml of 10.1M KBH4The aqueous solution was added to the mixture under vigorous stirring. Obtaining brown precipitate, standing for layering, decanting to remove supernatant, washing the catalyst with distilled water for multiple times, washing with anhydrous ethanol for two times, and storing in anhydrous ethanol for use. The catalyst composition is Ni75P13B12. Care was taken to avoid oxidation of the catalyst formed by air.
4.2 catalytic reactionProcess
400ml of 10% (w/w) glucose solution was prepared, the ratio of water to ethanol of the solvent was 1: 3, and 4g of nickel-phosphorus-boron catalyst was added. The glucose solution and the catalyst were added to the autoclave. Replacing air in the kettle with high-purity nitrogen for 4-5 times, charging hydrogen to 1.8MPa, stirring at 450 rpm, heating to 120 deg.C from room temperature, maintaining at 120 deg.C, lowering hydrogen pressure, repeatedly charging hydrogen, and no longer absorbing hydrogen after 2 hr. The reaction was then stopped. Cooling, opening the kettle and taking out the reactant. Filtering to remove catalyst, and evaporating to remove solvent to obtain D-sorbitol. The conversion was 92%, the selectivity was 88% and the yield was 81%.
Claims (6)
1. A process for preparing D-sorbitol features that the non-crystalline Ni-B alloy is prepared from glucose through hydrogenating in solvent in the presence of catalyst.
2. A process for preparing D-sorbitol features that the non-crystalline Ni-P-B alloy is prepared from glucose through hydrogenating in solvent in the presence of catalyst.
3. The process according to claim 1 or 2, wherein the solvent is water, ethanol, or a water-ethanol mixture.
4. The process for producing D-sorbitol as claimed in claim 1 or 2, wherein the amount of the catalyst is 4 to 10% by weight based on the weight of glucose.
5. The process for producing D-sorbitol as claimed in claim 1 or 2, wherein the hydrogenation is carried out in the presence of a catalyst at90 to 150 ℃.
6. The process according to claim 1 or 2, wherein the hydrogenation pressure is 0.5 to 2.5 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111312.5A CN1120829C (en) | 1998-05-25 | 1998-05-25 | Process for preparing D-sorbitol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111312.5A CN1120829C (en) | 1998-05-25 | 1998-05-25 | Process for preparing D-sorbitol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1236768A true CN1236768A (en) | 1999-12-01 |
| CN1120829C CN1120829C (en) | 2003-09-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98111312.5A Expired - Fee Related CN1120829C (en) | 1998-05-25 | 1998-05-25 | Process for preparing D-sorbitol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1120829C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381412C (en) * | 2006-09-14 | 2008-04-16 | 山东西王糖业有限公司 | Novel technique for preparing ethylene glycol |
| CN105148922A (en) * | 2015-09-29 | 2015-12-16 | 河北大学 | NiB amorphous alloy catalyst and preparation method thereof |
-
1998
- 1998-05-25 CN CN98111312.5A patent/CN1120829C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381412C (en) * | 2006-09-14 | 2008-04-16 | 山东西王糖业有限公司 | Novel technique for preparing ethylene glycol |
| CN105148922A (en) * | 2015-09-29 | 2015-12-16 | 河北大学 | NiB amorphous alloy catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1120829C (en) | 2003-09-10 |
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