CN110862298B - Preparation method of sorbitol - Google Patents
Preparation method of sorbitol Download PDFInfo
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- CN110862298B CN110862298B CN201911085282.9A CN201911085282A CN110862298B CN 110862298 B CN110862298 B CN 110862298B CN 201911085282 A CN201911085282 A CN 201911085282A CN 110862298 B CN110862298 B CN 110862298B
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- 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
- C07C29/14—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 of a —CHO group
- C07C29/141—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 of a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
The invention relates to a preparation method of sorbitol, which comprises the steps of pre-adjusting the pH value of a glucose aqueous solution, putting the glucose aqueous solution into a reaction kettle for reaction, slowly pumping an alkali solution in the reaction process, reducing the loss of Ni below 20mg/L, and simultaneously reducing the sorbitol content above 97.0 percent.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of sorbitol.
Background
Sorbitol is an important intermediate for synthesizing vitamin C, and is widely applied to the fields of food, tanning, daily cosmetics, paper making, detergents, toothpaste additives and the like. At present, a glucose catalytic hydrogenation process is generally adopted for preparing sorbitol in industry at home and abroad, and the production process mainly comprises the steps of preparation of a glucose solution, hydrogenation reaction, catalyst separation, ion exchange, solution evaporation, crystallization, drying and the like, wherein the hydrogenation reaction is a core technology.
Glucose solution with mass concentration of about 50% and hydrogen are mixed in a high-pressure reaction kettle, and the reaction temperature and pressure are well controlled under the catalytic action of a catalyst to produce sorbitol solution meeting the standard, so that the catalyst is the key in the whole process. The catalyst for preparing sorbitol by catalyzing glucose hydrogenation mainly comprises a Ru-based catalyst and a nickel-based catalyst, and Ru/C and Raney-Ni catalysts are more applied and researched.
At present, raney-Ni catalysts are mainly used in China.
Raney-Ni catalyst is a metal Ni-Al alloy catalyst with a spongy pore structure, and has become the most commonly used catalyst in sorbitol production due to the advantages of low price, easily available raw materials and the like. Since the gluconic acid which is a byproduct formed in the hydrogenation process is easy to cause a great amount of Ni and Al to run off, the performance of the catalyst is reduced. Ni is easily dissolved in sorbitol to cause loss, so that the activity is reduced, the quality of sorbitol is influenced, and the separation cost is increased.
According to the production index requirements of main downstream products of sorbitol, such as VC, solid sorbitol and the like, the Ni content in the sorbitol solution should be controlled. The existing technology for producing sorbitol by Raney Ni catalytic hydrogenation mainly adopts the measure of adjusting the Ni loss in sorbitol solution by adding a large amount of alkali (generally m is m) in the initial stage of reaction NaOH :m Glucose >=0.5%, pH much higher than 11), however, this method has a great influence on the yield of the product, and the amount of Ni loss is not so good.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of sorbitol, which comprises the following steps:
1) Mixing glucose and water, and heating to dissolve to obtain a glucose solution;
2) Cooling the glucose solution obtained in the step 1), and adding an alkali solution to adjust the pH value to 8-11;
3) Adding a nickel catalyst and the glucose solution obtained in the step 2) into a reaction container, performing air evacuation by using hydrogen and nitrogen, starting heating to perform hydrogenation reaction, pumping an alkali solution in the process of temperature rise, and maintaining the pH value at 8-11;
4) After the reaction is finished, filtering the catalyst to finish the hydrogenation reaction to obtain a sorbitol product.
The pH values of the steps 2) and 3) are preferably 8-10.5. Experiments have shown that when the pH is greater than 11, the purity of the resulting sorbitol product is reduced.
In the above method for producing sorbitol, the ratio of glucose: the mass ratio of water is 1.
In the above-mentioned process for the preparation of sorbitol, in step 2), a phosphate, for example NaH, may be added simultaneously with the adjustment of the pH 2 PO 4 The glucose solution is cooled to room temperature, naH is added 2 PO 4 Preferably NaH 2 PO 4 ·12H 2 O solids, the solids being 0.3 to 1% by mass of glucose. By multiple sets of experimental data (e.g., analogs including Na) 2 HPO 4 ) In contrast, the substance can suppress the loss of Al element.
In step 3) of the above-mentioned process for the preparation of sorbitol, when the temperature rises to 90 to 120 ℃, an alkali solution is pumped in.
In the preparation method of the sorbierite, the alkali solution is 0.1-2.0 mol/L NaOH and Na 2 CO 3 、NaHCO 3 And aqueous KOH solution.
The alkali solution is 0.1-2.0 mol/L NaOH aqueous solution. The pH value of the NaOH aqueous solution is quickly and conveniently adjusted, and the cost is economical.
The nickel catalyst comprises Raney Ni catalyst or Mo modified Raney nickel. The preparation method is suitable for common Raney nickel catalysts.
The amount of the nickel catalyst is 10-30% of the mass of the glucose. When the amount of the nickel catalyst is too high, the weight of the catalyst is too large, the stirring effect is poor, the selectivity of the catalyst is obviously reduced, and when the amount of the nickel catalyst is too low, the activity of the catalyst is poor, the reaction time is long and the stability is poor.
In the step 3), the pumping speed of the alkali solution is 0.5-5.00 ml/min, the Ni loss cannot be inhibited when the pumping speed is too high, the energy consumption is increased when the pumping time is too long when the pumping speed is too low, and the pumping standard of the alkali solution is that the Ni loss can be effectively inhibited and the sorbitol yield can be kept at a higher level (about 97-98%).
The loss of Ni metal in the reaction solution after hydrogenation reaction is measured by ICP to be 5-20 mg/L, and the content of sorbitol in the product is measured by liquid chromatography to be 97.0-98.5%.
The method can control the loss of Ni and simultaneously reduce the influence on the sorbitol content to a very low degree, so that the sorbitol content and the loss of Ni can be well controlled within the index range required by industrial production
Compared with the prior art, the invention has the following advantages:
1. the method controls the loss of Ni by adjusting the initial pH value of the reaction solution and adopting a mode of continuously dropwise adding alkali liquor (dropwise adding flow rate) in the reaction process, has simple process, simple and convenient operation, good effect of inhibiting the loss of Ni, environment-friendliness and stable yield at a high level of 97.0-98.5%.
2. The NaOH adopted by the invention has low price and good economy, is environment-friendly and meets the requirement of green chemistry.
Detailed Description
The following experimental examples are intended to further illustrate the invention but not to limit it. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Example 1
Raney Ni catalyst
Example 1
(1) Preparing an alkali solution: naOH solution with the concentration of 1.0mol/L is prepared.
(2) Glucose solutionInitial pH value adjustment: according to m Glucose :m Water (W) 1, heating glucose at a certain temperature to be completely dissolved to form an aqueous solution, and adding NaH accounting for 0.9% of the mass of the glucose after the aqueous solution is cooled to room temperature 2 PO 4 ·12H 2 And adjusting the pH value of the glucose solution to 9 by using the prepared alkali solution.
(3) Batch hydrogenation reaction: and (3) pouring the glucose solution with the adjusted pH value and Raney Ni catalyst (20 percent of the mass of glucose) into a 1L high-pressure reaction kettle, respectively emptying by using nitrogen and hydrogen for three times, and then introducing hydrogen to start hydrogenation reaction. The temperature was observed during the process, and when the reaction temperature reached 120 ℃, the high pressure pump was turned on to start pumping the alkali solution at a flow rate of 0.5mL/min and a volume of about 2.5mL was pumped in 5 min. Closing the high-pressure pump after the reaction is finished, and continuing to react until the pressure is not obviously changed; and filtering out the catalyst, and then sampling to be tested.
(4) The loss of Ni metal in the reaction solution after the hydrogenation reaction was measured by ICP was 15.44mg/L, and the sorbitol content in the product was measured by liquid chromatography to be 97.75%.
Examples 2-10 the procedure was the same as in example 1, and the specific data are shown in table 1:
TABLE 1 Raney Ni examples
Comparative example 1: initial adjustment and no dripping in the middle
(1) Preparing an alkali solution: naOH with the concentration of 1.0mol/L is prepared.
(2) Adjusting the initial pH value of the glucose solution: according to m Glucose :m Water (I) 1, heating glucose at a certain temperature to be completely dissolved to form an aqueous solution, and adding NaH accounting for 0.9% of the mass of the glucose after the aqueous solution is cooled to room temperature 2 PO 4 ·12H 2 O and 5ml of 1.0mol/L (excess lye) of the above prepared alkali solution.
(3) Batch hydrogenation reaction: the glucose solution with the adjusted pH value and Raney Ni catalyst (20 percent of the mass of glucose) are poured into a 1L high-pressure reaction kettle, and hydrogen is introduced to start hydrogenation reaction after nitrogen and hydrogen are respectively used for evacuation three times. Stopping the reaction until the pressure does not change obviously; and filtering out the catalyst, and then sampling to be tested.
(4) The loss of Ni metal in the reaction solution after the hydrogenation reaction was measured by ICP was 8.42mg/L, and the sorbitol content in the product was measured by liquid chromatography to be 93.07%.
Comparative example 2: initially unregulated and intermediately added
(1) Preparing an alkali solution: naOH with the concentration of 1.0mol/L is prepared respectively.
(2) Adjusting the initial pH value of the glucose solution: according to m Glucose :m Water (W) 1 at a certain temperature, heating glucose to be completely dissolved to form an aqueous solution, and cooling the aqueous solution to room temperature.
(3) And (3) intermittent hydrogenation reaction: the glucose solution and Raney Ni catalyst (20% of glucose mass) are poured into a 1L high-pressure reaction kettle, and hydrogen is introduced to start hydrogenation reaction after nitrogen and hydrogen are respectively used for evacuation three times. The temperature was observed during the process, when the reaction temperature reached 120 ℃, the high pressure pump was turned on to start pumping NaOH alkali solution at a flow rate of 0.5mL/min and a volume of 5mL in 10 min. Closing the high-pressure pump after the reaction is finished, and continuing to react until the pressure is not obviously changed; and filtering out the catalyst, and then sampling to be tested.
(4) The loss of Ni metal in the reaction solution after the hydrogenation reaction was measured by ICP was 25.36mg/L, and the sorbitol content in the product was measured by liquid chromatography to be 92.33%.
Comparative example summary
In comparative examples 1 to 2, it was found that if an excessive amount of alkali solution was directly added, and no alkali solution was added dropwise in the middle, the amount of Ni loss was reduced, but the sorbitol content was significantly reduced to 93.07%. If the pH value is not adjusted initially, 5ml of alkali liquor is dripped in the middle, the loss of Ni is high, and the content of sorbitol is low, namely 92.33%. Are not in accordance with the preparation requirement of the sorbierite.
Examples 11 to 14
Mo modified Raney Ni catalyst, see table 2.
TABLE 2 specific examples of Mo modified Raney Ni
Examples 11-14 show that when using Mo modified Raney Ni catalyst for sorbitol production, the preparation method can still control the Ni loss below 20mg/l, even below 15mg/l, and the sorbitol content is maintained between 97% -99%, thus meeting the requirements of the current high-purity sorbitol industrial production.
Claims (5)
1. The preparation method of the sorbitol is characterized by comprising the following steps:
1) Mixing glucose and water, and heating to dissolve to obtain a glucose solution;
2) Cooling the glucose solution obtained in the step 1), adding an alkali solution to adjust the pH value to 9 to 10.5, and adding NaH while adjusting the pH value by adding the alkali solution 2 PO 4 Or NaH 2 PO4 hydrate, adding NaH according to the proportion 2 PO 4 ·12H 2 The solid mass of O is calculated to be 0.3 to 1 percent of the mass of the glucose;
3) Adding a nickel catalyst and the glucose solution obtained in the step 2) into a reaction container, wherein the nickel catalyst comprises Raney Ni catalyst or Mo modified Raney nickel, the dosage of the Raney Ni catalyst or the Mo modified Raney nickel is 10-30% of the mass of glucose, after air evacuation is carried out by using hydrogen and nitrogen, heating is carried out for hydrogenation reaction, and when the temperature rises to 90-120 ℃, pumping alkali solution, and maintaining the pH value to be 9-10.5;
4) After the reaction is finished, filtering the catalyst to finish the hydrogenation reaction to obtain a sorbitol product.
2. The method for preparing sorbitol according to claim 1, wherein the ratio of glucose: the mass ratio of water is 1:0.5 to 2.
3. The method for preparing sorbitol according to claim 2, wherein the ratio of glucose: the mass ratio of water is 1:1.
4. the method for preparing sorbitol according to claim 1, wherein the alkali solution is 0.1 to 2.0mol/L NaOH or Na 2 CO 3 、NaHCO 3 And aqueous KOH solution.
5. The method for preparing sorbitol according to claim 4, wherein the alkali solution is 0.1 to 2.0mol/L NaOH aqueous solution.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB838766A (en) * | 1957-07-02 | 1960-06-22 | Udic Sa | A process for the production of polyhydric alcohol mixtures by degradative hydrogenation of sugars |
| US3329729A (en) * | 1962-12-31 | 1967-07-04 | Atlas Chem Ind | Production of mannitol and sorbitol by hydrogenating sugars under neutral, then alkaline and finally acidic conditions |
| US4322569A (en) * | 1980-08-01 | 1982-03-30 | Hydrocarbon Research, Inc. | Catalytic hydrogenation of glucose to produce sorbitol |
| CN1194965A (en) * | 1997-03-28 | 1998-10-07 | 中国发酵工业协会淀粉糖分会 | High aspect ratio saccharide continuous hydrogenation process and its equipment |
| CN1214333A (en) * | 1997-10-09 | 1999-04-21 | 中国石油化工总公司 | Process of hydrogenating glucose to prepare sorbierite |
| CN101199934A (en) * | 2006-12-13 | 2008-06-18 | 中国石油化工股份有限公司 | Process for preparing modified amorphous nickel alloy catalyst |
| CN104525074A (en) * | 2014-12-17 | 2015-04-22 | 浙江华康药业股份有限公司 | Online pH adjusting device and online pH adjusting process of catalytic hydrogenation reaction |
| CN104909986A (en) * | 2015-05-05 | 2015-09-16 | 浙江华康药业股份有限公司 | Method for preparing high-purity sorbitol and daily-chemical-grade sorbitol |
| CN105561894A (en) * | 2016-02-24 | 2016-05-11 | 浙江华康药业股份有限公司 | Self-organization flow division type control method and device for preparing sorbitol through integral reaction and separation |
| CN205599126U (en) * | 2016-02-24 | 2016-09-28 | 浙江华康药业股份有限公司 | Device of self -organizing shunting control of integrated reaction separation and preparation sorbitol |
| CN107262137A (en) * | 2017-07-13 | 2017-10-20 | 中国科学技术大学 | The preparation method of loaded catalyst, its preparation method and sorbierite |
| CN109305882A (en) * | 2018-09-28 | 2019-02-05 | 吉林省石油化工设计研究院 | A kind of glucose continuously hydrogen adding prepares the method and device of sorbierite |
| CN109336939A (en) * | 2018-12-01 | 2019-02-15 | 浙江华康药业股份有限公司 | A kind of hydrogenation process of sugar alcohol |
| CN208949158U (en) * | 2018-09-28 | 2019-06-07 | 吉林省石油化工设计研究院 | A kind of glucose continuously hydrogen adding prepares the device of sorbierite |
| CN110028382A (en) * | 2019-03-28 | 2019-07-19 | 山东天力药业有限公司 | A method of preparing sorbierite |
-
2019
- 2019-11-08 CN CN201911085282.9A patent/CN110862298B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB838766A (en) * | 1957-07-02 | 1960-06-22 | Udic Sa | A process for the production of polyhydric alcohol mixtures by degradative hydrogenation of sugars |
| US3329729A (en) * | 1962-12-31 | 1967-07-04 | Atlas Chem Ind | Production of mannitol and sorbitol by hydrogenating sugars under neutral, then alkaline and finally acidic conditions |
| US4322569A (en) * | 1980-08-01 | 1982-03-30 | Hydrocarbon Research, Inc. | Catalytic hydrogenation of glucose to produce sorbitol |
| CN1194965A (en) * | 1997-03-28 | 1998-10-07 | 中国发酵工业协会淀粉糖分会 | High aspect ratio saccharide continuous hydrogenation process and its equipment |
| CN1214333A (en) * | 1997-10-09 | 1999-04-21 | 中国石油化工总公司 | Process of hydrogenating glucose to prepare sorbierite |
| CN101199934A (en) * | 2006-12-13 | 2008-06-18 | 中国石油化工股份有限公司 | Process for preparing modified amorphous nickel alloy catalyst |
| CN104525074A (en) * | 2014-12-17 | 2015-04-22 | 浙江华康药业股份有限公司 | Online pH adjusting device and online pH adjusting process of catalytic hydrogenation reaction |
| CN104909986A (en) * | 2015-05-05 | 2015-09-16 | 浙江华康药业股份有限公司 | Method for preparing high-purity sorbitol and daily-chemical-grade sorbitol |
| CN105561894A (en) * | 2016-02-24 | 2016-05-11 | 浙江华康药业股份有限公司 | Self-organization flow division type control method and device for preparing sorbitol through integral reaction and separation |
| CN205599126U (en) * | 2016-02-24 | 2016-09-28 | 浙江华康药业股份有限公司 | Device of self -organizing shunting control of integrated reaction separation and preparation sorbitol |
| CN107262137A (en) * | 2017-07-13 | 2017-10-20 | 中国科学技术大学 | The preparation method of loaded catalyst, its preparation method and sorbierite |
| CN109305882A (en) * | 2018-09-28 | 2019-02-05 | 吉林省石油化工设计研究院 | A kind of glucose continuously hydrogen adding prepares the method and device of sorbierite |
| CN208949158U (en) * | 2018-09-28 | 2019-06-07 | 吉林省石油化工设计研究院 | A kind of glucose continuously hydrogen adding prepares the device of sorbierite |
| CN109336939A (en) * | 2018-12-01 | 2019-02-15 | 浙江华康药业股份有限公司 | A kind of hydrogenation process of sugar alcohol |
| CN110028382A (en) * | 2019-03-28 | 2019-07-19 | 山东天力药业有限公司 | A method of preparing sorbierite |
Non-Patent Citations (2)
| Title |
|---|
| 山梨醇的制备与应用;张晓英;《中国食品添加剂》;20011130(第5期);49-50 * |
| 葡萄糖催化加氢合成山梨醇的研究进展;黄阳卫;《浙江化工》;20010315(第1期);50-51 * |
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