KR101385628B1 - Preparing apparatus from sugar to sugar alcohols by catalytic hydrogenation - Google Patents

Abstract

An apparatus for producing sugar alcohols of the present invention is to produce a sugar alcohol by using a supported catalyst to the corresponding sugar alcohols by a hydrogenation reaction, hydrogen gas storage unit; Nitrogen gas storage; Sugar storage unit; A first mass flow meter connected to the hydrogen gas storage unit to control an injection amount of hydrogen gas; A second mass flow meter connected to the nitrogen gas storage unit to adjust an injection amount of nitrogen gas; The reactor is formed inside the catalyst support in the form of a mesh, the inlet for the hydrogen gas, nitrogen gas or sugar storage unit inlet, the outlet for discharging the reaction product completed reaction, and the first heater formed along the outer circumferential surface ; A reaction product storage unit for storing the reaction product discharged from the reactor; And a pressure control unit including a pressure gauge for adjusting the pressure and pressure gauge for measuring the pressure of the reactor; It includes, characterized in that connected to each other by a flow tube.

Description

Preparing apparatus from sugar to sugar alcohols by catalytic hydrogenation}

The present invention relates to an apparatus for continuously producing sugar alcohols by catalytic hydrogenation of sugars.

Prices of fossil raw materials such as oil, gas and coal are continuously rising due to the finite nature of the resources. Moreover, chemical products produced from fossil raw materials generate global warming gases and wastes as by-products in the manufacturing process, resulting in environmental pollution, which is rapidly declining the existing chemical industry.

In Korea, which relies on imports for most of its energy, it is essential to establish long-term energy supply and demand policies that can reduce dependency on energy imports as much as possible and to develop clean alternative energy sources in order to maintain national security and sustainable economic growth. In this reality, biomass is attracting attention as a field of alternative energy that can alleviate fossil fuel depletion and environmental pollution concerns. Stricter environmental regulations, such as the depletion of petroleum resources, oil supply anxiety due to high oil prices, and the emission of greenhouse gases from the use of fossil fuels, have been obstacles to the development of the world economy. In particular, the chemical industry, which is most directly affected by high oil prices and environmental regulations, is recognized as an important alternative to reducing the dependency on fossil fuels and changing to an environmentally friendly industrial structure. Therefore, it is necessary to develop environmentally friendly new biochemical processes that can replace chemical processes based on fossil raw materials, that is, using biomass as a raw material to minimize the consumption of fossil raw materials and the production of harmful wastes to human beings. .

One of the notable recent developments in the development of environmentally friendly biochemical processes is the emergence of bio-refineries using biomass. Biorefinery is a new concept that produces biofuels and chemicals without the use of fossil raw materials, but only through biological and chemical conversion from biomass.

Just as oil refineries, which use crude oil as raw material and produce industrial / transportation fuels and various chemical products, have been developed as a comprehensive integrated process, Bio Refineries has developed biomass feedstocks such as biofuels ethanol, butanol, acetone and chemical raw materials such as sorbitol, It is being developed as an integrated process that is composed of a technology to make xylitol, lactic acid, succinic acid, etc. and a comprehensive plant system to realize it.

Hexose sugars and pentose sugar alcohols such as sorbitol, mannitol, and xylitol are useful substances widely used in food additives, medicines, and cosmetics. In general, these sugar alcohols are mostly prepared by hydrogenation of the corresponding sugars.

The prior art has reported patents for the hydrogenation of ruthenium catalysts that do not dissolve in solution during the reaction, such as Ranickel. U.S. Patent No. 3,963,788 discloses a method of hydrogenating saccharides by supporting ruthenium on a zeolite carrier having a silica / alumina molar ratio of 3 or more. In this patent, zeolite is added to an aqueous solution of ruthenium chloride and stirred at 80 ° C in the form of a slurry. Subsequently, ruthenium is replaced by ion exchange method, and then rinsed with filtration and distilled water to remove ruthenium chloride which has not been substituted in the carrier. And the catalyst used after hydrogenation was regenerated by acid washing. However, this method has the disadvantage of complicated catalyst production method by using ion exchange method, long catalyst production time, high loss of ruthenium precursor, difficult control of ruthenium content, additional catalyst regeneration process, and high yield. As low as%, a separate separation process is required for the production of high purity sugar alcohols.

In addition, US Pat. No. 6,124,443 reports a process for the continuous hydrogenation of xylose using a nickel-iron-zirconia alloy catalyst. This method is advantageous in that xylose is converted to xylitol having a purity of 99.6% after hydrogenation of xylose under hydrogen pressure of 60 캜 and 300 kg / cm ² , but a reaction facility capable of withstanding high pressure is required, Nickel and iron are dissolved out, and when the reaction proceeds for a long time, the catalyst is gradually inactivated.

U.S. Patent No. 6,124,443 (2000.09.26) U.S. Patent No. 3,963,788 (1976.06.15)

An object of the present invention is to provide an apparatus for continuously producing sugar alcohols in high yield by catalytic hydrogenation of sugars.

The apparatus for producing sugar alcohols of the present invention is a sugar alcohol production apparatus (1) for producing sugar alcohols using a supported catalyst by a hydrogenation reaction to a corresponding sugar alcohol, hydrogen gas storage hydrogen gas is stored Part 100; A nitrogen gas storage unit 200 in which nitrogen gas is stored; A sugar storage unit 300 in which an aqueous glucose solution is stored; A first mass flow meter (110) connected to the hydrogen gas storage unit (100) to adjust the injection amount of hydrogen gas; A second mass flow meter (210) connected to the nitrogen gas storage unit (200) to adjust the injection amount of nitrogen gas; The catalyst support part 410 of the mesh type is installed inside, the inlet 420 for introducing hydrogen gas, nitrogen gas or sugar storage unit, the outlet 430 for discharging the reaction product after the reaction is completed, and formed along the outer peripheral surface A reactor 400 including a first heater 440 to be formed; A reaction product storage unit 500 in which the reaction product discharged from the reactor 400 is stored; A pressure control unit 600 including a pressure gauge 610 for measuring the pressure of the reactor 400 and a pressure control valve 620 for adjusting the pressure; It includes, characterized in that connected to each other by the flow pipe (700).

In addition, the sugar alcohol production apparatus 1 is characterized in that the reactor 400 is a fixed bed (fixed bed) reactor.

In addition, the sugar alcohol production apparatus 1 is characterized in that it comprises a second heater 800 of the hot wire form is installed on the outer circumferential surface of the flow pipe 700 connected to the front end of the inlet 420 at all times.

In addition, the sugar alcohol production apparatus 1 is characterized in that the temperature measuring sensor portion 450 made of a thermocouple is installed in the catalyst support portion 410 of the reactor 400.

In addition, the sugar alcohol production apparatus 1 further includes a sugar injection pump 310 connected to the sugar storage unit, and stored in the sugar storage unit by an operation of the sugar injection pump 310. It is characterized in that the aqueous glucose solution is injected into the reactor (400).

In addition, the sugar alcohol production apparatus 1 is characterized in that the diaphragm valve 220 is provided at the front and rear ends of the first mass flow meter 110 and the second mass flow meter 210, respectively.

In addition, the apparatus 1 for producing sugar alcohols is provided at a rear end of the first mass flow meter 110 and the second mass flow meter 210, and the first mass flow meter 110 and the second mass flow meter 210. The check valve 230 is provided between the diaphragm valve 220 provided.

In addition, the catalyst support part 410 is characterized in that the supported catalyst is coated with an oxide film of nickel metal on a single or mixture carrier selected from silica, alumina and titania, and ruthenium is supported by nanoparticles thereon.

In addition, the hydrogenation reaction is characterized in that it is carried out under the conditions of the reaction temperature of 60 to 200 ℃ and the reaction pressure of 2 to 200MPa.

The production apparatus of sugar alcohols according to the present invention produces high-purity sugar alcohols without dissolving or deactivating the catalyst components for a long time using a ruthenium-supported catalyst in the hydrogenation reaction of saccharides for a long time, and thus by-products and wastes are almost eliminated. It does not occur, there is an effect that can be produced sugar alcohols without complicated separation process.

1 is a view showing a sugar alcohol production apparatus according to the present invention.
Figure 2 is a view showing another sugar alcohol production apparatus according to the present invention.
3 is a view showing a reactor included in the production apparatus of another sugar alcohol according to the present invention.

Hereinafter, a sugar alcohol production apparatus according to the present invention as described above will be described in detail with reference to the accompanying drawings.

1 is a view showing a sugar alcohol production apparatus according to the present invention, Figure 2 is a view showing another sugar alcohol production apparatus according to the present invention, Figure 3 is another sugar alcohol according to the present invention A diagram showing a reactor included in the manufacturing apparatus of the.

The apparatus for producing sugar alcohols according to the present invention (1) is to produce a sugar alcohol corresponding to the sugar alcohols by hydrogenation reaction using a supported catalyst, hydrogen gas storage unit 100, nitrogen gas storage unit ( 200, the sugar storage unit 300, the first mass flow meter 110, the second mass flow meter 210, the reactor 400, the reaction product storage unit 500 and the pressure control unit 600, the flow pipe ( 700 is connected to each other by.

The first mass flow meter 110 controls the amount of hydrogen gas stored in the hydrogen gas storage unit 100 is injected into the reactor 400, and the second mass flow meter 210 controls the nitrogen gas storage unit ( The nitrogen gas stored in 200 is adjusted to be injected into the reactor 400.

The reactor 400 has a catalyst support 410 having a mesh shape therein, an inlet 420 into which hydrogen gas, nitrogen gas or a sugar storage unit is introduced, and an outlet 430 through which the reaction product in which the reaction is completed is discharged. And a first heater 440 formed along the outer circumferential surface thereof.

The catalyst supporting unit 410 may be provided with a temperature measuring sensor unit 450 made of a thermocouple. The thermocouple connects two kinds of metals and uses a thermoelectric power caused by a temperature difference generated at both ends of the connection unit to adjust the temperature. By measuring, the precision is high, and the shape can be changed suitably according to the used part, and it is suitable for measuring the reaction temperature of the catalyst carrying part.

The reaction product storage unit 500 stores the reaction product discharged from the reactor 400.

The pressure control unit 600 is formed to include a pressure gauge 610 for measuring the pressure of the reactor 400 and a pressure control valve 620 for adjusting the pressure, in the inlet 420 of the reactor 400 It may be connected to the flow pipe 700 is provided.

At this time, the reactor 400 may be a fixed bed type reactor made of SUS tubular. The fixed bed reactor has the advantage of high catalyst activity, high activity even after long time use, and no loss of catalyst, so there is no need to consider a separate reactor or reaction process for catalyst addition / emission and regeneration.

In addition, the sugar alcohol production apparatus 1 may be formed to include a second heater 800 of the heating wire type is installed on the outer peripheral surface of the flow connected to the front end of the inlet 420. The second heater 800 is to maintain a constant temperature of the reactant flowing into the reactor 400 in accordance with the reaction temperature.

In addition, the sugar alcohol production apparatus 1 further includes a sugar injection pump 310 connected to the sugar storage unit, and stored in the sugar storage unit by an operation of the sugar injection pump 310. Aqueous glucose solution is injected into the reactor 400.

As shown in FIG. 1, the apparatus 1 for producing a sugar alcohol according to the present invention includes a diaphragm valve 220 at the front and rear ends of the first mass flow meter 110 and the second mass flow meter 210, respectively. It may be provided.

The diaphragm valve 220 has an advantage that the resistance in the fluid passage is small, so that the fluid or pressure loss including gaseous and erosive acid and alkalis can be reduced.

Therefore, the apparatus 1 for producing sugar alcohols according to the present invention includes the first mass flow meter 110 and the second mass flow meter according to the air pressure applied from the hydrogen gas storage unit 100 and the nitrogen gas storage unit 200. The opening degree of the diaphragm valve 220 which is installed at the front end of the 210 is adjusted, and the hydrogen gas and the nitrogen gas introduced through the diaphragm valve 220 are the first mass flow meter 110 and the second mass flow meter 210. By the amount injected into the reactor 400 is controlled.

The apparatus 1 for producing sugar alcohols of the present invention includes a first mass flow meter 110 and a second mass flow meter 210 and a rear end of the first mass flow meter 110 and the second mass flow meter 210. A check valve 230 is provided between the diaphragm valves 220 provided to prevent the gas existing in the flowed direction from moving in the reverse direction.

On the other hand, the catalyst support portion 410 may be supported on a catalyst supported on the single or a mixture carrier selected from silica, alumina and titania with an oxide coating of nickel metal and on which ruthenium is supported as nanoparticles.

The sugar is not limited thereto, and for example, glucose, xylose, mannose, fructose, erythrose, galactose, sucrose, starch hydrolyzate, cellulose hydrolyzate and mixture of two or more selected from maltose Can be used.

Since sugars are generally in a solid state at room temperature, it is preferable to dissolve sugars in an appropriate solvent in order to improve reaction efficiency. In this case, as the solvent, sugars and sugar alcohols, which are products of a hydrogenation reaction, can be dissolved simultaneously, and any of them can be used. Generally, water or alcohol may be used alone or in combination. Examples of the alcohol may include methanol, ethanol, propanol, isopropanol or mixtures thereof. Preferably, water is used alone or in combination with water and ethanol.

Hydrogenation of the sugar using the supported catalyst in the production device (1) of the sugar alcohol according to the present invention may be preferably carried out at a reaction temperature of 60 to 200 ℃, if the reaction temperature is low the reaction rate may be slow and reaction If the temperature is too high, there may be a problem that the side reactions increase to lower the selectivity of the desired reactants.

In addition, the hydrogenation reaction may be preferably performed under the conditions of the reaction pressure of 2 to 200 MPa in consideration of the reaction rate and the safety of the reactor 400.

Silica, alumina, titania, etc. used as the carrier of the supported catalyst are not particularly limited, and may be of natural origin or synthesized.

In forming the nickel metal oxide film of the supported catalyst, it is possible to obtain a high activity even if a small amount of catalyst is used because the ruthenium is supported by nanoparticles so that the film is formed at 0.5 to 15% by weight based on the total weight of the supported catalyst. .

The particle diameter of the ruthenium nanoparticles supported on the supported catalyst is 1 to 10 nm, preferably 1.5 to 5 nm.

The content of ruthenium in the supported catalyst may be 0.2 to 15% by weight based on the total weight of the supported catalyst in consideration of the rate and economic efficiency of the hydrogenation reaction in the hydrogenation reaction of sugars.

The supported catalyst participating in such a hydrogenation reaction can be recovered without requiring a separate regeneration process and can be repeatedly used for the hydrogenation reaction of saccharides, and the catalyst component is not dissolved or deactivated even in repeated use. Therefore, sugar alcohols can be produced in high purity without generating by-products and waste and without complicated separation process.

Referring to Figure 1 describes the operation of the sugar alcohol production apparatus 1 according to the present invention,

Into the catalyst support portion 410, a catalyst consisting of ruthenium / nickel oxide / titania is inserted and adjusted to inject 5% of hydrogen gas into the reactor 400 through the first mass flow meter 110, and the second mass flow meter Through 210, 95% of nitrogen gas is adjusted to be injected into the reactor 400.

As a result, when hydrogen gas and nitrogen gas are mixed in the reactor 400, after raising the temperature to about 170 ° C. through the first heater 440 of the reactor 400, the catalyst is reduced for 3 hours.

At this time, the temperature of the reactor 400 is to be kept constant during the reaction by measuring the temperature through the temperature measuring sensor unit 450.

After the reduction, the reactor 400 adjusts the temperature to the reaction temperature and washes with hydrogen, so that the pressure is raised to 5.5MPa only with hydrogen gas. Next, the sugar injection pump 310 allows 20% aqueous glucose solution in the sugar storage unit 300 to be injected into the reactor 400 at a constant rate. Accordingly, the sugar alcohol production apparatus 1 according to the present invention can be produced continuously sugar alcohols.

After the reaction, the reaction product is collected in the reaction product storage unit 500.

The reaction product storage unit 500 may be further equipped with a rear pressure regulator, the rear pressure regulator serves to maintain a constant high pressure of the reactor 400.

On the other hand, as shown in Figure 2, the sugar alcohol production apparatus 1 according to the present invention by connecting a plurality of the reactor 400 in parallel, by the catalytic hydrogenation of different types of sugars simultaneously or sequentially It can be produced continuously with sugar alcohols.

Accordingly, the apparatus 1 for producing sugar alcohols according to the present invention can quickly produce various kinds of sugar alcohols, and can be manufactured at the same time through a single device, thereby greatly improving manufacturing efficiency.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It goes without saying that various modifications can be made.

1: manufacturing apparatus of sugar alcohols
100: hydrogen gas storage unit 110: the first mass flow meter
200: nitrogen gas storage unit 210: second mass flow meter
220: diaphragm valve 230: check valve
300: sugar storage unit 310: sugar injection pump
400: reactor
410: catalyst support 420: inlet
430: outlet 440: the first heater
450: temperature measuring sensor
500: reaction product storage unit
600: pressure control unit
610: pressure gauge 620: pressure control valve
700: flow tube
800: second heater

Claims (9)

In the manufacturing apparatus (1) of sugar alcohols which uses a supported catalyst to produce sugars into the corresponding sugar alcohols by hydrogenation reaction,
A hydrogen gas storage unit 100 in which hydrogen gas is stored;
A nitrogen gas storage unit 200 in which nitrogen gas is stored;
A sugar storage unit 300 in which an aqueous glucose solution is stored;
A first mass flow meter (110) connected to the hydrogen gas storage unit (100) to adjust the injection amount of hydrogen gas;
A second mass flow meter (210) connected to the nitrogen gas storage unit (200) to adjust the injection amount of nitrogen gas;
The catalyst support part 410 of the mesh type is installed inside, the inlet 420 for introducing hydrogen gas, nitrogen gas or sugar storage unit, the outlet 430 for discharging the reaction product after the reaction is completed, and formed along the outer peripheral surface A fixed bed reactor (400) formed including a first heater (440) to be formed;
A reaction product storage unit 500 in which the reaction product discharged from the reactor 400 is stored;
A pressure control unit 600 including a pressure gauge 610 for measuring the pressure of the reactor 400 and a pressure control valve 620 for adjusting the pressure; It includes, is connected to each other by the flow pipe 700,
The catalyst support unit 410 is
A supported catalyst having an oxide film coated with nickel metal on a single or mixture carrier selected from silica, alumina, and titania and carrying ruthenium as nanoparticles thereon is accommodated.
In forming a nickel metal oxide film of the supported catalyst, the coating device of the sugar alcohol, characterized in that the film is formed by 0.5 to 15% by weight relative to the total weight of the supported catalyst .
delete The method according to claim 1,
The sugar alcohol production apparatus (1)
The apparatus for producing sugar alcohols, comprising a second heater (800) in the form of a hot wire installed on the outer circumferential surface of the flow pipe (700) connected to the front end of the constant inlet (420).
The method of claim 3, wherein
The sugar alcohol production apparatus (1)
The apparatus for producing sugar alcohols, characterized in that the temperature measuring sensor portion 450 made of a thermocouple is installed in the catalyst support portion 410 of the reactor 400.
The method according to claim 1,
The sugar alcohol production apparatus (1)
Further comprising a sugar injection pump 310 is connected to the sugar storage unit is installed,
By the operation of the sugar injection pump 310, the glucose aqueous solution stored in the sugar storage unit is injected into the reactor 400, characterized in that the sugar alcohol production apparatus.
The method according to claim 1,
The sugar alcohol production apparatus (1)
The apparatus for producing sugar alcohols, characterized in that the diaphragm valve (220) is provided at the front and rear ends of the first mass flow meter (110) and the second mass flow meter (210), respectively.
The method according to claim 6,
The sugar alcohol production apparatus (1)
Check valve 230 between the first mass flow meter 110 and the second mass flow meter 210 and the diaphragm valve 220 provided at the rear ends of the first mass flow meter 110 and the second mass flow meter 210. ) Is provided with a sugar alcohol production apparatus characterized in that it is provided.
delete The method according to claim 1,
The hydrogenation reaction
Sugar alcohol alcohol production apparatus, characterized in that carried out under the conditions of the reaction temperature of 60 to 200 ℃ and the reaction pressure of 2 to 200MPa.

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