WO2009125906A1

WO2009125906A1 - Corn energy recycling system

Info

Publication number: WO2009125906A1
Application number: PCT/KR2008/007334
Authority: WO
Inventors: Jeong Rang Lee; Hyuck-Soo Lee
Original assignee: Jeong Rang Lee; Hyuck-Soo Lee
Priority date: 2008-04-11
Filing date: 2008-12-11
Publication date: 2009-10-15
Also published as: KR100866809B1

Abstract

The present invention is directed to manufacturing vegetable bio ethyl alcohol of purity 99.9% using vegetable raw material including sugar or starch such as corn and cassava, sugar beet, potato, fruits which are vegetable energy resources. In the present invention, a method for manufacturing ethyl alcohol using corn, and a method for recycling byproducts are invented while overcoming the problems of the conventional art. It is a first object of the present invention to manufacture an anhydride bio alcohol of purity 99.9% which does not cost a lot with the helps of a new manufacture technology such as a 3 -component azeotropic mixture distillation method among newly developed 2-tower azeotropic distillation principles and a dehydration method using zeolite ceramic while enhancing energy power by adapting a far infrared ceramic apparatus in a process for processing corn to ethyl alcohol.

Description

CORN ENERGY RECYCLING SYSTEM

Technical Field

The present has a lot of effects of growing as an economic agriculture product and applying as an environment friendly raw material and minimizing a discharge of pollutions by activating alcohol molecules based on a far infrared radiation method and enhancing an alcohol energy power and distilling a raw oil while obtaining a quality and performance much better than a conventional gasoline. It is possible to obtain a high valued added benefit by recycling byproducts.

Background Art

A. In a conventional art, many countries have manufactured alcohol using corn and have used for alcohol production. In recent years, a lot of alcohol fuel is manufactured using corn, and the alcohol is added to gasoline. The alcohol manufacture technologies in this field are similar.

B. However, the US patent registration number 5710030(published 20, 1998) discloses a method for extracting vegetable oil using corn and using byproducts(wastes of corn).

The above patent information is as follows.

(1) Title of the invention: Method for manufacturing fuel, alternate fuel and fuel additive from recyclable raw material

(2) Purpose of the invention: It is an object of the present invention to a method for obtaining glycerin and low concentration fat acid alkyl ester through ester substitution between vegetable oil and ethanol or alcohol using the byproducts obtained after low concentration fat acid alkyl ester(vegetable oil) is manufactured from oil seeds or other natural vegetable materials.

Technical conceptions and technical process

Vegetable oil is extracted from vegetable oil seeds, and byproducts are collected.

(1) A step for producing byproducts formed of complex polymeric carbon hydrates.

(2) A step for processing corresponding byproducts based on saccharification and obtaining sugar.

(3) A step for fermenting corresponding sugar and producing or collecting ethanol or alkyl alcohol.

(4) A step for producing glycerin and low concentration fat acid alkyl ester through ester substitution between collected vegetable oil and ethanol or alcohol.

The detailed manufacture process is as follows.

(1) Oil is extracted by compressing vegetable materials containing vegetable oil, and byproducts are obtained and saccharificated for thereby producing sugar. The saccharification method selected among acid saccharification method, acid enzyme saccharification method, and enzyme saccharification method.

(2) The produced sugar is fermented, and alkanol is obtained through a fermentation and azeotropic distillation process.

(3) alkanol and extracted oil are reacted and substituted with ester, and a low concentration fat acid ester is produced, which might be useful as fuel (oil fuel) or fuel additive.

As described above, the patents on using corn are disclosed in the US, but its content is directed to a technical patent for manufacturing oil using corn and manufacturing glycerin and low concentration fat acid alkyl alcohol by recycling byproducts(corn wastes) produced in the manufacture process.

However, the present invention relates to an energy application method of corn. The corn is ground and saccharificated and is cooled at 38°C, and a high temperature active dry ferment is added, and fermentation is performed based on a far infrared radiation method, and boil alcohol is produced through dehydration using a pressure down distillation using oil and water separation and 2-tower distillation principle and 3D azeotropic mixture.

The present invention relates to a technology for manufacturing a special paper using pulps as byproducts, and a first-ever technology for industrialization using new bio energy as compared to a conventional corn application method.

Since a conventional ethyl alcohol manufacture technology used in many countries is directed to manufacturing alcohol for drinks, which generally adapts an 8-tower distillation method. The above method is able to manufacture only purity 95% through 99% of ethyl alcohol. So as to manufacture purity 99.9% of ethyl alcohol, a molecular sieve catalyst should be used for removing remaining moisture of 1 through 5%, which leads to a high manufacturing cost. However, the new technology manufacture process according to the present invention does not use a molecular sieve catalyst, but uses a 3- component azeotropic mixture distillation method using a 2-tower azeotropic distillation principle and a 3-component azeotropic mixture using zeolite and ceramic ball for thereby manufacturing ethyl alcohol for fuel of purity 99.9%, which is different from the above US patent.

Disclosure of Invention

Accordingly, in the present invention, a method for manufacturing ethyl alcohol using corn, and a method for recycling byproducts are invented while overcoming the problems of the conventional art.

It is a first object of the present invention to manufacture an anhydride bio alcohol of purity 99.9% which does not cost a lot with the helps of a new manufacture technology such as a 3-component azeotropic mixture distillation method among newly developed 2-tower azeotropic distillation principles and a dehydration method using zeolite ceramic while enhancing energy power by adapting a far infrared ceramic apparatus in a process for processing corn to ethyl alcohol.

It is a second object of the present invention to industrialize corn as a next generation energy resource by recycling wastes produced after an alcohol production process, inner corn shank, corn shank and corn leaves as a valued added environment friendly product of biologically decomposable plastic raw material, pulp raw material, special paper, home items, architecture materials and fertilizers. The key technology of the present invention is directed to manufacturing an anhydride ethyl alcohol of purity 99.9% using a 3-component azeotropic mixture distillation method using a 2-tower azeotropic principle, and a zeolite ceramic ball and far infrared radiation method.

In addition, in a distillation process using a 2-tower azeotropic principle, moisture from the upper side of the tower and a small amount of n-pentane(or benzen) which is ethanol azeotropic mixture substance are separated, and n- pentane is collected from its upper side, and the remaining part is continuously azeotropic-processed, and a small amount of ethanol is collected by recovery- distilling the moisture of the lower part and a small amount of ethanol and is re- inputted into azeotropic distillation facility, and the remaining moisture and substance are drained.

In the ethanol manufacture process, an oil and water separation cannot be performed by an ordinary method, so it is selected among a method for changing pressure, a method for adding a third component and a method for absorbing water or extracting the same.

In addition, the present invention is directed to a method for manufacturing vegetable ethyl alcohol of purity 99.9%, and can save the manufacturing cost by 30% as compared to a conventional ethyl alcohol manufacture method.

The recycling technology of corn byproducts has importance in view of economy and business as compared to the method for producing ethanol.

For example, when 6 tons of ethyl alcohol is manufactured with 5.16 tons of corn, 800 US dollars can be earned, whereas when various environment friendly products are manufactured by recycling wastes such as byproducts(corn debris, inner corn shank, corn shank and corn leaves) which are discarded after manufacturing vegetable ethanol, 6000US dollars can be earned, which means earning more than about 7 times using the same amount of corn. The method of the present invention is a first-ever corn byproduct recycling technology.

The applicant of the present invention filed an energy resource recycling system of corn on November 10, 2007 and the application number 10-2007- 0113447, and receives an office action with a transmission number 9-5-2008- 011466743 (February 29, 2008) due to problems.

The present invention is directed to a re-filing with a new specification amended based on the office action.

The new technology of the present invention is as follows by its process.

1) Saccharification process

The corn is divided into corn bead, corn shank and inner shank, corn leaves as vegetable energy raw materials, and the corn bead is selected and ground so as to manufacture ethyl alcohol, and purified water is inputted into an oxidation tank and is well stirred for thereby producing corn liquid. Acid is added for disinfecting various bacteria, and saccharification enzyme is inputted and is processed for 12 hours in saccharification reaction, and then corn is saccharificated.

2) Fermentation process Ethanol ferment of 0.08weight% is added with respect to 100weight% of sugar raw material prepared in the step A and is fermented for 72 hours at 31 ~32°C, and a far infrared ray is emitted using a far infrared radiation heater installed in the interior of the fermentation tank for thereby promoting fermentation.

3) Distillation process

(1) A far infrared radiation heater(220volt, 350watt, ceramic type) is installed in the distillation tower 1 and the distillation tower 2 using the 2-tower azeotropic distillation principle, and a far infrared ceramic ball made of zeolite as principle material is installed for absorbing water from the floor, and the calorie of the ethanol and water of the distillation tower is increased, and water and oil are separated. At this time, alcohol and water become azeotropic mixture when the composition ratio of alcohol 95.6% is present, and the azeotropic point is a minimum value as 78.15°C.

(2) For example, when a mixture of ethanol and water is boiled, when boiling an aqueous solution of ethanol 10%, the azeotropic point is 92.5°C, and the ethanol concentration is 51%. In addition, in case of ethanol 75%, the azeotropic point is 80°C, and in case of ethanol, the azeotropic point is 78.15°C, which is the minimum value.

4) Dehydration process(oil and water separation)

(1) Cyclohexane is injected into ethyl alcohol solution using a 3D azeotropic mixture distillation method which uses a 2-tower azeotropic mixture distillation principle, and a 3-componnt azeotropic mixture formed of ethyl alcohol, dehydration agent and water is obtained.

(2) The boiling point of the 3-component azeotropic mixture formed of ethyl alcohol is lowest, and the amount of moisture is more than the amount of water of the 2-composition azeotropic mixture formed of ethyl alcohol and water. Water is removed from the distillation tower 2 during the distillation using the above principle.

(3) In the present invention, a far infrared ceramic ball manufactured using zeolite as principle material is installed on the floor of the distillation tower with a height of 5cm, and a far infrared ray is alternately radiated, which leads to an activation of ethanol molecular and water molecular. At this time, the alcohol molecular is transmitted to the distillation tower, and the water molecular is absorbed by means of far infrared ray ceramic ball installed on the floor of the distillation tower, and water can be dehydrated 100% using a water dehydration pulp.

With the above four processes, vegetable ethyl alcohol of a purity 99.9% can be prepared, which can save the manufacture cost by more than 30% as compared to the conventional method.

Effects

As described above, according to the present invention, it is possible to grow the corn as an economic agriculture product, and it is environment- friendly since vegetable raw materials are used instead of a conventional fossil fuel, and energy power can be enhanced by activating alcohol molecular by adapting a far infrared ray method, and the emission of pollutant can be minimized by distilling raw oil along with an excellent quality and performance as compared to a conventional gasoline. A value added industrialization product and raw material manufacture can be possible by recycling byproducts. It is possible to increase the profit by about 7~9 times using the same agriculture products in the same agriculture area in view of the agriculture productivity, and a non-pollution environment industry can be developed, and the present invention can be applied to related fields and applications.

Brief Description of the Drawings

Figure 1 is a view illustrating a corn energy recycling system according to the present invention.

Figure 2 is a view illustrating an ethyl alcohol manufacture process using corn according to the present invention.

Figure 3 and 4 is a view of a 2-tower azeotropic distillation principle and a distillation process according to the present invention.

Figure 5 is view illustrating a dehydration process of corn alcohol according to the present invention.

Figure 6 is a view illustrating a pulp raw material and a special paper recycled from wastes according to the present invention.

Figure 7 is a view illustrating a chemical raw material HMF manufacture process recycled from wastes according to the present invention. Best Mode for Carrying Out the Invention

The construction of the present invention will be described with reference to the accompanying drawings.

Figure 1 is a view of a flow chart for making corn a bio energy resource according to the present invention.

The embodiments of the present invention will be described as follows.

In the first embodiment of the present invention, corn is ground, and starch-processed, and saccharificated, and fermented using a certain far- infrared radiation method, and oil and water are separated, and a pressure down and dehydration are performed for thereby producing bio alcohol.

Figure 2 is a view of a production process of ethanol using corn according to the present invention.

As shown therein, the corn is ground, and saccharificated, and fermented and is further processed through a 2-tower azeotropic distillation and a 3-component azeotropic mixture distillation and a zeolite dehydration for thereby producing bio alcohol.

The saccharification process of corn in the ethanol production process of Figure 2 includes a step (1) in which corn beads are washed in clean, and are inputted into a buffer solution of phosphate having a concentration of 0.1 mol/L with pH 7.0 with a weight% of 1 :2 at 31 ~32°C for 30 hours, and then the solution is removed, and a step (2) in which the corn beads obtained from the step (1) are washed with water having a two times volume ratio and are ground, and the com powder is well stirred in the washed water and is inputted into an oxidation tank for thereby producing corn liquid.

The fermentation process will be described as shown in Figure 2.

A high temperature alpha-amylase is added into the corn liquid at a ratio of 6 micro per gram and is reacted at 90⁰C for 2 hours, and is cooled at 60⁰C, and saccharification enzyme is added 120 micro per gram, and saccharification reaction is performed for 12 hours, and the mixture is transferred into a fermentation tank, and a fermentation process is performed.

Figures 3 and 4 show the distillation process.

The distillation process is shown in Figures 3 and 4 , and reference numerals 11 and 13 are an under canted wine pre-heater, and 12 means is . standard of gasoline

(1) The 3D azeotropic mixture distillation method is adapted using the 2- tower distillation tower principle, and the far-infrared ray heater(220volt, 350watt, ceramic type) is installed in the distillation tower 1 and the distillation tower 2, and a far infrared ceramic ball made of zeolite as principle is installed in the floor, and the calorie of the ethanol and water is increased in the distillation tower for thereby promoting a separation of water and alcohol.

The composition can not be separated from the alcohol mixture by an ordinary distillation method, so a method for changing the pressure, a method (azeotropic mixture distillation) for adding a third component or a method for absorbing or extracting water is used. Figure 5 is a view illustrating a dehydration process.

It shows a dehydration process of the present invention, and 21 means an over heater, 22 means a heat radiator, 23 means a cooler, 24 means a liquidation cooler, 25 and 26 mean an absorption unit and 27 means a separator.

(1) A dehydration agent(cyclohexane) is injected into an ethyl alcohol solution using a 3-component azeotropic mixture distillation method using a 2- tower azeotropic mixture distillation principle for thereby producing a 3- compoent azeotropic mixture formed of ethyl alcohol, dehydration agent, and water.

(2) The burning point of the 3-component azeotropic mixture formed of ethyl alcohol is lowest, and the amount of mixture is more than the amount of water in the 2-component azeotropic mixture formed of ethyl alcohol and water. So, water can be removed from the distillation tower 2 during distillation using the above principle.

With the vegetable ethyl alcohol manufacture method which is used in many countries, it is possible to manufacture only ethyl alcohol of purity 95~99%, but so as to manufacture ethyl alcohol of purity 99.9%, an expensive molecular sieve catalyst is used so as to remove moisture of 1 ~5%, and since the catalyst should be exchanged depending on its use frequency, the manufacture costs a lot.

However, according to a new technology manufacture process according to the present invention, it is directed to a new technology of a 2- tower azeotropic distillation principle, a 3-component azeotropic mixture distillation method and a dehydration method using a zeolite ceramic ball without using a molecular sieve catalyst, and ethyl alcohol of purity 99.9% can be manufactured. So, a manufacture does not cost a lot as compared to the conventional method.

The construction of the present invention will be described in more detail.

The first embodiment 1 : Ethyl alcohol manufacture method The method comprises a step (A) in which the corn used as a vegetable energy raw material is classified into corn bead, corn shank and inner shank, and corn leaves, and the corn beads are selected and ground for producing ethyl alcohol and are inputted into an oxidation tank, and purified water is well stirred for thereby producing corn liquid, and acid is added for disinfecting various bacteria, and saccharification enzyme is added, and saccharification reaction is performed for 12 hours, so the corn liquid is saccharificated; and a step (B) in which ethanol production ferment is added by 0.08weight% with respect to the sugar raw material 100weight% produced in the step A, and is fermented for 72 hours at 31 ~32°Cm, and a far infrared ray is radiated from the far infrared ray hater installed in the interior of the fermentation tank for thereby promoting fermentation; and a step (c) in which the fermented liquid of the sugar material of the step B is inputted into the distillation tower, and the distillation tower is formed of two serial distillation towers, and a ceramic type far infrared ray heater of 220volts and 350watts and a ceramic ball for radiating far infrared ray are installed in the distillation towers, and the ethanol molecular and the water molecular are activated, and it is extracted based on the 3- component azeotropic mixture distillation method; and a step (d) in which the zeolite ceramic ball, which is a dehydration agent, is installed on the floor of the second distillation tower, and water is removed;

Along with the above fermentation, the fermentation is more promoted, and the fermentation time is shortened by 1/4, and the oil and water separation and the pressure down distillation process are shortened, and the anhydride alcohol, finally obtained, can be modified into bio alcohol for the use in internal combustion engine.

The second embodiment will be described.

Here, a certain far infrared ray apparatus is inputted into the mixture and reaction tank, and the far infrared ray apparatus is rotated using a motor installed in an outer side of the reaction tank for thereby activating energy.

The above reaction is a slight heating reaction which dos not need a cooler, and there is not difficulty for agitation.

[Table 1]

* I LTT-= Less then

As seen in the above table, the bio fuel of the present invention has the same manufacture cost and operation cost as compared to the conventional gasoline, but it is possible to reduce the environment pollutants such as CO2, Nox, SOX or the like by 35%.

Embodiment 3

The byproducts produced in the manufacture method of ethyl alcohol, corn debris, corn shank, inner corn shank, corn stem and leaves are energy raw material resources in the present invention, and the following shows various raw materials(resources) for manufacturing various environment friendly products.

Followings

1. Biologically decomposable plastic manufacture using corn A step (A) in which the corn debris of byproducts produced in the fermentation step (B) of the method for manufacturing anhydride ethyl alcohol of item 1 is dried and ground, and the ground powder, corn starch and lubricant are mixed and added, and are agitated for 25 minutes at a temperature of 180°C, and a modified starch is formed. A step (B) in which the modified starch of the step A is inputted into a reaction kettle, and a thermoplastic resin, plastic agent, oxidation promoter are mixed with the modified starch and are mixed and polymerized for 25 minutes at 110⁰C.

A step (C) in which the mixture keeps until the polymer obtained in the step B is condensed, and the temperature is decreased to 70~80°C, and the polymer is extruded through an extruding machine, and a biologically decomposable sheet is obtained under 130~200°C.

Descriptions of chemical solvents used

* Thermoplastic resin: One or two selected from PVA-poly vinyl alcohol, PA-polyamide, PLA-poly latic acid.

* Plastic agent: One selected from DOS-dioctyl sebacate, salad oil.

* Coupling agent: One selected from silane coupling agent, aluminate coupling agent.

* Lubricant: One selected from oxide DE polietileno, stearic acid.

* Oxidation decomposition promoter: corn oil

Semi-dry oil obtained by compression method from corn germ

B. Manufacture of pulp or paper raw material using com shank and manufacture debris

The corn debris of the byproducts produced during the fermentation step B of the method for manufacturing anhydride ethyl alcohol of item 1 is dried and ground into less than 0.5cm, and is mixed with corn starch, and the mixture made is mixed with lubricant, thermoplastic resin, oxidation decomposition promoter and plastic agent, and water is added by four times weight, and is deposited into a mixture liquid of caustic soda and sodium sulfate and is boiled at 170⁰C in a gruel state.

D. Manufacture of livestock feed with high protein using corn shank, stem and leaves

Corn shank and inner shank and corn leaves produced as byproducts in a method for manufacturing anhydride ethyl alcohol of item 1 are ground into 100-200 meshes and are disinfected, and the powder of corn debris, corn starch, elvan powder of 200 meshes and oligosaccharide aqueous solution obtained in the fermentation step B of the method for manufacturing anhydride ethyl alcohol of item 1 are mixed and made for the livestock feeds.

* Table of composition of D.D.G.S livestock feeds 5-30% of protein, 7-12% of moisture, 7-10% of millet fat, and 41 -58.5% of carbohydrate

E. Method for manufacturing chemical raw material using corn shank

F. As seen in the contents of items 1 through 5, the corn is a resource and has nothing to discard. It is possible to make profit as much as about 7 times as compared to when manufacturing ethyl alcohol. When the corn is industrialized, it might become a more economic crop as compared to other crops, and the corn is an energy resource which might be industrialized as an environmental friendly product.

In the item 1 , one is selected from sugar beet, cassava, potato, pig potato, Cyperus rotundus, acorn, rice particle, and is mixed with the bead of corn.

Descriptions of vegetable raw materials

* Sugar beet: Beta vulgaris var. saccharfera The production of alcohol per 1 ha is 4300kg/year

The production of alcohol of corn is more than 2050kg/year in 1 har

* Cyperus rotundus: Nutgrass galingale

It is a perennial herb of about 1 ~3.5cm with a dark brown skin having hairs which grows in ridge of rice field, ridge of field, sand field.

Amount of starch: 47%~60%

Amount of fuel alcohol: 23%~28%

As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described examples are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.

Claims

Claims:

1. A method for manufacturing anhydride ethyl alcohol, comprising: a step (a) in which corn is divided into corn bead, corn shank and inner shank, corn leaves as vegetable energy raw materials, and the corn bead is selected and ground so as to manufacture ethyl alcohol, and purified water is inputted into an oxidation tank and is well stirred for thereby producing corn liquid, and acid is added for disinfecting various bacteria, and saccharification enzyme is inputted and is processed for 12 hours in saccharification reaction, and then corn is saccharificated; a step (b) in which ethanol ferment of 0.08weight% is added with respect to 100weight% of sugar raw material prepared in the step A and is fermented for 72 hours at 31 ~32°C, and a far infrared ray is emitted using a far infrared radiation heater installed in the interior of the fermentation tank for thereby promoting fermentation. a step (c) in which the corn liquid fermented in the step B is inputted into the distillation tower, and the distillation tower is formed of two serial distillation towers, and a ceramic type far infrared ray heater of 220volts and 350watts and a ceramic ball for radiating far infrared ray are installed in the distillation towers, and the ethanol molecular and the water molecular are activated, and it is extracted based on the 3-component azeotropic mixture distillation method; and a step (d) in which the zeolite ceramic ball, which is a dehydration agent, is installed on the floor of the second distillation tower, and water is removed.

2. A method for manufacturing a biologically decomposable plastic raw material, comprising: a step (a) in which the corn debris of byproducts produced in the fermentation step (B) of the method for manufacturing anhydride ethyl alcohol of item 1 is dried and ground, and the ground powder, corn starch and lubricant are mixed and added, and are agitated for 25 minutes at a temperature of 18O⁰C, and a modified starch is formed; a step (b) in which the modified starch of the step A is inputted into a reaction kettle, and a thermoplastic resin, plastic agent, oxidation promoter are mixed with the modified starch and are mixed and polymerized for 25 minutes at 11O⁰C; and a step (c) in which the mixture keeps until the polymer obtained in the step B is condensed, and the temperature is decreased to 70~80°C, and the polymer is extruded through an extruding machine, and a biologically decomposable sheet is obtained under 130~200°C.

3. The method of claim 1 , wherein the corn debris of the byproducts produced during the fermentation step B of the method for manufacturing anhydride ethyl alcohol of item 1 is dried and ground into less than 0.5cm, and is mixed with corn starch, and the mixture made is mixed with lubricant, thermoplastic resin, oxidation decomposition promoter and plastic agent, and water is added by four times weight, and is deposited into a mixture liquid of caustic soda and sodium sulfate and is boiled at 17O⁰C in a gruel state.

4 The method of claim 1 , wherein com shank and inner shank and corn leaves produced as byproducts in a method for manufacturing anhydride ethyl alcohol of claim 1 are ground into 100~200 meshes and are disinfected, and the powder of corn debris, corn starch, elvan powder of 200 meshes and oligosaccharide aqueous solution obtained in the fermentation step B of the method for manufacturing anhydride ethyl alcohol of claim 1 are mixed and made for the livestock feeds.

5. The method of claim 1 , wherein one is selected from sugar beet, cassava, potato, pig potato, Cyperus rotundus, acorn, rice particle, and is mixed with the bead of com.