KR20140001021A - Oil production system from biomass and catalyst therefor - Google Patents

Abstract

Disclosed is an oil production system capable of producing oil with a good quality from biomass, plastic wastes and organic wastes, which is able to efficiently use energy by recycling energy, to reduce carbon dioxide emission, which is a greenhouse gas, and to remarkably contribute to the atmospheric environment, and a catalyst therefor, wherein wood hydrocarbon of residual barks after extracting oil from stems of crops, corn stems, palm, canola, Jatropha, which is discarded as non-edible materials or wastes, or algae or microalgae from sea or a lake are used as source materials to manufacture oil with an excellent quality from plastic wastes or organic wastes, and, therefore, to have a greenhouse gas reduction effect due to carbon dioxide reduction as well as a waste resource recycling effect.

Description

TECHNICAL FIELD [0001] The present invention relates to an oil production system for biomass,

The present invention relates to biomass as a crop stem, such as rice straw or straw, corn or sugar cane stem, Giant Cane and woody hydrocarbons such as palm, palm, canola and jatropha, And a system for producing an oil such as gasoline, light oil or heavy oil by catalytically processing biomass such as microalgae. The present invention also relates to catalysts that can be used in such systems.

Techniques for producing bio-diesel from soybean oil, rape oil, canola oil, palm oil, and jatropha oil as a new and renewable energy and technologies for producing bio-ethanol from starch crops such as corn, cassava, potato and sweet potato have been extensively studied and actually produced have. However, these technologies have made it difficult to avoid responsibility for the depletion of food resources around the world by obtaining oil from edible crops.

Therefore, to obtain oil from biomass such as crops stem, palm or palm, canola, jatropha, lime husks, woody hydrocarbons such as Giant Cane, algae and microalgae from the ocean or lake It is being tried. As an apparatus or method for treating waste, there is a method of producing bioethanol or biodiesel by heating with steam at 150 to 200 ° C. as in WO 2009/095693 A2, and as in US Pat. No. 5,190,226 There is a method of producing biodiesel in a batch in an autoclave. In addition, US Pat. No. 6,752,337 describes a process for producing continuous biodiesel using steam.

Japanese Patent Laid-Open No. 2002-285171, Japanese Patent Laid-Open No. 2002-121571, and Japanese Patent Laid-Open No. 2002-088379 describe methods and systems for gasifying biomass.

U.S. Patent Nos. 3,966,883, 4,088,739 and 4,017,590 disclose processes for preparing zeolite catalysts, but it is difficult to convert woody hydrocarbons to oil with these zeolites.

International Publication WO 2007/122967 discloses a method of decomposing waste plastics and organic materials by using titanium oxide. Japanese Patent Application Laid-Open No. 2009-270123 also discloses a process of decomposing waste plastics and organic materials using titanium oxide However, it is also difficult to directly convert woody hydrocarbons to oil.

U.S. Patent No. 5,190,226 U.S. Patent No. 6,752,337 Japanese Patent Application Laid-Open No. 2002-285171 Japanese Patent Application Laid-Open No. 2002-121571 Japanese Patent Application Laid-Open No. 2002-088379 U.S. Patent No. 3,966,883 U.S. Patent No. 4,088,739 U.S. Patent No. 4,017,590 International Publication WO 2007/122967 Japanese Patent Application Laid-Open No. 2009-270123

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of the prior art, and an object of the present invention is to provide a method and apparatus for extracting oil from palm or palm, palm, canola, and jatropha and removing the remaining shell, wood hydrocarbons such as Giant Cane, The present invention is to provide an oil producing system for producing high quality oil such as gasoline, kerosene, diesel oil, and heavy oil from biomass such as algae and microalgae.

Another object of the present invention is to provide a method and apparatus for use in the above-described system, for example, a crop stem, such as rice straw or straw, corn or sugar cane stem, Giant cane and the like, The present invention is to provide a catalyst for producing high-quality petroleum, kerosene, diesel, heavy oil, etc. from biomass such as woody hydrocarbons, algae obtained from the ocean or lake, and microalgae.

In order to achieve the above and other objects,

Corn stalks, giant cane, lignocellulosic hydrocarbons such as bark, oil extracted from palm or palm, canola, jatropha, etc., from the raw material input port (A) through the raw material input port (A) (Hereinafter, referred to as " refuse derived fuel "), or a mixture of two or more kinds of raw materials selected from the group consisting of biomass such as algae and microalgae obtained from a lake or lake and waste refuse derived fuel (RDF) B);

An extruder (C) for raising the temperature of the raw material from the crusher (B) and extruding the raw material;

(E) for agitating the raw material from the extruder (C) and a catalyst for raw material decomposition are provided so as to decompose the raw material from the extruder (C) to decompose the catalyst to decompose the raw material to generate water vapor, water soluble substance and gaseous oil and sludge Reactor (D);

A catalytic reformer (E ') for reforming gaseous oil from the catalytic cracking reactor (D) with gasoline, light oil and heavy oil; A heat exchanger (F ') for recovering the heat of the gaseous oil and a condenser (F) for condensing; A vacuum pump (V) for smoothly discharging the gaseous oil generated in the reactor;

A reservoir (G) for storing condensed oil from the condenser (F); And an oil-water separator (G ') for separating the water in the storage tank, the water-soluble material and the oily oil; The separated oil is transferred to the distillation column (H), and the remaining water and the water-soluble substance are heated to a temperature of 80 ° C or higher by the waste heat recovered through the heat exchanger (F ') and evaporated, Adipic acid derivative and grantrez copolymer remain as a residue after evaporation, which is recovered and commercialized.

The oil from the storage tank G is distilled by heating by the steam boiler P so that the heavy oil, the light oil and the gasoline or both of them are discharged to the heavy oil outlet port I, the diesel oil outlet port J, Port (K), or a distillation column (H) for recovering through both of them.

The high boiling point material obtained from the heavy oil outlet port (I) of the distillation column (H) is transferred to the heating unit (U) by the transfer pump (I ') and heated by the heating unit (U) again to the catalytic cracking reactor (D). As a result, the liquid phase catalyst in the catalytic reactor, which decreases as the reaction proceeds, is replenished. The catalytic cracking reactor (D) is temperature controlled in the boiler (Q) through the heat medium oil. The sludge remaining after the reaction in the catalytic reactor (D) is transferred to the incinerator (M) through the screw press (O) by the opening of the valve (R), and the liquid phase is heated by the heating unit (U) again. And recycled to the catalytic cracking reactor (D). The catalyst, which is burned in the incinerator (M) and the char solid form is oxidized and remained, is recovered through the catalyst recovery unit (N), and the post-combustion gas is sent to the catalytic oxidation column (L) to be decomposed into carbon dioxide and water, do. The heat generated at this time is recovered through the heat exchanger L '.

In the catalytic cracking reactor (D) and the catalytic reformer (E '), a mixture of Al ₂ O ₃ and a zeolite having a Si / Al ratio of 1 to 60 is used to decompose raw materials such as biomass, A catalyst impregnated with at least one of Sc, V, Fe, Ni, Co, Zn, Ge and Sn, Zr, Mo, Ce and Cs among the 4 periodic elements, A mixed catalyst of the ion-exchanged and the Al ₂ O ₃ impregnated with the metal may be used.

The catalyst was prepared by mixing Al ₂ O ₃ and the zeolite in a weight ratio of 100: 1 to 1: 100 and adding Sc, V, Fe, Ni, Co, Zn, Ge and Sn, Zr and Mo , Ce and Cs at a weight ratio of 0.01 to 15%, drying at a temperature of 100 ° C to 150 ° C for at least 6 hours, and then calcining at a temperature of 400 ° C to 700 ° C for 2 hours or more do. The catalyst thus prepared is used in an amount of preferably 0.01 to 30% by weight based on the raw material. If this ratio is exceeded, the efficiency of decomposition and oil production of biomass, waste plastics, organic wastes, etc. is remarkably reduced.

The zeolite may be at least one of Mordenite, Offretite, Faujasite, Ferrierite, Erionite, Zeolite-A and Zeolite-P, Is selectively treated with hydrochloric acid or sulfuric acid to dealumination to increase the Si / Al ratio, thereby selecting at least one zeolite having a Si / Al ratio of 1 to 60. The metal ion-exchanged in the zeolite is selected from the group consisting of Sc, V , Fe, Ni, Co, Zn, Ge and Sn, Zr, Mo, Ce, and Cs.

The metal to be ion-exchanged in the zeolite is at least one metal selected from Sc, V, Fe, Ni, Co, Zn and Ge and Sn, Zr, Mo, Ce and Cs among the four- Lt; / RTI >

The catalyst, in which the metal is ion-exchanged with the zeolite and Al ₂ O ₃ is impregnated with the metal, is characterized in that Sc, V, Fe, Ni, Co, Zn, Ge, Sn and Zr , Mo, Ce, and the ion exchange catalyst at least one metal among Cs by weight ratio of from 0.01 to 3%, of the 4-cycle element in the Al ₂ O ₃ Sc, V, Fe, Ni, Co, Zn, Ge and Sn , Zr, Mo, Ce, and Cs at a weight ratio of 0.01 to 15% is mixed at a weight ratio of 100: 1 to 1: 100, and the mixture is calcined at a temperature of 100 ° C to 150 ° C for 6 hours or more Followed by baking at a temperature of 400 ° C to 700 ° C for 2 hours or more. The catalyst thus prepared is used in an amount of 0.01 to 20% by weight based on the raw material in the catalytic cracking reactor (D). In the catalyst reformer (E '), it is used as a honeycomb type or granule or bead type catalyst, and the space velocity is used to be 3,000 to 100,000 / hr. If the above-mentioned ratios exceed the drying and calcination temperature ranges, the efficiency of decomposition and oil production of biomass, waste plastics, organic wastes, and the like is significantly deteriorated.

According to the present invention, woody hydrocarbons that have been discarded as non-edible and waste materials can be used as crops stem, corn stalks, woody hydrocarbons such as giant cane, palm, palm, canola and jatropha, It is possible to use lake algae, microalgae, and RDF as raw materials and to obtain good quality oil from organic waste, and it is possible to obtain greenhouse gas reduction effect at the same time by utilizing waste resources and CO ₂ reduction, And it can contribute to the improvement of the atmospheric environment by reducing the carbon dioxide emission which is the greenhouse gas.

1 is a schematic representation of an oil production system according to one preferred embodiment of the present invention for producing oil from biomass, organic waste, for example.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in more detail with reference to the following illustrative drawings.

The present invention relates to woody hydrocarbons, such as woody hydrocarbons, such as crop roots, corn stalks, giant canes, woody hydrocarbons such as bark remaining in oil extracted from palm, palm, canola and jatropha, The present invention provides an oil producing system capable of obtaining good quality oil such as gasoline, diesel oil, and heavy oil using biomass including algae and microalgae and refuse derived fuel (RDF) as raw materials.

Referring to FIG. 1, raw materials such as wood hydrocarbons, biomass including algae and microalgae, refuse derived fuel (RDF), and the like are fed into the grinder B through the feed inlet A.

The raw material is pulverized to a size of 3 cm or less in the pulverizer (B), then heated to 120 ° C to 450 ° C through the extruder (C) and transferred to the catalyst decomposition reactor (D).

In the catalytic cracking reactor (D), the catalytic cracking reaction is initiated by the heat medium oil boiler (Q) and the feed pump (Q ') while the heat medium flow is regulated at 250 ° C to 450 ° C. At this time, the agitator (E) is operated at 60 to 10,000 RPM to make continuous and uniform mixing.

The gaseous oil generated in the catalytic cracking reactor D is reformed into gasoline, light oil and heavy oil through the catalytic reformer E 'and recovered from the waste heat via the heat exchanger F' And the generated gaseous oil is vacuum distilled through the vacuum pump V to a pressure of 500 mmAq or less and is stored in the storage tank G through the heat exchanger and the condenser and is distilled in the distillation column H heated by the reboiler P . If the degree of vacuum is higher than the above degree of vacuum, decomposition reaction of biomass will not occur properly. In addition, the effluent from the reservoir G is separated through a water separator G 'installed at the bottom as shown in FIG. The separated oil is transferred to the distillation column H. The remaining water and the water-soluble substance are heated to a temperature of 80 ° C or higher in the evaporation heating unit M 'by the waste heat recovered through the heat exchanger F' The waste heat is recovered while passing through the heat exchanger (L '), and the adipic acid derivative or the grantrez copolymer remains as a by-product after evaporation, (W).

In the distillation column (H), gasoline is obtained at the outlet port (K) of the gasoline at 30 to 250 ° C due to the difference in boiling point, light oil is obtained at a boiling point of 250 to 350 ° C, Is obtained at the heavy oil outlet port (I). The high boiling point material obtained at the heavy oil outlet port I is conveyed to the catalytic cracking reactor D through the heating unit U through the transfer pump I '.

The gas escaping from the distillation column H is decomposed into carbon dioxide and water through the catalytic oxidation column L and is discharged to the outside air. The heat generated at this time is recovered through the heat exchanger L '.

The catalyst decomposition reactor (D) becomes a heating medium flow jacket heated by the boiler (Q) and is heated. When the raw material of the biomass is decomposed in the catalytic cracking reactor (D) and the amount of the solid content remaining in the char type increases, the valve (R) is opened and the screw press And the liquid phase generated while passing through the screw press O is recycled to the catalyst decomposition reactor D through the heating unit U by the pump S.

The solid discharged through the screw press O is mixed with the catalyst and Char which is burned in the incinerator M and the heat of the exhaust gas at that time is recovered through the heat exchanger Y to be supplied to the steam boiler P, And the generator (T), and the exhaust gas is connected to the catalytic oxidation column (L) to be decomposed into carbon dioxide and water. The heat generated at this time is recovered through the heat exchanger L '. The catalyst remaining in the incinerator (M) is recovered in the catalyst recovery tank (N) and reused.

The steam and the exhaust gas generated from the raw material by the heating of the extruder B are connected to the catalytic oxidation column L and decomposed into carbon dioxide and water to be harmless and discharged to the outside air. It is recovered while passing.

In the initial reaction, UCO (unconverted oil) in which sulfur is removed from crude oil or bunker C in the catalyst decomposition reactor (D), or high boiling point material obtained at a temperature of 350 ° C. or higher in the distillation tower when refining crude oil, And a mixture of two or more selected from the group of liquid phase catalysts composed of the high boiling point material obtained from the heavy fuel outlet port (I) is used in a weight ratio of 20: 1 to 1:20 with respect to the raw material of the biomass. If the above ratio is exceeded, the decomposition reaction is slow or the oil production yield is remarkably deteriorated.

In the catalytic cracking reactor (D) and the catalytic reformer (E '), a mixture of Al ₂ O ₃ and a zeolite having a Si / Al ratio of 1 to 60 is used to decompose raw materials such as biomass, A catalyst impregnated with at least one of Sc, V, Fe, Ni, Co, Zn, Ge and Sn, Zr, Mo, Ce and Cs among the 4 periodic elements, A mixed catalyst of the ion-exchanged and the Al ₂ O ₃ impregnated with the metal may be used.

The catalyst was prepared by mixing Al ₂ O ₃ and the zeolite in a weight ratio of 100: 1 to 1: 100 and adding Sc, V, Fe, Ni, Co, Zn, Ge and Sn, Zr and Mo , Ce and Cs at a weight ratio of 0.01 to 15%, drying at a temperature of 100 ° C to 150 ° C for at least 6 hours, and then calcining at a temperature of 400 ° C to 700 ° C for 2 hours or more do. The catalyst thus prepared is used in an amount of preferably 0.01 to 30% by weight based on the raw material. In the catalyst reformer (E '), it is used as a honeycomb type or granule or bead type catalyst, and the space velocity is used to be 3,000 to 100,000 / hr. If this ratio is exceeded, the efficiency of decomposition and oil production of biomass, waste plastics, organic wastes, etc. is remarkably reduced.

The zeolite may be at least one of Mordenite, Offretite, Faujasite, Ferrierite, Erionite, Zeolite-A and Zeolite-P, Is selectively treated with hydrochloric acid or sulfuric acid to dealumination to increase the Si / Al ratio, thereby selecting at least one zeolite having a Si / Al ratio of 1 to 60. The metal ion-exchanged in the zeolite is selected from the group consisting of Sc, V , Fe, Ni, Co, Zn, Ge and Sn, Zr, Mo, Ce, and Cs.

The metal to be ion-exchanged in the zeolite is at least one metal selected from Sc, V, Fe, Ni, Co, Zn and Ge and Sn, Zr, Mo, Ce and Cs among the four- Lt; / RTI >

The catalyst, in which the metal is ion-exchanged with the zeolite and Al ₂ O ₃ is impregnated with the metal, is characterized in that Sc, V, Fe, Ni, Co, Zn, Ge, Sn and Zr , Mo, Ce, and the ion exchange catalyst at least one metal among Cs by weight ratio of from 0.01 to 3%, of the 4-cycle element in the Al ₂ O ₃ Sc, V, Fe, Ni, Co, Zn, Ge and Sn , Zr, Mo, Ce, and Cs at a weight ratio of 0.01 to 15% is mixed at a weight ratio of 100: 1 to 1: 100, and the mixture is calcined at a temperature of 100 ° C to 150 ° C for 6 hours or more Followed by baking at a temperature of 400 ° C to 700 ° C for 2 hours or more. The catalyst thus prepared is used in an amount of 0.01 to 30% by weight based on the raw material. In the catalyst reformer (E '), it is used as a honeycomb type or granule or bead type catalyst, and the space velocity is used to be 3,000 to 100,000 / hr. If the above-mentioned ratios exceed the drying and calcination temperature ranges, the efficiency of decomposition and oil production of biomass, waste plastics, organic wastes, and the like is significantly deteriorated.

The catalyst used in the present invention is a zeolite containing ZSM-5 zeolite which is generally used, and the cracking of the CC bond or the CH bond by the cracking catalyst by the cracking catalyst mainly produces gas components of C ₄ or less and the remainder is produced in the form of tar (C ₆ H ₁₀ O ₅ ) n, hemicellulose (C ₆ H ₁₀ O ₅ C ₅ H ₈ O ₄ ) n, and average lignin (CH _0.8 · 0.3 (H ₂ O )) n, and the average CO 2 bond is first broken at the woody matter (CH _0.2 · 0.66 (H ₂ O)) n. At low temperatures below about 400 ° C, mainly cellulose or hemicellulose is primarily converted to anhydrous cellulose, , The CO bond in the anhydrous cellulose is firstly broken, and then the CC bond is broken. Then, the water and the water-soluble substance are produced first, and as a result of the diesel oil C ₁₁ -C ₂₁ oil Some are converted to C ₅ -C ₁₀ fraction and some remain in Char form. On the other hand, water and water-soluble materials are evaporated at a temperature of 80 ° C or higher to produce an adipic acid derivative or a grantrez copolymer.

Hereinafter, the present invention will be described based on the following examples and comparative examples. The following examples and comparative examples are only for illustrating the present invention, and the present invention is not limited to the following examples and comparative examples.

Example 1

Giant cane was pulverized as a biomass feedstock in the raw material feed port (A) to a size of 3 cm or less in the grinder (B), then heated to 350 ° C. through the extruder (C), transferred to the catalyst decomposition reactor (D) Q) at a temperature of 380 캜, wherein the agitator (E) is operated at 9,000 rpm and is continuously stirred to be homogeneously mixed to perform a catalytic cracking reaction. The gaseous oil produced therein is supplied to a catalytic reformer Gas oil and heavy oil is cooled through the condenser F and stored in the storage tank G. The water is separated by the oil water separator G ' Gasoline is obtained at port (K) between 30 and 250 ° C due to the difference in boiling point between boiling point (I) and light oil is obtained at port (J) between boiling point 250 and 350 ° C, Lt; RTI ID = 0.0 > C < / RTI >Lt; / RTI > The gaseous oil produced in the catalytic cracking reactor D is vacuumed at 450 mmAq through the vacuum pump V and is smoothly stored in the storage tank G via the heat exchanger F 'and the condenser F. The effluent from the reservoir G is separated through a water separator G 'installed at the bottom as shown in Fig. The separated oil is transferred to the distillation column H. The remaining water and the water-soluble substance are heated to 100 DEG C in the evaporation heating unit M 'by the waste heat recovered through the heat exchanger F' The waste heat is recovered while passing through the heat exchanger L 'and the adipic acid derivative or the grantrez copolymer remains as a by-product after evaporation, (W). The steam and the exhaust gas generated in the raw material by the heating of the extruder B are connected to the catalytic oxidation column L and are decomposed into carbon dioxide and water to be harmless and discharged to the outside air. ). Giant cane is decomposed in the catalytic cracking reactor (D), and the amount of the solid content remaining in the char form is increased. When the volume of the catalyst is more than 1/2 volume of the catalyst cracking reactor (D), the valve (R) is opened and sent to the screw press The liquid phase generated while passing through the press O is recycled to the catalytic cracking reactor D through the heating unit U by the pump S. The solids discharged through the screw press O are mixed with catalyst and Char which are burned in the incinerator M and the heat of the exhaust gas at that time is recovered through the heat exchanger Y to be supplied to the steam boiler P Is used as a heat source for the generator T and is connected to the catalytic oxidation tower L and decomposed into carbon dioxide and water to be harmless and discharged to the outside air to reduce air pollutants. Respectively. The catalyst remaining in the incinerator (M) is recovered in the catalyst recovery tank (N) and reused. By-products were obtained from the residue-material recovery tank (W) after heating at 100 占 폚 in a heating evaporator (M '). In the initial reaction, UCO (un converted oil) was used as a liquid catalyst in the catalytic cracking reactor (D) at a weight ratio of 15: 1 to the Giant Cane.

In order to increase the efficiency of decomposition of Giant Cane and oil production as a biomass raw material, mordenite is immersed in hydrochloric acid at 3N concentration for 1 hour by using catalyst in catalytic cracking reactor (D) and catalytic reformer (E '). After alumination and washing, the 1: 1 weight% mixture of zeolite and Al ₂ O ₃ having a Si / Al ratio of 3 was impregnated with 13 weight% of the mixture, dried at 150 ° C. for 8 hours, and then 3 hours at 550 ° C. The calcined catalyst was used in the catalytic cracker (D) 0.1% by weight based on the raw material, and was used in the catalytic reformer (E ') so that the space velocity was 4,000 / hr.

Example 2

The RDF was fed into the raw material feed port A as a raw material for biomass and the temperature was raised to 150 ° C. through the extruder C and transferred to the catalytic cracking reactor D and the catalytic cracking reaction was carried out at a temperature of 430 ° C. Wherein the stirrer E operates at 5,000 rpm and the gaseous oil produced in the catalytic cracking reactor D is vacuumed at 200 mmAq through a vacuum pump V to smoothly flow through the heat exchanger F ' Zeolite was immersed in 3 N hydrochloric acid for 3 hours as a catalyst used in the catalyst decomposition reactor D and the catalyst reformer E ' by de-aluminate was Nation washed with Si / Al ratio of 55 in a zeolite and Al ₂ O ₃ 90 a: the Fe-impregnated be 0.1% by weight of the mixture to 1% by weight of mixture at 450 ℃ after drying for 12 hours at 120 ℃ 1 wt% of the catalyst calcined for 3 hours was used for the raw material, The catalyst thus prepared was used in the catalytic cracking reactor (D) in an amount of 1% by weight based on the raw material, and used in the catalytic reformer (E ') so as to have a space velocity of 50,000 / hr. In the case of refining the crude oil with a liquid catalyst in)) was carried out in the same manner as in Example 1 except that a high boiling point material obtained at 350 ℃ or more in a distillation column was used in a weight ratio of 10: 1 to RDF.

Example 3

The rice straw was put into the feed inlet (A), and the temperature was raised to 250 ° C. through the extruder (C) and transferred to the catalytic cracking reactor (D). The catalytic cracking reaction was carried out at 280 ° C. by the heat oil boiler (Q) The gas phase oil produced in the catalytic cracking reactor D is vacuumed at 30 mmAq through the vacuum pump V to smoothly flow through the heat exchanger F ' F and then stored in a storage tank G. The catalyst used for the catalyst decomposition reactor D and the catalyst reformer E 'was dia- lumated by immersing Erionite in 3N hydrochloric acid for 6 hours And the mixture was impregnated with 7 wt% of Zn and Sn in a weight ratio of 1: 1 to a 1: 90 wt% mixture of zeolite and Al ₂ O _{3 having} a Si / Al ratio of 30 and dried at 100 ° C for 24 hours And then calcined at 650 ° C for 3 hours to prepare a catalyst 18 wt% was used in the reactor (D), and the catalyst was used in the catalyst reformer (E ') such that the space velocity was 95,000 / hr. The same procedure as in Example 1 was carried out except that the high boiling point material obtained in I) was used at a weight ratio of 1:15 relative to rice straw.

Example 4

Into the raw material inlet (A), green algae, green algae dried as a biomass raw material, were put in an extruder (C), heated to 300 ° C, transferred to a catalytic cracking reactor (D), and heated to 350 ° C by a thermal oil boiler (Q). The catalyst is reacted at a temperature of, wherein the stirrer (E) operates at 1,000 RPM, does not use a vacuum pump (V), and is a zeolite as a catalyst used in the catalytic cracking reactor (D) and the catalytic reformer (E '). -P was immersed in 3N sulfuric acid for 4 hours to dealuminate and washed, so that Co and Zr were 1: 1 in a weight ratio of 10: 1% by weight of a mixture of zeolite having a Si / Al ratio of 10 and Al ₂ O ₃ . Impregnated to 2% by weight of the mixture and dried at 150 ° C. for 6 hours, and then calcined at 600 ° C. for 3 hours, 6 wt% of the catalyst was used in the catalytic cracking reactor (D) for the raw material, and the space velocity was 10,000 / hr. Example 1 except that it was used in the catalytic reformer (E ') It was carried out in the same way as.

Example 5

Extract the oil from the jatropha as a raw material of biomass into the raw material inlet (A), and put the remaining shells. The temperature is increased to 250 ° C. through an extruder (C) and transferred to the catalytic cracking reactor (D). Catalytic reaction at a temperature of ℃, wherein the stirrer (E) is operated at 100 RPM, does not use a vacuum pump (V), the catalyst used in the catalytic cracking reactor (D) and catalytic reformer (E ') The 5: 1 wt% mixture of Ferrierite and SiO ₂ was impregnated to 1 wt% of Ni and Ge in a weight ratio of 1: 1 by weight of the mixture, dried at 130 ° C. for 7 hours, and then dried at 500 ° C. 3 The catalyst calcined for a period of time was used in the catalytic cracking reactor (D) 12% by weight based on the raw material, was used in the catalytic reformer (E ') so that the space velocity is 30,000 / hr, the liquid phase in the catalytic cracking reactor (D) during the initial reaction UCO as a catalyst weighs 1: 15 for biomass feedstock It carried out by the same method as Example 1 except having used as a ratio.

Example 6

Into the raw material inlet (A), squeeze palm oil as a raw material of biomass, and put the remaining shells. The temperature is increased to 450 ° C. through an extruder (C) and transferred to the catalytic cracking reactor (D). And the agitator (E) operates at 3,000 RPM, does not use a vacuum pump (V), and is a catalyst used in the catalytic reactor (D) and the catalytic reformer (E '). After immersion in sulfuric acid for 6 hours to dealumination and washing, ion exchanged 2% by weight of V in zeolite-A having a Si / Al ratio of 5, and Ge and Ce in a weight ratio of 1: 1 in Al ₂ O ₃ The weight ratio of impregnated to 60% by weight was mixed to 60: 1, dried at 150 ° C. for 6 hours, and then calcined at 700 ° C. for 3 hours in a catalytic decomposition reactor (D) based on 28 wt%. The rate was 95,000 / hr was used in the catalytic reformer (E '), In the same manner as in Example 1 except that the high boiling point material obtained in the heavy oil outlet port (I) in Example 2 was used as a liquid catalyst in the catalytic cracking reactor (D) at a weight ratio of 1: 3 to the biomass raw material. Was performed.

Example 7

Put sugarcane stems and corn stems in a weight ratio of 1: 1 as biomass raw materials in the raw material inlet (A), raise the temperature to 360 ° C. through an extruder (C), transfer them to a catalytic cracking reactor (D), and heat the oil oil boiler ( Catalytic decomposition reaction at a temperature of 360 ℃ by Q), does not use a vacuum pump (V), the catalyst used in the catalytic cracking reactor (D) and catalytic reformer (E ') 8 hours in 3N sulfuric acid. Dilution and dialumination followed by washing to 1: 1 mixture of zeolite-X and Modernite with 1% by weight of Mo to zeolite-X and Modernite, respectively, to Fausersite with a Si / Al ratio of 40 and V to Al ₂ O ₃ And the catalyst which was impregnated to 5 weight% so that 1: 1 by weight ratio and 1: 1 by weight ratio was mixed to 1: 2, dried at 150 ° C for 6 hours, and then calcined at 400 ° C for 3 hours. 10% by weight was used in (D), and the space velocity was 70,000 / hr. It was used in the catalytic reformer (E '), and used as a liquid catalyst in the catalytic cracking reactor (D) during the initial reaction at a weight ratio of 3: 1 to the raw material of the high boiling point material obtained in the heavy outlet port (I) in Example 5. Other than this was carried out in the same manner as in Example 1.

Comparative Example 1

The same procedure as in Example 1 was carried out except that the liquid catalyst and the catalyst component were not added to the catalyst decomposition reactor (D).

Comparative Example 2

The procedure of Example 1 was repeated except that 10 wt% of a HZSM-5 catalyst impregnated with 2 wt% of Pt as a catalyst component was used as the liquid catalyst in the catalyst decomposition reactor (D).

Comparative Example 3

(USY (ultra stable Y-zeolite) which is a FCC (fluid catalytic cracking) catalyst commercially available as a catalyst component and HX zeolite which is hydrogen-ion-exchanged at a weight ratio of 1: 1 to 10 Was used in place of the weight-average molecular weight.

The catalysts prepared from the examples and comparative examples were placed in the catalytic cracking reactor (D) of the oil production system from the biomass, waste plastic and organic waste of the present invention, and the properties of the resulting oil were analyzed and shown in Table 1 .

As shown in Table 1, it is possible to convert biomass, RDF and the like into high-quality gasoline, diesel, and heavy oil using the catalyst decomposition reaction as in the embodiment of the present invention. Thus, the lignocellulosic hydrocarbons and organic wastes It is possible to obtain the effect of reducing greenhouse gas by using waste resources and reducing CO ₂ at the same time, and by efficiently using energy by reusing energy and reducing greenhouse gas CO ₂ emissions, The effect that greatly contributes to the improvement of the environment can be obtained at the same time. Adipic acid derivatives and grantrez copolymers can also be obtained and high-value by-products can be obtained.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined in the following claims. It can be understood that it is possible.

A: Feed hopper, B: Grinder, C: Extruder, D: Catalytic cracking reactor,
E: stirrer, E ': catalyst reformer, F': heat exchanger, F: condenser,
G: storage tank, G ': oil water separator
H: distillation column, I: heavy oil outlet port, J: diesel outlet port, I ': transfer pump
K: gasoline outlet port, L: catalytic oxidation tower, L ': heat exchanger, M: incinerator,
M: heating evaporator, N: catalyst recovery tank, O: screw press, P: reboiler
Q: Heat transfer oil boiler, Q ': Transfer pump, R: Valve, S: Transfer pump, T: Generator, U: Heating unit, V: Vacuum pump, W:
Y: Heat exchanger

Claims (12)

(E) for agitating one kind of raw material selected from the group consisting of woody hydrocarbons and biomass including algae and microalgae, and a catalyst for decomposing raw materials are provided so that the raw materials are decomposed A catalytic cracking reactor (D) for producing water vapor, water soluble substances and gaseous oils and sludge;
A heat exchanger (F ') for recovering the heat of the gaseous oil from the catalytic cracking reactor (D); A condenser (F) for condensing gaseous oil;
A reservoir (G) for storing condensed oil from the condenser (F); And an oil water separator (G ') for separating the water from the reservoir (G) at a lower portion of the reservoir (G);
The oil from the reservoir G is distilled by heating by the steam boiler P so that the heavy oil, the light oil and the gasoline or all of them are separated into the heavy oil outlet port I, the diesel outlet port J, Port (K) or both of them through a distillation column (H)
After the sludge from the catalytic reactor (D) is transferred to the screw press (O) by the opening operation of the valve (R) connected to the lower portion, the solid sludge is transferred to the incinerator (M) to be burned, and the liquid Is transferred to the heating unit (U) by the pump (S) and heated to be recycled to the catalytic cracking reactor (D), and the heat generated from the incinerator (M) is recovered by the heat exchanger (Y) Used as a heat source of the boiler (P) and is converted into electrical energy by the generator (T), the gas generated from the incinerator (M) is transferred to the catalytic oxidation tower (L) to be decomposed into carbon dioxide and water, and the incinerator ( The residual catalyst from M) is configured to be recovered through the catalyst recovery portion (N). The oil producing system according to claim 1, further comprising a vacuum pump (V) for smoothly extracting gaseous substances generated in the catalytic cracking reactor (D). The oil production system according to claim 1, further comprising a catalytic reformer (E ') for reforming the gaseous material produced in the catalytic cracking reactor (D) into gasoline, light oil or heavy oil. The method of claim 1,
(B) for crushing a part or the whole of the raw material and an extruder (B) for feeding the raw material from the crusher (B) to the catalyst decomposition reactor (D) (C). ≪ / RTI >  The oil producing system according to claim 4, wherein in the extruder (C), the raw material is heated to a temperature of 120 ° C to 450 ° C. The residual material recovery tank according to claim 1, wherein the evaporation part (M ') for evaporating the water-soluble substance from the water separator (G') and the residual material by-products are collected at the bottom of the oil / water separator (G '). (W) is further provided with an oil generating system. 7. The method according to any one of claims 1 to 6,
The sludge from the catalytic cracking reactor D is transferred to the screw press O by the opening operation of the valve R connected to the bottom of the catalyst decomposing reactor D and then the solid sludge is transferred to the incinerator M for burning, The liquid is recycled by the pump (S) to the catalytic cracking reactor (D)
The heat generated from the incinerator M is recovered by the heat exchanger Y and then converted into electric energy by the generator T. The gas generated from the incinerator M is discharged into the exhaust gas pipe Y Wherein the catalyst is recovered through the catalyst recovery unit (N) by causing the catalyst to be decomposed into carbon dioxide and water by being transported to the catalytic oxidation column (L) through the catalyst recovery unit (N). 8. The method of claim 7,
The catalytic oxidation column L decomposes the water vapor and the exhaust gas generated from the extruder C, the exhaust gas generated from the distillation column H, and the gas generated from the incinerator M into carbon dioxide and water, Characterized in that part or all of the heat from the catalytic oxidation column (L) is recovered by the heat exchanger (L '). 7. A process according to any one of claims 1 to 6, wherein the catalytic cracking reaction in the catalytic cracking reactor (D) is initiated by a heating oil boiler (Q) at a temperature of 250 DEG C to 450 DEG C, To 10,000 RPM, < / RTI > The method according to any one of claims 1 to 6, wherein the catalytic reaction reactor (D) removes sulfur from crude oil or bunker C in the catalytic reaction reactor (D) during the initial reaction, or 350 ° C. or more in a distillation column when refining crude oil. One or two or more mixtures selected from the group of liquid catalysts composed of a high boiling point material obtained from a high boiling point material or a high boiling point material obtained from a heavy oil outlet port (I) after catalytic treatment of a biomass in the reactor may be used. Oil production system, characterized in that used in a weight ratio of 1 to 1: 20. The catalyst according to any one of claims 1 to 6, wherein the catalyst used in the catalyst decomposition reactor (D) and the catalyst reformer (E ') is a mixture of Al ₂ O ₃ and a zeolite having a Si / Al ratio of 1 to 60 A catalyst impregnated with at least one of Sc, V, Fe, Ni, Co, Zn and Ge and Sn, Zr, Mo, Ce and Cs among the four periodic elements or a catalyst in which a Si / Al ratio is 1 to 60, Wherein the metal is a mixed catalyst of ion-exchanged and Al ₂ O ₃ impregnated with the metal. The catalyst is used in the catalytic reformer (E ') in an amount of 0.01 to 30% by weight in the catalytic cracking reactor (D) relative to the raw material, the space velocity is 3,000 / hr to 100,000 / hr. Oil generating system, characterized in that.

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