CN102029179B

CN102029179B - Catalyst for light oil conversion and production method thereof

Info

Publication number: CN102029179B
Application number: CN2009101773468A
Authority: CN
Inventors: 金炳玗; 金文璨
Original assignee: EPEL CO Ltd
Current assignee: EPEL CO Ltd
Priority date: 2009-09-30
Filing date: 2009-09-30
Publication date: 2012-10-31
Anticipated expiration: 2029-09-30
Also published as: CN102029179A

Abstract

The invention relates to a catalyst for light oil conversion and a production method thereof, which belong to the field of catalysts. The catalyst is in a three-dimensional net structure, and belongs to an isometric system. Two adjacent unit cells have one common oxygen atom. The catalyst is a zeolite catalyst made from an alkali metal compound, an alkaline earth metal compound and crystal water molecules and is a mixed crystal of manganese aluminium silicate with the chemical formula of Mn2Al4Si5O18 and manganese treated sodium aluminosilicate of which the chemical formula is Na6MnAl4Si8O26, wherien the molar ratio of Si to Al is bigger than 1. The catalyst for light oil conversion not only can be used for reclaiming high-quality light oil from waste plastics, wood hydrocarbon compounds, waste oil and similar substances, but also can reduce waste plastics, wood hydrocarbon compounds, waste oil and similar substances. Therefore, the catalyst for the light oil conversion is favorable for environment protection.

Description

The light oil conversion is with catalyst and manufacturing approach thereof

Technical field

The present invention relates to a kind of catalyst and manufacturing approach thereof, relate in particular to a kind of light oil conversion, belong to catalyst field with catalyst and manufacturing approach thereof.

Background technology

In new production of renewable energy resources field; From using the production of energy manufacturing technology aspect of living beings; The technology of using at present is main as follows: with amylum crops such as corn, cassavas is the production technology of raw-material optimization biochemical alcohol (bio-ethanol); With grease class plants such as rape or vegetablefats is the production technology of raw-material biochemical diesel oil (bio-diesel); Use after the wooden type directly burning heat or with the method for applying flexibly after its wood chipization in thermal power station; Processing waste, apply flexibly the technology of garbage derivatived fuel (RDF) or plastic garbage (RPF), utilize elevated temperature heat to decompose the technology that timber or discarded object are produced artificial oil, waste oil is filtered or adds the technology that low-grade fuel is refined in thermal distillation; Biogas biogas (bio-gas) directly flexible Application in the field of the energy; Utilize the technology of LDF Ga s generating to handle and vessel Waste is handled, the methanation technology of livestock products waste water treatment plant is by extensive employing with urban sewage, at present with wooden type of biogas biogas convert to biological butanol fuel and with its application or the like technology all in trying out.

Non-plant property biomass liquid fuel technology is regarded as WeiLai Technology; Be that main exploitation produces the technology of thing butanols next life through the decomposition of microorganism, and can mix biological butanes (bio-butane) fuel of use or the technology of low-quality synthetic fuel production method with gasoline after the gasification (Gasification).At German EVK, developing the technology of using zeolites catalyst Direct Production diesel oil in discarded object.Above-mentioned three kinds of its technical characterictics of each tool of method, according to the fuel that said method is produced, the difference of its characteristic and quality is also very big.

The kind of above-mentioned technology and level are just verified through many methods, are raw material because of it uses the high import food grain of original cost, so have limitation; Again because of it holds the technology before using for a long time, be not reasons such as source catalyst technology simultaneously, its limitation also comes out gradually.The exploitation of sources such as technology, catalyst and engineering technology of non-consumption living beings that can decompose cellulosic classes such as vegetation class, agricultural by product at present is extremely urgent.

Decompose for waste plastics and use catalyst, introduced the ion-exchange waste plastics decomposition that converts clinoptilolite type zeolites into hydrogen in No. the 0330929th, the Korean Patent with catalyst and use the waste plastics decomposition method of this catalyst.In addition, introduced in No. the 0322663rd, the Korean Patent and made nickel and nickel alloy contact catalyst, the plain reaction of dehydration has taken place, put into silicate alumina class solid acid catalyst again after, contact the method for decomposition at fluidized bed.

In addition, in No. the 0801539th, No. the 0350776th, Korean Patent, No. the 0297321st, Korean Patent, No. the 0335657th, Korean Patent, No. the 0656177th, Korean Patent, No. the 0474965th, Korean Patent, Korean Patent, also introduced the method for using multiple raw material material synthetic zeolite class respectively.Also have in the patents such as No. the 3966883rd, United States Patent (USP), No. the 4088739th, United States Patent (USP), No. the 4017590th, United States Patent (USP) and introduced multiple zeolites hydrothermal synthesis method.

But said method is difficult to zeolites is recycled into high-quality light oil from process object materials such as waste plastics, wooden hydrocarbon and waste oil.

Summary of the invention

The present invention is directed to existing method and be difficult to zeolites is recycled into the deficiency of high-quality light oil from process object materials such as waste plastics, wooden hydrocarbon and waste oil; Provide a kind of light oil conversion with catalyst and manufacturing approach thereof, this catalyst can reclaim high-quality light oil come out from materials such as a large amount of discharges, difficult processing, expense height and the waste plastics of destruction environment, wooden hydrocarbon, waste oil.

The technical scheme that the present invention solves the problems of the technologies described above is following: a kind of light oil conversion has tridimensional network with catalyst; Belong to cubic system; Has total oxygen atom on adjacent two structure cells; Said catalyst is the zeolites catalyst, is processed by alkali metal compound component, alkaline earth metal compound component and crystallization water molecule, is that chemical formula is Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The hybrid junctions crystal of manganese sodium aluminosilicate, wherein, the mol ratio of Si/Al is greater than 1.

The invention has the beneficial effects as follows: light oil conversion of the present invention not only can be reclaimed high-quality light oil with catalyst from waste plastics, wooden hydrocarbon, waste plastics, waste oil and similar substance; Can also reduce the existence of waste plastics, wooden hydrocarbon, waste plastics, waste oil and similar substance, thereby help the protection of environment.

On the basis of technique scheme, the present invention can also do following improvement.

Further, said catalyst makes through hydrogen ion exchange contact decomposition.

Further, said alkali metal compound component is for containing Na ⁺Or K ⁺The compound composition, said alkaline earth metal compound component is for containing Ca ²⁺Or Mg ²⁺The compound composition.

The present invention also provides a kind of technical scheme that solves the problems of the technologies described above following: the conversion of a kind of light oil is used the manufacturing approach of catalyst to comprise silicate and chemical formula are NaAlO ₂Sodium aluminate or calcium albuminate put into reactor with the mol ratio of 1:1～20:1, and in said reactor, to add the chemical formula be equivalent to sodium aluminate 1 weight %～20 weight % be Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and the NaOH that is equivalent to 2 times of weight of sodium aluminate; In said reactor, add the hydrochloric acid that is equivalent to the water of 10 times of sodium aluminates～25 times of weight and is equivalent to NaOH 1 weight %～10 weight % again; Then at normal temperatures; Rotating speed with greater than 300rpm stirs the mixture in the said reactor, and said mixing time was put into autoclave with the mixture that stirs then greater than 1 hour; Under 80 ℃～300 ℃, carry out 6 hours～160 hours hydrothermal synthesis reaction, can form chemical formula is Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The hybrid junctions crystal of manganese sodium aluminosilicate.

If when the mole of said silicate and sodium aluminate is lower than 1:1 for a short time, can influence the formation of hybrid junctions crystal; When if the mol ratio of said silicate and sodium aluminate exceeds 20:1; Not only can influence the formation of hybrid junctions crystal; The mol ratio of Si/Al raises simultaneously; Waste plastics and wooden hydrocarbon and catalyst carry out catalytic and contact when decomposing, and the high score subring meeting in waste plastics and the wooden hydrocarbon is removed, thereby generate a large amount of materials lower than light oil boiling point.

If the addition of manganese aluminosilicate during less than sodium aluminate 1 weight %, just can not generate the hybrid junctions crystal of manganese aluminosilicate and manganese sodium aluminosilicate; If the addition of manganese aluminosilicate is during greater than sodium aluminate 20 weight %, unnecessary manganese can hinder the generation of hybrid junctions crystal.If the addition of NaOH is during greater than the weight of 2 times of sodium aluminates, the formation speed of hybrid junctions crystal can be slack-off, also requires sound field under the condition of high temperature and high pressure simultaneously.If the addition of water in the scope that is equivalent to 10 times of sodium aluminates～25 times of weight, will not influence the generation of hybrid junctions crystal.If the addition of hydrochloric acid is during less than NaOH 1 weight %, manganese sodium aluminosilicate (Na only ₆MnAl ₄Si ₈O ₂₆) can generate crystallization, manganese aluminosilicate (Mn ₂Al ₄Si ₅O ₁₈) almost can not generate crystallization, therefore above-mentioned two kinds of crystallization meetings produce comprehensive effect, improve the catalytic Contact decomposition efficiency, but can not produce identical effect.If the addition of hydrochloric acid during greater than NaOH 10 weight %, can make the formation speed of hybrid junctions crystal slack-off, only manganese aluminosilicate (Mn ₂Al ₄Si ₅O ₁₈) can generate crystallization, manganese sodium aluminosilicate (Na ₆MnAl ₄Si ₈O ₂₆) almost can not generate crystallization, also can influence comprehensive effect, the contact decomposition efficiency is reduced.

In autoclave, under 80 ℃～300 ℃, carry out 6 hours～160 hours hydrothermal synthesis reaction, at manganese sodium aluminosilicate (Na ₆MnAl ₄Si ₈O ₂₆) and manganese aluminosilicate (Mn ₂Al ₄Si ₅O ₁₈) hybrid junctions crystal generative process in, if temperature is lower than 80 ℃, then can not generate the hybrid junctions crystal; If temperature is higher than 300 ℃, can cause the form of hybrid junctions crystal to change, can not generate needed hybrid junctions crystal.In addition, the hydro-thermal generated time is if be lower than 6 hours, and then the crystallization degree can fall sharply, if exceed 160 hours, then can not reach desirable crystallization degree.

The conversion of a kind of light oil is used the manufacturing approach of catalyst to comprise silicate solutions and chemical formula are NaAlO ₂Sodium aluminate or calcium albuminate put into reactor with the mol ratio of 1:1～20:1; And in said reactor, add the NaOH be equivalent to 2 times of weight of sodium aluminate; In said reactor, add the hydrochloric acid that is equivalent to the water of 10 times of sodium aluminates～25 times of weight and is equivalent to NaOH 1 weight %～10 weight % again; Then at normal temperatures; Rotating speed with greater than 300rpm stirs the mixture in the said reactor, and said mixing time was put into autoclave with the mixture that stirs then greater than 1 hour; Under 80 ℃～300 ℃, carry out 6 hours～160 hours hydrothermal synthesis reaction, again manganese nitrate and HCl solution being processed chemical formula through ion-exchange is Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The hybrid junctions crystal of manganese sodium aluminosilicate; Again said hybrid junctions crystal is carried out drying under 100 ℃～150 ℃, the time of said drying was placed on dried hybrid junctions crystal in the air greater than 6 hours then; And under 300 ℃～600 ℃, be cured, the time of said curing was greater than 2 hours.

The above-mentioned manganese aluminosilicate (Mn that contains manganese ₂Al ₄Si ₅O ₁₈) and manganese sodium aluminosilicate (Na ₆MnAl ₄Si ₈O ₂₆) the zeolites catalyst that forms of mixed crystallization can become the H of ion-exchange ₆MnAl ₄Si ₈O ₂₆Structure is becoming under the situation of said structure, will generate to have manganese aluminosilicate (Mn ₂Al ₄Si ₅O ₁₈) and manganese sodium aluminosilicate (Na ₆MnAl ₄Si ₈O ₂₆) the zeolites catalyst of mixed crystallization structure.

Said ion-exchange is with NH ₄Cl or HCl solution come ion-exchange to process manganese aluminosilicate (Mn ₂Al ₄Si ₅O ₁₈) and manganese sodium aluminosilicate (Na ₆MnAl ₄Si ₈O ₂₆) the hybrid junctions crystal, said baking temperature carries out the drying more than 6 hours in 100 ℃～150 ℃ scope, dry back in 300 ℃～600 ℃ scope, in air, carry out more than 2 hours be cured as good.

Light oil conversion of the present invention is compared with the manufacturing approach of general zeolites catalyst with the manufacturing approach of catalyst, and reaction temperature is lower, has improved the efficient of the energy, and light oil has remarkable washability simultaneously, can be made into high-quality light oil products.

Form the raw material of pulverizing with mixing after the pulverizing such as wooden hydrocarbon, waste plastics, waste oil; The light oil conversion of the raw-material 0.1 weight %～20 weight % that are equivalent to again to pulverize is added in the raw material after the pulverizing with catalyst ratio; Then; The raw material that are added with catalyst are put into the fluidized bed reactor, under 280 ℃～400 ℃, carry out ion-exchange and generate liquid substance and gaseous matter, and the liquid substance and the gaseous matter that generate are carried out condensation; For improving its purity, condensed material can obtain light oil via destilling tower.If the addition of said catalyst during less than the raw-material 0.1 weight % that pulverizes, then can influence light oil and reclaim normally carrying out of reaction; If the addition of said catalyst during less than the raw-material 20 weight % that pulverize, then can cause ash content too much, influence light oil and reclaim and react, increase financial burden simultaneously.

In the present invention; Materials such as the polyethylene in waste plastics, polypropylene, polystyrene, polyester, ABS resin, polyurethane are separately or in the mixture and wooden hydrocarbon of above-mentioned substance; When last putty mixture independent or above-mentioned substance decomposes after mustard seeds, palm, the tung tree oil expression, all can use light oil conversion of the present invention to use catalyst.Light oil of the present invention conversion to be put into reactor in the lump with the raw material of catalyst and waste plastics class and hydrocarbon, under 280 ℃～400 ℃ temperature, exchange, it is reflected at 1 minute～carries out in 2 hours, can generate C ₁₂～C ₂₃Hydrocarbon, thereby obtain belonging to the liquid product of light oil type, also can obtain a part of C ₅～C ₁₁The liquid gasoline composition, and C ₁～C ₄The gas product.

Be appreciated that said waste plastics, wooden hydrocarbon, waste oil not only are confined in the above-mentioned content, it comprises defined all the elements on the common chemical constitution.

Description of drawings

Fig. 1 is the X-ray diffraction analysis figure of light oil conversion of the present invention with catalyst;

Fig. 2 is the electron micrograph of light oil conversion of the present invention with catalyst.

The specific embodiment

Below in conjunction with accompanying drawing principle of the present invention and characteristic are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.

With three embodiment light oil conversion of the present invention is done further detailed description with catalyst and manufacturing approach thereof below.

Embodiment 1

At first, with sodium aluminate 2g, chemical formula is Na ₂SiO ₃Sodium metasilicate 5g, NaOH 4g and hydrochloric acid 0.2g put into 400g water, the manganese aluminosilicate of putting into 0.1g again forms mixture; Then, at normal temperatures, with 2, the rotating speed of 000rpm carries out 3 hours stirring to said mixture; Then, the mixture that stirs is put into the reactor of polytetrafluoroethylene (PTFE) material, and after sealing fully, put it in the autoclave, under 95 ℃ temperature, carry out 12 hours hydrothermal synthesis reaction; Then, use the above-mentioned product of center of circle separator separates, will under 120 ℃ temperature, carry out 12 hours drying through the product that separate in the center of circle, can form chemical formula is Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The hybrid junctions crystal of manganese sodium aluminosilicate.Fig. 1 is the X-ray diffraction analysis figure of light oil conversion of the present invention with catalyst.As shown in Figure 1, the corresponding peak values of three dark circles appear at respectively: 2 θ=8.65,8.77 and 3.40 position, this is corresponding to aluminosilicate (Mn ₂Al ₄Si ₅O ₁₈) phase; The corresponding peak values of three black appear at respectively: 2 θ=3.99,3.56 and 2.67 position, this is corresponding to manganese sodium aluminosilicate (Na ₆MnAl ₄Si ₈O ₂₆) phase, this shows that the catalyst through the present embodiment manufacturing is the hybrid junctions crystal of manganese aluminosilicate and manganese sodium aluminosilicate.Fig. 2 is the electron micrograph of light oil conversion of the present invention with catalyst.As shown in Figure 2, the catalyst of present embodiment manufacturing belongs to cubic crystal structure.

Embodiment 2

At first, with calcium albuminate 2g, sodium aluminosilicate 5g, calcium hydroxide 4g and hydrochloric acid 0.2g put into the water of 400g, and the manganese aluminosilicate of putting into 0.1g again forms mixture; Then, at normal temperatures, with 2, the rotating speed of 000rpm carries out 3 hours stirring to said mixture; Then, the mixture that stirs is put into the reactor of polytetrafluoroethylene (PTFE) material, and after sealing fully, put it into autoclave, under 95 ℃ temperature, carry out 12 hours hydrothermal synthesis reaction; Then, use the above-mentioned product of center of circle separator separates, will under 120 ℃ temperature, carry out 12 hours drying through the product that separate in the center of circle, can form chemical formula is Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The hybrid junctions crystal of manganese sodium aluminosilicate.

Embodiment 3

At first, with sodium aluminate 2g, calcium aluminosilicate 5g, the water that NaOH 4g and hydrochloric acid 0.2g put into 400g forms mixture, and at normal temperatures, with 2, the rotating speed of 000rpm carries out 3 hours stirring to said mixture; Then, the mixture that stirs is put into the reactor of polytetrafluoroethylene (PTFE) material, and after sealing fully, put it into autoclave, under 95 ℃ temperature, carry out 12 hours hydrothermal synthesis reaction; Next, in product, put into the aqueous hydrochloric acid solution 1g of manganese nitrate and 0.1mol of 0.1g after, put into again and concentrate rotary evaporator; Speed with 500rpm; Under 90 ℃ temperature, carry out 12 hours ion-exchange, and then under 120 ℃ temperature, carry out 12 hours drying, last under 500 ℃ temperature; Carry out 2 hours air set, can form chemical formula is Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The hybrid junctions crystal of manganese sodium aluminosilicate.

Do further detailed description to using light oil conversion of the present invention with the process of catalyst recovery light oil with three embodiment below.

Embodiment 4

With polypropylene 3g, polyethylene 3g, polyester 3g, ABS resin 3g and polystyrene 3g and chemical formula are Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The zeolites catalyst 0.5g of mixed crystallization of manganese sodium aluminosilicate mix to form mixture; Then said mixture is put into 1 liter reactor; Next with said mixture under 280 ℃, 340 ℃ and 400 ℃; The recovery of light oil is carried out in stirring so that the speed of 500rpm was carried out 60 minutes, and its product is analyzed, and analysis result is as shown in table 1.

Table 1 mixed plastic decomposition reaction product distributes

Visible by above-mentioned table 1, along with temperature increases, residuals reduces gradually, and the product of gas and liquid also increases thereupon, C in the liquid product ₁₂～C ₂₃The washability of the light oil composition in the scope increases to some extent.Can know that by The above results catalyst of the present invention has improved the earning rate of light oil greatly.Simultaneously, when using general zeolites, need be up to the temperature more than 400 ℃, its gas componant accounts for major part, and residuals is on the high side, can not the high-quality light oil of output.

Embodiment 5

With putty 5g after the putty 5g after the mustard seeds oil expression, the palm oil expression and putty 5g and the chemical formula after the tung tree oil expression is Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The zeolites catalyst 0.5g of mixed crystallization of manganese sodium aluminosilicate mix to form mixture; Then said mixture is put into 1 liter reactor; Next with said mixture under 280 ℃, 340 ℃ and 400 ℃; The recovery of light oil is carried out in stirring so that the speed of 500rpm was carried out 60 minutes, and its product is analyzed, and analysis result is as shown in table 2.

Table 2 mixes wooden hydrocarbon mixture decomposition reaction product and distributes

Visible by above-mentioned table 2, along with temperature increases, residuals reduces gradually, and the product of gas and liquid also increases thereupon, C in the liquid product ₁₂～C ₂₃The washability of the light oil composition in the scope increases to some extent.Can know that by The above results the catalyst among the present invention has improved the earning rate of light oil greatly.

Embodiment 6

With the putty 5g after the putty 5g after the mustard seeds oil expression, the palm oil expression, the putty 5g after the tung tree oil expression, polypropylene 3g, polyethylene 3g, polyester 3g, ABS resin 3g, polystyrene 3g and engine motor oil 3g and chemical formula are Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The zeolites catalyst 1g of mixed crystallization of manganese sodium aluminosilicate mix to form mixture; Then said mixture is put into 1 liter reactor; Next with said mixture under 280 ℃, 340 ℃ and 400 ℃; The recovery of light oil is carried out in stirring so that the speed of 500rpm was carried out 60 minutes, and its product is analyzed, and analysis result is as shown in table 3.

Table 3 mixed plastic distributes with the decomposition reaction product that mixes wooden hydrocarbon mixture

Visible from above-mentioned table 3, to mixed plastic with mix hydrocarbon, and the mixture that mixes of waste oil is when reacting, its temperature is below 400 ℃, also can obtain superior returns, high-quality light oil through catalyst of the present invention.Simultaneously, visible by above-mentioned table 3, along with temperature increases, residuals reduces gradually, and the product of gas and liquid also increases thereupon, C in the liquid product ₁₂～C ₂₃The washability of the light oil composition in the scope increases to some extent.Can know that by The above results the catalyst among the present invention has improved the earning rate of light oil greatly.

Catalyst among the present invention not only from waste plastics, wooden hydrocarbon, waste oil, reclaiming the effect that high-quality light oil has brilliance, can also solve relevant environmental problem simultaneously, reduces the relevant environment spending.

The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims

1. catalyst is used in a light oil conversion; It is characterized in that said catalyst has tridimensional network, belongs to cubic system; Has total oxygen atom on adjacent two structure cells; Said catalyst is the zeolites catalyst, is processed by alkali metal compound component, alkaline earth metal compound component and crystallization water molecule, is that chemical formula is Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The hybrid junctions crystal of manganese sodium aluminosilicate, wherein, the mol ratio of Si/Al is greater than 1.

2. catalyst is used in light oil conversion according to claim 1, it is characterized in that, said catalyst makes through hydrogen ion exchange contact decomposition.

3. catalyst is used in light oil conversion according to claim 1, it is characterized in that said alkali metal compound component is for containing Na ⁺Or K ⁺The compound composition, said alkaline earth metal compound component is for containing Ca ²⁺Or Mg ²⁺The compound composition.

4. a light oil is changed the manufacturing approach with catalyst, it is characterized in that said manufacturing approach comprises that with silicate solutions and chemical formula be NaAlO ₂Sodium aluminate or calcium albuminate put into reactor with the mol ratio of 1:1～20:1, and in said reactor, to add the chemical formula be equivalent to sodium aluminate 1 weight %～20 weight % be Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and the NaOH that is equivalent to 2 times of weight of sodium aluminate; In said reactor, add the hydrochloric acid that is equivalent to the water of 10 times of sodium aluminates～25 times of weight and is equivalent to NaOH 1 weight %～10 weight % again; Then at normal temperatures; Rotating speed with greater than 300rpm stirs the mixture in the said reactor, and said mixing time was put into autoclave with the mixture that stirs then greater than 1 hour; Under 80 ℃～300 ℃, carry out 6 hours～160 hours hydrothermal synthesis reaction, can form chemical formula is Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The hybrid junctions crystal of manganese sodium aluminosilicate.

5. a light oil is changed the manufacturing approach with catalyst, it is characterized in that said manufacturing approach comprises that with silicate solutions and chemical formula be NaAlO ₂Sodium aluminate or calcium albuminate put into reactor with the mol ratio of 1:1～20:1; And in said reactor, add the NaOH be equivalent to 2 times of weight of sodium aluminate; In said reactor, add the hydrochloric acid that is equivalent to the water of 10 times of sodium aluminates～25 times of weight and is equivalent to NaOH 1 weight %～10 weight % again; Then at normal temperatures; Rotating speed with greater than 300rpm stirs the mixture in the said reactor, and said mixing time was put into autoclave with the mixture that stirs then greater than 1 hour; Under 80 ℃～300 ℃, carry out 6 hours～160 hours hydrothermal synthesis reaction, again manganese nitrate and HCl solution being processed chemical formula through ion-exchange is Mn ₂Al ₄Si ₅O ₁₈Manganese aluminosilicate and chemical formula be Na ₆MnAl ₄Si ₈O ₂₆The hybrid junctions crystal of manganese sodium aluminosilicate; Again said hybrid junctions crystal is carried out drying under 100 ℃～150 ℃, the time of said drying was placed on dried hybrid junctions crystal in the air greater than 6 hours then; And under 300 ℃～600 ℃, be cured, the time of said curing was greater than 2 hours.