CN103773438B - A kind of hydrodesulfurizationprocess process of distillate - Google Patents
A kind of hydrodesulfurizationprocess process of distillate Download PDFInfo
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Abstract
The invention discloses the hydrodesulfurizationprocess process of a kind of distillate.The method includes: use fixed bed hydrotreating reactors, raw oil and hydrogen enter reactor from top, contact with Hydrobon catalyst, hydrodesulfurization reaction is carried out under the conditions of hydrodesulfurization reaction, reacting rear material discharges reactor from bottom, Hydrobon catalyst wherein used is with Mo and Ni and/or Co as active metal component, P is auxiliary agent, alkali metal salt containing heteropoly acid, this catalyst has higher specific surface area, bigger pore volume and aperture, active metal component preferably coordinates with heteropolyacid salt, two kinds of catalyst gratings are especially at least used to use, while reaching deep desulfuration, liquid yield is high.
Description
Technical field
The present invention relates to the hydrodesulfurizationprocess process of a kind of distillate, a kind of light ends oil uses the method for combination catalyst hydrodesulfurization.
Background technology
It is known that air pollution is a serious environmental problem, and substantial amounts of engine emission is one of major reason causing air pollution.In recent years, along with the sharp increase of motor vehicles usage quantity, exhaust emissions amount is increasing, and the combustion product of the sulfide in fuel oil is the main harmful substance causing acid rain.On the other hand, along with growth in the living standard, people are more and more higher to the requirement of environmental quality.Therefore, strict standard of fuel has all been formulated in oil-fired prescription increasingly stringent, countries in the world by people.Eu III standard was implemented in 2000 in Europe, it is stipulated that sulfur content in gasoline is not more than 150 ug/g, and within 2005, implements the Europe IV standard, it is desirable to sulfur content is down to 50 ug/g.BeiJing, China came into effect EuropeⅢ emission standard in 2005, within 2008, rises and comes into effect Europe IV discharge standard, and China's on July 1st, 2011 whole nation performs Europe IV discharge standard.Following require the sulfur content in oil product in countries in the world will be more and more lower, produces the significant problem that enterprise of super-low sulfur oil product Shi Ge great oil refining is faced.
CN101307255A and CN101089129A discloses a kind of method that deep desulfuration produces low-sulphur oil, Hydrobon catalyst used uses a kind of highly active Hydrobon catalyst and the SA Hydrobon catalyst of one, the most highly active Hydrobon catalyst is positioned at the upstream of SA Hydrobon catalyst, i.e. reduces along logistics direction activity.Owing to hydrodesulfurization can produce substantial amounts of reaction heat, in reactor, the relatively low downstream catalyst bed of activity makes full use of the reaction heat that upstream produces, and reduces hydrogen consumption, effectively utilizes system thermal, it is achieved that deep desulfuration produces low-sulphur oil.
CN101797512A discloses a kind of high-activity hydrocracking catalyst and preparation method thereof.This catalyst includes acidic components, hydrogenation component and carrier, and acidic components are phosphotungstic acid cesium salt, and hydrogenation component is nickel, and carrier is silicon oxide.The method is with tetraethyl orthosilicate for silicon source, and citric acid is chelating agent, and water soluble nickel salt, water soluble cesium salts are added separately in complexing agent aqueous solution to obtain solution A；Silicon source is joined solution A obtains solution B；Again heteropoly acid aqueous solution is joined in solution B, be evaporated solution, be dried, roasting, obtain catalyst.Although the method contributes to metal component and acidic components preferably disperse, but the heteropoly acid used is phosphotungstic acid, the strongest acidity is shown owing to phosphotungstic acid content is higher, add during catalyst plastic, its highly acid and the course of reaction of generation phosphotungstic acid cesium salt, formation on Support Silica pore structure affects bigger, cause the specific surface area of catalyst, pore volume and aperture are the most relatively small, have impact on the hydrocracking reaction activity of catalyst, and owing in catalyst, Tricesium dodecatungstophosphate salt content is higher and acidity is stronger, hydrodesulfurization reaction it is not suitable for the most yet.
Sulfur-containing compound in oil product is mainly thiophene and derivatives, and wherein in deep desulfuration and ultra-deep desulfurization stage, sulfur-containing compound is mainly dibenzothiophenes class sulfide.The catalyst that deep desulfuration requirement to be realized is used not only to have strong hydrogenation activity, to have certain acidity simultaneously, and catalyst is typically all by adding molecular sieve, makes catalyst have certain strong acid center.
If Hydrobon catalyst acidity is the most weak, then cannot realize deep desulfuration；If acid too strong, cracking catalyst hyperactivity, can cause liquid product yield to decline.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides the hydrodesulfurizationprocess process of a kind of distillate.The method, by using acid different combination catalyst, reaches the deep desulfuration effect of distillate, has acidity of catalyst adjustable, and lytic activity is moderate, liquid product yield advantages of higher.
The hydrodesulfurizationprocess process of distillate of the present invention, including: using fixed bed hydrotreating reactors, raw oil and hydrogen enter reactor from top, contact with Hydrobon catalyst, carrying out hydrodesulfurization reaction under the conditions of hydrodesulfurization reaction, reacting rear material discharges reactor from bottom；Wherein said Hydrobon catalyst, with Mo and Ni and/or Co as active metal component, P is auxiliary agent, containing the alkali metal salt of heteropoly acid, on the basis of the weight of catalyst, MoO3Content be the content of 5 % ~ 20 %, NiO and/or CoO be 0.5 % ~ 6 %, P content is 0.5 % ~ 4 %, and the alkali metal salt content of heteropoly acid is 1% ~ 10%, and surplus is silicon oxide, and the character of described Hydrobon catalyst is as follows: specific surface area is 460 ~ 650 m2/ g, pore volume is 0.60 ~ 0.90 mL/g, and average pore diameter is 5.5 ~ 7.5
nm。
Hydrobon catalyst used by the inventive method preferably at least uses two kinds, and wherein in Hydrobon catalyst, the content of the alkali metal salt of heteropoly acid increases successively along fluid flow direction.
In the inventive method, described Hydrobon catalyst preferably employs a kind of low in acidity Hydrobon catalyst and a kind of peracidity Hydrobon catalyst, the alkali metal salt content that wherein low in acidity Hydrobon catalyst contains heteropoly acid is 1% ~ 5%, and in peracidity Hydrobon catalyst, the content containing heteropoly acid alkali metal salt is higher 4 ~ 9 percentage points than low in acidity Hydrobon catalyst.
Described low in acidity Hydrobon catalyst, with Mo and Ni and/or Co as active metal component, P is auxiliary agent, containing the alkali metal salt of heteropoly acid, on the basis of the weight of catalyst, MoO3Content be the content of 5 % ~ 20 %, NiO and/or CoO be 0.5 % ~ 6 %, P content is 0.5 % ~ 4 %, and the alkali metal salt content of heteropoly acid is 1% ~ 5%, and surplus is silicon oxide, and the character of described Hydrobon catalyst is as follows: specific surface area is 460 ~ 650 m2/ g, pore volume is 0.60 ~ 0.90 mL/g, and average pore diameter is 5.5 ~ 7.5
nm。
Described peracidity Hydrobon catalyst, with Mo and Ni and/or Co as active metal component, P is auxiliary agent, containing the alkali metal salt of heteropoly acid, on the basis of the weight of catalyst, MoO3Content be the content of 5 % ~ 20 %, NiO and/or CoO be 0.5 % ~ 6 %, P content is 0.5 % ~ 4 %, and the alkali metal salt content of heteropoly acid is 6% ~ 10%, and surplus is silicon oxide；The character of described Hydrobon catalyst is as follows: specific surface area is 460 ~ 650 m2/ g, pore volume is 0.60 ~ 0.90 mL/g, and average pore diameter is 5.5 ~ 7.5
nm。
Described low in acidity Hydrobon catalyst and the volume ratio of peracidity Hydrobon catalyst are 9/1～1/9, and wherein low in acidity Hydrobon catalyst is positioned at the upstream of peracidity Hydrobon catalyst.
In described Hydrobon catalyst, heteropoly acid alkali metal salt content increases successively along fluid flow direction, and the content of hydrogenation metal can be identical, it is also possible to increases successively along fluid flow direction.
In the alkali metal salt of described heteropoly acid, alkali metal is 0.5 ~ 2.0 with the mol ratio of heteropoly acid.Described alkali metal is one or more in potassium, caesium.Described heteropoly acid is one or more in silico-tungstic acid, phosphotungstic acid.
The preparation method of described Hydrobon catalyst, including:
(1) preparation is containing Mo, Ni and/or Co, the solution of P；
(2) aqueous solution of alkali metal salt is joined in heteropoly acid aqueous solution, obtain emulsion A；
(3) solution that step (1) obtains is joined in emulsion A, be sufficiently stirred for, obtain mixed liquid B；
(4) silicon source is joined in mixed liquid B, 2.0 h ~ 12.0 hs are stirred at room temperature, then heat to 50 DEG C ~ 80 DEG C, continue stirring to solution and be evaporated；
(5) step (4) gained solid is dried 5 h ~ 10 h at 100 DEG C ~ 120 DEG C, at 300 DEG C ~ 600 DEG C roasting 3 h ~ 5 h, obtains catalyst；
Wherein, step (2) or step (3) add template and organic acid.
In step (1), the preparation containing Mo, Ni and/or Co, the solution of P can be by method preparation commonly used in the art, and wherein Mo(is with MoO3Meter) concentration be that 0.05 ~ 0.2 g/mL, Ni and/or Co(is in terms of NiO and/or CoO) concentration be 0.005 ~ 0.06 g/mL, the concentration of P is 0.005 ~ 0.04 g/mL.When preparing above-mentioned solution, molybdenum source can use molybdenum trioxide, and nickel source can use basic nickel carbonate, and cobalt source can use cobalt carbonate, and phosphorus source can use phosphoric acid.
Described organic acid is one or more in citric acid, tartaric acid, malic acid, lauric acid, and described organic acid is 0.05 ~ 1 with step (4) silicon source mol ratio in terms of silicon oxide；Described template be cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, sodium lauryl sulphate, triblock polymer P123, triblock polymer F127, triblock polymer F108, molecular weight be Polyethylene Glycol, one or more in methylcellulose of 1000 ~ 10000, described template is 0.01 ~ 1.0 with step (4) silicon source mol ratio in terms of silicon oxide.
In step (2), described alkali metal salt is one or more in carbonate, nitrate, and the concentration of alkali metal salt is 0.05 ~ 0.15
g/mL。
In step (2), in heteropoly acid aqueous solution, the concentration of heteropoly acid is 0.5 ~ 2.0
g/mL。
In step (4), described silicon source is one or more in tetraethyl orthosilicate, Ludox.
The hydrodesulfurization condition that the present invention uses: reaction pressure is 0.5 MPa ~ 5 MPa, and reaction temperature is 250 DEG C ~ 330 DEG C, and during liquid, volume space velocity is 0.5 h-1~8 h-1, hydrogen to oil volume ratio is 100 ~ 1000.
Hydrobon catalyst used by the present invention, is introducing before silicon source, first makes alkali metal salt and heteropoly acid react and generates heteropolyacid salt, its content is less, and does not have water solublity, it is to avoid catalyst pore structure is adversely affected by the highly acid of heteropoly acid.Additionally, the use of template not only makes catalyst have higher specific surface area and bigger pore volume and aperture, and make more heteropolyacid salt be distributed in catalyst surface, improve the utilization rate of heteropolyacid salt；The use of organic acid can not only promote the hydrolysis in silicon source, and potentially acts as the effect of chelating agent, promotes that active metal component spreads more evenly across at catalyst surface, makes active metal component preferably coordinate with heteropolyacid salt, reach the effect of deep desulfuration.Hydrobon catalyst used by the present invention has higher specific surface area and bigger pore volume and aperture, and acid moderate, active center can be fully utilized, and complicated big structural molecule is easier to contact active center.
The inventive method is preferably along logistics direction, and low in acidity catalyst is positioned at upstream, and the catalyst of peracidity is positioned at downstream.Raw oil is through being positioned at the low in acidity catalyst of upstream, and in its sulfur-containing compound, most sulfur is removed, it is more difficult to the sulfur of the removing peracidity catalyst through downstream is removed, thus reaches the effect of deep desulfuration.If the Hydrobon catalyst being used alone low in acidity can not reach the effect of deep desulfuration, need to improve reaction temperature or reaction pressure could realize；If being used alone the Hydrobon catalyst of peracidity, although the effect of deep desulfuration can be reached, but owing to its acidity is relatively strong, lytic activity is higher, and liquid product yield can be caused on the low side.Acid different Hydrobon catalyst is applied in combination, and can make up deficiency when being used alone.Can adapt to process raw material and the change of product index requirement by adjusting the use ratio of catalyst, operating flexibility is greatly improved simultaneously.Being applied in combination of the Hydrobon catalyst of low in acidity and the Hydrobon catalyst of peracidity, can extend the service life of catalyst, the combined reaction performance of reaction system can be made to improve, have higher hydrodesulfurization activity and liquid product yield.
Detailed description of the invention
The solution of the present invention and effect is further illustrated below by specific embodiment.Wt% is mass fraction.
Embodiment 1
(1)
The preparation of Mo-Ni-P aqueous solution:
By 3.7 g phosphoric acid H3PO4(concentration 85wt%) is dissolved in 97 mL water, is subsequently adding 10 g molybdenum trioxides and 3.4 g basic nickel carbonates, is warming up to 100 DEG C and is stirred at reflux 0.5 h, filtering and i.e. obtain Mo-Ni-P aqueous solution.Wherein MoO3Concentration be 0.1 g/mL, the concentration of NiO is 0.02 g/mL, and the concentration of P is 0.01 g/mL.
(2) preparation of Hydrobon catalyst A:
It is 0.1 by 3.2 mL concentration
G/mL cesium carbonate aqueous solution adds in 3.74 g silicon tungsten acid solutions, after being sufficiently stirred for, adds 100
After mLMo-Ni-P solution stirring is uniform, add 248 g template cetyl trimethylammonium bromide and 143 g citric acids, after stirring, add 305 mL tetraethyl orthosilicates, 8.0 hs are stirred at room temperature, then heat to 70 DEG C, continue stirring to solution to be evaporated, gained solid is dried 8 h at 110 DEG C, at 450 DEG C of roasting 4 h, obtain catalyst, wherein MoO3Content is 10 wt%, and NiO content is 2 wt%, and P content is 1 wt%, Cs1.5H2.5SiW12O40Content is 4 wt%, SiO2Content is 80.7 wt%.The physico-chemical property of catalyst is shown in Table 1.
(3) preparation of Hydrobon catalyst B:
It is 0.1 by 1.9 mL concentration
G/mL cesium carbonate aqueous solution adds in 6.84 g silicon tungsten acid solutions, after being sufficiently stirred for, adds 100
After mLMo-Ni-P solution stirring is uniform, add 378 g template cetyl trimethylammonium bromide and 249 g citric acids, after stirring, add 294 mL tetraethyl orthosilicates, 8.0 hs are stirred at room temperature, then heat to 70 DEG C, continue stirring to solution to be evaporated, gained solid is dried 8 h at 110 DEG C, at 450 DEG C of roasting 4 h, obtain catalyst, wherein MoO3Content is 10 wt%, and NiO content is 2 wt%, and P content is 1 wt%, Cs0.5H3.5SiW12O40Content is 7 wt%, SiO2Content is 77.7 wt%.The physico-chemical property of catalyst is shown in Table 1.
Embodiment 2
Selecting catalyst A and B by volume 4:1 ratio mixing in embodiment 1, after totally 20 mL catalyst load the isothermal section in the middle of reaction tube, be passed through hydrogen, response system steps up pressure to 2.0
MPa, check air tight after, response system is warming up to 320 DEG C, with containing 2wt % CS2Cyclohexane solution carry out presulfurization 2 h, then drop to reaction temperature 280 DEG C, incision model reaction thing, containing 5 wt% thiophene and the cyclohexane solution of 0.8 wt% dibenzothiophenes, starts to gather sample after reacting 1 h.Operation condition is: pressure 2 MPa, and liquid volume air speed is 2 h-1, hydrogen and reaction feed volume ratio are 600, reaction raw materials sample size 40 mL/h, hydrogen flowing quantity 40 mL/min.Detection catalyst hydrodesulfurization activity at reaction conditions, the results are shown in Table 2.
Embodiment 3
In embodiment 2, selecting catalyst A and B by volume 3:1 ratio mixing in embodiment 1, other experimental condition is constant, and evaluation result is shown in Table 2.
Embodiment 4
In embodiment 3, being changed into by model reaction thing containing 5 wt% thiophene and the cyclohexane solution of 1.2 wt% dibenzothiophenes, other experimental condition is constant, and evaluation result is shown in Table 2.
Embodiment 5
In embodiment 4, reaction temperature changing 290 DEG C into, other experimental condition is constant, and evaluation result is shown in Table 2.
Embodiment 6
In embodiment 4, selecting catalyst A and B by volume 2:1 ratio mixing in embodiment 1, other experimental condition is constant, and evaluation result is shown in Table 2.
Embodiment 7
Selecting single catalyst A in embodiment 1 to be evaluated test, other experimental condition is with embodiment 2, and evaluation result is shown in Table 2.
Embodiment 8
Selecting single catalyst B in embodiment 1 to be evaluated test, other experimental condition is with embodiment 2, and evaluation result is shown in Table 2.
Comparative example 1
Prepared by the method that this comparative example catalyst is provided according to patent CN101797512A, prepared by the Hydrobon catalyst A consumption with reference to embodiment 1.
It is the cesium carbonate solution of 0.1 g/mL, 100 mLMo-Ni-P solution and 143 by 3.2 mL concentration
ML concentration is that the citric acid solution of 1 g/mL is configured to mixed solution, then adds 305
Ml tetraethyl orthosilicate, stirs 0.5 h at 60 DEG C, adds 3.74 g silicon tungsten acid solutions, stirs to be evaporated solution at 80 DEG C, gained solid is dried 24 h.Will dry after solids in muffle furnace with 2 DEG C of min-1Speed rise to 450 DEG C, constant temperature 4 h, prepare catalyst C.Wherein MoO3Content is 10
Wt%, NiO content is 2 wt%, and P content is 1 wt%, Cs1.5H2.5SiW12O40Content is 4 wt%, SiO2Content is 80.7 wt%.The physico-chemical property of catalyst is shown in Table 1.
Selecting single catalyst C to be evaluated test, other experimental condition is with embodiment 7, and evaluation result is shown in Table 2.
Comparative example 2
In embodiment 1, being added without template cetyl trimethylammonium bromide, remaining is identical with Hydrobon catalyst A consumption, obtains catalyst D.Wherein MoO3Content is 10 wt%, and NiO content is 2 wt%, and P content is 1 wt%, Cs1.5H2.5SiW12O40Content is 4 wt%, SiO2Content is 80.7 wt%.The physico-chemical property of catalyst is shown in Table 1.
Selecting single catalyst D to be evaluated test, other experimental condition is with embodiment 7, and evaluation result is shown in Table 2.
The main physico-chemical property of table 1 embodiment catalyst
| Project | Catalyst A | Catalyst B | Catalyst C | Catalyst D |
| MoO3, wt% | 10 | 10 | 10 | 10 |
| NiO, wt% | 2 | 2 | 2 | 2 |
| P, wt% | 1 | 1 | 1 | 1 |
| Heteropolyacid salt forms | Cs1.5H2.5SiW12O40 | Cs0.5H3.5SiW12O40 | Cs1.5H2.5SiW12O40 | Cs1.5H2.5SiW12O40 |
| Heteropolyacid salt content, wt% | 4 | 7 | 4 | 4 |
| Specific surface area, m2/g | 560 | 540 | 390 | 435 |
| Pore volume, mL/g | 0.80 | 0.81 | 0.47 | 0.55 |
| Average pore diameter, nm | 5.7 | 6.0 | 4.8 | 5.1 |
The hydrogenation cracking activity of table 2 each example catalyst and selectivity
| Embodiment | HDS, wt% | Liquid yield, wt% |
| Embodiment 2 | 96.5 | 97.5 |
| Embodiment 3 | 98.8 | 97.0 |
| Embodiment 4 | 94.2 | 97.2 |
| Embodiment 5 | 97.6 | 96.8 |
| Embodiment 6 | 98.5 | 96.7 |
| Embodiment 7 | 92.5 | 98.0 |
| Embodiment 8 | 99.8 | 95.0 |
| Comparative example 1 | 85.8 | 98.2 |
| Comparative example 2 | 88.2 | 98.1 |
Claims (12)
1. the hydrodesulfurizationprocess process of a distillate, including: using fixed bed hydrotreating reactors, raw oil and hydrogen enter reactor from top, contact with Hydrobon catalyst, carrying out hydrodesulfurization reaction under the conditions of hydrodesulfurization reaction, reacting rear material discharges reactor from bottom；Wherein said Hydrobon catalyst, with Mo and Ni and/or Co as active metal component, P is auxiliary agent, and containing the alkali metal salt of heteropoly acid, described alkali metal is one or more in potassium, caesium, and described heteropoly acid is one or more in silico-tungstic acid, phosphotungstic acid；On the basis of the weight of catalyst, MoO3Content be the content of 5 % ~ 20 %, NiO and/or CoO be 0.5 % ~ 6 %, P content is 0.5 % ~ 4 %, and the alkali metal salt content of heteropoly acid is 1% ~ 10%, and surplus is silicon oxide, and the character of described Hydrobon catalyst is as follows: specific surface area is 460 ~ 650 m2/ g, pore volume is 0.60 ~ 0.90 mL/g, and average pore diameter is 5.5 ~ 7.5 nm；Hydrobon catalyst used at least uses two kinds, and wherein in Hydrobon catalyst, the content of the alkali metal salt of heteropoly acid increases successively along fluid flow direction.
The most in accordance with the method for claim 1, it is characterized in that described Hydrobon catalyst uses a kind of low in acidity Hydrobon catalyst and a kind of peracidity Hydrobon catalyst, the alkali metal salt content that wherein low in acidity Hydrobon catalyst contains heteropoly acid is 1% ~ 5%, and in peracidity Hydrobon catalyst, the content containing heteropoly acid alkali metal salt is higher 4 ~ 9 percentage points than low in acidity Hydrobon catalyst.
The most in accordance with the method for claim 2, it is characterised in that described low in acidity Hydrobon catalyst and the volume ratio of peracidity Hydrobon catalyst are 9/1～1/9, and wherein low in acidity Hydrobon catalyst is positioned at the upstream of peracidity Hydrobon catalyst.
The most in accordance with the method for claim 1, it is characterised in that in described Hydrobon catalyst, heteropoly acid alkali metal salt content increases successively along fluid flow direction, and the content of hydrogenation metal is identical or increases successively along fluid flow direction.
The most in accordance with the method for claim 1, it is characterised in that in described Hydrobon catalyst, in the alkali metal salt of heteropoly acid, the mol ratio of alkali metal and heteropoly acid is 0.5 ~ 2.0.
The most in accordance with the method for claim 1, it is characterised in that described hydrodesulfurization reaction condition: reaction pressure is 0.5 MPa ~ 5.0 MPa, reaction temperature is 250 DEG C ~ 330 DEG C, and during liquid, volume space velocity is 0.5 h-1~8 h-1, hydrogen to oil volume ratio is 100 ~ 1000.
The most in accordance with the method for claim 1, it is characterised in that the preparation method of described Hydrobon catalyst, including:
(1) preparation is containing Mo, Ni and/or Co, the solution of P；
(2) aqueous solution of alkali metal salt is joined in heteropoly acid aqueous solution, obtain emulsion A；
(3) solution that step (1) obtains is joined in emulsion A, be sufficiently stirred for, obtain mixed liquid B；
(4) silicon source is joined in mixed liquid B, 2.0 h ~ 12.0 hs are stirred at room temperature, then heat to 50 DEG C ~ 80 DEG C, continue stirring to solution and be evaporated；
(5) step (4) gained solid is dried 5 h ~ 10 h at 100 DEG C ~ 120 DEG C, at 300 DEG C ~ 600 DEG C roasting 3 h ~ 5 h, obtains catalyst；
Wherein, step (2) or step (3) add template and organic acid.
The most in accordance with the method for claim 7, it is characterised in that in step (1), containing Mo, Ni and/or Co, P solution in, MoO3The concentration that concentration is 0.05 ~ 0.2 g/mL, NiO and/or CoO be 0.005 ~ 0.06 g/mL, the concentration of P is 0.005 ~ 0.04 g/mL.
The most in accordance with the method for claim 7, it is characterised in that described organic acid is one or more in citric acid, tartaric acid, malic acid, lauric acid, described organic acid is 0.05 ~ 1 with step (4) silicon source mol ratio in terms of silicon oxide.
The most in accordance with the method for claim 7, it is characterized in that described template be cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, sodium lauryl sulphate, triblock polymer P123, triblock polymer F127, triblock polymer F108, molecular weight be Polyethylene Glycol, one or more in methylcellulose of 1000 ~ 10000, described template is 0.01 ~ 1.0 with step (4) silicon source mol ratio in terms of silicon oxide.
11. in accordance with the method for claim 7, it is characterised in that in step (2), and described alkali metal salt is one or more in carbonate, nitrate, and the concentration of alkali metal salt is 0.05 ~ 0.15 g/mL；In heteropoly acid aqueous solution, the concentration of heteropoly acid is 0.5 ~ 2.0 g/mL.
12. in accordance with the method for claim 7, it is characterised in that in step (4), and described silicon source is one or more in tetraethyl orthosilicate, Ludox.
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