CN103586028B - Method for preparing methanation catalyst through glucose complexation process - Google Patents

Abstract

The invention relates to a method for preparing a methanation catalyst through a glucose complexation process. If there is no assistant, the method comprises the following steps: preparing an activated alumina or pseudo-boehmite microsphere particle, preparing a glucose-magnesium complex solution, preparing an alumna sphere particle with the surface having a layer of MgAl2O4@Al2O3 composite structure carrier having an MgAl2O4 spinel shell, preparing a glucose-nickel complex solution, and preparing an NiO/MgAl2O4@Al2O3 catalyst; and if there is an assistant, the method comprises the following steps: preparing the activated alumina or pseudo-boehmite microsphere particle, preparing the glucose-magnesium complex solution, preparing the alumna sphere particle with the surface having a layer of MgAl2O4@Al2O3 composite structure carrier having an MgAl2O4 spinel shell, preparing a glucose-M complex solution, preparing an M/MgAl2O4@Al2O3 catalyst, preparing a glucose-nickel complex solution, and preparing the NiO/MgAl2O4@Al2O3 catalyst. The method substantially improves the activity, the stability and the carbon deposition resistance of the catalyst.

Description

Glucose complexometry prepares the method for methanation catalyst

Technical field

The present invention relates to preparation and the applied technical field thereof of catalyst, be specifically related to the method that glucose complexometry prepares methanation catalyst.

Background technology

Having in the coal resources of China is the brown coal of low-quality greatly, and direct utilization ratio is low, it is large to pollute.Transformed as raw material by brown coal, produce high-grade energy natural gas, the utilization for China's low-grade coal provides a kind of new means.The committed step of coal synthetic natural gas technique is the synthesis gas CO after coal gasification _xcomponent full methanation reacts.Mainly CO, CO is comprised in the synthesis gas that coal gasification produces ₂, H ₂, CH ₄and N ₂deng composition, after the techniques such as conversion and purification, made CO, the CO in synthesis gas by methanation reaction ₂and H ₂be converted into CH under certain conditions ₄, finally by the technique such as decarburization and enrichment, obtain CH ₄the synthetic natural gas of content more than 90% (SNG).

Methanation catalyst is generally made up of a few parts such as catalytic active component, auxiliary agent, catalyst carriers.At present, the active component of most of methanation catalyst is the transition metal of VIII, and nickel-alumina catalyst is widely used methanation catalyst system.

Prepare nickel-alumina methanation catalyst, the method of usual employing chemical precipitation, aluminium source carrier presoma, nickel oxide precursor, auxiliary agent presoma and precipitant mix are precipitated, then after filtration, washing, drying, roasting, the operating unit such as shaping, catalyst needed for finally obtaining.Patent US3988262, US3988263 utilize co-precipitation and precipitation from homogeneous solution technology to prepare nickel-alumina methanation catalyst respectively.

Be carrier by infusion process by aluminium oxide simultaneously, the hybrid infusions such as dipping nickel active component, auxiliary agent, drying, calcining, shapingly make nickel-alumina methanation catalyst.As patent CN 102259004A uses the precipitation method to obtain Al ₂o ₃carrier, then adopts infusion process to load on carrier by active component and auxiliary agent, to obtain the methanation catalyst of active high, Heat stability is good after high-temperature roasting.

But be a certain amount of nickel aluminate of all inevasible generation of infusion process or the precipitation method, this is due to active component nickel oxide and carrier A l under high-temperature calcination state ₂o ₃caused by effect, thus the utilization rate reducing active component makes catalyst performance decline.

Chinese patent CN102139218A discloses a kind of method, by Al ₂o ₃carrier and MgO mechanical mixture are to even, be placed in calcining in 1000 ~ 1500 DEG C of high-temperature calcination stoves, the two agency part is made to generate magnesium aluminate spinel, this novel carriers can reduce the generation of nickel aluminate to improve the activity of catalyst at oxide impregnation nickel presoma when calcining, but this method preparation temperature is high, energy consumption is huge, and the catalyst performance simultaneously generated is unstable, still has room for improvement.

Summary of the invention

In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide glucose complexometry to prepare the method for methanation catalyst, improving activity, stability, the coking resistivity of catalyst.

In order to achieve the above object, technical scheme of the present invention is:

Glucose complexometry prepares the method for methanation catalyst, is divided into and does not need auxiliary agent during preparation and need auxiliary agent two kinds of situations,

Do not need auxiliary agent during preparation, comprise the following steps:

Step one, in aluminium oxide or boehmite, add the alcohol dispersant of quality of alumina 10 ~ 40wt%, on ball mill, ball milling 20 ~ 60min is to reach the effect of surface active, makes aluminium oxide or the pseudo boehmite microsphere particle of activation; Al in described boehmite ₂o ₃mass content is 74wt%;

Step 2, by glucose solution and Mg (NO ₃) ₂6H ₂o carries out mole complexing such as grade, configuration glucose-magnesium complex solution;

Step 3, by glucose-magnesium complex solution impregnation to activation aluminium oxide or pseudo boehmite microsphere particulate vector on, the addition of glucose-magnesium complex solution counts MgAl with MgO ₂o ₄@Al ₂o ₃5 ~ 30% of composite construction carrier quality content, dry overnight at room temperature, 105 DEG C of drying 2 ~ 4h, at the roasting temperature 4 ~ 6h of 400 ~ 600 DEG C, drop to room temperature naturally, and obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier;

Step 4, by mole complexings such as glucose solution and nickel nitrate carry out, prepare glucose-nickel complex solution;

Step 5, by glucose-nickel complex solution impregnation to MgAl ₂o ₄@Al ₂o ₃on composite construction carrier, the addition of glucose-nickel complex solution counts 5 ~ 55% of catalyst gross mass content with NiO, dry at room temperature over night, 105 DEG C of dry 4h, put into calcining furnace again, at the temperature lower calcination 4 ~ 6h of 400 ~ 600 DEG C, obtained NiO/MgAl ₂o ₄@Al ₂o ₃catalyst;

Need auxiliary agent during preparation, comprise the following steps:

Step one, in aluminium oxide or boehmite powder, add the alcohol dispersant of quality of alumina 10 ~ 40wt%, on planetary ball mill, ball milling 20 ~ 60min carries out surface activation process, makes aluminium oxide or the pseudo boehmite microsphere particle of activation; Al in described boehmite powder ₂o ₃mass content is 74wt%;

Step 2, by glucose solution and Mg (NO ₃) ₂6H ₂o carries out mole complexing such as grade, configuration glucose-magnesium complex solution;

Step 3, by glucose-magnesium complex solution impregnation to activation aluminium oxide or pseudo boehmite microsphere particulate vector on, the addition of glucose-magnesium complex solution counts MgAl with MgO ₂o ₄@Al ₂o ₃5 ~ 30% of composite construction carrier quality content, dry overnight at room temperature, 105 DEG C of drying 2 ~ 4h, at the temperature lower calcination 4 ~ 6h of 400 ~ 600 DEG C, drop to room temperature naturally, and obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier;

Step 4, by mole complexings such as the nitrate of glucose solution and auxiliary agent M, prepare glucose-M complex solution, described auxiliary agent M to be selected from the oxide of Ce, Ca, Co, La, Zr, Sm, Ba, Mn, Fe, Mo, Ti and Cu metal one or more;

Step 5, glucose-M complex solution is impregnated into MgAl ₂o ₄@Al ₂o ₃on composite construction carrier, the addition of glucose-M complex solution counts 1 ~ 25% of catalyst gross mass content with M, dry at room temperature over night, 105 DEG C of dry 4h, then put into Muffle furnace, at the temperature lower calcination 4 ~ 6h of 400 ~ 600 DEG C, naturally room temperature is dropped to, i.e. obtained M/MgAl ₂o ₄@Al ₂o ₃catalyst;

Step 6, by mole complexings such as glucose solution and nickel nitrate carry out, prepare glucose-nickel complex solution;

Step 7, by glucose-nickel complex solution impregnation to M/MgAl ₂o ₄@Al ₂o ₃on composite construction carrier, the addition of glucose-nickel complex solution counts 5 ~ 55% of catalyst gross mass content with NiO, dry at room temperature over night, 105 DEG C of dry 4h, then put into Muffle furnace, at the roasting temperature 4 ~ 6h of 400 ~ 600 DEG C, naturally room temperature is dropped to, i.e. obtained NiO-M/MgAl ₂o ₄@Al ₂o ₃catalyst.

Methanation catalyst prepared by the present invention's glucose complexometry, contrasts with existing method, has the following advantages:

1. MgAl is prepared by method of the present invention ₂o ₄@Al ₂o ₃during composite construction carrier, use magnesium-complex solution, serve good dispersion effect, make activated alumina or boehmite surface can form the uniform magnesium aluminate spinel shell of one deck, the possibility of generating nickel aluminate is reduced while improving the utilization rate of Mg, due to prepare presoma that magnesium aluminate spinel uses for magnesium-complex solution thus calcining heat also technique is more in the past much lower, thus reduce energy consumption.

2. with MgAl prepared by method of the present invention ₂o ₄@Al ₂o ₃in composite construction carrier, the effect of magnesium aluminate spinel shell can be good at intercepting between active component nickel oxide and alumina catalyst support and acts on, with the activity of the utilization rate thus raising catalyst that improve active component.

3. NiO/MgAl is prepared by method of the present invention ₂o ₄@Al ₂o ₃catalyst and the NiO-M/MgAl containing M auxiliary agent ₂o ₄@Al ₂o ₃during catalyst, preferential impregnation aids M-complex solution can interact with carrier thus produce and act synergistically in calcination process, and to improve the conversion ratio of catalyst and selective, this can improve activity, stability, the coking resistivity of catalyst greatly.

Detailed description of the invention

Below in conjunction with specific embodiment, the present invention is described in further detail, but this does not form and imposes any restrictions the present invention.The known technology part that the present invention relates to does not describe in detail.Unstripped gas of the present invention can be coal based synthetic gas, coal bed gas base synthesis gas, Biomass Syngas one or more, those skilled in the art, according to the description of the present embodiment, can understand and adopt different material gas to complete the present invention.

Embodiment one

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 90.0 grams of aluminium oxide, add 9.0 grams of ethanol, put into planetary ball mill ball milling 20min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.25mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the roasting temperature 4h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier.MgAl ₂o ₄the content of spinelle shell is expressed as 10.0% with the content of MgO;

Step 4, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 5, take 88.8 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into calcining furnace, at the temperature lower calcination 4h of 550 DEG C, is obtained 11.2%NiO/MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment two

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 118.8 grams of boehmites, add 12.0 grams of ethanol, put into planetary ball mill ball milling 30min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.30mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the roasting temperature 4h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 12.1% with the content of MgO;

Step 4, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 5, take 88.8 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into calcining furnace, at the temperature lower calcination 4h of 550 DEG C, is obtained 11.2%NiO/MgAl ₂o ₄@Al ₂o ₃(BL) catalyst, (BL) represents with boehmite to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment three

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 85.9 grams of aluminium oxide, add 14.0 grams of ethanol, put into planetary ball mill ball milling 30min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.35mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the roasting temperature 5h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 14.1% with the content of MgO;

Step 4, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 5, take 92.5 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-nickel complex solution containing 0.10mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into calcining furnace, at the temperature lower calcination 4h of 550 DEG C, is obtained 7.5%NiO/MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment four

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 113.4 grams of boehmites, add 18.0 grams of ethanol, put into planetary ball mill ball milling 40min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.40mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the roasting temperature 6h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 16.1% with the content of MgO;

Step 4, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 5, take 73.9 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-nickel complex solution containing 0.35mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into calcining furnace, at the temperature lower calcination 4h of 550 DEG C, is obtained 26.1%NiO/MgAl ₂o ₄@Al ₂o ₃(BL) catalyst, (BL) represents with boehmite to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment five

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 79.8 grams of aluminium oxide, add 16.0 grams of ethanol, put into planetary ball mill ball milling 40min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.50mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the roasting temperature 5h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 20.1% with the content of MgO;

Step 4, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 5, take 88.8 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into calcining furnace, at the temperature lower calcination 4h of 550 DEG C, is obtained 11.2%NiO/MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment six

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 85.9 grams of aluminium oxide, add 15.0 grams of ethanol, put into planetary ball mill ball milling 30min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.35mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the roasting temperature 5h of 400 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 14.1% with the content of MgO;

Step 4, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 5, take 81.3 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-nickel complex solution containing 0.25mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into calcining furnace, at the temperature lower calcination 4h of 550 DEG C, is obtained 18.7%NiO/MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment seven

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 113.4 grams of boehmites, add 18.0 grams of ethanol, put into planetary ball mill ball milling 40min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.40mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the roasting temperature 6h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 16.1% with the content of MgO;

Step 4, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 5, take 55.2 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-nickel complex solution containing 0.60mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into calcining furnace, at the temperature lower calcination 4h of 550 DEG C, is obtained 44.8%NiO/MgAl ₂o ₄@Al ₂o ₃(BL) catalyst, (BL) represents with boehmite to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment eight

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 85.9 grams of aluminium oxide, add 15.0 grams of ethanol, put into planetary ball mill ball milling 30min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.35mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the temperature lower calcination 5h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 14.1% with the content of MgO;

Step 4, take 18.0 grams of (0.1mol) glucose and to be dissolved in deionized water obtained glucose solution, take 43.3 grams of (0.1mol) lanthanum nitrates and be dissolved in obtained lanthanum nitrate hexahydrate in deionized water, equimolar glucose and lanthanum nitrate are carried out complexing, makes glucose-lanthanum complex solution;

Step 5, take 85.6 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-lanthanum complex solution containing 0.02mol lanthanum, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into Muffle furnace, at the temperature lower calcination 4h of 400 DEG C, i.e. and the obtained MgAl containing lanthanum auxiliary agent ₂o ₄@Al ₂o ₃carrier.

Step 6, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 7, step 5 prepare containing lanthanum auxiliary agent MgAl ₂o ₄@Al ₂o ₃in carrier, add the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then put into Muffle furnace, at the roasting temperature 4h of 550 DEG C, naturally drop to room temperature, namely obtained 11.2%NiO-3.2%La ₂o ₃/ MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment nine

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 113.4 grams of boehmites, add 18.0 grams of ethanol, put into planetary ball mill ball milling 40min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.40mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the temperature lower calcination 6h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 16.1% with the content of MgO;

Step 4, take 18.0 grams of (0.1mol) glucose and to be dissolved in deionized water obtained glucose solution, 39.3 grams of (0.1mol) zirconium nitrates are dissolved in obtained zirconium nitrate solution in deionized water, equimolar glucose and zirconium nitrate are carried out complexing, makes glucose-zirconium complex solution;

Step 5, take 82.6 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-zirconium complex solution containing 0.05mol zirconium, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into Muffle furnace, at the temperature lower calcination 4h of 400 DEG C, i.e. and the obtained MgAl containing zirconium auxiliary agent ₂o ₄@Al ₂o ₃carrier;

Step 6, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 7, step 5 prepare containing zirconium auxiliary agent MgAl ₂o ₄@Al ₂o ₃in carrier, add the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then put into Muffle furnace, at the roasting temperature 4h of 550 DEG C, naturally drop to room temperature, be obtained 11.2%NiO-6.2%ZrO ₂/ MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment ten

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 85.9 grams of aluminium oxide, add 15.0 grams of ethanol, put into planetary ball mill ball milling 30min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.35mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the temperature lower calcination 5h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 14.1% with the content of MgO;

Step 4, take 18.0 grams of (0.1mol) glucose and to be dissolved in deionized water obtained glucose solution, take 40.4 grams of (0.1mol) ferric nitrates and be dissolved in obtained iron nitrate solution in deionized water, equimolar glucose and ferric nitrate are carried out complexing, makes glucose-iron complex solution;

Step 5, take 83.2 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-iron complex solution containing 0.035mol iron, dry at room temperature over night, 105 DEG C of dry 4h, then puts into Muffle furnace, at the temperature lower calcination 4h of 400 DEG C, is the MgAl of obtained iron content auxiliary agent ₂o ₄@Al ₂o ₃carrier;

Step 6, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 7, the iron content auxiliary agent MgAl prepared in step 5 ₂o ₄@Al ₂o ₃in carrier, add the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then put into Muffle furnace, at the roasting temperature 4h of 550 DEG C, naturally drop to room temperature, be obtained 11.2%NiO-5.6%Fe ₂o ₃/ MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment 11

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 113.4 grams of boehmites, add 18.0 grams of ethanol, put into planetary ball mill ball milling 40min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.40mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the temperature lower calcination 6h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 16.1% with the content of MgO;

Step 4, take 18.0 grams of (0.1mol) glucose and to be dissolved in deionized water obtained glucose solution, take 29.1 grams of (0.1mol) cobalt nitrates and be dissolved in obtained cobalt nitrate solution in deionized water, equimolar glucose and cobalt nitrate are carried out complexing, makes glucose-cobalt complex solution;

Step 5, take 83.5 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-cobalt complex solution containing 0.07mol cobalt, dry at room temperature over night, 105 DEG C of dry 4h, then puts into Muffle furnace, at the temperature lower calcination 4h of 400 DEG C, is the obtained MgAl containing cobalt auxiliary agent ₂o ₄@Al ₂o ₃carrier;

Step 6, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 7, step 5 prepare containing cobalt auxiliary agent MgAl ₂o ₄@Al ₂o ₃add the glucose-nickel complex solution of 0.15mol nickel in carrier, dry at room temperature over night, 105 DEG C of dry 4h, then put into Muffle furnace, at the roasting temperature 4h of 550 DEG C, naturally drop to room temperature, be obtained 11.2%NiO-5.3%CoO/MgAl ₂o ₄@Al ₂o ₃(BL) catalyst, (BL) represents with boehmite to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

Embodiment 12

Glucose complexometry prepares the method for methanation catalyst, comprises the following steps:

Step one, take 85.9 grams of aluminium oxide, add 15.0 grams of ethanol, put into planetary ball mill ball milling 30min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of (1.0mol) magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.35mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the temperature lower calcination 5h of 400 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 14.1% with the content of MgO;

Step 4, take 18.0 grams of (0.1mol) glucose and to be dissolved in deionized water obtained glucose solution, take 24.1 grams of (0.1mol) copper nitrates and be dissolved in obtained copper nitrate solution in deionized water, equimolar glucose and copper nitrate are carried out complexing, makes glucose-copper complex solution;

Step 5, take 83.2 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-copper complex solution containing 0.07mol copper, dry at room temperature over night, 105 DEG C of dry 4h, then puts into Muffle furnace, at the temperature lower calcination 4h of 400 DEG C, is the MgAl of obtained cupric auxiliary agent ₂o ₄@Al ₂o ₃carrier;

Step 6, take 180.2 grams of (1.0mol) glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of (1.0mol) nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 7, the cupric auxiliary agent MgAl prepared in step 5 ₂o ₄@Al ₂o ₃in carrier, add the glucose-nickel complex solution containing 0.15mol nickel, dry at room temperature over night, 105 DEG C of dry 4h, then put into Muffle furnace, at the roasting temperature 4h of 550 DEG C, naturally drop to room temperature, be obtained 11.2%NiO-5.6%CuO/MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

The composition of catalyst and Activity evaluation are in table one.

The catalytic activity of the above embodiment of the present invention gained methanation catalyst measures, and carries out in fixed bed reactors.Get 40 ~ 60 object catalyst granules to load in reactors, then logical people's hydrogen, at the temperature of 550 DEG C, reduce 4h, be the catalyst of reduction activation.After reduction terminates, by the temperature stabilization of beds under the reaction temperature of specifying, switch to H ₂/ CO ratio be the synthesis gas of 3.08 as unstripped gas, carry out methanation reaction in atmospheric conditions.The composition of unstripped gas and reactor outlet gas all by gas chromatograph on-line analysis, by calculating the conversion ratio of methanation reaction and the selective of product.

Illustrated by embodiment, the methanation catalyst prepared according to method of the present invention has the advantages such as catalytic activity is good, preparation technology is simple, with low cost, is a kind of synthesis gas methanation catalyst having very much actual application prospect.

The methanation catalyst Activity evaluation of table one, each embodiment catalyst

Claims (7)

1. glucose complexometry prepares the method for methanation catalyst, is divided into and does not need auxiliary agent during preparation and need auxiliary agent two kinds of situations, it is characterized in that:

Do not need auxiliary agent during preparation, comprise the following steps:

Step one, in aluminium oxide or boehmite, add the alcohol dispersant of quality of alumina 10 ~ 40wt%, on ball mill, ball milling 20 ~ 60min is to reach the effect of surface active, makes aluminium oxide or the pseudo boehmite microsphere particle of activation; Al in described boehmite ₂o ₃mass content is 74wt%;

Step 2, by glucose solution and Mg (NO ₃) ₂6H ₂o carries out mole complexing such as grade, configuration glucose-magnesium complex solution;

Step 3, by glucose-magnesium complex solution impregnation to activation aluminium oxide or pseudo boehmite microsphere particulate vector on, the addition of glucose-magnesium complex solution counts MgAl with MgO ₂o ₄@Al ₂o ₃5 ~ 30% of composite construction carrier quality content, dry overnight at room temperature, 105 DEG C of drying 2 ~ 4h, at the roasting temperature 4 ~ 6h of 400 ~ 600 DEG C, drop to room temperature naturally, and obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier;

Step 4, by mole complexings such as glucose solution and nickel nitrate carry out, prepare glucose-nickel complex solution;

Step 5, by glucose-nickel complex solution impregnation to MgAl ₂o ₄@Al ₂o ₃on composite construction carrier, the addition of glucose-nickel complex solution counts 5 ~ 55% of catalyst gross mass content with NiO, dry at room temperature over night, 105 DEG C of dry 4h, put into calcining furnace again, at the temperature lower calcination 4 ~ 6h of 400 ~ 600 DEG C, obtained NiO/MgAl ₂o ₄@Al ₂o ₃catalyst;

Need auxiliary agent during preparation, comprise the following steps:

Step one, in aluminium oxide or boehmite powder, add the alcohol dispersant of quality of alumina 10 ~ 40wt%, on planetary ball mill, ball milling 20 ~ 60min carries out surface activation process, makes aluminium oxide or the pseudo boehmite microsphere particle of activation; Al in described boehmite powder ₂o ₃mass content is 74wt%;

Step 2, by glucose solution and Mg (NO ₃) ₂6H ₂o carries out mole complexing such as grade, configuration glucose-magnesium complex solution;

Step 3, by glucose-magnesium complex solution impregnation to activation aluminium oxide or pseudo boehmite microsphere particulate vector on, the addition of glucose-magnesium complex solution counts MgAl with MgO ₂o ₄@Al ₂o ₃5 ~ 30% of composite construction carrier quality content, dry overnight at room temperature, 105 DEG C of drying 2 ~ 4h, at the temperature lower calcination 4 ~ 6h of 400 ~ 600 DEG C, drop to room temperature naturally, and obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier;

Step 4, by mole complexings such as the nitrate of glucose solution and auxiliary agent M, prepare glucose-M complex solution, described auxiliary agent M to be selected from Ce, Ca, Co, La, Zr, Sm, Ba, Mn, Fe, Mo, Ti and Cu one or more;

Step 5, glucose-M complex solution is impregnated into MgAl ₂o ₄@Al ₂o ₃on composite construction carrier, the addition of glucose-M complex solution counts 1 ~ 25% of catalyst gross mass content with M, dry at room temperature over night, 105 DEG C of dry 4h, then put into Muffle furnace, at the temperature lower calcination 4 ~ 6h of 400 ~ 600 DEG C, naturally room temperature is dropped to, i.e. obtained M/MgAl ₂o ₄@Al ₂o ₃catalyst;

Step 6, by mole complexings such as glucose solution and nickel nitrate carry out, prepare glucose-nickel complex solution;

Step 7, by glucose-nickel complex solution impregnation to M/MgAl ₂o ₄@Al ₂o ₃on composite construction carrier, the addition of glucose-nickel complex solution counts 5 ~ 55% of catalyst gross mass content with NiO, dry at room temperature over night, 105 DEG C of dry 4h, then put into Muffle furnace, at the roasting temperature 4 ~ 6h of 400 ~ 600 DEG C, naturally room temperature is dropped to, i.e. obtained NiO-M/MgAl ₂o ₄@Al ₂o ₃catalyst.

2. glucose complexometry according to claim 1 prepares the method for methanation catalyst, it is characterized in that, comprises the following steps:

Step one, take 90.0 grams of aluminium oxide, add 9.0 grams of ethanol, put into planetary ball mill ball milling 20min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.25mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the roasting temperature 4h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier.MgAl ₂o ₄the content of spinelle shell is expressed as 10.0% with the content of MgO;

Step 4, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 5, take 88.8 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into calcining furnace, at the temperature lower calcination 4h of 550 DEG C, is obtained 11.2%NiO/MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

3. glucose complexometry according to claim 1 prepares the method for methanation catalyst, it is characterized in that, comprises the following steps:

Step one, take 118.8 grams of boehmites, add 12.0 grams of ethanol, put into planetary ball mill ball milling 30min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.30mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the roasting temperature 4h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 12.1% with the content of MgO;

Step 4, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 5, take 88.8 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into calcining furnace, at the temperature lower calcination 4h of 550 DEG C, is obtained 11.2%NiO/MgAl ₂o ₄@Al ₂o ₃(BL) catalyst, (BL) represents with boehmite to be the catalyst that carrier complexometry obtains.

4. glucose complexometry according to claim 1 prepares the method for methanation catalyst, it is characterized in that, comprises the following steps:

Step one, take 85.9 grams of aluminium oxide, add 14.0 grams of ethanol, put into planetary ball mill ball milling 30min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.35mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the roasting temperature 5h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 14.1% with the content of MgO;

Step 4, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 5, take 92.5 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-nickel complex solution containing 0.10mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into calcining furnace, at the temperature lower calcination 4h of 550 DEG C, is obtained 7.5%NiO/MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

5. glucose complexometry according to claim 1 prepares the method for methanation catalyst, it is characterized in that, comprises the following steps:

Step one, take 85.9 grams of aluminium oxide, add 15.0 grams of ethanol, put into planetary ball mill ball milling 30min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.35mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the temperature lower calcination 5h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 14.1% with the content of MgO;

Step 4, take 18.0 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 43.3 grams of lanthanum nitrates and be dissolved in obtained lanthanum nitrate hexahydrate in deionized water, equimolar glucose and lanthanum nitrate are carried out complexing, makes glucose-lanthanum complex solution;

Step 5, take 85.6 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-lanthanum complex solution containing 0.02mol lanthanum, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into Muffle furnace, at the temperature lower calcination 4h of 400 DEG C, i.e. and the obtained MgAl containing lanthanum auxiliary agent ₂o ₄@Al ₂o ₃carrier.

Step 6, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 7, step 5 prepare containing lanthanum auxiliary agent MgAl ₂o ₄@Al ₂o ₃in carrier, add the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then put into Muffle furnace, at the roasting temperature 4h of 550 DEG C, naturally drop to room temperature, namely obtained 11.2%NiO-3.2%La ₂o ₃/ MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

6. glucose complexometry according to claim 1 prepares the method for methanation catalyst, it is characterized in that, comprises the following steps:

Step one, take 113.4 grams of boehmites, add 18.0 grams of ethanol, put into planetary ball mill ball milling 40min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.40mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the temperature lower calcination 6h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 16.1% with the content of MgO;

Step 4, take 18.0 grams of glucose and to be dissolved in deionized water obtained glucose solution, 39.3 grams of zirconium nitrates are dissolved in obtained zirconium nitrate solution in deionized water, equimolar glucose and zirconium nitrate are carried out complexing, makes glucose-zirconium complex solution;

Step 5, take 82.6 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-zirconium complex solution containing 0.05mol zirconium, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then puts into Muffle furnace, at the temperature lower calcination 4h of 400 DEG C, i.e. and the obtained MgAl containing zirconium auxiliary agent ₂o ₄@Al ₂o ₃carrier;

Step 6, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 7, step 5 prepare containing zirconium auxiliary agent MgAl ₂o ₄@Al ₂o ₃in carrier, add the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then put into Muffle furnace, at the roasting temperature 4h of 550 DEG C, naturally drop to room temperature, be obtained 11.2%NiO-6.2%ZrO ₂/ MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.

7. glucose complexometry according to claim 1 prepares the method for methanation catalyst, it is characterized in that, comprises the following steps:

Step one, take 85.9 grams of aluminium oxide, add 15.0 grams of ethanol, put into planetary ball mill ball milling 30min, be the aluminum oxide micro-sphere particle of surface active;

Step 2, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 256.4 grams of magnesium nitrates and be dissolved in obtained magnesium nitrate solution in deionized water, equimolar glucose and magnesium nitrate are carried out complexing, makes glucose-magnesium complex solution;

Glucose-magnesium complex solution containing 0.35mol magnesium is added in step 3, the aluminium oxide that activates in step one, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, at the temperature lower calcination 5h of 600 DEG C, naturally drop to room temperature, obtained aluminum oxide micro-sphere particle surface has one deck MgAl ₂o ₄the MgAl of spinelle shell ₂o ₄@Al ₂o ₃composite construction carrier, MgAl ₂o ₄the content of spinelle shell is expressed as 14.1% with the content of MgO;

Step 4, take 18.0 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 40.4 grams of ferric nitrates and be dissolved in obtained iron nitrate solution in deionized water, equimolar glucose and ferric nitrate are carried out complexing, makes glucose-iron complex solution;

Step 5, take 83.2 grams of MgAl ₂o ₄@Al ₂o ₃composite construction carrier, adds the glucose-iron complex solution containing 0.035mol iron, dry at room temperature over night, 105 DEG C of dry 4h, then puts into Muffle furnace, at the temperature lower calcination 4h of 400 DEG C, is the MgAl of obtained iron content auxiliary agent ₂o ₄@Al ₂o ₃carrier;

Step 6, take 180.2 grams of glucose and to be dissolved in deionized water obtained glucose solution, take 290.8 grams of nickel nitrates and be dissolved in obtained nickel nitrate solution in deionized water, equimolar glucose and nickel nitrate are carried out complexing, makes glucose-nickel complex solution;

Step 7, the iron content auxiliary agent MgAl prepared in step 5 ₂o ₄@Al ₂o ₃in carrier, add the glucose-nickel complex solution containing 0.15mol nickel, dipping also dried overnight under room temperature, 105 DEG C of dry 4h, then put into Muffle furnace, at the roasting temperature 4h of 550 DEG C, naturally drop to room temperature, be obtained 11.2%NiO-5.6%Fe ₂o ₃/ MgAl ₂o ₄@Al ₂o ₃(AL) catalyst, (AL) represents with aluminium oxide to be the catalyst that carrier complexometry obtains.