CN103191744A - Modified vermiculite supported nickel catalyst and preparation method thereof - Google Patents

Modified vermiculite supported nickel catalyst and preparation method thereof Download PDF

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CN103191744A
CN103191744A CN2013101345156A CN201310134515A CN103191744A CN 103191744 A CN103191744 A CN 103191744A CN 2013101345156 A CN2013101345156 A CN 2013101345156A CN 201310134515 A CN201310134515 A CN 201310134515A CN 103191744 A CN103191744 A CN 103191744A
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vermiculite
performance
catalyst
modified vermiculite
modified
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CN103191744B (en
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闫世友
陈朝阳
王军华
郝斌
谢永新
范艳伟
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention relates to a modified vermiculite supported nickel catalyst and a preparation method thereof. The catalyst comprises nickel and modified vermiculite; and according to the method, firstly modified vermiculite support is prepared, treated in an acid solution and washed and dried to obtain modified vermiculite catalyst, and then the modified vermiculite supported nickel catalyst is prepared by a polyhydric alcohol liquid phase high temperature reduction method. The method has the advantages of simple catalyst composition, easy operation of preparation process, low in production cost and the like, the catalyst prepared according to the method has the advantages of small average grain size, uniform dispersing, good resistance against carbon deposition, good stability and the like; and the modified vermiculite supported nickel catalyst and the preparation method thereof are applied to the production of syngas based on methane and carbon dioxide reforming, and have a good prospect.

Description

A kind of PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst and preparation method thereof
Technical field
The present invention relates to PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst and preparation method thereof, belong to gas chemical industry and catalyst manufacturing engineering technical field, this catalyst is used for the methane carbon dioxide reformation reaction.
Background technology
In Copenhagen global climate conference of holding in 2009, Premier Wen Jiabao proposes the year two thousand twenty China per GDP emission greenhouse gas flow will be than the reduction of discharging target of decline 40-45% in 2005.Reduction of discharging as main greenhouse gases-carbon dioxide is shouldered heavy responsibilities.In addition, there is abundant natural gas resource in China, and the exploration result shows that the prospective reserves of China's natural gas resource is about 26-33 trillion m3, accounts for 10% of world's prospective reserves.As the main component-methane of natural gas, also be simultaneously one of six kinds of main greenhouse gas of Kyoto Protocol regulation.React the efficient utilization that can realize greenhouse gases by methane carbon dioxide reformation, can produce basic chemical industry raw material-synthesis gas, and then synthetic various chemical products, chemical industry broken away to the single dependence of petroleum.Therefore, the methane reforming CO 2 technology still is that gas chemical industry's development already is all significant to the reduction of discharging of greenhouse gases.
For the methane carbon dioxide reformation reaction, having under the condition of catalyst, carbon dioxide conversion can reach more than 90%; Under the catalyst-free condition, carbon dioxide conversion is zero substantially.Therefore, catalyst is the greatest factor of restriction methane carbon dioxide reformation reaction development.At present, to CH 4, CO 2, O 2The catalyst that the process study of catalytic oxidation preparing synthetic gas by reforming gets at most is load type metal catalyst, comprising noble metal catalyst and transition-metal catalysts such as Ni, Co such as Rh, Ru, Ir, Pt.Noble metal catalyst has advantages such as active height, good stability, anti-carbon deposit, but because it is expensive, resource-constrained, commercial Application is restricted.Ni is catalyst based to have the activity close with noble metal catalyst with selective, and have that cost is low, intensity is high, be easy to advantages such as preparation, it is the catalyst that application prospect is arranged most, but under high temperature, high-speed, Ni is catalyst based easily because active component and carrier interact, active component sintering and loss and inactivation.Simultaneously carbon-collecting problem also is the catalyst based problem that can not be ignored of Ni, and can how to improve the catalyst based stability of Ni just becomes it and realize industrialized key.
Improving the catalyst based stability of Ni at present mainly can be by adding approach such as auxiliary agent, support modification, employing novel carriers material.Wherein carrier has very important influence to structure, stability and the catalytic performance of catalyst.Document (synthetic chemistry, 2008,16 (5): 495) reported that the carrier Acidity of Aikalinity is to nickel-base catalyst CH 4/ CO 2Reforming reaction Effect on Performance, result show that the size of carrier Acidity of Aikalinity and specific area directly has influence on the reactivity worth of catalyst.Document (the catalysis journal, 2007,10 (10): 865) studies show that interaction partners CH between metal-carrier 4/ CO 2The catalytic performance of catalyst plays an important role.Document (Energy﹠amp; Fuels, 2007,21:2950) reported that the nickel-base catalyst of different carriers load is to CH 4/ CO 2The catalytic performance of reforming reaction performance, the result shows that the catalyst that catalyst granules is uniformly dispersed, average grain diameter is little shows best activity and stable.
Chinese invention patent (publication number CN1939587) discloses a kind of monoblock type Ni catalyst, and this method adopts the mesopore molecular sieve SBA15 Ni-SBA15 that has been preparing carriers earlier; Then Al 2O 3Be coated on the FeCrAl alloy sheet and make Al 2O 3/ FeCrAl; Again Ni-SBA15 and Al 2O 3The mixed slurries that get; Make Ni-SBA15/Al at last 2O 3/ FeCrAl integral catalyzer.Results of property shows that this catalyst has higher activity and selective, and is too loaded down with trivial details but its shortcoming is preparation process.
A kind of cordierite-base body catalyst of Chinese invention patent (publication number CN102407119A) and preparation method thereof, this method has been introduced the cordierite matrix on the basis of integral catalyzer, and Preparation of catalysts comprises three steps: the one, and the acid treatment process of cordierite; The 2nd, the preparation of catalyst precipitation liquid; The 3rd, the high pressure roasting process of cordierite and precipitated liquid, making with the cordierite is the catalyst of matrix.This carbon deposition quantity of catalyst of test shows is less as a result for 20 hours carbon distributions, and stability better.This method preparation process is also comparatively loaded down with trivial details, and catalyst activity and selectively not high.
To sum up, the high temperature coking deactivation of nickel-base catalyst and the not good problem of stability are that methane carbon dioxide reformation is produced one of major issue that synthesis gas reaction faces.Some present technical measures can improve the stability of catalyst to a certain extent as adding noble metal, add auxiliary agent, adopting integral catalyzer etc., but have also that the catalyst cost is too high, preparation process is complicated, a performance problem such as high inadequately.In addition, there are some researches show that grain diameter can effectively suppress the generation of carbon distribution process less than the nano-metal particle of certain size, thereby make catalyst have good anti-carbon deposit performance.Vermiculite is a kind of silicate mineral with layered nano-structure, itself has excellent high-temperature stability, and its special layered nano-structure has the effect of space confinement, can stop the high temperature of nano particle to be assembled and grow up.Therefore, reactive metal (as nickel) and high-temperature stability is good, as to have nanometer laminated structure vermiculite carrier combines, and is expected effectively to improve anti-carbon deposit performance and the stability of catalyst.
Summary of the invention
The object of the invention is, a kind of PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst and preparation method thereof is provided, this catalyst is made up of nickel and PERFORMANCE OF MODIFIED VERMICULITE, adopt preparation PERFORMANCE OF MODIFIED VERMICULITE carrier earlier, by in acid solution, handling, obtain the PERFORMANCE OF MODIFIED VERMICULITE catalyst through the washing drying, be equipped with the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst through polyalcohol liquid phase high temperature reduction legal system again.The present invention has catalyst and forms advantages such as simple, that preparation process is easy to operate, production cost is low, the catalyst of preparing have average grain diameter little, be uniformly dispersed, advantage such as anti-carbon deposit performance and good stability, be applied to methane carbon dioxide reformation and produce synthesis gas reaction and have good prospect.
A kind of PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst of the present invention, each constituent mass mark of this catalyst is: nickel 5-15%, PERFORMANCE OF MODIFIED VERMICULITE is sour modification raw ore vermiculite or expanded vermiculite 85%-95%.
The preparation method of described a kind of PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst follows these steps to carry out:
The preparation of PERFORMANCE OF MODIFIED VERMICULITE carrier:
A, select even centimetre of grain diameter, PERFORMANCE OF MODIFIED VERMICULITE that lamellar structure is good is raw ore vermiculite or expanded vermiculite, is sized to the 200-300 order after ball mill is pulverized, and obtains the vermiculite powder;
B, the vermiculite powder is joined in the acid solution that hydrogen ion concentration is 0.5-10mol/L, be warming up to 80-120 ℃, stir down fast and handled 3 hours, obtain solidliquid mixture;
C, solidliquid mixture being filtered, is 7 with a large amount of deionized water cyclic washings to pH, and the solid that obtains 120 ℃ of oven dry of temperature 12 hours, obtains the PERFORMANCE OF MODIFIED VERMICULITE powder after grinding;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
D, take by weighing NiC 2O 42H 2O is dissolved in the ethylene glycol, add the PERFORMANCE OF MODIFIED VERMICULITE powder among the step c, stir and flood, adding NaOH regulator solution pH again is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, can obtain the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst.
Acid solution described in the step b is hydrochloric acid, nitric acid or sulfuric acid solution.
A kind of PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst of the present invention and preparation method thereof, described catalyst is to go up the load active component metallic nickel in PERFORMANCE OF MODIFIED VERMICULITE (MVMT), namely this catalyst is carrier with the PERFORMANCE OF MODIFIED VERMICULITE, be active component with the nano nickel particles, this catalyst can be labeled as Ni/MVMT, and wherein Ni content accounts for the 5-15% of total catalyst weight.
The present invention compared with prior art, its characteristics are:
1, catalyst is formed simply, and preparation process is easy to operate.
2, utilize the advantage that specific area is big, absorption property is strong after the vermiculite modification, can realize high dispersive and the high activity of Ni catalyst, the average grain diameter of the Ni catalyst granules of preparation only has 2nm.
3, utilize the special nanometer laminated structure of vermiculite to the confinement effect of catalyst granules, make the stability of Ni catalyst improve greatly.
A kind of PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst of the present invention, the application process in the methane carbon dioxide reformation reaction is as follows:
Take by weighing the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst, after compressing tablet, screening, make 20-40 purpose catalyst, pack in the reaction tube, carry out catalytic reforming reaction at fixed bed reactors, before reaction, need catalyst is reduced processings, process is as follows: the speed with 10 ℃/min of temperature is warming up to 500 ℃, feeding 10%H 2/ N 2Gaseous mixture carries out reductase 12 hour, switches to high-purity N then 2Purged 0.5 hour, and after reduction finishes temperature was adjusted to 750 ℃, feed the CH of 1:1 mixing by volume 4/ CO 2Gaseous mixture reacts, reaction carries out adopting after 1 hour on-line gas chromatography that reaction end gas is analyzed, and carried out the single injected sampling analysis every 1 hour, testing time is 30 hours, adopt thermal analyzer that the catalyst sample after having reacted is carried out thermogravimetric-differential scanning calorimetric analysis (TG-DSC), test its carbon deposition quantity.Description of drawings
Fig. 1 is the TEM figure of the embodiment of the invention 2 catalyst;
Fig. 2 is the TEM figure of Comparative Examples 1 catalyst of the present invention.
The specific embodiment
The present invention is further elaborated below by specific embodiment, is interpreted as, and the purpose of following examples only is used for explanation technical scheme of the present invention and technique effect, is not that protection scope of the present invention is limited.
Embodiment 1:
Taking by weighing mass fraction is: Ni10%, raw ore vermiculite 90%;
The PERFORMANCE OF MODIFIED VERMICULITE preparing carriers:
Select even centimetre of grain diameter, raw ore vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 200 orders, obtain raw ore vermiculite powder;
10g raw ore vermiculite powder is joined in the hydrochloric acid solution that the 500ml hydrogen ion concentration is 0.5mol/L, be warming up to 100 ℃, stir fast down and handled 3 hours, obtain solidliquid mixture;
Solidliquid mixture is filtered, be 7 with the deionized water cyclic washing to pH, the solid that obtains was 120 ℃ of oven dry of temperature 12 hours, obtain modification raw ore vermiculite powder (MVMT) after grinding, adopting ASAP2000 type specific area tester to record its specific area is 318m 2/ g;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take by weighing 3.15g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, can obtain the Ni mass content and be 10% PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst (see figure 1).
Embodiment 2:
Taking by weighing mass fraction is: Ni10%, expanded vermiculite 90%;
The PERFORMANCE OF MODIFIED VERMICULITE preparing carriers:
Select even centimetre of grain diameter, expanded vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 300 orders, obtain the expanded vermiculite powder;
10g expanded vermiculite powder is joined in the hydrochloric acid solution that the 500ml hydrogen ion concentration is 3mol/L, be warming up to 100 ℃, stir fast down and handled 3 hours, obtain solidliquid mixture;
Solidliquid mixture is filtered, and is 7 with the deionized water cyclic washing to pH, and the solid that obtains obtains modified expanded vermiculite powder (MVMT) 120 ℃ of oven dry of temperature 12 hours after grinding, and adopting ASAP2000 type specific area tester to record its specific area is 482m 2/ g;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take by weighing 3.15g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the modified expanded vermiculite powder (MVMT) that 9g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, obtain the Ni mass content and be 10% modified expanded vermiculite supported nickel catalyst.
Embodiment 3:
Taking by weighing mass fraction is: Ni10%, raw ore vermiculite 90%;
The preparation of PERFORMANCE OF MODIFIED VERMICULITE carrier:
Select even centimetre of grain diameter, raw ore vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 250 orders, obtain raw ore vermiculite powder;
10g raw ore vermiculite powder is joined in the hydrochloric acid solution that the 500ml hydrogen ion concentration is 5mol/L, be warming up to 100 ℃, stir fast down and handled 3 hours, obtain solidliquid mixture;
Solidliquid mixture is filtered, and is 7 with the deionized water cyclic washing to pH, and the solid that obtains obtains modification raw ore vermiculite powder (MVMT) 120 ℃ of oven dry of temperature 12 hours after grinding, and adopting ASAP2000 type specific area tester to record its specific area is 450m 2/ g;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take by weighing 3.15g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the modification raw ore vermiculite powder (MVMT) that 9g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, obtain the Ni mass content and be 10% modification raw ore vermiculite supported nickel catalyst.
Embodiment 4:
Taking by weighing mass fraction is: Ni10%, expanded vermiculite 90%.
The PERFORMANCE OF MODIFIED VERMICULITE preparing carriers
Select even centimetre of grain diameter, expanded vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 200 orders, obtain the expanded vermiculite powder;
10g expanded vermiculite powder is joined in the salpeter solution that the 500ml hydrogen ion concentration is 10mol/L, be warming up to 100 ℃, stir fast down and handled 3 hours, obtain solidliquid mixture;
Solidliquid mixture is filtered, and is 7 with the deionized water cyclic washing to pH, and the solid that obtains obtains modified expanded vermiculite powder (MVMT) 120 ℃ of oven dry of temperature 12 hours after grinding, and adopting ASAP2000 type specific area tester to record its specific area is 158m 2/ g;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take by weighing 3.15g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the modified expanded vermiculite powder that 9g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, obtain the Ni mass content and be 10% modified expanded vermiculite supported nickel catalyst.
Embodiment 5:
Taking by weighing mass fraction is: Ni5%, raw ore vermiculite 95%;
The PERFORMANCE OF MODIFIED VERMICULITE preparing carriers:
Select even centimetre of grain diameter, raw ore vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 300 orders, obtain raw ore vermiculite powder;
10g raw ore vermiculite powder is joined in the sulfuric acid solution that the 500ml hydrogen ion concentration is 3mol/L, be warming up to 100 ℃, stir fast down and handled 3 hours, obtain solidliquid mixture;
Solidliquid mixture is filtered, and is 7 with the deionized water cyclic washing to pH, and the solid that obtains obtains modification raw ore vermiculite powder (MVMT) 120 ℃ of oven dry of temperature 12 hours after grinding;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take by weighing 1.58g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9.5g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, obtain the Ni mass content and be 5% modification raw ore vermiculite supported nickel catalyst.
Embodiment 6:
Taking by weighing mass fraction is: Ni15%, raw ore vermiculite 85%;
The preparation of PERFORMANCE OF MODIFIED VERMICULITE carrier:
Select even centimetre of grain diameter, raw ore vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 250 orders, obtain raw ore vermiculite powder;
10g raw ore vermiculite powder is joined in the salpeter solution that the 500ml hydrogen ion concentration is 3mol/L, be warming up to 100 ℃, stir fast down and handled 3 hours, obtain solidliquid mixture;
Solidliquid mixture is filtered, and is 7 with the deionized water cyclic washing to pH, and the solid that obtains obtains modification raw ore vermiculite powder (MVMT) 120 ℃ of oven dry of temperature 12 hours after grinding.
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take by weighing 4.73g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the modification raw ore vermiculite powder that 8.5g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, obtain the Ni mass content and be 15% modification raw ore vermiculite supported nickel catalyst.
Embodiment 7:
Taking by weighing mass fraction is: Ni10%, raw ore vermiculite 90%;
The preparation of PERFORMANCE OF MODIFIED VERMICULITE carrier:
Select even centimetre of grain diameter, raw ore vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 300 orders, obtain raw ore vermiculite powder;
10g raw ore vermiculite powder is joined in the hydrochloric acid solution that the 500ml hydrogen ion concentration is 3mol/L, be warming up to 80 ℃, stir fast down and handled 3 hours, obtain solidliquid mixture;
Solidliquid mixture is filtered, and is 7 with the deionized water cyclic washing to pH, and the solid that obtains obtains modification raw ore vermiculite powder (MVMT) 120 ℃ of oven dry of temperature 12 hours after grinding;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take by weighing 3.15g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, can obtain the Ni mass content and be 10% PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst.
Embodiment 8:
Taking by weighing mass fraction is: Ni10%, raw ore vermiculite 90%;
The preparation of PERFORMANCE OF MODIFIED VERMICULITE carrier:
Select even centimetre of grain diameter, raw ore vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 200 orders, obtain raw ore vermiculite powder;
10g raw ore vermiculite powder is joined in the hydrochloric acid solution that the 500ml hydrogen ion concentration is 3mol/L, be warming up to 120 ℃, stir fast down and handled 3 hours, obtain solidliquid mixture;
Solidliquid mixture is filtered, and is 7 with a large amount of deionized water cyclic washings to pH, and the solid that obtains obtains modification raw ore vermiculite powder (MVMT) 120 ℃ of oven dry of temperature 12 hours after grinding;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take by weighing 3.15g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, can obtain the Ni mass content and be 10% PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst.
Embodiment 9:
Taking by weighing mass fraction is: Ni10%, raw ore vermiculite 90%;
The preparation of PERFORMANCE OF MODIFIED VERMICULITE carrier:
Select even centimetre of grain diameter, raw ore vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 300 orders, obtain raw ore vermiculite powder;
10g raw ore vermiculite powder is joined in the salpeter solution that the 500ml hydrogen ion concentration is 3mol/L, be warming up to 100 ℃, stir fast down and handled 3 hours, obtain solidliquid mixture;
Solidliquid mixture is filtered, and is 7 with the deionized water cyclic washing to pH, and the solid that obtains obtains modification raw ore vermiculite powder (MVMT) 120 ℃ of oven dry of temperature 12 hours after grinding;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take by weighing 3.15g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, can obtain the Ni mass content and be 10% PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst.
Embodiment 10:
Taking by weighing mass fraction is: Ni10%, raw ore vermiculite 90%;
The preparation of PERFORMANCE OF MODIFIED VERMICULITE carrier:
Select even centimetre of grain diameter, raw ore vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 300 orders, obtain raw ore vermiculite powder;
10g raw ore vermiculite powder is joined in the sulfuric acid solution that the 500ml hydrogen ion concentration is 3mol/L, be warming up to 100 ℃, stir fast down and handled 3 hours, obtain solidliquid mixture;
Solidliquid mixture is filtered, and is 7 with the deionized water cyclic washing to pH, and the solid that obtains obtains modification raw ore vermiculite powder (MVMT) 120 ℃ of oven dry of temperature 12 hours after grinding;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take by weighing 3.15g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, can obtain the Ni mass content and be 10% PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst.
Embodiment 11(contrast 1):
According to taking by weighing mass fraction among the embodiment 1 be: Ni10%, raw ore vermiculite 90% takes by weighing 3.15gNiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, directly add 9g raw ore vermiculite powder, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, can obtain the Ni mass content and be 10% PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst, TEM Fig. 2 of catalyst.
Embodiment 12(contrast 2)
Taking by weighing mass fraction is: Ni10%, and raw ore vermiculite 90% is selected even centimetre of grain diameter, raw ore vermiculite that lamellar structure is good, putting into temperature and be 850 ℃ Muffle furnace handled 5 minutes, prepare expanded vermiculite, after ball mill is pulverized, be sized to 300 orders, obtain the expanded vermiculite powder;
Take by weighing 3.15g NiC 2O 42H 2O is dissolved in the 50ml ethylene glycol, add the expanded vermiculite powder that 9g obtains, after stirring and flooding 0.5h, adding NaOH regulator solution pH is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, can obtain the Ni mass content and be 10% PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst.
Each catalyst of embodiment 1-12 is produced the performance evaluation of synthesis gas reaction to methane carbon dioxide reformation, and the results are shown in Table 1:
The catalytic perfomance of table 1 different catalysts
Figure 20131013451561000021
* initial conversion refers to react the conversion ratio after 1 hour, and the end of a period conversion ratio refers to react the conversion ratio after 30 hours, and carbon deposition quantity refers to react the carbon deposition quantity of 30 hours rear catalysts.

Claims (3)

1. PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst, it is characterized in that each constituent mass mark of this catalyst is: nickel 5-15%, PERFORMANCE OF MODIFIED VERMICULITE is sour modification raw ore vermiculite or expanded vermiculite 85%-95%.
2. require the preparation method of described a kind of PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst according to right 1, it is characterized in that following these steps to carrying out:
The preparation of PERFORMANCE OF MODIFIED VERMICULITE carrier:
A, select even centimetre of grain diameter, PERFORMANCE OF MODIFIED VERMICULITE that lamellar structure is good is raw ore vermiculite or expanded vermiculite, is sized to the 200-300 order after ball mill is pulverized, and obtains the vermiculite powder;
B, the vermiculite powder is joined in the acid solution that hydrogen ion concentration is 0.5-10mol/L, be warming up to 80-120 ℃, stir down fast and handled 3 hours, obtain solidliquid mixture;
C, solidliquid mixture being filtered, is 7 with a large amount of deionized water cyclic washings to pH, and the solid that obtains 120 ℃ of oven dry of temperature 12 hours, obtains the PERFORMANCE OF MODIFIED VERMICULITE powder after grinding;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
D, take by weighing NiC 2O 42H 2O is dissolved in the ethylene glycol, add the PERFORMANCE OF MODIFIED VERMICULITE powder among the step c, stir and flood, adding NaOH regulator solution pH again is 10, be warming up to 160 ℃ and kept 3 hours, the mixture that reaction obtains after finishing after filtration, washing, dry, grind, can obtain the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst.
3. method according to claim 2 is characterized in that the acid solution described in the step b is hydrochloric acid, nitric acid or sulfuric acid solution.
CN201310134515.6A 2013-04-17 2013-04-17 Modified vermiculite supported nickel catalyst and preparation method thereof Expired - Fee Related CN103191744B (en)

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CN114272927A (en) * 2022-01-06 2022-04-05 天津大学 Preparation method of zirconium dioxide modified layered porous vermiculite supported nickel-based catalyst
CN114308043A (en) * 2022-01-06 2022-04-12 天津大学 Preparation method of acidified two-dimensional layered vermiculite supported nickel-based catalyst

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CN105642290A (en) * 2014-12-06 2016-06-08 中国石油化工股份有限公司 Preparation method of catalyst for reforming of methane and carbon dioxide to prepare syngas
CN105727975A (en) * 2014-12-06 2016-07-06 中国石油化工股份有限公司 Preparation method of catalyst for ethane oxidative dehydrogenation to ethylene
CN105727975B (en) * 2014-12-06 2018-01-16 中国石油化工股份有限公司 A kind of preparation method of catalyst for making ethylene from ethane oxidative dehydrogenation
CN105642290B (en) * 2014-12-06 2018-02-09 中国石油化工股份有限公司 A kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst
CN110010288A (en) * 2019-04-04 2019-07-12 广州澳通电线电缆有限公司 Crosslinked polyetylene insulated polyolefin jacket zero-halogen low-smoke flame-retardant B1Grade power cable
CN111195519A (en) * 2020-01-15 2020-05-26 广东工业大学 Cobalt-nickel columnar vermiculite catalyst for high-selectivity preparation of diesel oil fraction by high-efficiency catalytic plastic cracking, and preparation method and application thereof
CN111195519B (en) * 2020-01-15 2022-11-22 广东工业大学 Cobalt-nickel columnar vermiculite catalyst for high-selectivity preparation of diesel oil fraction by high-efficiency catalytic plastic cracking, and preparation method and application thereof
CN114272927A (en) * 2022-01-06 2022-04-05 天津大学 Preparation method of zirconium dioxide modified layered porous vermiculite supported nickel-based catalyst
CN114308043A (en) * 2022-01-06 2022-04-12 天津大学 Preparation method of acidified two-dimensional layered vermiculite supported nickel-based catalyst

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