[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN103191744B - Modified vermiculite supported nickel catalyst and preparation method thereof - Google Patents

Modified vermiculite supported nickel catalyst and preparation method thereof Download PDF

Info

Publication number
CN103191744B
CN103191744B CN201310134515.6A CN201310134515A CN103191744B CN 103191744 B CN103191744 B CN 103191744B CN 201310134515 A CN201310134515 A CN 201310134515A CN 103191744 B CN103191744 B CN 103191744B
Authority
CN
China
Prior art keywords
vermiculite
catalyst
performance
modified vermiculite
modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201310134515.6A
Other languages
Chinese (zh)
Other versions
CN103191744A (en
Inventor
闫世友
陈朝阳
王军华
郝斌
谢永新
范艳伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinjiang Technical Institute of Physics and Chemistry of CAS
Original Assignee
Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xinjiang Technical Institute of Physics and Chemistry of CAS filed Critical Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority to CN201310134515.6A priority Critical patent/CN103191744B/en
Publication of CN103191744A publication Critical patent/CN103191744A/en
Application granted granted Critical
Publication of CN103191744B publication Critical patent/CN103191744B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Catalysts (AREA)

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 methane reforming with carbon dioxide.
Background technology
In Copenhagen global climate conference to hold for 2009, Premier Wen Jiabao proposes the year two thousand twenty China per GDP emission greenhouse gas flow by the emission reduction targets than 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 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, be also one of six kinds of main greenhouse gas of Kyoto Protocol regulation simultaneously.The efficiency utilization of greenhouse gases can be realized by methane reforming with carbon dioxide, basic chemical industry raw material-synthesis gas can be produced, and then synthesize various chemical products, break away from the single dependence of chemical industry to petroleum.Therefore, the development of methane reforming CO 2 technology to the reduction of discharging of greenhouse gases or natural gasification industry is all significant.
For methane reforming with carbon dioxide, under the condition having catalyst, carbon dioxide conversion can reach more than 90%; Under catalyst-free condition, carbon dioxide conversion is zero substantially.Therefore, catalyst is the most important factor of restriction methane reforming with carbon dioxide development.At present, to CH 4, CO 2, O 2the catalytic oxidation preparing synthetic gas by reforming process study catalyst obtained at most is load type metal catalyst, comprising transition-metal catalysts such as noble metal catalyst and Ni, Co such as Rh, Ru, Ir, Pt.Noble metal catalyst has the advantages such as activity is high, good stability, anti-carbon deposit, but expensive due to it, and resource-constrained, commercial Application is restricted.Ni is catalyst based has the activity and selectivity close with noble metal catalyst, and have that cost is low, intensity is high, be easy to the advantages such as preparation, it is the catalyst having application prospect most, but under high temperature, high-speed, Ni is catalyst based easily because active component and carrier interact, and active component sinters and runs off and inactivation.Simultaneously carbon-collecting problem is also 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.
The catalyst based stability of current raising Ni mainly can by adding the approach such as auxiliary agent, support modification, employing novel carriers material.Wherein carrier has very important impact to the structure of catalyst, stability and catalytic performance.Document (synthetic chemistry, 2008,16 (5): 495) reports effect of acidity and basicity to nickel-base catalyst CH 4/ CO 2the impact of reforming reaction performance, result shows that the size of effect of acidity and basicity and specific area directly has influence on the reactivity worth of catalyst.The research of document (catalysis journal, 2007,10 (10): 865) shows that interaction between Metal-Support is to CH 4/ CO 2the catalytic performance of catalyst plays an important role.Document (Energy & Fuels, 2007,21:2950) reports the nickel-base catalyst of different carriers load to CH 4/ CO 2the catalytic performance of reforming reaction performance, result shows that the catalyst that catalyst granules is uniformly dispersed, average grain diameter is little shows best activity and stability.
Chinese invention patent (publication number CN1939587) discloses a kind of monoblock type Ni catalyst, and the method first adopts mesopore molecular sieve SBA15 to be that carrier has prepared Ni-SBA15; Then Al 2o 3be coated in obtained Al on FeCrAl alloy sheet 2o 3/ FeCrAl; Again Ni-SBA15 and Al 2o 3the obtained slurries of mixing; Finally obtained Ni-SBA15/Al 2o 3/ FeCrAl integral catalyzer.Results of property shows that this catalyst has higher activity and selectivity, but to be preparation process too loaded down with trivial details for its shortcoming.
Chinese invention patent (publication number CN102407119A) a kind of cordierite substrates Catalysts and its preparation method, the method introduces cordierite substrates on the basis of integral catalyzer, and the preparation of catalyst comprises three steps: one is the acid treatment process of cordierite; Two is preparations of catalyst precipitated liquid; Three is high pressure roasting process of cordierite and precipitated liquid, and obtained take cordierite as the catalyst of matrix.Carbon distribution result test in 20 hours shows that this carbon deposition quantity of catalyst is less, and stability is better.The method preparation process is also comparatively loaded down with trivial details, and catalyst activity and selectivity is 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 producing synthesis gas reacts one of major issue faced.Some current technical measures, as added noble metal, adding auxiliary agent, adopting integral catalyzer etc., can improve the stability of catalyst to a certain extent, but also there is the problems such as catalyst high cost, preparation process is complicated, performance is high not.In addition, there are some researches show, the nano-metal particle that grain diameter is less than certain size effectively can suppress the generation of carbon distribution process, thus makes catalyst have excellent coking resistivity.Vermiculite is a kind of silicate mineral with layered nano-structure, itself have excellent high-temperature stability, and its special layered nano-structure has the effect of space confinement, can stop the high temperature agglomeration of nano particle.Therefore, active metal (as nickel) and high-temperature stability vermiculite carrier that is good, that have nanometer laminated structure are combined, is expected the coking resistivity and the stability that effectively improve 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 and first prepare PERFORMANCE OF MODIFIED VERMICULITE carrier, by processing in an acidic solution, PERFORMANCE OF MODIFIED VERMICULITE catalyst is obtained through washing drying, then through polyalcohol liquid phase high temperature reduction legal system for PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst.The present invention has the advantages such as catalyst composition is simple, preparation process is easy to operate, production cost is low, the catalyst prepared have average grain diameter little, be uniformly dispersed, the advantage such as coking resistivity and good stability, be applied to the reaction of methane carbon dioxide reformation producing synthesis gas and there is 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%, and 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, after ball mill pulverized, be sized to 200-300 order, obtain vermiculite powder;
B, vermiculite powder is joined hydrogen ion concentration is in the acid solution of 0.5-10mol/L, is warming up to 80-120 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
C, filtered by solidliquid mixture, be 7 with a large amount of deionized water cyclic washing to pH, the solid obtained, dries 12 hours temperature 120 DEG C, after grinding, obtain PERFORMANCE OF MODIFIED VERMICULITE powder;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
D, take NiC 2o 42H 2o is dissolved in ethylene glycol, add the PERFORMANCE OF MODIFIED VERMICULITE powder in step c, stir and flood, adding NaOH again regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst can be obtained.
Acid solution described in 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 at the upper load active component metallic nickel of PERFORMANCE OF MODIFIED VERMICULITE (MVMT), namely this catalyst take PERFORMANCE OF MODIFIED VERMICULITE as carrier, take nano nickel particles as active component, this catalyst can be labeled as Ni/MVMT, and wherein Ni content accounts for the 5-15% of total catalyst weight.
Compared with prior art, its feature is in the present invention:
1, catalyst composition is simple, and preparation process is easy to operate.
2, utilize the advantage that the modified specific area of vermiculite is large, absorption property is strong, 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, the stability of Ni catalyst is improved greatly.
A kind of PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst of the present invention, the application process in methane reforming with carbon dioxide is as follows:
Take PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst, obtained 20-40 object catalyst after compressing tablet, screening, load in reaction tube, fixed bed reactors carry out catalytic reforming reaction, before the reaction, need carry out reduction treatment to catalyst, process is as follows: with the ramp to 500 DEG C of temperature 10 DEG C/min, pass into 10%H 2/ N 2gaseous mixture carries out reductase 12 hour, then switches to high-purity N 2purge 0.5 hour, after reduction, temperature is adjusted to 750 DEG C, pass into the CH of 1:1 mixing by volume 4/ CO 2gaseous mixture reacts, on-line gas chromatography is adopted to analyze reaction end gas after reaction carries out 1 hour, and carried out single injected sampling analysis every 1 hour, testing time is 30 hours, adopt thermal analyzer to carry out thermogravimetric-differential scanning calorimetric analysis (TG-DSC) to the catalyst sample after having reacted, test its carbon deposition quantity.Accompanying drawing explanation
Fig. 1 is the TEM figure of the embodiment of the present invention 2 catalyst;
Fig. 2 is the TEM figure of comparative example 1 catalyst of the present invention.
Detailed description of the invention
Below by specific embodiment, the present invention is further elaborated, is interpreted as, and the object of following examples, only for illustration of technical scheme of the present invention and technique effect, not limits protection scope of the present invention.
Embodiment 1:
Taking mass fraction is: Ni10%, raw ore vermiculite 90%;
Prepared by 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;
It is in the hydrochloric acid solution of 0.5mol/L that 10g raw ore vermiculite powder is joined 500ml hydrogen ion concentration, is warming up to 100 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
Solidliquid mixture is filtered, be 7 with deionized water cyclic washing to pH, the solid obtained, dries 12 hours temperature 120 DEG C, after grinding, obtain modification raw ore vermiculite powder (MVMT), adopting ASAP2000 type specific-surface area detection instrument to record its specific area is 318m 2/ g;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take 3.15g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst (see figure 1) that Ni mass content is 10% can be obtained.
Embodiment 2:
Taking mass fraction is: Ni10%, expanded vermiculite 90%;
Prepared by PERFORMANCE OF MODIFIED VERMICULITE carrier:
Select even centimetre of grain diameter, expanded vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 300 orders, obtain expanded vermiculite powder;
It is in the hydrochloric acid solution of 3mol/L that 10g expanded vermiculite powder is joined 500ml hydrogen ion concentration, is warming up to 100 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
Solidliquid mixture is filtered, be 7 with deionized water cyclic washing to pH, the solid obtained is dried 12 hours temperature 120 DEG C, after grinding, obtain modified expanded vermiculite powder (MVMT), and adopting ASAP2000 type specific-surface area detection instrument to record its specific area is 482m 2/ g;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take 3.15g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add the modified expanded vermiculite powder (MVMT) that 9g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, obtain the modified expanded vermiculite supported nickel catalyst that Ni mass content is 10%.
Embodiment 3:
Taking 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;
It is in the hydrochloric acid solution of 5mol/L that 10g raw ore vermiculite powder is joined 500ml hydrogen ion concentration, is warming up to 100 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
Solidliquid mixture is filtered, be 7 with deionized water cyclic washing to pH, the solid obtained is dried 12 hours temperature 120 DEG C, after grinding, obtain modification raw ore vermiculite powder (MVMT), and adopting ASAP2000 type specific-surface area detection instrument to record its specific area is 450m 2/ g;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take 3.15g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add modification raw ore vermiculite powder (MVMT) that 9g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, obtain the modification raw ore vermiculite supported nickel catalyst that Ni mass content is 10%.
Embodiment 4:
Taking mass fraction is: Ni10%, expanded vermiculite 90%.
Prepared by PERFORMANCE OF MODIFIED VERMICULITE carrier
Select even centimetre of grain diameter, expanded vermiculite that lamellar structure is good, after ball mill is pulverized, be sized to 200 orders, obtain expanded vermiculite powder;
It is in the salpeter solution of 10mol/L that 10g expanded vermiculite powder is joined 500ml hydrogen ion concentration, is warming up to 100 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
Solidliquid mixture is filtered, be 7 with deionized water cyclic washing to pH, the solid obtained is dried 12 hours temperature 120 DEG C, after grinding, obtain modified expanded vermiculite powder (MVMT), and adopting ASAP2000 type specific-surface area detection instrument to record its specific area is 158m 2/ g;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take 3.15g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add the modified expanded vermiculite powder that 9g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, obtain the modified expanded vermiculite supported nickel catalyst that Ni mass content is 10%.
Embodiment 5:
Taking mass fraction is: Ni5%, raw ore vermiculite 95%;
Prepared by 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;
It is in the sulfuric acid solution of 3mol/L that 10g raw ore vermiculite powder is joined 500ml hydrogen ion concentration, is warming up to 100 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
Being filtered by solidliquid mixture, is 7 with deionized water cyclic washing to pH, and the solid obtained is dried 12 hours temperature 120 DEG C, after grinding, obtain modification raw ore vermiculite powder (MVMT);
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take 1.58g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9.5g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, obtain the modification raw ore vermiculite supported nickel catalyst that Ni mass content is 5%.
Embodiment 6:
Taking 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;
It is in the salpeter solution of 3mol/L that 10g raw ore vermiculite powder is joined 500ml hydrogen ion concentration, is warming up to 100 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
Being filtered by solidliquid mixture, is 7 with deionized water cyclic washing to pH, and the solid obtained is dried 12 hours temperature 120 DEG C, after grinding, obtain modification raw ore vermiculite powder (MVMT).
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take 4.73g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add the modification raw ore vermiculite powder that 8.5g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, obtain the modification raw ore vermiculite supported nickel catalyst that Ni mass content is 15%.
Embodiment 7:
Taking 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;
It is in the hydrochloric acid solution of 3mol/L that 10g raw ore vermiculite powder is joined 500ml hydrogen ion concentration, is warming up to 80 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
Being filtered by solidliquid mixture, is 7 with deionized water cyclic washing to pH, and the solid obtained is dried 12 hours temperature 120 DEG C, after grinding, obtain modification raw ore vermiculite powder (MVMT);
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take 3.15g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst that Ni mass content is 10% can be obtained.
Embodiment 8:
Taking 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;
It is in the hydrochloric acid solution of 3mol/L that 10g raw ore vermiculite powder is joined 500ml hydrogen ion concentration, is warming up to 120 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
Being filtered by solidliquid mixture, is 7 with a large amount of deionized water cyclic washing to pH, and the solid obtained is dried 12 hours temperature 120 DEG C, after grinding, obtain modification raw ore vermiculite powder (MVMT);
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take 3.15g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst that Ni mass content is 10% can be obtained.
Embodiment 9:
Taking 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;
It is in the salpeter solution of 3mol/L that 10g raw ore vermiculite powder is joined 500ml hydrogen ion concentration, is warming up to 100 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
Being filtered by solidliquid mixture, is 7 with deionized water cyclic washing to pH, and the solid obtained is dried 12 hours temperature 120 DEG C, after grinding, obtain modification raw ore vermiculite powder (MVMT);
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take 3.15g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst that Ni mass content is 10% can be obtained.
Embodiment 10:
Taking 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;
It is in the sulfuric acid solution of 3mol/L that 10g raw ore vermiculite powder is joined 500ml hydrogen ion concentration, is warming up to 100 DEG C, processes 3 hours, obtain solidliquid mixture under rapid stirring;
Being filtered by solidliquid mixture, is 7 with deionized water cyclic washing to pH, and the solid obtained is dried 12 hours temperature 120 DEG C, after grinding, obtain modification raw ore vermiculite powder (MVMT);
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
Take 3.15g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add the modification raw ore vermiculite powder that 9g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst that Ni mass content is 10% can be obtained.
Embodiment 11(contrast 1):
According to taking mass fraction in embodiment 1 be: Ni10%, raw ore vermiculite 90%, takes 3.15gNiC 2o 42H 2o is dissolved in 50ml ethylene glycol, directly add 9g raw ore vermiculite powder, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst that Ni mass content is 10% can be obtained, TEM Fig. 2 of catalyst.
Embodiment 12(contrast 2)
Taking mass fraction is: Ni10%, raw ore vermiculite 90%, selects even centimetre of grain diameter, raw ore vermiculite that lamellar structure is good, put into temperature be 850 DEG C Muffle furnace process 5 minutes, prepare expanded vermiculite, after ball mill is pulverized, be sized to 300 orders, obtain expanded vermiculite powder;
Take 3.15g NiC 2o 42H 2o is dissolved in 50ml ethylene glycol, add the expanded vermiculite powder that 9g obtains, to stir and after flooding 0.5h, adding NaOH regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, the PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst that Ni mass content is 10% can be obtained.
Each for embodiment 1-12 catalyst is listed in table 1 to the Evaluation results that methane carbon dioxide reformation producing synthesis gas reacts:
The catalytic perfomance of table 1 different catalysts
* initial conversion refers to the conversion ratio of reaction after 1 hour, and end of a period conversion ratio refers to the conversion ratio of reaction after 30 hours, and carbon deposition quantity refers to the carbon deposition quantity of reaction 30 hours rear catalysts.

Claims (1)

1. a preparation method for 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%, and concrete operations follow these steps to carry out:
The preparation of PERFORMANCE OF MODIFIED VERMICULITE carrier:
A, to select the PERFORMANCE OF MODIFIED VERMICULITE that grain diameter is even, lamellar structure is good be raw ore vermiculite or expanded vermiculite, is sized to 200-300 order, obtains vermiculite powder after ball mill is pulverized;
B, vermiculite powder is joined hydrogen ion concentration is in the acid solution of 0.5-10mol/L, is warming up to 80-120 DEG C, and process 3 hours under rapid stirring, obtain solidliquid mixture, wherein acid solution is hydrochloric acid, nitric acid or sulfuric acid solution;
C, filtered by solidliquid mixture, be 7 with a large amount of deionized water cyclic washing to pH, the solid obtained, dries 12 hours temperature 120 DEG C, after grinding, obtain PERFORMANCE OF MODIFIED VERMICULITE powder;
The preparation of the Raney nickel of PERFORMANCE OF MODIFIED VERMICULITE load:
D, take NiC 2o 42H 2o is dissolved in ethylene glycol, add the PERFORMANCE OF MODIFIED VERMICULITE powder in step c, stir and flood, adding NaOH again regulates pH value of solution to be 10, be warming up to 160 DEG C and keep 3 hours, the mixture obtained after completion of the reaction after filtration, washing, dry, grinding, PERFORMANCE OF MODIFIED VERMICULITE supported nickel catalyst can be obtained.
CN201310134515.6A 2013-04-17 2013-04-17 Modified vermiculite supported nickel catalyst and preparation method thereof Expired - Fee Related CN103191744B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310134515.6A CN103191744B (en) 2013-04-17 2013-04-17 Modified vermiculite supported nickel catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310134515.6A CN103191744B (en) 2013-04-17 2013-04-17 Modified vermiculite supported nickel catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103191744A CN103191744A (en) 2013-07-10
CN103191744B true CN103191744B (en) 2015-07-08

Family

ID=48714664

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310134515.6A Expired - Fee Related CN103191744B (en) 2013-04-17 2013-04-17 Modified vermiculite supported nickel catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103191744B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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
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
CN114308043A (en) * 2022-01-06 2022-04-12 天津大学 Preparation method of acidified two-dimensional layered vermiculite supported nickel-based catalyst
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1309079A (en) * 2000-12-14 2001-08-22 中国科学院兰州化学物理研究所 Catalyst for preparing synthetic gas by reforming methane and CO2
RU2375114C1 (en) * 2008-07-11 2009-12-10 Учреждение Российской Академии Наук Ордена Трудового Красного Знамени Институт Нефтехимического Синтеза Им. А.В. Топчиева Ран (Инхс Ран) Method of producing catalyst for vapour conversion of methane-containing hydrocarbons
CN102161000A (en) * 2010-12-24 2011-08-24 黑龙江大学 Method for preparing carbon nano tube loaded nano nickel powder material by liquid-phase reduction method
CN102658106A (en) * 2012-05-10 2012-09-12 中国科学院新疆理化技术研究所 Method for preparing acidification stripped vermiculite supported TiO2 photocatalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1309079A (en) * 2000-12-14 2001-08-22 中国科学院兰州化学物理研究所 Catalyst for preparing synthetic gas by reforming methane and CO2
RU2375114C1 (en) * 2008-07-11 2009-12-10 Учреждение Российской Академии Наук Ордена Трудового Красного Знамени Институт Нефтехимического Синтеза Им. А.В. Топчиева Ран (Инхс Ран) Method of producing catalyst for vapour conversion of methane-containing hydrocarbons
CN102161000A (en) * 2010-12-24 2011-08-24 黑龙江大学 Method for preparing carbon nano tube loaded nano nickel powder material by liquid-phase reduction method
CN102658106A (en) * 2012-05-10 2012-09-12 中国科学院新疆理化技术研究所 Method for preparing acidification stripped vermiculite supported TiO2 photocatalyst

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Catalyst for Methane Vapor Reforming Fabricated on the Basis of Natural Oxides and Stable in H2S Medium: Activity, Selectivity, and Nanostructure Evolution;M. V. Tsodikov et al.;《Nanotechnologies in Russia》;20121231;第7卷;第464页 *
Conversion of methane/carbon dioxide mixtures on vermiculite;L. N. Russiyan et al.;《Bulletin of the Russian Academy of Sciences》;19920731;第41卷;第1165页 *
NICKEL CATALYSTS SUPPORTED ON MgO/SMECTITE-TYPE NANOCOMPOSITES FOR METHANE REFORMING;ALEXANDER MORONTA et al.;《Clays and Clay Minerals》;20051231;第53卷(第6期);摘要，第623页 *
Preparation, Characterization, and Catalytic Properties of Clay-Based Nickel Catalysts for Methane Reforming;Shaobin Wang et al.;《JOURNAL OF COLLOID AND INTERFACE SCIENCE》;19981231;第204卷;第128-129页 *

Also Published As

Publication number Publication date
CN103191744A (en) 2013-07-10

Similar Documents

Publication Publication Date Title
Li et al. Remarkably efficient and stable Ni/Y2O3 catalysts for CO2 methanation: Effect of citric acid addition
Du et al. Ni nanoparticles dispersed on oxygen vacancies-rich CeO2 nanoplates for enhanced low-temperature CO2 methanation performance
Zhu et al. Enhanced selective photocatalytic CO2 reduction into CO over Ag/CdS nanocomposites under visible light
Hou et al. Hydrogen production from ethanol steam reforming over Rh/CeO2 catalyst
CN103191744B (en) Modified vermiculite supported nickel catalyst and preparation method thereof
Yu et al. Ultrasmall silver nanoparticles supported on silica and their catalytic performances for carbon monoxide oxidation
CN113209976B (en) Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof, and methanol steam reforming hydrogen production reaction
Meshksar et al. Promoted nickel–cobalt bimetallic catalysts for biogas reforming
Shi et al. Fabricating Cu2O-CuO submicron-cubes for efficient catalytic CO oxidation: The significant effect of heterojunction interface
Shi et al. The homojunction formed by h-In2O3 (1 1 0) and c-In2O3 (4 4 0) promotes carbon dioxide hydrogenation to methanol on graphene oxide modified In2O3
CN105964259A (en) {0><}0{>Preparation method of polynuclear core-shell structure nickel-based catalyst
Shi et al. Engineering the crystal facets of Pt/In2O3 catalysts for high-efficiency methanol synthesis from CO2 hydrogenation
Wu et al. Engineering of the Cu+/Cu0 interface by chitosan-glucose complex for aqueous phase reforming of methanol into hydrogen
Zheng et al. High-loaded sub-6 nm Cu catalyst with superior hydrothermal-stability and efficiency for aqueous phase reforming of methanol to hydrogen
WO2021042874A1 (en) Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof
Xia et al. Lamellar cross-linking Ni/CeO2 as an efficient and durable catalyst for dry reforming of methane
Xie et al. Noble metal modified copper-exchanged mordenite zeolite (Cu-ex-MOR) catalysts for catalyzing the methane efficient gas-phase synthesis methanol
Sharma et al. Metal and metal oxide sub nano cluster; emerging aspirant for catalytic applications
CN101380575A (en) High stability nano gold catalyst for CO normal temperature oxidation and preparation method thereof
Pu et al. Promoting surface lattice oxygen and oxygen vacancy of CeO2 for photothermal methane dry reforming over Ni/CeO2 catalysts
Duan et al. Effects of preparation methods on the size and interface of Ni–W bimetallic catalysts for dry reforming of methane
Khani et al. Production of clean hydrogen fuel on a bifunctional iron catalyst via chemical loop reforming of methanol
CN110075889B (en) Catalyst for hydrogen production by methanol reforming and preparation method thereof
ZHANG et al. Investigation of the promotion effect of metal oxides on the water-gas shift reaction activity over Pt-MOx/CeO2 catalysts for aqueous phase reforming
CN105944733B (en) A kind of rare earth modified multi-stage porous loading type nickel-based catalyst, preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150708

Termination date: 20200417