CN103170340A - Catalyst for preparing synthetic natural gas and preparation method thereof - Google Patents
Catalyst for preparing synthetic natural gas and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for preparing synthetic natural gas and a preparation method thereof, and relates to a catalyst. The catalyst is scandium-enhanced coprecipitation type nickle-cobalt-based catalyst, the chemical formula is NiiZrjSck, wherein the subscripts i, j and k in the formula are the molar ratio factor of Ni, Zr and Sc in the catalyst; the catalyst comprises the following components in percent by weight: 48%-62% of Ni, 3%-25% of Sc and the balance of Zr. The preparation method comprises the following steps of: mixing and preparing metered Ni(NO3)2.6H2O, Zr(NO3)4.3H2O and Sc(NO3) into aqueous solution, carrying out coprecipitation reaction with K2CO3 aqueous solution, filtering feed liquid after reaction, cleaning, drying and roasting on filtered cakes, and then obtaining the NiiZrjSck catalyst for methanation of coal or biomass-based synthetic natural gas. The catalyst disclosed by the invention has the advantages that the activity is high and stable, the heat resistance is good, the conversion rate of hydrogenated methanation of CO and CO2 and the per pass yield of a product (methane) can be effectively improved.
Description
Technical field
The present invention relates to a kind of catalyst, especially relate to a kind of catalyst for coal or Biomass Syngas hydrogenation methanation synthetic natural gas processed.
Background technology
The energy and environment are one of current global focuses of paying close attention to most, and the complex optimum of fossil and biomass energy resource utilizes extremely urgent.The rich coal of China, few oil, lean gas.Optimize and utilize relatively abundant coal resources (particularly broken coal inferior) synthetic natural gas processed (SNG), both can increase the supply of the high SNG of capacity usage ratio, can greatly reduce again the discharging of greenhouse gases, have great economy concurrently and be worth and social effect.On the other hand, biomass energy is a kind of important regenerative resource, contains a large amount of carbonaceous materials in living beings, utilizes living beings to produce SNG, not only can reduce in a large number the CO that it discharges because of burning
2, alleviate greenhouse effects, can also promote the quality of the energy.In recent years, existing many survey articles about Development of Coal or biomass-making SNG appear in the newspapers both at home and abroad.
The technical foundation of coal or biomass-making SNG is that coal or gasification of biomass generate synthesis gas, and synthesis gas is after purifying, then the combustion gas for preparing high methane content through methanation reaction.Methanation reaction typically refers to CO or CO
2Hydrogenation generates CH under catalyst action
4And H
2The strong exothermal reaction of O.Methanation catalyst is one of two large core technologies (catalyst and reactor) of coal or biomass-making SNG technique.The scientific and technological circle of catalysis have both at home and abroad carried out a large amount of basic research and application and development.Reported that the catalyst that external three large methanation technologies (it is strange that Britain wears dimension, Denmark Top rope, German Shandong) adopt has: the models such as CRG, CRG-H, CEG-LH, MCR-2, MCR-2X and MCR-4 are mainly the high nickel-base catalysts of high-temperature behavior and good stability.More domestic units also develop the nickel-base catalyst of the models such as KD-306, SG-100.Can obtain following information: Ni catalyst based (high Ni content, 20%～70%) from the basic research result of open report and interrelated data is the main flow catalyst; The catalyst based easy coking deactivation of Fe; The catalyst based tolerance of Co is strong, but poor selectivity; The catalyst based activity of Ru is catalyst based higher than Ni, but cost is high; Ru, Rh, the catalyst based cryogenic property of Pd are better.The auxiliary agent or the carrier material that adopt have ZrO
2(four directions be better than monocline, cube), TiO
2, CaO, La
2O
3, CeO
2, Al
2O
3, SiO
2, MgO, MoS
2, ZnO, sepiolite (sepolite), MgAl
2O
4Deng; The loaded catalyst type has [Zhao Lijun etc., Shenhua science and technology, 2011,9 (1): 87-91 such as Ca-Ti ore type, hydrotalcite type, amorphous alloy type; Lu Xia etc., petrochemical industry, 2010,39 (3): 340-345].Bibliographical information [Zhao Gangwei etc., pottery, 2009,11,21-26] show, the sequence of some metal pair methanation catalytic activitys is: Ru〉Fe〉Ni〉Co〉Rh〉Pd〉Pt〉Ir, and as the result of study of ammonia synthesis catalyst, volcano shape curve [Zhao Lijun etc., Shenhua science and technology appear, 2011,9 (1): 87-91].The Fe-Ni alloy catalyst has better CO and a CO than Ni is catalyst based
2The methanation catalytic activity, and can reduce costs; But rope company of Denmark Top has developed the methanation catalyst [Zhao Lijun etc., Shenhua science and technology, 2011,9 (1): 87-91] of practical application accordingly.
Requirement to coal or biomass-making SNG industrial catalyst is mainly: efficient (that is: the hydrogen-carbon ratio wide ranges of unstripped gas, CO and CO
2Conversion ratio high, CH
4Selective height, the CH in SNG
4Content 〉=95%), good stability (that is: wear-resisting, heatproof, the resistive connection charcoal, anti-poisoning), long service life, cost are low.On thermodynamics, cryogenic high pressure is conducive to the forward reaction of synthesis gas methanation, also should prevent as far as possible the generation of back reaction and side reaction, but higher reaction temperature can produce high steam, better economy.Reach these requirements, the compositing formula of catalyst and the choose reasonable of fabricating technology are crucial.
Summary of the invention
Purpose of the present invention aims to provide to be had active highly and stable, and heat resistance is good, can effectively improve CO and CO
2Hydrogenation conversion and a kind of Catalysts and its preparation method for the preparation of synthetic natural gas of the characteristics such as one-pass yield of product methane.
Described catalyst for the preparation of synthetic natural gas is co-precipitation type nickel-Zirconium-base catalyst that scandium promotes, comprises major constituent and promoter, and described major constituent is Ni, Zr, and promoter is Sc, and chemical formulation is: Ni
iZr
jSc
k, in formula, subscript i, j, k are the molar ratio coefficient of Ni, Zr, Sc in catalyst, the mass percent of catalyst each component is respectively: Ni:48%～62%, preferred 50%～56%; Sc:3%～25%, preferred 5%～15%; Surplus is Zr.
Preparation method for the preparation of the catalyst of synthetic natural gas is as follows:
1) add water after nickel salt, zirconates and the scandium salts mixing of composition and ratio with metering by catalyst and make solution A, in solution A, 3 kinds of metal cation total yield concentration are 1.0～1.5N/L;
2) with the K that measures
2CO
3The water-soluble solution B of making, K in solution B
+The equivalent concentration of ion is identical with 3 kinds of metal cation total yield concentration in solution A;
3) under constant temperature, stirring condition, solution A and solution B are injected in reaction vessel, carry out coprecipitation reaction, make the pH value of reaction system remain on 7.0～7.8 by the addition that regulates and controls solution B, after reaction, feed liquid is filtered, get sediment;
4) sediment is washed K to the leacheate through deionized water
+Ion concentration is rear the filtration below 0.1ppm, the filter cake oven dry, and roasting namely gets Ni
iZr
jSc
kCatalyst (oxidation state).
In step 1), described nickel salt can be selected from Ni (NO
3)
2Or Ni (CH
3COO)
2Deng; Described zirconates can be selected from Zr (NO
3)
4Or ZrO (NO
3)
2Deng; Described scandium salts can be selected from Sc (NO
3)
3Deng.
In step 3), described will preferably solution A and solution B constant speed also streams in the injection reaction vessel in solution A and solution B injection reaction vessel; The temperature of described coprecipitation reaction can be 70～90 ℃, and the reaction time can be 0.5～1h.
In step 4), the temperature of described oven dry can be 105～120 ℃, and the time of oven dry can be 16～20h; The temperature of described roasting can be 360～425 ℃, and the time of roasting can be 3～5h.
Described catalyst for the preparation of synthetic natural gas carries out on atmospheric fixed bed continuous flow reactor-GC combined system the activity rating of synthesis gas methanation.Each test catalyst consumption is 100mg (approximately 0.1mL) and is placed in reactor with the 100mg quartz sand mixed diluting of same order number.The synthesis gas methanation reaction is at normal pressure, and 200～600 ℃, material synthesis gas consists of V (H
2)/V (CO) V (CO
2)/V (N
2Carry out under the condition of GHSV=40000mL/ (hg))=75/15/5/5.Before reaction, oxidized catalyst is carried out original position prereduction activation by certain heating schedule in normal pressure, pure hydrogen (99.999%) reduction air-flow (flow velocity is 30mL/min), and whole process is lasted 12h, and the highest reduction temperature is 500 ℃; After that temperature is transferred to reaction is temperature required, switch to import the reaction raw materials synthesis gas and carry out methanation reaction.The reaction end gas of discharging from reactor outlet is through the sampling of utilidor (temperature remains on 130 ℃) direct sending gas chromatograph six-way valve, united by the thermal conductivity detector (TCD) (TCD) of GC-950 type gas chromatograph (sea, Shanghai glad chromatographic apparatus company product) and hydrogen flame detector (FID) and does on-line analysis.The former chromatographic column filler is TDX-201 carbon molecular sieve (Tianjin chemical reagent Co., Ltd product), and column length 2m uses H
2Do carrier gas, for separating of detecting CO, N
2(as interior mark) and CO
2Latter's chromatographic column filler is Porapak Q-S(USA product), column length 2m uses N
2Do carrier gas, for separating of detecting lower carbon number hydrocarbons and other carbon containing hydrogenation products.CO and CO
2Conversion ratio by N
2Internal standard method measuring and calculating, selectively being calculated by C base normalization method of methane and other carbon containing hydrogenation products.
The prepared catalyst activity for the preparation of synthetic natural gas of the present invention is high and stable, the selective height of product methane, and heat resistance is good, CO and CO
2Hydrogenation conversion and the space-time yield of methane all apparently higher than existing similar catalyst, and simple for production, good reproducibility.
Description of drawings
Fig. 1 is Ni
6Zr
3Sc
1The reactivity of catalyst synthesis gas methanation and operational stability figure.In figure, abscissa is reaction time (h), and ordinate is CO or CO
2The conversion ratio of hydrogenation methanation (%), or selective (%) of product methane; Mark-zero-be the CO conversion ratio ,--be CO
2Conversion ratio ,-★-be methane selectively; Reaction condition is: normal pressure, 300 ℃, material synthesis gas consists of V (H
2)/VCO/V (CO
2)/V (N
2)=75/15/5/5, air speed GHSV=40000mL/ (hg).
Fig. 2 is Ni
6Zr
3Sc
1Catalyst is used for catalysis CO and CO
2The evaluation result of hydrogenation methanation system " synthetic natural gas " heat resistance.In figure, abscissa is reaction time (h), and ordinate is (CO+CO
2) total conversion (%) of hydrogenation methanation, or selective (%) of product methane, or reaction temperature (℃); Mark-◆-be reaction temperature ,--being (CO+CO
2) total conversion ,-★-be methane selectively; Reaction condition is: normal pressure, reactor feed gas forms V (H
2)/V (CO) V (CO
2)/V (N
2)=75/15/5/5, air speed GHSV=40000mL/ (hg).
Fig. 3 is the former matrix Ni of non-promotion
6Zr
4Catalyst is used for catalysis CO and CO
2The evaluation result of hydrogenation methanation system " synthetic natural gas " heat resistance.In figure, abscissa is reaction time (h), and ordinate is (CO+CO
2) total conversion (%) of hydrogenation methanation, or selective (%) of methane, or reaction temperature (℃); Mark-◆-be reaction temperature ,--being (CO+CO
2) total conversion ,-★-be methane selectively; Reaction condition is: normal pressure, reactor feed gas forms V (H
2)/V (CO) V (CO
2)/V (N
2)=75/15/5/5, air speed GHSV=40000mL/ (hg).
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
With 6.979gNi (NO
3)
26H
2O, 4.719g Zr (NO
3)
43H
2O and 0.924g Sc (NO
3)
3(purity is the AR level) is mixed together, and adds the 90mL deionized water to be mixed with solution A; Separately with 7.837gAR level anhydrous K
2CO
3Be dissolved in the 95mL deionized water and be mixed with solution B; With in solution A and solution B constant speed and stream injection reaction vessel (charge velocity is 12mL/min), carry out coprecipitation reaction under 80 ℃ of constant temperature and the continuous condition that stirs, by regulation and control K at 80 ℃ of temperature
2CO
3The addition of the aqueous solution makes the pH value of precipitated liquid remain on 7.3～7.6, and reinforced Bi Jixu stops stirring after stirring 30min, immediately feed liquid is filtered, and the gained sediment washs K to the leacheate through deionized water
+Ion concentration (detects with the flame ion absorption process) below 0.1ppm, and by filtration, filter cake is dried 18h at 110 ℃ of temperature, and 400 ℃ of roasting temperature 4h namely get the catalyst (oxidation state) of institute's wish preparation, and its chemical expression formula is Ni
6Zr
3Sc
1
Catalyst carries out on atmospheric fixed bed continuous flow reactor (Φ 5mm)-GC combined system the activity rating of synthesis gas methanation.Catalyst amount is 100mg (approximately 0.1mL) and is placed in reactor with the 100mg quartz sand mixed diluting of same order number.Before reaction, oxidized catalyst is carried out original position prereduction activation by certain heating schedule in normal pressure, pure hydrogen (99.999%) reduction air-flow (flow velocity is 30mL/min), and the highest reduction temperature is 500 ℃, and whole process is lasted 12h; After cool the temperature to 250 ℃, switch to import reactor feed gas, consist of V (H at 250～600 ℃, unstripped gas
2)/V (CO) V (CO
2)/V (N
2CO/CO is carried out under the reaction condition of air speed GHSV=40000mL/ (hg) in)=75/15/5/5
2The hydrogenation methanation reaction.The reaction end gas of discharging from reactor outlet is through the sampling of utilidor (temperature remains on 130 ℃) direct sending gas chromatograph six-way valve, united by the thermal conductivity detector (TCD) (TCD) of GC-950 type gas chromatograph (sea, Shanghai glad chromatographic apparatus company product) and hydrogen flame detector (FID) and does on-line analysis.The former chromatographic column filler is TDX-201 carbon molecular sieve (Tianjin chemical reagent Co., Ltd product), and column length 2m uses H
2Do carrier gas, for separating of detecting CO, N
2(as interior mark) and CO
2Latter's chromatographic column filler is Porapak Q-S(USA product), column length 2m uses N
2Do carrier gas, for separating of detecting lower carbon number hydrocarbons and other carbon containing hydrogenation products.CO and CO
2Conversion ratio by N
2Internal standard method measuring and calculating, selectively being calculated by C base normalization method of methane and other carbon containing hydrogenation products.
Evaluation result shows, at normal pressure, 300 ℃, V (H
2)/VCO/V (CO
2)/V (N
2)=75/15/5/5, air speed are under the reaction condition of GHSV=40000mL/ (hg), CO and CO
2Conversion ratio reach respectively 〉=99.9% and 87.7%, methane is unique carbon containing hydrogenation products that GC detects, and selectively reaches 100%, corresponding methane space-time yield is 5.54g/ (hg
-catalyst), this value is the former matrix Ni of non-promotion
6Zr
4Analog value (5.16g/ (the hg of catalyst under same reaction conditions
-catalyst)) 1.07 times (seeing Table 1).Omnidistance 350hNi
6Zr
3Sc
1The catalyst operational stability is good, and having no its activity and selectivity has the decline (see figure 1).
The catalytic performance test result of table 1 embodiment 1 catalyst to synthesis gas hydrogenation methanation SNG processed
Reaction condition: normal pressure, 300 ℃, V (H
2)/V (CO) V (CO
2)/V (N
2)=75/15/5/5, GHSV=40000mL/ (hg).
Fig. 2 illustrates Ni
6Zr
3Sc
1The heat resistant test result of catalyst.With the reaction temperature of operating conditions catalyst from 300 ℃ rise to successively respectively 400,500,600,700 ℃ totally 4 temperature spots carry out " heat-resisting processing " each lasting 24h, then be down to the catalyst of 300 ℃ of reaction 8h after to heat-resisting processing and make activity rating.Result shows: stand the catalyst of 400,500,600 ℃ 3 reaction temperature points " heat-resisting processing ", and when reaction temperature is fallen when being back to 300 ℃, its catalysis CO and CO
2The total conversion of hydrogenation methanation and generate methane selectively all large activation return back to " heat-resisting processing " front level (namely being respectively 97% and 100%); Only continue to process 24h, then fall when being back to 300 ℃ CO and CO when heat resistant test temperature increase to 700 ℃
2The total conversion of hydrogenation methanation just descends (being down to 80%) to some extent, but product methane selectively still remain 100%.This shows Ni
6Zr
3Sc
1Catalyst has good heat resistance, and the safety operation temperature of its temperature end can be up to 600 ℃.Referring to Fig. 3, as a comparison, the former matrix Ni of non-promotion
6Zr
4Catalyst is standing 600 ℃ of " heat-resisting processing " 24h, is then falling when being back to 300 ℃ its CO and CO
2The total conversion of hydrogenation methanation has dropped to 70% and the trend that continues decline is arranged with the continuity in reaction time, shows that the safety operation temperature of its temperature end can not be higher than 500 ℃.
Embodiment 2
With 6.979gNi (NO
3)
26H
2O, 3.932gZr (NO
3)
43H
2O and 1.386g Sc (NO
3)
3(purity is the AR level) is mixed together, and adds the 90mL deionized water to be mixed with solution A; Separately with 7.691gAR level anhydrous K
2CO
3Be dissolved in the 95mL deionized water and be mixed with solution B; With in solution A and solution B constant speed and stream injection one reaction vessel (charge velocity is 12mL/min), carry out coprecipitation reaction under 85 ℃ of constant temperature and the continuous condition that stirs, by regulation and control K at 85 ℃ of temperature
2CO
3The addition of the aqueous solution makes the pH value of precipitated liquid remain on 7.0～7.5, and reinforced Bi Jixu stops stirring after stirring 30min, immediately feed liquid is filtered, and the gained sediment washs K to the leacheate through deionized water
+Ion concentration (detects with the flame ion absorption process) below 0.1ppm, and by filtration, filter cake is dried 16h at 115 ℃ of temperature, and 420 ℃ of roasting temperature 3h namely get the catalyst (oxidation state) of institute's wish preparation, and its chemical expression formula is Ni
6Zr
2.5Sc
1.5
The catalyst activity evaluation experimental is with embodiment 1.Evaluation result shows (seeing Table 2), and at normal pressure, 300 ℃, unstripped gas consists of V (H
2)/V (CO) V (CO
2)/V (N
2)=75/15/5/5, under the reaction condition of air speed GHSV=40000mL/ (hg), CO and CO
2Conversion ratio reach respectively 〉=99.9% and 85.9%, product methane selectively reach 100%, corresponding methane space-time yield is 5.51g/ (hg
-catalyst).
Embodiment 3
With 6.979gNi (NO
3)
26H
2O, 5.505gZr (NO
3)
43H
2O and 0.462g Sc (NO
3)
3(purity is the AR level) is mixed together, and adds the 90mL deionized water to be mixed with solution A; Separately with 7.982gAR level anhydrous K
2CO
3Be dissolved in the 95mL deionized water and be mixed with solution B; With in solution A and solution B constant speed and stream injection one reaction vessel (charge velocity is 12mL/min), carry out coprecipitation reaction under 80 ℃ of constant temperature and the continuous condition that stirs, by regulation and control K at 80 ℃ of temperature
2CO
3The addition of the aqueous solution makes the pH value of precipitated liquid remain on 7.3～7.8, and reinforced Bi Jixu stops stirring after stirring 30min, immediately feed liquid is filtered, and the gained sediment washs K to the leacheate through deionized water
+Ion concentration (detects with the flame ion absorption process) below 0.1ppm, and by filtration, filter cake is dried 20h at 105 ℃ of temperature, and 375 ℃ of roasting temperature 5h namely get the catalyst (oxidation state) of institute's wish preparation, and its chemical expression formula is Ni
6Zr
3.5Sc
0.5.
The catalyst activity evaluation experimental is with embodiment 1.Evaluation result shows (seeing Table 2), and at normal pressure, 300 ℃, unstripped gas consists of V (H
2)/V (CO) V (CO
2)/V (N
2)=75/15/5/5, under the reaction condition of air speed GHSV=40000mL/ (hg), CO and CO
2Conversion ratio reach respectively 〉=99.9% and 84.8%, product methane selectively reach 100%, corresponding methane space-time yield is 5.50g/ (hg
-catalyst).
Embodiment 4
With 6.979gNi (NO
3)
26H
2O, 3.146gZr (NO
3)
43H
2O and 1.847g Sc (NO
3)
3(purity is the AR level) is mixed together, and adds the 90mL deionized water to be mixed with solution A; Separately with 7.546gAR level anhydrous K
2CO
3Be dissolved in the 95mL deionized water and be mixed with solution B; With in solution A and solution B constant speed and stream injection one reaction vessel (charge velocity is 12mL/min), carry out coprecipitation reaction under 75 ℃ of constant temperature and the continuous condition that stirs, by regulation and control K at 75 ℃ of temperature
2CO
3The addition of the aqueous solution makes the pH value of precipitated liquid remain on 7.2～7.6, and reinforced Bi Jixu stops stirring after stirring 30min, immediately feed liquid is filtered, and the gained sediment washs K to the leacheate through deionized water
+Ion concentration (detects with the flame ion absorption process) below 0.1ppm, and by filtration, filter cake is dried 16h at 115 ℃ of temperature, and 400 ℃ of roasting temperature 4h namely get the catalyst (oxidation state) of institute's wish preparation, and its chemical expression formula is Ni
6Zr
2Sc
2
The catalyst activity evaluation experimental is with embodiment 1.Evaluation result shows (seeing Table 2), and at normal pressure, 300 ℃, unstripped gas consists of V (H
2)/V (CO) V (CO
2)/V (N
2)=75/15/5/5, under the reaction condition of air speed GHSV=40000mL/ (hg), CO and CO
2Conversion ratio reach respectively 〉=99.9% and 84.5%, product methane selectively reach 100%, corresponding methane space-time yield is 5.49g/ (hg
-catalyst).
With 6.979gNi (NO
3)
26H
2O, 2.359gZrO (NO
3)
2With 2.309g Sc (NO
3)
3(purity is the AR level) is mixed together, and adds the 90mL deionized water to be mixed with solution A; Separately with 7.401gAR level anhydrous K
2CO
3Be dissolved in the 95mL deionized water and be mixed with solution B; With in solution A and solution B constant speed and stream injection one reaction vessel (charge velocity is 12mL/min), carry out coprecipitation reaction under 85 ℃ of constant temperature and the continuous condition that stirs, by regulation and control K at 85 ℃ of temperature
2CO
3The addition of the aqueous solution makes the pH value of precipitated liquid remain on 7.2～7.6, and reinforced Bi Jixu stops stirring after stirring 30min, immediately feed liquid is filtered, and the gained sediment washs K to the leacheate through deionized water
+Ion concentration (detects with the flame ion absorption process) below 0.1ppm, and by filtration, filter cake is dried 16h at 120 ℃ of temperature, and 420 ℃ of roasting temperature 3h namely get the catalyst (oxidation state) of institute's wish preparation, and its chemical expression formula is Ni
6Zr
1.5Sc
2.5
The catalyst activity evaluation experimental is with embodiment 1.Evaluation result shows (seeing Table 2), and at normal pressure, 300 ℃, unstripped gas consists of V (H
2)/V (CO) V (CO
2)/V (N
2)=75/15/5/5, under the reaction condition of air speed GHSV=40000mL/ (hg), CO and CO
2Conversion ratio reach respectively 〉=99.9% and 83.8%, product methane selectively reach 100%, corresponding methane space-time yield is 5.48g/ (hg
-catalyst).
Embodiment 6
With 6.979gNi (CH
3COO)
2, 1.573gZr (NO
3)
43H
2O and 2.771g Sc (NO
3)
3(purity is the AR level) is mixed together, and adds the 90mL deionized water to be mixed with solution A; Separately with 7.256gAR level anhydrous K
2CO
3Be dissolved in the 95mL deionized water and be mixed with solution B; With in solution A and solution B constant speed and stream injection one reaction vessel (charge velocity is 12mL/min), carry out coprecipitation reaction under 80 ℃ of constant temperature and the continuous condition that stirs, by regulation and control K at 80 ℃ of temperature
2CO
3The addition of the aqueous solution makes the pH value of precipitated liquid remain on 7.2～7.6, and reinforced Bi Jixu stops stirring after stirring 30min, immediately feed liquid is filtered, and the gained sediment washs K to the leacheate through deionized water
+Ion concentration (detects with the flame ion absorption process) below 0.1ppm, and by filtration, filter cake is dried 18h at 110 ℃ of temperature, and 400 ℃ of roasting temperature 4h namely get the catalyst (oxidation state) of institute's wish preparation, and its chemical expression formula is Ni
6Zr
1Sc
3
The catalytic performance test result of table 2 embodiment 1～6 catalyst to synthesis gas hydrogenation methanation SNG processed
The catalyst activity evaluation experimental is with embodiment 1.Evaluation result shows (table 2), and at normal pressure, 300 ℃, unstripped gas consists of V (H
2)/V (CO) V (CO
2)/V (N
2)=75/15/5/5, under the reaction condition of air speed GHSV=40000mL/ (hg), CO and CO
2Conversion ratio reach respectively 〉=99.9% and 83.4%, product methane selectively reach 100%, corresponding methane space-time yield is 5.47g/ (hg
-catalyst).
Claims (10)
1. the catalyst for the preparation of synthetic natural gas, is characterized in that comprising major constituent and promoter for the co-precipitation type nickel-Zirconium-base catalyst of scandium promotion, and described major constituent is Ni, Zr, and promoter is Sc, and chemical formulation is: Ni
iZr
jSc
k, in formula, subscript i, j, k are the molar ratio coefficient of Ni, Zr, Sc in catalyst, the mass percent of catalyst each component is respectively: Ni:48%～62%; Sc:3%～25%; Surplus is Zr.
2. a kind of catalyst for the preparation of synthetic natural gas as claimed in claim 1, is characterized in that the mass percent of catalyst each component is respectively: Ni:50%～56%; Sc:5%～15%; Surplus is Zr.
3. a kind of preparation method of the catalyst for the preparation of synthetic natural gas as claimed in claim 1 is characterized in that comprising the following steps:
1) add water after nickel salt, zirconates and the scandium salts mixing of composition and ratio with metering by catalyst and make solution A, in solution A, 3 kinds of metal cation total yield concentration are 1.0～1.5N/L;
2) with the K that measures
2CO
3The water-soluble solution B of making, K in solution B
+The equivalent concentration of ion is identical with 3 kinds of metal cation total yield concentration in solution A;
3) under constant temperature, stirring condition, solution A and solution B are injected in reaction vessel, carry out coprecipitation reaction, make the pH value of reaction system remain on 7.0～7.8 by the addition that regulates and controls solution B, after reaction, feed liquid is filtered, get sediment;
4) sediment is washed K to the leacheate through deionized water
+Ion concentration is rear the filtration below 0.1ppm, the filter cake oven dry, and roasting namely gets Ni
iZr
jSc
kCatalyst (oxidation state).
4. a kind of preparation method of the catalyst for the preparation of synthetic natural gas as claimed in claim 3, is characterized in that in step 1), and described nickel salt is selected from Ni (NO
3)
2Or Ni (CH
3COO)
2
5. a kind of preparation method of the catalyst for the preparation of synthetic natural gas as claimed in claim 3, is characterized in that in step 1), and described zirconates is selected from Zr (NO
3)
4Or ZrO (NO
3)
2
6. a kind of preparation method of the catalyst for the preparation of synthetic natural gas as claimed in claim 3, is characterized in that in step 1), and described scandium salts is selected from Sc (NO
3)
3
7. a kind of preparation method of the catalyst for the preparation of synthetic natural gas as claimed in claim 3, is characterized in that in step 3), described will solution A and solution B to inject in reaction vessel be that solution A and solution B constant speed and stream are injected in reaction vessel.
8. a kind of preparation method of the catalyst for the preparation of synthetic natural gas as claimed in claim 3, is characterized in that in step 3), and the temperature of described coprecipitation reaction is 70～90 ℃, and the reaction time is 0.5～1h.
9. a kind of preparation method of the catalyst for the preparation of synthetic natural gas as claimed in claim 3, is characterized in that in step 4), and the temperature of described oven dry is 105～120 ℃, and the time of oven dry is 16～20h.
10. a kind of preparation method of the catalyst for the preparation of synthetic natural gas as claimed in claim 3, is characterized in that in step 4), and the temperature of described roasting is 360～425 ℃, and the time of roasting is 3～5h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112589090A (en) * | 2020-11-06 | 2021-04-02 | 中国科学院金属研究所 | Preparation method of metal nano powder blended in elementary substance state and oxidation state |
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| US20100168257A1 (en) * | 2007-03-13 | 2010-07-01 | Matthias Duisberg | Metal-doped nickel oxides as catalysts for the methanation of carbon monoxide |
| CN102407126A (en) * | 2011-10-24 | 2012-04-11 | 厦门大学 | Catalyst used for preparing synthetic natural gas by using coal derived synthesis gas and preparation method thereof |
| CN102658156A (en) * | 2012-05-04 | 2012-09-12 | 厦门大学 | Methanation catalyst for synthetic natural gas from coal and preparation method for methanation catalyst |
| CN101890353B (en) * | 2010-07-01 | 2012-12-05 | 神华集团有限责任公司 | High-temperature methanation catalyst, preparation method and application thereof |
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| US20100168257A1 (en) * | 2007-03-13 | 2010-07-01 | Matthias Duisberg | Metal-doped nickel oxides as catalysts for the methanation of carbon monoxide |
| CN101890353B (en) * | 2010-07-01 | 2012-12-05 | 神华集团有限责任公司 | High-temperature methanation catalyst, preparation method and application thereof |
| CN102407126A (en) * | 2011-10-24 | 2012-04-11 | 厦门大学 | Catalyst used for preparing synthetic natural gas by using coal derived synthesis gas and preparation method thereof |
| CN102658156A (en) * | 2012-05-04 | 2012-09-12 | 厦门大学 | Methanation catalyst for synthetic natural gas from coal and preparation method for methanation catalyst |
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