CN105797785A - Pre-reduction type high-temperature methanation catalyst and preparation method thereof - Google Patents
Pre-reduction type high-temperature methanation catalyst and preparation method thereof Download PDFInfo
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a pre-reduction type high-temperature methanation catalyst. The catalyst comprises an active component, a carrier and an auxiliary, wherein the active component is reduction state nickel, the carrier is Al2O3, and the auxiliary is one or more of Mg oxide, Ca oxide, Ba oxide and La oxide. The invention further discloses a preparation method of the catalyst. The preparation method comprises the steps that nickel nitrate, aluminum nitrate and soluble salt of the auxiliary oxide are prepared into an aqueous solution, the prepared aqueous solution is added into a reaction kettle, oxalate precipitator is added for stirring and heating, and a semi-finished catalyst is obtained after washing and filtering; calcination is conducted after drying, cooling passivating is conducted, graphite and water are added, the mixture is mixed evenly, and then the catalyst is obtained through compression molding. The pre-reduction type high-temperature methanation catalyst is prepared through the method of oxalate precipitating and inert atmosphere calcination and has high specific surface area, CO produced through oxalic acid decomposing is used for reduction, the reduction type catalyst is directly obtained, the reduction degree of the passivated finished product is 80% or above, plenty of time is saved, and using is convenient.
Description
Technical field
The invention belongs to catalyst and preparing technical field thereof, be specifically related to a kind of pre-reduction type high-temperature methanation catalyst, the preparation method that the invention still further relates to this catalyst.
Background technology
China is raw coal big producing country, and the energy resource structure based on coal is the major reason causing the current serious atmospheric pollution of China.Natural gas has combustion heat value height, harmful gas emission feature little, that produce without solid grain contamination, is a kind of clean energy resource, and the ratio in global Energy Consumption is about 24%.China's natural gas resource is relatively poor, and the ratio that natural gas accounts for primary energy is relatively low, and within 2014, this numerical value is 5.6%.Therefore, greatly develop natural gas and be conducive to improving China's energy resource structure, alleviate problem of environmental pollution serious at present.Country proposes the year two thousand twenty in 13 ENERGY PLANNING, and natural gas proportion in primary energy is consumed rises to 10%.But natural gas development faces the problem of scarcity of resources, China's natural gas general import amount in 2014 is close to 600 billion cubic meters.Therefore, development coal gas is possible not only to promote the clean utilization of coal resources, it is also possible to alleviate the situation of China's natural gas resource scarcity, promotes China's energy structure optimizing, meets the current energy development present situation of China.
The core process of coal gas is methanation process, and methanation process it is crucial that methanation catalyst.Methanation reaction is strong exothermal reaction, and adiabatic temperature rise is big, and the CO methanation of generally every 1% can produce the adiabatic temperature rise of 74 DEG C, every CO of 1%2Methanation can produce the adiabatic temperature rise of 60 DEG C, and in adiabatic methanation process, reaction bed temperature is up to 600～700 DEG C.In order to prevent carbon distribution reaction and control reaction temperature, in addition it is also necessary to add a large amount of water vapour.Therefore, methanation catalyst is it is crucial that solve the catalyst efflorescence when high temperature, high liquid to steam ratio and active center Sintering Problem.At present, such catalyst of domestic use still relies primarily on import, although domestic correlational study report is more, but all unrealized industrialization.Therefore, domestic still in the urgent need to such catalyst is developed.
High-temperature methanation catalyst is generally with nickel for main active component, and the active component nickel in finished catalyst, greatly all in oxidation state, needs to reduce before use.And pre-reduction type methanation catalyst is easy to use, it is possible to save the substantial amounts of recovery time.
Summary of the invention
It is an object of the invention to provide a kind of pre-reduction type high-temperature methanation catalyst, solve in existing methanation catalyst active component nickel greatly all in oxidation state, the problem needing before use to carry out reducing.
The preparation method that it is a further object to provide a kind of pre-reduction type high-temperature methanation catalyst.
The technical solution adopted in the present invention is, a kind of pre-reduction type high-temperature methanation catalyst, its composition includes active component, carrier and auxiliary agent, and its active component is the nickel of reduction-state, and carrier is Al2O3, auxiliary agent is one or more in Mg, Ca, Ba, La oxide.
The feature of the present invention also resides in,
In this catalyst, the mass percent of each component is: Ni15～45%, Al2O330～75%, auxiliary agent 2～18%, graphite 2～8%, surplus is water.
Second technical scheme of the present invention is, the preparation method of a kind of pre-reduction type high-temperature methanation catalyst comprises the steps:
Step 1, by nickel nitrate, aluminum nitrate, auxiliary agent oxide soluble-salt be configured to aqueous solution；
Step 2, aqueous solution step 1 made adds in reactor, stirring, and heating, to 50～80 DEG C, is subsequently adding oxalate precipitation agent solution, and is 7 with 10% ammonia adjustment pH, and washing and filtering obtains catalyst semi-finished product；
Step 3, by catalyst semi-finished product dry roasting, is then cooled to 100～200 DEG C, passes into a small amount of air and roasting afterproduct is passivated, be eventually adding graphite and water, compressing and get final product after mix homogeneously.
The feature of the present invention also resides in,
In solution described in step 1, nickel ion concentration is 0.1～0.55mol/L, and aluminium ion concentration is 0.2～2.5mol/L, and assistant concentration is 0.002～0.12mol/L.
The soluble-salt of auxiliary agent oxide is one or more in magnesium nitrate, calcium nitrate, barium nitrate, Lanthanum (III) nitrate.
Oxalate precipitation agent concentration described in step 2 is 0.1～1.5mol/L, and oxalate precipitation agent is the one in oxalic acid, ammonium oxalate, potassium oxalate, Disodium oxalate..
In step 3, baking temperature 80～150 DEG C, time are 5～20h.
In step 3, roasting is at noble gas N2Or the lower roasting 2～12h of Ar protection, sintering temperature 350～650 DEG C.
Reduction degree >=80% of nickel in prepared catalyst.
The invention has the beneficial effects as follows, pre-reduction type high-temperature methanation catalyst of the present invention, prepared by the method using oxalate precipitation and inert atmosphere roasting, there is higher specific surface area, utilizing oxalic acid to decompose the CO produced to reduce, directly obtain reduction catalyst, the finished product reduction degree after passivation is more than 80%, save the plenty of time, easy to use；Active component nickel is uniformly dispersed and nickel crystallite is little, and activity is high.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
Following example are merely to illustrate and explain the present invention, but the present invention is not limited by embodiment.
Embodiment 1
(1) 44.6g nickel nitrate, 264.8g aluminum nitrate, 6.6g Lanthanum (III) nitrate are dissolved in 800mL water；
(2) adding in reactor by above-mentioned aqueous solution, stirring, heating, to 70 DEG C, is subsequently adding the oxalic acid solution that 1500mL concentration is 0.48mol/L, and is 7 with 10% ammonia adjustment pH, and washing and filtering obtains catalyst semi-finished product；
(3) by gained semi-finished product dry 10h at 150 DEG C；
(4) by dried material at noble gas N2The lower roasting 3h of protection, sintering temperature 350 DEG C；
(5) it is cooled to 120 DEG C, passes into a small amount of air and roasting afterproduct is passivated；
(6) graphite of 5% and a small amount of water it are mixed into, after mix homogeneously, compressing finished catalyst.
In embodiment 1 gained catalyst, each constituent content is Ni15%, Al2O370%, La2O34.5%, graphite 5%, surplus is water, and wherein the nickel of partial oxidation state also amounts to into Ni calculating.
Embodiment 2
(1) 61.9g nickel nitrate, 228.0g aluminum nitrate, 4.0g Lanthanum (III) nitrate, 16.0g magnesium nitrate are dissolved in 1000mL water；
(2) adding in reactor by above-mentioned aqueous solution, stirring, heating, to 70 DEG C, is subsequently adding the ammonium oxalate solution that 1200mL concentration is 0.65mol/L, and is 7 with 10% ammonia adjustment pH, and washing and filtering obtains catalyst semi-finished product；
(3) by gained semi-finished product dry 10h at 150 DEG C；
(4) by dried material at noble gas N2The lower roasting 3h of protection, sintering temperature 400 DEG C；
(5) it is cooled to 120 DEG C, passes into a small amount of air and roasting afterproduct is passivated；
(6) graphite of 5% and a small amount of water it are mixed into, after mix homogeneously, compressing finished catalyst.
In embodiment 2 gained catalyst, each constituent content is Ni23%, Al2O360%, La2O32.5%, MgO4.5%, graphite 5%, surplus is water.
Embodiment 3
(1) 74.3g nickel nitrate, 202.3g aluminum nitrate, 16.0g magnesium nitrate, 10.5g calcium nitrate are dissolved in 1200mL water；
(2) adding in reactor by above-mentioned aqueous solution, stirring, heating, to 70 DEG C, is subsequently adding the oxalic acid solution that 1500mL concentration is 0.54mol/L, and is 7 with 10% ammonia adjustment pH, and washing and filtering obtains catalyst semi-finished product；
(3) by gained semi-finished product dry 10h at 150 DEG C；
(4) by dried material at noble gas N2The lower roasting 3h of protection, sintering temperature 450 DEG C；
(5) it is cooled to 120 DEG C, passes into a small amount of air and roasting afterproduct is passivated；
(6) graphite of 5% and a small amount of water it are mixed into, after mix homogeneously, compressing finished catalyst.
In embodiment 3 gained catalyst, each constituent content is Ni28%, Al2O351%, MgO4.5%, CaO4.5%, graphite 5%, surplus is water.
Embodiment 4
(1) 86.7g nickel nitrate, 165.5g aluminum nitrate, 6.6g Lanthanum (III) nitrate, 16.0g magnesium nitrate, 10.5g calcium nitrate are dissolved in 1500mL water；
(2) adding in reactor by above-mentioned aqueous solution, stirring, heating, to 70 DEG C, is subsequently adding the oxalic acid solution that 1500mL concentration is 0.54mol/L, and is 7 with 10% ammonia adjustment pH, and washing and filtering obtains catalyst semi-finished product；
(3) by gained semi-finished product dry 10h at 150 DEG C；
(4) by dried material at noble gas N2The lower roasting 3h of protection, sintering temperature 500 DEG C；
(5) it is cooled to 120 DEG C, passes into a small amount of air and roasting afterproduct is passivated；
(6) graphite of 5% and a small amount of water it are mixed into, after mix homogeneously, compressing finished catalyst.
In embodiment 4 gained catalyst, each constituent content is Ni32%, Al2O342%, La2O34.5%, MgO4.5%, CaO4.5%, graphite 5%, surplus is water.
Embodiment 5
(1) 99.0g nickel nitrate, 150.8g aluminum nitrate, 7.97g Lanthanum (III) nitrate, 16.9g calcium nitrate are dissolved in 1500mL water；
(2) adding in reactor by above-mentioned aqueous solution, stirring, heating, to 70 DEG C, is subsequently adding the oxalic acid solution that 1500mL concentration is 0.53mol/L, and is 7 with 10% ammonia adjustment pH, and washing and filtering obtains catalyst semi-finished product；
(3) by gained semi-finished product dry 10h at 150 DEG C；
(4) by dried material at noble gas N2The lower roasting 5h of protection, sintering temperature 550 DEG C；
(5) it is cooled to 120 DEG C, passes into a small amount of air and roasting afterproduct is passivated；
(6) graphite of 5% and a small amount of water it are mixed into, after mix homogeneously, compressing finished catalyst.
In embodiment 5 gained catalyst, each constituent content is Ni39%, Al2O338%, La2O35.4%, CaO7.5%, graphite 5%, surplus is water.
Embodiment 6
(1) 61.9g nickel nitrate, 228.0g aluminum nitrate, 4.0g Lanthanum (III) nitrate, 16.0g magnesium nitrate are dissolved in 1000mL water；
(2) adding in reactor by above-mentioned aqueous solution, stirring, heating, to 50 DEG C, is subsequently adding the ammonium oxalate solution that 1200mL concentration is 0.65mol/L, and is 7 with 10% ammonia adjustment pH, and washing and filtering obtains catalyst semi-finished product；
(3) by gained semi-finished product dry 15h at 100 DEG C；
(4) by dried material roasting 2h, sintering temperature 600 DEG C under noble gas Ar protects；
(5) it is cooled to 200 DEG C, passes into a small amount of air and roasting afterproduct is passivated；
(6) graphite of 5% and a small amount of water it are mixed into, after mix homogeneously, compressing finished catalyst.
In embodiment 6 gained catalyst, each constituent content is Ni23%, Al2O360%, La2O32.5%, MgO4.5%, graphite 5%, surplus is water.
Embodiment 7
(1) 86.7g nickel nitrate, 165.5g aluminum nitrate, 6.6g Lanthanum (III) nitrate, 16.0g magnesium nitrate, 10.5g calcium nitrate are dissolved in 1500mL water；
(2) adding in reactor by above-mentioned aqueous solution, stirring, heating, to 60 DEG C, is subsequently adding the oxalic acid solution that 1500mL concentration is 0.54mol/L, and is 7 with 10% ammonia adjustment pH, and washing and filtering obtains catalyst semi-finished product；
(3) by gained semi-finished product dry 5h at 120 DEG C；
(4) by dried material at noble gas N2The lower roasting 8h of protection, sintering temperature 650 DEG C；
(5) it is cooled to 100 DEG C, passes into a small amount of air and roasting afterproduct is passivated；
(6) graphite of 5% and a small amount of water it are mixed into, after mix homogeneously, compressing finished catalyst.
In embodiment 7 gained catalyst, each constituent content is Ni32%, Al2O342%, La2O34.5%, MgO4.5%, CaO4.5%, graphite 5%, surplus is water.
Embodiment 8
(1) 99.0g nickel nitrate, 150.8g aluminum nitrate, 7.97g Lanthanum (III) nitrate, 16.9g calcium nitrate are dissolved in 1500mL water；
(2) adding in reactor by above-mentioned aqueous solution, stirring, heating, to 80 DEG C, is subsequently adding the oxalic acid solution that 1500mL concentration is 0.53mol/L, and is 7 with 10% ammonia adjustment pH, and washing and filtering obtains catalyst semi-finished product；
(3) by gained semi-finished product dry 20h at 80 DEG C；
(4) by dried material roasting 12h, sintering temperature 350 DEG C under noble gas Ar protects；
(5) it is cooled to 180 DEG C, passes into a small amount of air and roasting afterproduct is passivated；
(6) graphite of 5% and a small amount of water it are mixed into, after mix homogeneously, compressing finished catalyst.
In embodiment 8 gained catalyst, each constituent content is Ni39%, Al2O338%, La2O35.4%, CaO7.5%, graphite 5%, surplus is water.
The correlated performance test result of the catalyst that embodiment 1～5 obtains is as shown in table 1.Catalyst first reduces before carrying out Activity determination, and reducing condition is logical 3:1 hydrogen and nitrogen gas (total flow 50mL/min) 350 DEG C reduction 30min.
Catalyst activity testing conditions: catalyst breakage is granularity 0.25mm～0.42mm, loadings 0.5mL, interior consists of N through the quartz ampoule fixed bed reactors of 6mm, normal pressure, unstrpped gas2:H2: CO=1:3:1, reaction temperature is 300 DEG C, air speed 30000h-1.Outlet testing conditions is: the auspicious grand SP-7890 type gas chromatograph of Shandong Lunan, TDX-01 chromatographic column Ф 3mm × 2m, carrier gas is H2, detector thermal conductivity cell detector, detects CO and CH4Content.
Prepared catalyst is not when reducing; namely reaction temperature it is warming up under nitrogen protection; namely there is methanation reaction activity; catalyst such as embodiment 5; without reduction reaction when 280 DEG C, CO conversion ratio is up to more than 85%, after reaction a period of time; part of nickel of not reducing is reduced, and conversion ratio can bring up to more than 93%.
Table 1 catalyst performance test result
| Sample number | CO conversion ratio (%) | CH4Selectivity (%) |
| Embodiment 1 | 75 | 88 |
| Embodiment 2 | 84 | 89.5 |
| Embodiment 3 | 86 | 87.1 |
| Embodiment 4 | 92 | 90.4 |
| Embodiment 5 | 99 | 93.5 |
Being illustrated by embodiment, good catalyst activity prepared by the method, for pre-reduction type catalyst, reduction apparatus that need not be special in production process, is a kind of methanation catalyst for adiabatic methanation process having very much actual application prospect.
Claims (9)
1. a pre-reduction type high-temperature methanation catalyst, it is characterised in that its composition includes active component, carrier and auxiliary agent, and its active component is the nickel of reduction-state, and carrier is Al2O3, auxiliary agent is one or more in Mg, Ca, Ba, La oxide.
2. pre-reduction type high-temperature methanation catalyst according to claim 1, it is characterised in that in this catalyst, the mass percent of each component is: Ni15～45%, Al2O330～75%, auxiliary agent 2～18%, graphite 2～8%, surplus is water.
3. the preparation method of a pre-reduction type high-temperature methanation catalyst as claimed in claim 1 or 2, it is characterised in that comprise the steps:
Step 1, by nickel nitrate, aluminum nitrate, auxiliary agent oxide soluble-salt be configured to aqueous solution；
Step 2, aqueous solution step 1 made adds in reactor, stirring, and heating, to 50～80 DEG C, is subsequently adding oxalate precipitation agent solution, and is 7 with 10% ammonia adjustment pH, and washing and filtering obtains catalyst semi-finished product；
Step 3, by catalyst semi-finished product dry roasting, is then cooled to 100～200 DEG C, passes into a small amount of air and roasting afterproduct is passivated, be eventually adding graphite and water, compressing and get final product after mix homogeneously.
4. the preparation method of pre-reduction type high-temperature methanation catalyst according to claim 3, it is characterized in that, in solution described in step 1, nickel ion concentration is 0.1～0.55mol/L, and aluminium ion concentration is 0.2～2.5mol/L, and assistant concentration is 0.002～0.12mol/L.
5. the preparation method of the pre-reduction type high-temperature methanation catalyst according to claim 3 or 4, it is characterised in that the soluble-salt of described auxiliary agent oxide is one or more in magnesium nitrate, calcium nitrate, barium nitrate, Lanthanum (III) nitrate.
6. the preparation method of pre-reduction type high-temperature methanation catalyst according to claim 3, it is characterized in that, oxalate precipitation agent concentration described in step 2 is 0.1～1.5mol/L, and oxalate precipitation agent is the one in oxalic acid, ammonium oxalate, potassium oxalate, Disodium oxalate..
7. the preparation method of pre-reduction type high-temperature methanation catalyst according to claim 3, it is characterised in that in step 3, baking temperature 80～150 DEG C, time are 5～20h.
8. the preparation method of pre-reduction type high-temperature methanation catalyst according to claim 3, it is characterised in that in step 3, roasting is at noble gas N2Or the lower roasting 2～12h of Ar protection, sintering temperature 350～650 DEG C.
9. the preparation method of pre-reduction type high-temperature methanation catalyst according to claim 3, it is characterised in that reduction degree >=80% of nickel in prepared catalyst.
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| CN107224975A (en) * | 2016-03-24 | 2017-10-03 | 中国石油化工股份有限公司 | Preparation method without the methanation of carbon monoxide catalyst of reduction activation |
| CN107497447A (en) * | 2017-09-18 | 2017-12-22 | 江苏亘德科技有限公司 | A kind of methanation catalyst and preparation method thereof |
| CN109395735A (en) * | 2018-10-25 | 2019-03-01 | 中国科学院过程工程研究所 | A kind of methanation catalyst, preparation method and the method for preparing methane using it |
| CN110004292A (en) * | 2019-04-19 | 2019-07-12 | 湖南雅城新材料有限公司 | A kind of technique that the purification of waste sulfate manganese solution reduces calcium-magnesium content |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107224975A (en) * | 2016-03-24 | 2017-10-03 | 中国石油化工股份有限公司 | Preparation method without the methanation of carbon monoxide catalyst of reduction activation |
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| CN107497447A (en) * | 2017-09-18 | 2017-12-22 | 江苏亘德科技有限公司 | A kind of methanation catalyst and preparation method thereof |
| CN109395735A (en) * | 2018-10-25 | 2019-03-01 | 中国科学院过程工程研究所 | A kind of methanation catalyst, preparation method and the method for preparing methane using it |
| CN110004292A (en) * | 2019-04-19 | 2019-07-12 | 湖南雅城新材料有限公司 | A kind of technique that the purification of waste sulfate manganese solution reduces calcium-magnesium content |
| CN110004292B (en) * | 2019-04-19 | 2020-12-29 | 湖南雅城新材料有限公司 | Process for purifying waste manganese sulfate solution to reduce content of calcium and magnesium |
| CN110085863A (en) * | 2019-04-26 | 2019-08-02 | 桑顿新能源科技有限公司 | Graphite cathode material and preparation method thereof, battery |
| CN110085863B (en) * | 2019-04-26 | 2024-03-12 | 桑顿新能源科技有限公司 | Graphite negative electrode material, preparation method thereof and battery |
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