CN102836721A - Preparation method for catalyst for hydrogen production by hydrocarbon reforming - Google Patents
Preparation method for catalyst for hydrogen production by hydrocarbon reforming Download PDFInfo
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Abstract
The invention relates to a preparation method for a catalyst for hydrogen production by hydrocarbon reforming. The method is characterized by comprising the following steps of: adding La(NP3)2 into deionized water to prepare a solution; placing an alumina-based carrier into the impregnating solution obtained above for isopyknic impregnation; drying after the impregnation; roasting the catalyst obtained above for 2-6 hours, and cooling to room temperature; preparing a Ni(NO3)2 solution by using Ni(NO3)2, deionized water and a surfactant; placing the catalyst prepared above into the Ni(NO3)2 solution for isopyknic impregnation; drying the sample obtained above, and then roasting; placing the sample obtained above into the Ni(NO3)2 solution again for another isopyknic impregnation the, and then drying and roasting again to obtain a product. The prepared catalyst for hydrogen production by hydrocarbon reforming has stabilized high activity; and when using hydrocarbon gas containing a large amount of C2-C4 hydrocarbons as a raw material, catalytic cracking and steam reforming of the C2-C4 hydrocarbons can be realized quickly by the prepared catalyst, preventing the C2-C4 hydrocarbons from moving down to a high temperature bed for carbon deposition.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocarbon conversion catalyst for preparing hydrogen, belong to chemical field.
Background technology
The reformation hydrogen production of fossil fuel is the main flow of hydrogen producing technology at present.For the needed hydrogen of petrochemical plant, the most feasible technology mainly is to adopt lighter hydrocarbons conversion method hydrogen producing technology.Alkene and sulphur impurity in the raw material are deviate from the preliminary treatment that generally comprises raw material of natural gas hydrogen preparation method, so that the activity of guard catalyst and macrocyclic operation.Pretreated raw material gets into the light hydrocarbon steam conversion reactor and carries out light hydrocarbon steam conversion generation with H
2, CO, CO
2, CH
4It is main mixed synthesis gas; The light hydrocarbon steam conversion reactor mainly is made up of several external-heat pipe type solid bed bioreactors; The active component of this light hydrocarbon steam reforming catalyst is a metallic nickel; The carrier of catalyst mainly contains calcium aluminate carrier, refractory material carrier (mainly be the aluminium oxide or the magnalium point stone of high-temperature calcination, the content that wherein requires calcium oxide and silica is less than 0.1%), and reaction temperature is greater than 850 ℃. and it is relatively stricter to the requirement of raw material that the light hydrocarbon steam conversion method prepares hydrogen; For gas raw material, require wherein olefin(e) centent less than 1%; For the light oil raw material, require its arene content less than 13%, naphthene content less than 36%, sulfur content is less than 100ppm.Therefore the technology of present light hydrocarbon steam conversion method hydrogen manufacturing becomes problems such as product condition harshness in that raw material is alternative poor, technological process is long, process is complicated.
The catalyst that is used for hydrocarbon cracking hydrogen manufacturing all is to be the loaded catalyst of main active component with nickel mostly, and with to wherein adding various auxiliary agents, patent CN1689699A discloses a kind of Ni/Ce
(1-X)Zr
XO
2/ SiO
2Loaded catalyst, it has higher conversion ratio to catalytic methane cracking hydrogen production.But the carbon accumulation resisting ability of this catalyst is relatively poor, and easy inactivation influences the stability of catalyst.
CN101439287 the invention discloses a kind of hydrocarbon catalytic cracking catalyst for preparing hydrogen and preparation method thereof, and described hydrogen production from hydrocarbon catalyst is with MO
y/ CNFs is carrier loaded active component Ni, and wherein the weight portion of each component is: Ni element 10～50, MO
y5～70, CNFs 2～45; Its preparation method is with MO
yPretreated CNFs adds in the nickel salt aqueous solution with process, and adding alkali lye adjusting pH value then is 6～8, leaves standstill after the stirring, and the sediment that obtains promptly gets through filtration, washing, drying, and doing carrier with CNFs has the high shortcoming of price.
CN1058546 discloses a kind of catalyst for preparing hydrogen, it is characterized in that by active component Ni9～11% (weight) and modifier rare earth metal 1.0～1.4% (weight) alkaline-earth metal 0.5～0.7% (weight) and modified support.Adopted lignocellulosic as expanding agent, lanthana is an active modifier, but its reactive metal is not the rod-shaped particle structure.
Summary of the invention
Not enough according to prior art, technical problem to be solved by this invention is: a kind of preparation method of hydrocarbon conversion catalyst for preparing hydrogen is provided, and the hydrocarbon conversion catalyst for preparing hydrogen of production has stable high activity, and the penetrability in duct improves.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of hydrocarbon conversion catalyst for preparing hydrogen is provided, it is characterized in that following steps:
(a) with La (NO
3)
2Add in the deionized water, be mixed with the solution that concentration is 0.2～0.4mol/l;
(b) alumina-based supports is put into step (a) maceration extract, carry out incipient impregnation;
(c) behind step (b) dipping, 100-130 ℃ of oven dry 1-10 hour;
(d) step (c) oven dry rear catalyst at 800-900 ℃ of roasting 2-6 hour, is reduced to room temperature;
(e) get Ni (NO
3)
2, deionized water and surfactant, be mixed with Ni (NO
3)
2Concentration is the solution of 1.0～5.0mol/l, and free acid is less than 0.01mol/l, surfactant and Ni (NO
3)
2The ratio of weight be 0.01-0.3: 1;
(f) catalyst of step (d) preparation is put into step (e) solution, carry out incipient impregnation;
(g) step (f) sample is 100-130 ℃ of oven dry 1-10 hour, then at 400-600 ℃ of roasting 3-8 hour;
(h) step (g) is put into step (e) solution again, carries out incipient impregnation again, then 100-130 ℃ of oven dry 1-10 hour, again at 400-600 ℃ of roasting 3-8 hour, gets product.
Described La (NO
3)
2Be that the nitric acid billows are industrial nitric acid billows, LaO content accounts for the 1-5% of material gross weight.
Described Ni (NO
3)
2Six industrial water nickel nitrates, NiO content accounts for the 14-20% of material gross weight.
Described surfactant is lecithin, phosphoric acid fat, AEO, aliphatic acid polyethenoxy ether, APES, aliphatic amine polyoxyethylene ether, polyethylene glycol, tall oil acid amides, dodecyl alcohol acyl phosphatide, SP-40, SP-60, SP-65, SP-80, SP-85, M-201, fatty acid monoglyceride and two sweet esters, ethylene glycol monostearate, diglycol monostearate or propyleneglycoles list dodecyl ester, and surfactant and Ni (NO
3)
2The ratio of weight be 0.01-0.3: 1.
Described alumina-based supports is made by following steps:
(1) gets high temperature alumina, to wherein adding pure calcium aluminate cement, modified additive ZrO in order successively
2, kapok and graphite, the composition mixture material;
(2) in material, add entry, water accounts for 15～25% of material gross mass, mixes thoroughly, all over balling ratio 80-95%, through drying baker 100-150 ℃ of oven dry 3-6 hour, crosses 8 mesh sieve granulations, air-dry 2-10 hour through briquetting press precompressed 4-5;
(3) compression molding on tablet press machine, specification 16 * 15mm;
(4) carrying out first pressing, first pressing intensity is 30～50N/;
(5) with steam curing 24-72 hour;
(6) carrier was at 1100-1200 ℃ of activation 2-8 hour.
Wherein behind compression molding on the tablet press machine, specification is 16 * 15mm (four holes, endoporus Φ 4.0mm).
Described high temperature alumina is an Alpha-alumina, and Alpha-alumina accounts for 25～40% of alumina-based supports gross weight.
Described modified additive ZrO
2Account for 0.1～5% of alumina-based supports gross weight.
Described binding agent pure calcium aluminate cement accounts for 35～55% of alumina-based supports gross weight.
Described graphite accounts for 1～10% of alumina-based supports gross weight.
The fibre diameter of described kapok is 5-30 μ m, and length is 20-100 μ m, accounts for 0.1～5% of alumina-based supports gross weight.
Hydrocarbon conversion catalyst for preparing hydrogen of the present invention comprises alumina-based supports and active metal component, contains the penetrability duct in the wherein said carrier.After the activation carrier side pressure strength >=400N/, carrier water absorption rate 20～25% after the activation.
Detailed programs method to some property testings of catalyst of the present invention comprises: the meleic acid assay, adopted infra-red sepectrometry to measure; Radially the mensuration of crushing strength is to adopt intensity meter to measure; Pore volume, specific surface, average pore size, pore size distribution, porosity record with nitrogen adsorption method; The mensuration of bulk density adopts the graduated cylinder method.
Contain bar-shaped reactive metal NiO in the hydrocarbon conversion catalyst for preparing hydrogen of the present invention, the character of active modifier LaO catalyst is following: the diameter of bar-shaped reactive metal NiO is 60-100nm, and length is 300-800nm.Bulk density, 1.05～1.15, crushing strength＞500 radially.
The invention has the beneficial effects as follows: prepared hydrocarbon conversion catalyst for preparing hydrogen has stable high activity, uses to contain a large amount of C
2～C
4When gaseous hydrocarbon is done raw material, can be rapidly with C
2～C
4Hydrocarbon catalytic cracking and steam-reforming prevent C
2～C
4Move down into the high temperature bed and carbon distribution.Adopt the character in kapok improvement duct, through adding the kapok pore creating material, the penetrability in duct is improved, the big molecule of carbon deposit that therefore generates diffuses out catalyst inside easily, keeps the unimpeded of duct.ZrO
2Modifier add the strong interaction make aluminium oxide and reactive metal and reduce the maximum effect of bringing into play reactive metal.The adding of rare-earth metal La O increases the activity of reactive metal.The adding of surfactant makes NiO in the process of crystallization, and the micella of surfactant will retrain the NiO crystal formation and carry out crystallization with rod-shaped particle, and this is because micella character determines.Rod-shaped particle will maximumly be brought into play the reactive metal utilization rate, and rod-shaped particle has more limit and angle than spheroidal particle, and the anti-carbon deposition ability of rod-shaped particle is higher than spheroidal particle in addition.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of the embodiment of the invention 1;
Fig. 2 is the scanning electron microscope diagram of the embodiment of the invention 2.
The specific embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
Get the 320g Alpha-alumina, again to wherein adding 480g pure calcium aluminate cement, 3.2g ZrO in order successively
2, 4g kapok and 32g graphite, the composition mixture material.Add deionized water 21g, stir, with briquetting press precompressed 4 times, balling ratio reaches 90%.Put into drying baker,, cross 8 mesh sieve granulations, air-dry 8 hours 120 ℃ of oven dry 6 hours.Compression molding on tablet press machine, specification 16 * 15mm (four holes, endoporus Φ 4.0mm).When first pressing intensity is 30N/, carried out steam curing 36 hours, carrier was 1150 ℃ of activation 6 hours.Obtain the S1 carrier.
With a certain amount of La (NO
3)
2, deionized water is mixed with the solution that concentration is 0.4mol/l.Carrier after the activation is put into the step maceration extract, carry out incipient impregnation.Catalyst was 100 ℃ of oven dry 10 hours.The oven dry rear catalyst, 900 ℃ of roastings 2 hours, cooling.Get Ni (NO
3)
26H
2O, deionized water and 45g SP-80 are mixed with concentration and become to contain Ni (NO
3)
21.0mol/l solution.The catalyst of preparation is put into above-mentioned solution, carries out incipient impregnation.Sample was 100 ℃ of oven dry 10 hours.Then 550 ℃ of roastings 8 hours.Carry out incipient impregnation again, sample was 130 ℃ of oven dry 6 hours.550 ℃ of roastings 6 hours, obtain C1 catalyst of the present invention then.
Embodiment 2
Get the 380g Alpha-alumina, again to wherein adding 420g pure calcium aluminate cement, 30gZrO in order successively
2, 2g kapok and 25g graphite, the composition mixture material.Add deionized water 270g, stir, with briquetting press precompressed 5 times, balling ratio reaches 80%.Put into drying baker,, cross 8 mesh sieve granulations, air-dry 10 hours 150 ℃ of oven dry 6 hours.Compression molding on tablet press machine, specification 16 * 15mm (four holes, endoporus Φ 4.0mm).When first pressing intensity is 50N/, carried out steam curing 24 hours, carrier was 1100 ℃ of activation 8 hours.Obtain the S2 carrier.
With a certain amount of La (NO
3)
2, deionized water is mixed with the solution that concentration is 0.2mol/l.Carrier after the activation is put into the step maceration extract, carry out incipient impregnation.Catalyst was 130 ℃ of oven dry 1 hour.The oven dry rear catalyst, 800 ℃ of roastings 6 hours, cooling.Get 420gNi (NO
3)
26H
2O, deionized water and 24g NPE (15) are mixed with the solution of 1L.The catalyst of preparation is put into above-mentioned solution, carries out incipient impregnation.Sample was 130 ℃ of oven dry 1 hour.Then 400 ℃ of roastings 8 hours.Carry out incipient impregnation again, sample was 130 ℃ of oven dry 3 hours.590 ℃ of roastings 3 hours, obtain C2 catalyst of the present invention then.Fig. 1 and Fig. 2 are the scanning electron microscope diagrams of C2 catalyst, demonstrate bar-shaped reactive metal and duct, and bar-shaped metallic is diameter 60-100nm, and length is 300-800nm, the about 600-800nm in catalyst duct.
Comparative Examples 1
Adopt Alpha-alumina pottery powder, on ball mill, grind.Be milled to more than 90% through 220 orders, with 100 parts of weights meet granularity requirements Alpha-alumina, add the aluminum nitrate of 2 parts of weights, 5 parts of heavy lignocellulosics and 3 parts of carbon blacks grind.Mix, and adding 13ml water reaches the inferior ring forming of suitable humidity.1200 ℃ of roastings, 2 hours, 1420 ℃, 4 hours.
At Al, Ba is in the La mixed liquor with 40 gram carrier impregnation.Maceration extract is by the Al (NO of 4N
3)
3, 7.7ml, the La (NO of 3N
3), 12ml at room temperature flooded 10 hours.Through three dippings, 110 ℃ dry 1.5-2 hour, 700 ℃ of roastings 2.5 hours obtain the comparative example catalyst.
The character of table 1 embodiment of the invention carrier
| Sample | S1 | S2 | Z1 |
| Specific surface/m 2.g -1 | 52.3 | 55.1 | 53.4 |
| Average pore diameter/nm | 3.4 | 3.5 | 3.4 |
| Side pressure strength, N/ | 480 | 440 | 432 |
| Water absorption rate, % | 24 | 25 | 21 |
Table 2 catalyst physical property
Table 3 catalyst activity and conversion ratio
Coke content on table 4 evaluate catalysts
| The sample position | 1 | 2 | 3 | 4 |
| C1，％ | 1.25 | 1.42 | 0.37 | 0.14 |
| C2，％ | 1.37 | 1.44 | 0.21 | 0.15 |
| W1，％ | 3.47 | 5.19 | 1.76 | 0.47 |
Claims (10)
1. the preparation method of a hydrocarbon conversion catalyst for preparing hydrogen is characterized in that following steps:
(a) with La (NO
3)
2Add in the deionized water, be mixed with the solution that concentration is 0.2～0.4mol/l;
(b) alumina-based supports is put into step (a) maceration extract, carry out incipient impregnation;
(c) behind step (b) dipping, 100-130 ℃ of oven dry 1-10 hour;
(d) step (c) oven dry rear catalyst at 800-900 ℃ of roasting 2-6 hour, is reduced to room temperature;
(e) get Ni (NO
3)
2, deionized water and surfactant, be mixed with Ni (NO
3)
2Concentration is the solution of 1.0～5.0mol/l, free acid 0-0.01mol/l, surfactant and Ni (NO
3)
2The ratio of weight be 0.01-0.3: 1;
(f) catalyst of step (d) preparation is put into step (e) solution, carry out incipient impregnation;
(g) step (f) sample is 100-130 ℃ of oven dry 1-10 hour, then at 400-600 ℃ of roasting 3-8 hour;
(h) step (g) is put into step (e) solution again, carries out incipient impregnation again, then 100-130 ℃ of oven dry 1-10 hour, again at 400-600 ℃ of roasting 3-8 hour, gets product.
2. according to the preparation method of right 1 described hydrocarbon conversion catalyst for preparing hydrogen, it is characterized in that described La (NO
3)
2Be that the nitric acid billows are industrial nitric acid billows, LaO content accounts for the 1-5% of material gross weight.
3. according to the preparation method of right 1 described hydrocarbon conversion catalyst for preparing hydrogen, it is characterized in that described Ni (NO
3)
2Six industrial water nickel nitrates, NiO content accounts for the 14-20% of material gross weight.
4. according to the preparation method of right 1 described hydrocarbon conversion catalyst for preparing hydrogen; It is characterized in that described surfactant is lecithin, phosphoric acid fat, AEO, aliphatic acid polyethenoxy ether, APES, aliphatic amine polyoxyethylene ether, polyethylene glycol, tall oil acid amides, dodecyl alcohol acyl phosphatide, SP-40, SP-60, SP-65, SP-80, SP-85, M-201, fatty acid monoglyceride and two sweet esters, ethylene glycol monostearate, diglycol monostearate or propyleneglycoles list dodecyl ester, and surfactant and Ni (NO
3)
2The ratio of weight be 0.01-0.3: 1.
5. the preparation method of hydrocarbon conversion catalyst for preparing hydrogen according to claim 1 is characterized in that described alumina-based supports is made by following steps:
(1) gets high temperature alumina, to wherein adding pure calcium aluminate cement, modified additive ZrO in order successively
2, kapok and graphite, the composition mixture material;
(2) in material, add entry, water accounts for 15～25% of material gross mass, mixes thoroughly, all over balling ratio 80-95%, through drying baker 100-150 ℃ of oven dry 3-6 hour, crosses 8 mesh sieve granulations, air-dry 2-10 hour through briquetting press precompressed 4-5;
(3) compression molding on tablet press machine, specification 16 * 15mm;
(4) carrying out first pressing, first pressing intensity is 30～50N/;
(5) with steam curing 24-72 hour;
(6) alumina-based supports was at 1100-1200 ℃ of activation 2-8 hour.
6. according to the preparation method of right 5 described hydrocarbon conversion catalyst for preparing hydrogen, it is characterized in that described high temperature alumina is an Alpha-alumina, Alpha-alumina accounts for 25～40% of alumina-based supports gross weight.
7. according to the preparation method of right 5 described hydrocarbon conversion catalyst for preparing hydrogen, it is characterized in that described modified additive ZrO
2Account for 0.1～5% of alumina-based supports gross weight.
8. according to the preparation method of right 5 described hydrocarbon conversion catalyst for preparing hydrogen, it is characterized in that described binding agent pure calcium aluminate cement, account for 35～55% of alumina-based supports gross weight.
9. according to the preparation method of right 5 described hydrocarbon conversion catalyst for preparing hydrogen, it is characterized in that described graphite accounts for 1～10% of alumina-based supports gross weight.
10. according to the preparation method of right 5 described hydrocarbon conversion catalyst for preparing hydrogen, the fibre diameter that it is characterized in that described kapok is 5-30 μ m, and length is 20-100 μ m, accounts for 0.1～5% of alumina-based supports gross weight.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268836A (en) * | 2016-07-14 | 2017-01-04 | 安徽海德石油化工有限公司 | A kind of petroleum hydrocarbon hydrogen manufacturing pre-converting catalyst with superior low temperature reproducibility |
| CN106892649A (en) * | 2015-12-21 | 2017-06-27 | 中国石油天然气股份有限公司 | Preparation method of spherical alumina |
| CN110385133A (en) * | 2019-07-22 | 2019-10-29 | 四川蜀泰化工科技有限公司 | A kind of pre-converting catalyst and preparation method thereof |
| CN111097546A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst carrier, catalyst and preparation method thereof |
| CN111097447A (en) * | 2018-10-29 | 2020-05-05 | 中国石油天然气股份有限公司 | Catalyst for low-temperature catalytic cracking of methane to produce hydrogen, preparation method thereof and low-temperature catalytic cracking method for methane to produce hydrogen |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042696A (en) * | 1989-10-28 | 1990-06-06 | 齐鲁石油化工公司研究院 | Hydrocarbon steam conversion catalyst and application |
| CN101306368A (en) * | 2008-07-09 | 2008-11-19 | 山西大学 | Preparation method of butanediol secondary hydrogenation catalyst by butynediol two-step hydrogenation |
-
2011
- 2011-06-20 CN CN201110165485.6A patent/CN102836721B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042696A (en) * | 1989-10-28 | 1990-06-06 | 齐鲁石油化工公司研究院 | Hydrocarbon steam conversion catalyst and application |
| CN101306368A (en) * | 2008-07-09 | 2008-11-19 | 山西大学 | Preparation method of butanediol secondary hydrogenation catalyst by butynediol two-step hydrogenation |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892649A (en) * | 2015-12-21 | 2017-06-27 | 中国石油天然气股份有限公司 | Preparation method of spherical alumina |
| CN106892649B (en) * | 2015-12-21 | 2020-06-09 | 中国石油天然气股份有限公司 | Preparation method of spherical alumina |
| CN106268836A (en) * | 2016-07-14 | 2017-01-04 | 安徽海德石油化工有限公司 | A kind of petroleum hydrocarbon hydrogen manufacturing pre-converting catalyst with superior low temperature reproducibility |
| CN111097546A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst carrier, catalyst and preparation method thereof |
| CN111097447A (en) * | 2018-10-29 | 2020-05-05 | 中国石油天然气股份有限公司 | Catalyst for low-temperature catalytic cracking of methane to produce hydrogen, preparation method thereof and low-temperature catalytic cracking method for methane to produce hydrogen |
| CN110385133A (en) * | 2019-07-22 | 2019-10-29 | 四川蜀泰化工科技有限公司 | A kind of pre-converting catalyst and preparation method thereof |
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