CN1087657C - Process for preparing catalyst for producing synthetic gas from hydrocarbons - Google Patents
Process for preparing catalyst for producing synthetic gas from hydrocarbons Download PDFInfo
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- CN1087657C CN1087657C CN96117858A CN96117858A CN1087657C CN 1087657 C CN1087657 C CN 1087657C CN 96117858 A CN96117858 A CN 96117858A CN 96117858 A CN96117858 A CN 96117858A CN 1087657 C CN1087657 C CN 1087657C
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- catalyst
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- mgo
- synthetic gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000002994 raw material Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910020068 MgAl Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- -1 rare earth salt Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 16
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 abstract 1
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052594 sapphire Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000000629 steam reforming Methods 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003091 Methocel™ Polymers 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910002642 NiO-MgO Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- WDNQRCVBPNOTNV-UHFFFAOYSA-N dinonylnaphthylsulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 WDNQRCVBPNOTNV-UHFFFAOYSA-N 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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 present invention relates to a method for preparing a catalyst for producing synthetic gas from hydrocarbons. Which is characterized in that alpha-Al2O3, MgO and CaCO3 (or RE2O3 and heavy rare-earth oxides) are used as raw materials, and the raw materials are mixed, shaped and calcined to obtain a carrier; then, the carrier is immersed and roasted, and the catalyst is prepared. The catalyst prepared by the present invention is particularly suitable for the reaction process for preparing synthetic gas or reducing gas by high-temperature conversion under the conditions of low water-carbon ratio and low oxygen-carbon ratio, and the catalyst has the advantages of good high-temperature oxidation resistance, good carbon deposit resistance, high conversion activity, high strength and long service life.
Description
The invention belongs to the synthesis gas preparation field, particularly about the preparation of catalyst for producing synthetic gas from hydrocarbons.
Take the method for hydro carbons as the raw material preparing synthetic gas, mainly contain two kinds, i.e. steam reforming and partial oxidation process.Steam reforming be with light hydrocarbons such as natural gases with after heating steam mixes, on the Ni catalyst, be converted into synthesis gas, conversion reaction is generally carried out under 650 ℃～900 ℃.Partial oxidation process is with lighter hydrocarbons and oxidant (air, O such as natural gases
2Deng) in a reacting furnace, carry out partial oxidation and catalytic conversion reaction, still adopting Ni is main active constituent, reaction temperature is generally carried out under 1000 ℃～1200 ℃.
Existing catalyst is greatly mainly with α-Al
2O
3Be the Ni catalyst of carrier, transform under the high temperature (as steam reforming one, secondary reformer) adopt chromium (Cr) ball of corundum to make protective agent.The problem of the on-stream appearance of catalyst is: 1. coking fragmentation, and cause bed resistance to increase and stop, it is reported to account for more than 70%; 2. under high-temperature oxydation atmosphere, alumina support and NiO effect generate the nickel aluminate (NiAl of non-activity
2O
4).
With MgAl
2O
4NiO/MgAl for carrier
2O
4Steam reforming catalysts be the sixties by Denmark Tops Φ e Developed, name and be RKS type catalyst.Document is thought: NiO/MgAl
2O
4Type catalyst RKS-1 can be successfully used to side burning type primary reformer, secondary reformer and high temperature self-heating stove, but its low temperature active is poor, and easily hydration can not be used for the Kellogg primary reformer, thereby domestic application is few.
In order to address the above problem, Chinese scholars has been carried out a large amount of research.Made Ni/Al such as Cao Lixin (Journal of Molecular Catalysis, 1994,8 (5), 375), Xu Hengyong (petrochemical industry, 1992,21 (3), 147～153) etc.
2O
3The research of type catalyst, Qin Yongning (Journal of Chemical Industry and Engineering, 1990,41 (4), 436～443) etc. in the Ni catalyst, add the light rare earth oxides such as La, Le, Li Ming (chemistry of fuel journal, 1982,10 (3), 203～212) etc. made Ni/CaO-MgO-A1
2O
3The research of type catalyst, CN85102194.8 has also studied at Ni/Al
2O
3-Al (OH)
3Add heavy rare-earth oxide (RE in the type catalyst
2O
3) effect.The catalyst of foreign study has (GB2,274,234) of adopting platinum group, contains Ti (JP93,245,374), or contains (JP93,168,924 of Zr; JP93,261,286; WO94,24,042) etc.
The object of the present invention is to provide a kind of preparation method, the catalyst of preparation is specially adapted under low steam carbon ratio, low carbon ratio condition, the course of reaction of pyrolytic conversion preparing synthetic gas or reducing gases, performance with good resistance to high temperature oxidation and anti-carbon deposit, the activity of conversion height, the intensity height, the life-span is long.
The object of the present invention is achieved like this:
With α-Al
2O
3, MgO, RE
2O
3(heavy rare-earth oxide) is raw material, and its proportioning (mol ratio) is: α-Al
2O
3: MgO: RE
2O
3=0.95～1.84: 0.98: 0.02, through mixing, moulding, 1300 ℃～1600 ℃ lower calcinings, get MgO-RE
2O
3-Al
2O
3Type carrier [A] soaks carrier A and drills in 35% to 100% the nickel salt solution, is filtered dry again, and getting ni content 450 ℃～650 ℃ roastings is 3%～8% NiO/A catalyst, or with α-Al
2O
3, MgO, CaCO
3Be raw material, add expanding agent and lubricant, its proportioning (mol ratio) is: α-Al
2O
3: MgO: CaCO
3=1.05～2.65: 0.835: 0.165, expanding agent and lubricant were 3%～5% of raw material proportioning weight, through mixing, moulding, 1350 ℃～1550 ℃ lower calcinings, got CaO-MgO-Al
2O
3Type carrier [B], it is in 10%～55% the heavy rare earth nitrate solution that carrier B be impregnated in earlier concentration, through being filtered dry, gets RE 450 ℃～650 ℃ roastings
2O
3Behind/B the modified support, again with RE
2O
3It is that through being filtered dry, getting nickel content 450 ℃～650 ℃ roastings is 6%12%, contains RE in 35% to 100% the nickel salt solution that/B modified support impregnated in concentration
2O
3Amount is 0.5%～5% NiO-RE
2O
3/ B catalyst.
Wherein, nickel salt is Ni (NO
3)
2, NiCO
3Or Ni (OOCCH
3)
2Expanding agent is one or more in carbonate, nitrate, graphite, cellulose family, starch or the macromolecular compound; Lubricant is that stearate is or/and paraffin; Heavy rare earth salt is that (main component is Y to commercially available Rare Earth Mine
2O
3) nitrate.
The moulding of A type carrier can be used equal pressing forming technology, makes spherical or porous spherical; The moulding of Type B carrier can be made industrial Raschig ring or porous spherical with pressure ring or mould injection forming technology.
The phase of A type carrier forms with MgAl
2O
4Be main, its content should greater than 50%, contain a small amount of Al
5Y
3O
12And α-Al
2O
3The phase of Type B carrier forms with MgAl
2O
4Be main, its content should greater than 50%, contain a small amount of CaAl
4O
7α-Al with trace
2O
3
NiO/A type catalyst can be directly used in the top of partial oxidation furnace and make protective agent; Under 600 ℃～800 ℃ in H
2After being reduced into Ni/A type catalyst in the atmosphere, can be used for the top of steam-reforming primary reformer and the top of secondary reformer.NiO-RE
2O
3/ Type B catalyst can be directly used in the bottom of steam-reforming primary reformer bottom, secondary reformer and partial oxidation furnace.
Difference with the prior art of the present invention is:
1. add CaCO
3With Al
2O
3Effect generates the Ca-Al spinel structure, can improve intensity; Add RE
2O
3Can improve anti-charcoal performance.
2. the employing equal pressing forming technology improves the intensity of carrier, and pore volume increases.
3. carrier floods earlier the order of soaking nickel behind the heavy rare earth, is conducive to improve the decentralization of nickel, thereby improves active and anti-charcoal performance.
4. catalyst is made porous spherical, and it is long-pending to increase geometric outer surface, reaches the purpose that improves activity of conversion.
The present invention adopts the mobile gradientless reactor of thermosyphon circulation to measure low temperature (550 ℃～750 ℃) the steam-reforming activity of the catalyst of industrial granularity, with reaction rate γ
s(γ
s=CH
4Conversion molal quantity/cm
3.Cat.h) or γ
g(γ
g=CH
4Conversion molal quantity/represent that g.Cat.h) condition determination is: p=3.0MPa, CH
4Flow velocity: 50～100N1 (mark rises)/h, H
2O/CH
4=2.0～3.0 (moles).Measure the activity of high temperature (800 ℃～1100 ℃) catalytic partial oxidation reaction of catalyst with continuous-flow tubular fixed-bed reactor (Φ 18 * 2, the Ni25Cr20 steel pipe), with methane conversion
With the CO selectivity
Represent that condition determination is: p=0.5MPa, GHSV (gas hourly space velocity)=2 * 10
3h
-1, CH
4: O
2: H
2O=1: 0.45: 0.8, Vcat=40ml, granularity: Φ=5～6mm.
The contrast of the catalyst that the present invention is prepared and RKS type activity of such catalysts sees Table 1 and table 2.
The activity contrast of table 1 NiO/A type and RKS-1 type
| Catalyst | Reaction temperature (℃) | Methane conversion (%) | Reaction rate | |
| γ s | γ g | |||
| NiO/A (3 hole sphere) | 600 | 9.81 | 0.0240 | 0.0714 |
| RKS-1 (drawing the low ring in west) | 600 | 8.72 | 0.0218 | 0.0570 |
Table 2 NiO-RE
2O
3The activity contrast of/Type B and RKS-2 type
| Catalyst | Reaction temperature (℃) | Methane conversion (%) | Selectively (%) | The coking situation of catalyst | |
| CO | CO 2 | ||||
| NiO-RE 2O 3/ B (7 hole sphere) | 875 | 98.5 | 83.8 | 16.2 | Do not have |
| RKS-2 (drawing western epipodium) | 875 | 96.4 | 78.3 | 21.7 | Little |
NiO/A type, NiO-RE that the present invention is prepared
2O
3/ Type B reforming catalyst matches, and is used for take natural gas with water vapour and oxygen are finished the course of reaction of partial oxidation burning and catalyzed conversion preparing synthetic gas as raw material in Self-heat Reformer on a small quantity.At daily output 300～500m
3Turned round 200 hours continuously on the synthesis gas expanding test device, methane conversion reaches 97～98%, and synthesis gas consists of: H
2/ CO (V/V)=2.7～2.9 is applicable to the production of synthesizing methanol.At O
2/ CH
4Turned round 6 months continuously in=0.55 (mole), 950 ℃～1050 ℃ heat absorption type reaction tube, its product gas consists of (V%): H
242.05; CO19.64; N
237.82; CH
40.12; CO
20.37; The aerogenesis quality is applicable to controlled atmosphere heat treatment protection gas technological requirement fully.
Above result shows that the prepared catalyst of the present invention has good high temperature resistance and anti-carbon deposit performance, the activity of conversion height, and the life-span is long, is easy to push to industrial applications.
Below be embodiments of the invention.
Embodiment one
Take by weighing 32.65 grammes per square metre matter MgO, 15.99 gram CaCO
3, 152.87 gram α-Al
2O
3, after in porcelain dish, mixing, add again concentration and be 1.3% methocel solution 22ml, calcium stearate 7.55 grams, carbon dust 0.9 gram mixes moulding (Raschig ring, pressure＞300Kg/cm
3), 1500 ℃ ± 10 ℃ lower calcinings 5 hours, get CaO-MgO-Al again
2O
3Type [B] carrier.Measure MgAl
2O
4Content is 71.9%, and side pressure strength is 24.7Kg/cm.
Embodiment two
Take by weighing 32.65 grammes per square metre matter MgO, 15.99 gram CaCO
3, 214.08 gram α-Al
2O
3, concentration is 1.3% methocel solution 23ml, calcium stearate 9.85 grams, and carbon dust 1.0 grams, calcining heat is 1350 ℃, other gets the Type B carrier with embodiment one.Measure MgAl
2O
4Content is 51.3%, and side pressure strength is 19.2Kg/cm.
Embodiment three
Take by weighing 32.65 grammes per square metre matter MgO, 15.99 gram CaCO
3, 133.76 gram α-Al
2O
3, concentration is 1.3% methocel solution 20ml, calcium stearate 6.84 grams, and carbon dust 0.8 gram, calcining heat is 1590 ℃ ± 10 ℃, other gets the Type B carrier with embodiment one.Measure MgAl
2O
4Content is 84.0%, and its side pressure strength is 26.8Kg/cm.
Embodiment four
Get the one made Type B carrier 30 as one kind gram by embodiment, the concentration of drawing certain volume is 46% Ni (NO
3)
2Solution (being advisable with the submergence carrier), be not more than under 70 ℃～95 ℃ the temperature dipping 0.5 hour, be filtered dry, in air atmosphere, 500 ℃ of lower roastings 0.5 hour get NiO/B, and repeated impregnations, roasting be once under similarity condition then, get the NiO-NiO/B catalyst, ni content is respectively 8.7% (for the first time) and 5.1% (for the second time).
Embodiment five
Press embodiment four preparation NiO/B type, wherein Ni (NO
3)
2Concentration is 93%, gets ni content and be 12.7% NiO/B, is 35% RE again with concentration
2(NO
3)
3Solution impregnation, dipping, roasting condition must contain RE with embodiment four
2O
3Amount is 2.3% RE
2O
3-NiO/B type catalyst.
Embodiment six
Getting the one made Type B carrier 30 as one kind gram by embodiment, is 35% RE (NO with concentration
3)
3Solution impregnation, be filtered dry, roasting, get RE
2O
3/ B is 80% Ni (NO again with concentration
3)
2Solution impregnation, be filtered dry, roasting.Immersion condition is with embodiment four, and 600 ℃ of sintering temperatures 0.5 hour, must contain RE
2O
3Be 2.9%, contain Ni and be 11.0% NiO-RE
2O
3/ Type B catalyst.
Embodiment four, embodiment five and embodiment six prepared catalyst activity and selectivity contrasts see Table 3.
The contrast of table 3 catalyst activity and selectivity
| Catalyst | Methane conversion | CO is selective | ||
| 800 ℃ | 900 ℃ | 800 ℃ | 900 ℃ | |
| NiO-NiO/B (5.1 ℃ of %～8.7%) | 75.0 | 91.6 | 73.5 | 81.7 |
| RE 2O 3-NiO/B (2.3%12.7%) | 77.0 | 92.4 | 74.6 | 85.7 |
| NiO-RE 2O 3/ B (11.0 ℃ of %～2.9%) | 84.1 | 93.0 | 81.9 | 87.9 |
Embodiment seven
Press embodiment six operations, just the Type B carrier is used respectively KNO
3, Mg (NO
3)
2, RE
2(NO
3)
3Solution impregnation makes K
2O/B, MgO/B, RE
2O
3Behind/B the modified support, use respectively again Ni (NO
3)
2Solution impregnation makes NiO-K
2O/B, NiO-MgO/B, NiO-RE
2O
3Three kinds of catalyst of/B, its activity and coke content thereof are as shown in table 4.
Table 4 normal heptane Steam Reforming activity and coke content
| Catalyst | 500 ℃ of lower reacting gas form (dry gas, V%) | Selectively (%) | Coke content | ||
| CO | CO 2 | CH 4 | CO/ (CO+CO 2) | (%, wt) | |
| NiO-K 2O/B | 2.40 | 14.19 | 0.35 | 14.47 | 0.62 |
| NiO-MgO/B | 2.81 | 17.35 | 1.75 | 13.94 | 1.56 |
| NiO-RE 2O 3/ B | 5.05 | 16.87 | 0.55 | 23.04 | 0.20 |
Take by weighing α-Al
2O
3106.28 gram, MgO36.54 gram, RE
2O
34.13 gram be spherical by isostatic compaction (3000 tons of hydraulic pressure) behind the mixing, 1570 ℃ ± 10 ℃ lower calcinings 5 hours, gets MgO-RE
2O
3-Al
2O
3Type [A] carrier is 46% Ni (NO again in concentration with the A carrier impregnation
3)
2In the solution, be filtered dry again, roasting, dipping and roasting condition get nickel content and are 3.7% NiO/A type catalyst with embodiment four.
Embodiment nine
Take by weighing α-Al
2O
3106.28 gram, MgO 36.54 grams, RE
2O
34.13 gram, calcining heat is 1370 ℃ ± 10 ℃, Ni (NO
3)
2Concentration is 80%, and all the other are with embodiment eight, gets nickel content and be 8.3% NiO/A catalyst.
Embodiment ten
Press embodiment six operations, just RE (NO
3)
3Concentration be 15%, Ni (NO
3)
2Concentration be 55%, must contain RE
2O
3Be 0.5%, contain Ni and be 6.3% NiO-RE
2O
3/ Type B catalyst.
Embodiment 11
Press embodiment six operations, just RE (NO
3)
3Concentration be 55%, melting Ni (NO
3)
2Solution, 600 ℃ of sintering temperatures must contain RE
2O
3Be 4.3%, contain Ni and be 11.9% NiO-RE
2O
3/ Type B catalyst.
Claims (4)
1. the preparation method of a catalyst for producing synthetic gas from hydrocarbons is characterized in that with α-Al
2O
3, MgO, RE
2O
3(heavy rare-earth oxide) is raw material, and its proportioning is α-Al
2O
3: MgO: RE
2O
3=0.95～1.84: 0.98: 0.02 (mol ratio) through mixing, moulding, 1300 ℃～1600 ℃ lower calcinings, gets MgO-RE
2O
3-Al
2O
3Type carrier [A] impregnated in carrier A concentration again and is in 35% to 100% the nickel salt solution, through being filtered dry, 450 ℃～650 ℃ lower roastings, gets nickel content and be 3%～8% NiO/A type catalyst; Or with α-Al
2O
3, MgO, CaCO
3Be raw material, add expanding agent and lubricant, its proportioning is α-Al
2O
3: MgO: CaCO
3=1.05～2.65: 0.835: 0.165 (mol ratio), expanding agent and lubricant are 3%～5% of raw material proportioning weight, through mixing, moulding, 1350 ℃～1550 ℃ lower calcinings, get MgO-CaO-Al
2O
3Type carrier [B], it is in 10%～55% the heavy rare earth salting liquid that carrier B be impregnated in earlier concentration, through being filtered dry, in 450 ℃～650 ℃ lower roastings, gets RE
2O
3Behind/B the modified support, again with RE
2O
3It is that through being filtered dry, getting nickel content in 450 ℃～650 ℃ lower roastings is 6%～12%, contains RE in 35% to 100% the nickel salt solution that/B modified support impregnated in concentration
2O
3Amount is 0.5%～5% NiO-RE
2O
3/ Type B catalyst.
2. the preparation method of catalyst for producing synthetic gas from hydrocarbons according to claim 1, it is characterized in that: nickel salt is Ni (NO
3)
2, Ni (CO)
3Or Ni (OOCCH
3)
2Expanding agent is one or more in carbonate, nitrate, graphite, cellulose family, starch or the macromolecular compound; Lubricant is that stearate is or/and paraffin; Heavy rare earth salt is that commercially available main component is Y
2O
3Nitrate.
3. the preparation method of catalyst for producing synthetic gas from hydrocarbons according to claim 1 and 2, it is characterized in that: the moulding of A type carrier can be used equal pressing forming technology, makes spherical or porous spherical; The moulding of Type B carrier can be made industrial Raschig ring or porous spherical with pressure ring or mould injection forming technology.
4. the preparation method of catalyst for producing synthetic gas from hydrocarbons according to claim 1 is characterized in that: the phase of A type carrier forms with MgAl
2O
4Be main, its content should greater than 50%, contain a small amount of Al
5Y
3O
12And α-Al
2O
3The phase of Type B carrier forms with MgAl
2O
4Be main, its content should greater than 50%, contain a small amount of CaAl
4O
7α-Al with trace
2O
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117858A CN1087657C (en) | 1996-12-30 | 1996-12-30 | Process for preparing catalyst for producing synthetic gas from hydrocarbons |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117858A CN1087657C (en) | 1996-12-30 | 1996-12-30 | Process for preparing catalyst for producing synthetic gas from hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1156641A CN1156641A (en) | 1997-08-13 |
| CN1087657C true CN1087657C (en) | 2002-07-17 |
Family
ID=5124674
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96117858A Expired - Fee Related CN1087657C (en) | 1996-12-30 | 1996-12-30 | Process for preparing catalyst for producing synthetic gas from hydrocarbons |
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| Country | Link |
|---|---|
| CN (1) | CN1087657C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093433C (en) * | 1999-02-10 | 2002-10-30 | 石油大学(北京) | Catalyst for self-heating oxidation and reforming of natural gas to produce synthetic gas and its preparation process |
| US8877673B2 (en) | 2010-11-12 | 2014-11-04 | Air Products And Chemicals, Inc. | Supported catalyst and use thereof for reforming of steam and hydrocarbons |
| CN104258867B (en) * | 2014-08-22 | 2016-06-29 | 江西庞泰环保股份有限公司 | Natural gas steam reforming catalyst and preparation method thereof |
| CN109718770B (en) * | 2017-10-31 | 2022-04-12 | 中国石油化工股份有限公司 | Catalyst carrier and supported catalyst, preparation method and application thereof, and method for combined reforming of methane |
| CN119701965B (en) * | 2023-09-27 | 2025-10-03 | 中国石油化工股份有限公司 | Hydrocarbon steam conversion catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090254A (en) * | 1992-12-21 | 1994-08-03 | 阿莫科公司 | Preparation of Syngas Using Nickel as Catalyst |
| CN1110248A (en) * | 1994-04-05 | 1995-10-18 | 中国科学院兰州化学物理研究所 | Catalyst for converting methane into synthetic gas and its process |
| CN1120469A (en) * | 1995-06-15 | 1996-04-17 | 华南理工大学 | Catalyst for producing synthetic gas by methane selectively oxidizing |
| CN1130150A (en) * | 1995-02-28 | 1996-09-04 | 中国科学院大连化学物理研究所 | Producing synthetic gas reaction by methane partial oxidation and its catalyst |
| CN1131638A (en) * | 1995-03-23 | 1996-09-25 | 中国科学院成都有机化学研究所 | Catalyst for preparing synthetic gas by natural gas partial oxidation and its preparation method |
-
1996
- 1996-12-30 CN CN96117858A patent/CN1087657C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090254A (en) * | 1992-12-21 | 1994-08-03 | 阿莫科公司 | Preparation of Syngas Using Nickel as Catalyst |
| CN1110248A (en) * | 1994-04-05 | 1995-10-18 | 中国科学院兰州化学物理研究所 | Catalyst for converting methane into synthetic gas and its process |
| CN1130150A (en) * | 1995-02-28 | 1996-09-04 | 中国科学院大连化学物理研究所 | Producing synthetic gas reaction by methane partial oxidation and its catalyst |
| CN1131638A (en) * | 1995-03-23 | 1996-09-25 | 中国科学院成都有机化学研究所 | Catalyst for preparing synthetic gas by natural gas partial oxidation and its preparation method |
| CN1120469A (en) * | 1995-06-15 | 1996-04-17 | 华南理工大学 | Catalyst for producing synthetic gas by methane selectively oxidizing |
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| Publication number | Publication date |
|---|---|
| CN1156641A (en) | 1997-08-13 |
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