CN100463716C - A low-grade alkalization hydrocarbons water vapour conversion catalyst and its preparing method - Google Patents
A low-grade alkalization hydrocarbons water vapour conversion catalyst and its preparing method Download PDFInfo
- Publication number
- CN100463716C CN100463716C CNB2007100504874A CN200710050487A CN100463716C CN 100463716 C CN100463716 C CN 100463716C CN B2007100504874 A CNB2007100504874 A CN B2007100504874A CN 200710050487 A CN200710050487 A CN 200710050487A CN 100463716 C CN100463716 C CN 100463716C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hours
- carrier
- water vapour
- cao
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 32
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 42
- 238000006243 chemical reaction Methods 0.000 title claims description 32
- 238000000034 method Methods 0.000 title description 11
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 27
- 229910052700 potassium Inorganic materials 0.000 claims description 18
- 239000011591 potassium Substances 0.000 claims description 18
- -1 potassium aluminates Chemical class 0.000 claims description 18
- 239000004568 cement Substances 0.000 claims description 16
- 239000011265 semifinished product Substances 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 238000000354 decomposition reaction Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000000629 steam reforming Methods 0.000 abstract description 3
- 230000003113 alkalizing effect Effects 0.000 abstract 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses mild alkalizing hydrocarbon steam reforming catalyst, which is high-temperature sintered type multi-component heterogeneous catalyst taking nickel oxide (NiO) as an active component and taking CaO-Al2O3-K2O composite oxide as a carrier. The catalyst has good transformation and catalytic activity, simultaneously also has good carbon-deposition resistant performance. The invention also discloses a preparation method for the mild alkalizing hydrocarbon steam reforming catalyst.
Description
Technical field
The invention belongs to chemical technology field, particularly a kind of low-grade alkalization hydrocarbons water vapour reforming hydrogen manufacturing, synthetic ammonia, methyl methanol syngas, town gas Catalysts and its preparation method.
Background technology
Continuous mutually exploitation of thirties company of Centrica, West Germany LURGI is that raw material, water vapour transform the technology of making synthesis gas, town gas and plant hydrogen with the naphtha.This process roughly be higher hydrocarbons and water vapour in the presence of Raney nickel, under 400～500 ℃, the condition of pressure 3.0～4.0MPa, be converted into and be rich in methane gas, through one section steam-reforming methane or the gas that contains a small amount of high-carbon hydrocarbon are converted into again and contain CO and H
2Gas, then according to different requirements, further be processed into hydrogen, synthetic ammonia, methyl methanol syngas again or directly use as town gas.This course of reaction is very complicated, and it is a multiple parallel reaction and the simultaneous complex reaction system of cascade reaction, thermal cracking, catalytic pyrolysis, dehydrogenation, polymerization, knot carbon, the water vapour that the comprises higher hydrocarbon reactions such as carbon, water vapour conversion, methanation that disappear.The catalyst that comparatively is widely used at present this technology in the world mainly is 65-2, the 25-4/57-4 catalyst of G1-80, G90B catalyst and the Britain ICI company of German BASF AG, domestic still not with it corresponding product in industrial production, use.
Generally speaking, in hydrocarbon steam conversion catalyst, introduce K
2Alkali metal such as O can suitably improve the carbon resistance performance of catalyst, but because catalyst is under the high-temperature water vapor partial pressure conditions, compounds such as sylvite can decompose free alkali, so not only can be deposited in the corrosion that the back operation causes equipment, and free alkali can cover the activated centre at catalyst surface, causes catalyst activity reduction.Therefore, the contradiction between fixing and the solution catalyst carbon resistance performance and the activity of need close attention potash in catalyst invention process.
Summary of the invention
The purpose of this invention is to provide a kind of new catalyst that low-grade alkalization hydrocarbons water vapour reforming hydrogen manufacturing, synthetic ammonia, methyl methanol syngas, town gas are used etc. that is used for.This catalyst has good catalytic conversion activity, also possesses good carbon resistance performance simultaneously.
Another object of the present invention provides a kind of preparation method of above-mentioned low-grade alkalization hydrocarbons water vapour conversion catalyst.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of low-grade alkalization hydrocarbons water vapour conversion catalyst, it is to be active constituent, to contain CaO-Al with nickel oxide (NiO)
2O
3-K
2The composite oxides of O are the polynary multiphase catalyst of high temperature sintering type of carrier.
The described CaO-Al that contains
2O
3-K
2The composite oxide carrier of O is to adopt a-Al
2O
3, many potassium aluminates, pure calcium aluminate cement, heavy CaCO
3Deng being primary raw material, mainly contain CaO, Al through what mixing, moulding, calcining made
2O
3, K
2O and an amount of stabilizer T iO
2Porous carrier, also may contain a spot of other impurity such as SiO
2, Fe
2O
3, Na
2O etc.; A-Al wherein
2O
3, many potassium aluminates, pure calcium aluminate cement, heavy CaCO
3Weight portion proportioning Deng raw material is as follows:
A-Al
2O
3: 35～45 parts,
Many potassium aluminates: 20～30 parts,
Pure calcium aluminate cement: 35～45 parts,
Heavy CaCO
3: 10～20 parts.
Described many potassium aluminates are meant with a-Al
2O
3, heavy CaCO
3, TiO
2, K
2CO
3Be primary raw material, through the alkalization component that mixing, calcination etc. make, the weight portion proportioning of its primary raw material is as follows:
A-Al
2O
3: 90～110 parts,
Heavy CaCO
3: 10～20 parts,
TiO
2: 1～5 part,
K
2CO
3: 25～35 parts.
Described pure calcium aluminate cement is meant and mainly contains Al
2O
3Alumina cement with CaO; The Al that generally contains weight percentage about 60%
2O
3, about 40% CaO and trace SiO
2, Fe
2O
3Deng material.
The described CaO-Al that contains
2O
3-K
2Also can comprise 1～10 part of lubricant in the raw material of the composite oxide carrier of O, as graphite, stearate or paraffin etc., this class material can decompose in catalyst preparation process of the present invention to be removed, and contains hardly in the final catalyst finished product.
In the above-mentioned low-grade alkalization hydrocarbons water vapour conversion catalyst, described nickel oxide active constituent and contain CaO-Al
2O
3-K
2In the composite oxide carrier of O, mainly comprise following components in weight portions:
NiO:10～25 part,
CaO:9～18 part,
Al
2O
3: 60～70 parts,
K
2O:1～5 part,
TiO
2: 0.1～2 part.
In addition, also may from pure calcium aluminate cement, bring a spot of SiO into
2, Fe
2O
3, Na
2Components such as O are in the catalyst finished product, and its content in catalyst of the present invention also is trace, as in weight percentage, and SiO
2≤ 0.2%, Fe
2O
3≤ 0.2%, Na
2O≤0.5%.
The above-mentioned low-grade alkalization hydrocarbons water vapour conversion catalyst of the present invention can prepare by the method that comprises following key step:
(1), prepare many potassium aluminates:
Get the a-Al of described proportioning
2O
3, heavy CaCO
3And TiO
2, with three kinds of materials in batch mixer, grind mix 0.5～1 hour stand-by;
Take by weighing the K of described proportioning
2CO
3, add the solution of being dissolved into 20～50g/ml in the deionized water, treat to dissolve fully in the above-mentioned three kinds of materials of back adding and mediate to soft shape;
Material after mediating sent in the pressurization banded extruder make the column that diameter is 100～200mm, cut into the block back oven dry (about 15～30 hours) naturally that length is 20～30mm with cutting equipment, send in the drying equipment, in 100～150 ℃ of dryings 4～8 hours, then (1000～1500) ℃ ± 20 ℃ roasting 2～6 hours (in the actual calcination process, temperature also can be at ± 20 ℃ with interior fluctuation on 1000～1500 ℃ of bases of setting value), be crushed to 200～400 orders again;
(2), preparation contains CaO-Al
2O
3-K
2The composite oxide carrier of O:
Take by weighing the a-Al of described proportioning
2O
3, pure calcium aluminate cement, heavy CaCO
3, many potassium aluminates, lubricant, with above-mentioned material in batch mixer, grind mix 0.5～2 hour after, add percentage by weight by the material total amount and be about 8～15% deionized water, be shaped to catalyst carrier semi-finished product of the present invention;
Above-mentioned carrier semi-finished product are carried out following preliminary treatment successively:
A. carry out air natural curing 6～12 hours at normal temperatures;
B. under 4～8MPa pressure condition, carry out steam curing 2～10 hours;
C. under 120～300 ℃ of temperature conditions dry 8～12 hours;
Then above-mentioned pretreated semi-finished product are sent in the high temperature furnace in (1000～1400) ℃ ± 20 ℃ calcining 2～5 hours (in the actual calcination process, temperature is on 1000～1400 ℃ of bases of setting value, also can be at ± 20 ℃ with interior fluctuation), promptly get the carrier of catalyst of the present invention;
(3), make the catalyst finished product:
Above-mentioned carrier is put into nickel nitrate solution, and continuous impregnating, decomposition twice promptly get catalyst finished product of the present invention; Wherein, the condition of dipping, decomposition is as follows:
Dipping nickel solution concentration: 200～250g/l,
The nickel solution temperature: 80～95 ℃,
Dip time: 10 minutes～1 hour,
Decomposition temperature: 450～600 ℃,
Resolving time: 2 hours～5 hours.
Can be preferably:
Dipping nickel solution concentration: 230g/l,
The nickel solution temperature: 90 ℃,
Dip time: 0.5 hour,
Decomposition temperature: 550 ℃,
Resolving time: 4 hours.
Compared with prior art, the invention has the beneficial effects as follows:
Low-grade alkalization hydrocarbons water vapour conversion catalyst of the present invention has good catalytic conversion activity, also possesses good carbon resistance performance simultaneously.
Description of drawings:
Fig. 1 is the preparation flow schematic diagram of low-grade alkalization hydrocarbons water vapour conversion catalyst of the present invention.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
The present embodiment low-grade alkalization hydrocarbons water vapour conversion catalyst is to be active constituent, CaO-Al with nickel oxide (NiO)
2O
3-K
2The O composite oxides are the polynary multiphase catalyst of high temperature sintering type of carrier, and wherein, the weight portion proportioning of each component is as follows:
| Project | Al 2O 3 | NiO | CaO | SiO 2 | Fe 2O 3 | K 2O | Na 2O | TiO 2 |
| Part ratio | 64 | 18 | 14.5 | 0.1 | 0.1 | 2.5 | 0.3 | 0.5 |
The preparation flow of present embodiment low-grade alkalization hydrocarbons water vapour conversion catalyst as shown in Figure 1, its method mainly comprises the steps:
(1), prepare many potassium aluminates:
Take by weighing greater than 250 purpose a-Al
2O
3Powder 100g, greater than 320 purpose heavy CaCO
315g and greater than 300 purpose TiO
22.5g, with three kinds of materials in batch mixer, grind mix 0.5 hour stand-by;
Take by weighing K
2CO
330g adds in about 100ml deionized water, is dissolved into the solution of 30g/ml, treats to dissolve fully in the above-mentioned three kinds of materials of back adding and mediates to soft shape;
Material after mediating sent in the pressurization banded extruder make the column that diameter is about 150mm, cutting into length with cutting equipment is that the block back of 20～30mm dried 20 hours naturally, send into drying equipment in 120 ℃ of dryings 5 hours, 1000 ℃ ± 20 ℃ roastings are crushed to about 200 orders after 6 hours;
(2), preparation CaO-Al
2O
3-K
2The O composite oxide carrier:
Take by weighing greater than 300 purpose a-Al
2O
3Powder 400g, pure calcium aluminate cement 400g, heavy CaCO
3150g, many potassium aluminates 250g, graphite 56g, with above-mentioned material in batch mixer, grind mix 1 hour after, add percentage by weight by the material total amount and be about 10% deionized water, be shaped to catalyst carrier semi-finished product of the present invention;
Above-mentioned carrier semi-finished product are carried out following preliminary treatment successively:
A. carry out about 12 hours of air natural curing at normal temperatures,
B. under about 8MPa pressure condition, carry out about 10 hours of steam curing,
C. under 120 ℃ of temperature, carried out drying about 12 hours;
It is interior in 1400 ± 20 ℃ of calcinings 4 hours then above-mentioned pretreated carrier semi-finished product to be sent into high temperature furnace, promptly gets the carrier of catalyst of the present invention;
(3), make the catalyst finished product:
Above-mentioned carrier is put into nickel nitrate solution, and continuous impregnating, decomposition twice promptly get catalyst finished product of the present invention; Each dipping, decomposition condition are all as follows:
Dipping: nickel nitrate solution concentration: 250g/l,
The nickel nitrate solution temperature: about 80 ℃,
Dip time: about 0.5 hour;
Decompose: temperature: about 550 ℃,
Time: about 4 hours.
Embodiment 2
The present embodiment low-grade alkalization hydrocarbons water vapour conversion catalyst is to be active constituent, CaO-Al with nickel oxide (NiO)
2O
3-K
2The O composite oxides are the polynary multiphase catalyst of high temperature sintering type of carrier, and wherein, the weight portion proportioning of each component is as follows:
| Project | Al 2O3 | NiO | CaO | SiO 2 | Fe 2O 3 | K 2O | Na 2O | TiO 2 |
| Part ratio | 60 | 25 | 9.0 | 0.2 | 0.1 | 5.0 | 0.5 | 0.1 |
The preparation flow of present embodiment low-grade alkalization hydrocarbons water vapour conversion catalyst as shown in Figure 1, its method mainly comprises the steps:
(1), prepare many potassium aluminates:
Take by weighing a-Al
2O
3Powder 90g, heavy CaCO
310g and TiO
21g, with three kinds of materials in batch mixer, grind mix 1 hour stand-by;
Take by weighing K
2CO
335g adds in about 70ml deionized water, is dissolved into the solution of 50g/ml, treats to dissolve fully in the above-mentioned three kinds of materials of back adding and mediates to soft shape;
Material after mediating sent in the pressurization banded extruder make the column that diameter is about 100mm, cutting into length with cutting equipment is that the block back of 20～30mm dried 15 hours naturally, send into drying equipment in 150 ℃ of dryings 4 hours, 1300 ℃ ± 20 ℃ roastings are crushed to about 300 orders after 4 hours;
(2), preparation CaO-Al
2O
3-K
2The O composite oxide carrier:
Take by weighing a-Al
2O
3Powder 350g, pure calcium aluminate cement 350g, heavy CaCO
3200g, many potassium aluminates 300g, odium stearate 10g, with above-mentioned material in batch mixer, grind mix 0.5 hour after, add percentage by weight by the material total amount and be about 15% deionized water, be shaped to catalyst carrier semi-finished product of the present invention;
Above-mentioned carrier semi-finished product are carried out following preliminary treatment successively:
A. carry out about 8 hours of air natural curing at normal temperatures,
B. under about 4MPa pressure condition, carry out about 6 hours of steam curing,
C. under 300 ℃ of temperature, carried out drying about 8 hours;
It is interior in 1300 ± 20 ℃ of calcinings 2 hours then above-mentioned pretreated carrier semi-finished product to be sent into high temperature furnace, promptly gets the carrier of catalyst of the present invention;
(3), make the catalyst finished product:
Above-mentioned carrier is put into nickel nitrate solution, and continuous impregnating, decomposition twice promptly get catalyst finished product of the present invention; Each dipping, decomposition condition are all as follows:
Dipping: nickel nitrate solution concentration: 230g/l,
The nickel nitrate solution temperature: about 90 ℃,
Dip time: about 1 hour;
Decompose: temperature: about 450 ℃,
Time: about 5 hours.
Embodiment 3
The present embodiment low-grade alkalization hydrocarbons water vapour conversion catalyst is to be active constituent, CaO-Al with nickel oxide (NiO)
2O
3-K
2The O composite oxides are the polynary multiphase catalyst of high temperature sintering type of carrier, and wherein, the weight portion proportioning of each component is as follows:
| Project | Al 2O 3 | NiO | CaO | SiO 2 | Fe 2O 3 | K 2O | Na 2O | TiO 2 |
| Part ratio | 70 | 10 | 18 | 0.1 | 0.2 | 1 | 0.2 | 2 |
The preparation flow of present embodiment low-grade alkalization hydrocarbons water vapour conversion catalyst as shown in Figure 1, its method mainly comprises the steps:
(1), prepare many potassium aluminates:
Take by weighing a-Al
2O
3Powder 110g, heavy CaCO
320g and TiO
24g, with three kinds of materials in batch mixer, grind mix 0.5 hour stand-by;
Take by weighing K
2CO
325g adds in about 125ml deionized water, is dissolved into the solution of 20g/ml, treats to dissolve fully in the above-mentioned three kinds of materials of back adding and mediates to soft shape;
Material after mediating sent in the pressurization banded extruder make the column that diameter is about 200mm, cutting into length with cutting equipment is that the block back of 20～30mm dried 30 hours naturally, send into drying equipment in 100 ℃ of dryings 8 hours, 1500 ℃ ± 20 ℃ roastings are crushed to about 400 orders after 2 hours;
(2), preparation CaO-Al
2O
3-K
2The O composite oxide carrier:
Take by weighing a-Al
2O
3Powder 450g, pure calcium aluminate cement 450g, heavy CaCO
3100g, many potassium aluminates 200g, paraffin 100g, with above-mentioned material in batch mixer, grind mix 2 hours after, add percentage by weight by the material total amount and be about 8% deionized water, be shaped to catalyst carrier semi-finished product of the present invention;
Above-mentioned carrier semi-finished product are carried out following preliminary treatment successively:
A. carry out about 6 hours of air natural curing at normal temperatures,
B. under about 6MPa pressure condition, carry out about 2 hours of steam curing,
C. under 150 ℃ of temperature, carried out drying about 10 hours;
It is interior in 1000 ± 20 ℃ of calcinings 5 hours then above-mentioned pretreated carrier semi-finished product to be sent into high temperature furnace, promptly gets the carrier of catalyst of the present invention;
(3), make the catalyst finished product:
Above-mentioned carrier is put into nickel nitrate solution, and continuous impregnating, decomposition twice promptly get catalyst finished product of the present invention; Each dipping, decomposition condition are all as follows:
Dipping: nickel nitrate solution concentration: 200g/l,
The nickel nitrate solution temperature: about 95 ℃,
Dip time: about 10 minutes;
Decompose: temperature: about 600 ℃,
Time: about 2 hours.
Embodiment 4
The inventor has carried out following anti-analyse charcoal and anti-steam oxidation performance evaluation to the low-grade alkalization hydrocarbons water vapour conversion catalyst of the foregoing description 1～3:
1, the anti-charcoal performance evaluation of analysing
In order to investigate the anti-charcoal performance of analysing of catalyst, in natural gas, add 92g/m in test
3Benzinum, at 640 ℃ of temperature, pressure 3.0MPa, steam/hydrocarbons ratio 2.5, carbon space velocity 30000h
-1Under the condition, investigate the anti-charcoal performance of analysing of the embodiment of the invention 1～3 catalyst, it the results are shown in following table 1.
The anti-charcoal performance evaluation result that analyses of table 1
2, anti-steam oxidation performance evaluation
Water vapour is raw material, heat carrier in operation process, also is oxidant simultaneously, and different catalyst is to the adaptive capacity difference of water vapour.Catalyst is under the high steam partial pressure for a long time, and catalyst can be because of oxidation, and crystalline phase changes and causes destruction to make catalyst generation clinkering aging, causes the decline of catalyst conversion performance.Therefore, investigate the stability that catalyst can reflect catalyst structure to a certain extent with steam treatment process, the anti-steam oxidation results of property of the embodiment of the invention 1～3 catalyst sees the following form 2.
The catalyst oxidation condition is: pressure 3.0MPa, medium are water vapour, 800 ℃ of temperature, steam air speed 5000h
-1, 10 hours time;
Appreciation condition is: pressure 3.0MPa, medium are that natural gas, 520 ℃ of temperature, steam/hydrocarbons ratio are 2.0, carbon space velocity 30000h
-1
Conversion performance after table 2 catalyst oxidation
Comprehensive above-mentioned table 1 and table 2 result are as seen, because catalyst of the present invention has adopted special potash to add mode, the Stability Analysis of Structures of carrier after preliminary treatment and high-temperature calcination, thereby its activity, carbon resistance performance etc. have solved the contradictory problems between catalyst activity and the carbon resistance performance smoothly all apparently higher than the comparative catalyst.
Claims (6)
1. low-grade alkalization hydrocarbons water vapour conversion catalyst, it is to be active constituent, to contain CaO-Al with nickel oxide NiO
2O
3-K
2The composite oxides of O are the polynary multiphase catalyst of high temperature sintering type of carrier.
2. low-grade alkalization hydrocarbons water vapour conversion catalyst according to claim 1 is characterized in that:
The described CaO-Al that contains
2O
3-K
2The composite oxide carrier of O is to adopt a-Al
2O
3, many potassium aluminates, pure calcium aluminate cement, heavy CaCO
3Be primary raw material, mainly contain CaO, Al through what mixing, moulding, calcining made
2O
3, K
2O and stabilizer T iO
2Porous carrier; Raw material a-Al wherein
2O
3, many potassium aluminates, pure calcium aluminate cement, heavy CaCO
3The weight portion proportioning as follows:
A-Al
2O
3: 35～45 parts,
Many potassium aluminates: 20～30 parts,
Pure calcium aluminate cement: 35～45 parts,
Heavy CaCO
3: 10～20 parts;
Wherein said many potassium aluminates are with a-Al
2O
3, heavy CaCO
3, TiO
2, K
2CO
3Be primary raw material, through the alkalization component that mixes, calcining makes, the weight portion proportioning of its primary raw material is as follows:
A-Al
2O
3: 90～110 parts,
Heavy CaCO
3: 10～20 parts,
TiO
2: 1～5 part,
K
2CO
3: 25～35 parts.
3. low-grade alkalization hydrocarbons water vapour conversion catalyst according to claim 2 is characterized in that:
Described pure calcium aluminate cement is meant and mainly contains Al
2O
3Alumina cement with CaO.
4. low-grade alkalization hydrocarbons water vapour conversion catalyst according to claim 2 is characterized in that:
The described CaO-Al that contains
2O
3-K
2Also comprise 1～10 part of lubricant in the raw material of the composite oxide carrier of O, lubricant is selected from graphite, stearate, paraffin.
5. according to each described low-grade alkalization hydrocarbons water vapour conversion catalyst in the claim 1～4, it is characterized in that: in the described low-grade alkalization hydrocarbons water vapour conversion catalyst, mainly comprise following components in weight portions:
NiO:10～25 part,
CaO:9～18 part,
Al
2O
3: 60～70 parts,
K
2O:1～5 part,
TiO
2: 0.1～2 part.
6. the preparation method of the described low-grade alkalization hydrocarbons water vapour conversion catalyst of claim 1 mainly comprises the steps:
(1), prepare many potassium aluminates:
Get the a-Al of described proportioning
2O
3, heavy CaCO
3And TiO
2, with three kinds of materials in batch mixer, grind mix 0.5～1 hour stand-by;
Take by weighing the K of described proportioning
2CO
3, add the solution of being dissolved into 20～50g/ml in the deionized water, treat to dissolve fully in the above-mentioned three kinds of materials of back adding and mediate to soft shape;
Material after mediating sent in the pressurization banded extruder make the column that diameter is 100～200mm, cut into the block back oven dry naturally that length is 20～30mm with cutting equipment, send in the drying equipment, in 100～150 ℃ of dryings 4～8 hours, then (1000～1500) ℃ ± 20 ℃, roasting 2～6 hours is crushed to 200～400 orders again;
(2), preparation contains CaO-Al
2O
3-K
2The composite oxide carrier of O:
Take by weighing the a-Al of described proportioning
2O
3, pure calcium aluminate cement, heavy CaCO
3, many potassium aluminates, lubricant, with above-mentioned material in batch mixer, grind mix 0.5～2 hour after, adding percentage by weight by the material total amount is 8～15% deionized water, is shaped to catalyst carrier semi-finished product of the present invention;
Above-mentioned carrier semi-finished product are carried out following preliminary treatment successively:
A. carry out air natural curing 6～12 hours at normal temperatures;
B. under 4～8MPa pressure condition, carry out steam curing 2～10 hours;
C. under 120～300 ℃ of temperature conditions dry 8～12 hours;
Then above-mentioned pretreated semi-finished product are sent in the high temperature furnace in (1000～1400) ℃ ± 20 ℃ calcining 2～5 hours, promptly got the carrier of catalyst of the present invention;
(3), make the catalyst finished product:
The carrier that above-mentioned (2) step makes is put into nickel nitrate solution, and continuous impregnating, decomposition twice promptly get catalyst finished product of the present invention; Wherein, the condition of dipping, decomposition is as follows:
Dipping nickel solution concentration: 200～250g/l,
The nickel solution temperature: 80～95 ℃,
Dip time: 10 minutes～1 hour,
Decomposition temperature: 450～600 ℃,
Resolving time: 2 hours～5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100504874A CN100463716C (en) | 2007-11-13 | 2007-11-13 | A low-grade alkalization hydrocarbons water vapour conversion catalyst and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100504874A CN100463716C (en) | 2007-11-13 | 2007-11-13 | A low-grade alkalization hydrocarbons water vapour conversion catalyst and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101157036A CN101157036A (en) | 2008-04-09 |
| CN100463716C true CN100463716C (en) | 2009-02-25 |
Family
ID=39305341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100504874A Expired - Fee Related CN100463716C (en) | 2007-11-13 | 2007-11-13 | A low-grade alkalization hydrocarbons water vapour conversion catalyst and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100463716C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102091631A (en) * | 2010-12-29 | 2011-06-15 | 公主岭国家农业科技园区三剂化工厂 | Natural gas catalyst manufactured by coal and manufacturing method thereof |
| CN105457640A (en) * | 2015-11-17 | 2016-04-06 | 西南化工研究设计院有限公司 | Improved novel catalyst for hydrocarbon steam reforming |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079981A (en) * | 1993-03-25 | 1993-12-29 | 中国石油化工总公司 | Hydrocarbons water vapor conversion lower section catalyst and method for making |
-
2007
- 2007-11-13 CN CNB2007100504874A patent/CN100463716C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079981A (en) * | 1993-03-25 | 1993-12-29 | 中国石油化工总公司 | Hydrocarbons water vapor conversion lower section catalyst and method for making |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101157036A (en) | 2008-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101391218B (en) | Coke-oven gas methanation catalyst preparation method | |
| Denardin et al. | Tuning the acidity and reducibility of Fe/ZSM-5 catalysts for methane dehydroaromatization | |
| Mahammadunnisa et al. | Catalytic nonthermal plasma reactor for dry reforming of methane | |
| CN102451696B (en) | Catalyst for reaction of hydrogen preparation or carbonyl synthesis gas preparation by hydrocarbon steam conversion | |
| CN105944751A (en) | Catalyst for directly preparing synthesis gas into aromatic compounds and preparation method and application of catalyst | |
| CN101219392B (en) | Catalyst for producing gas rich in hydrogen with coke oven gas and method for producing the same | |
| EP1732688A1 (en) | Nickel supported on titanium stabilized promoted calcium aluminate carrier | |
| CN110479283B (en) | Catalyst with nickel loaded on surface of copper ferrite spinel, preparation method and application thereof | |
| Tian et al. | Catalytic Performance of In/HZSM‐5 for Coupling Propane with CO2 to Propylene | |
| CN100463716C (en) | A low-grade alkalization hydrocarbons water vapour conversion catalyst and its preparing method | |
| CN101260323A (en) | Cerium oxide high-temperature gas desulfurizer and preparation thereof | |
| CN101703934A (en) | Natural gas catalyst manufactured by coal and manufacturing method thereof | |
| CN105435801B (en) | Load typed iron catalyst and its preparation method and application | |
| CN101402041B (en) | Self-heating conversion catalyst rich in methane gas and method of producing the same | |
| CN111644169B (en) | Metal composite modified nano zirconium oxide catalyst and preparation method and application thereof | |
| CN101992123B (en) | Adhesive-free mordenite/MCM-22 intergrowth molecular sieve catalyst and preparation method thereof | |
| CN101695662B (en) | CO sulfur tolerant shift catalyst and preparation method thereof | |
| CN110015939B (en) | Method and device for producing hydrogen and co-producing methane by coal | |
| CN102019183A (en) | Catalyst for producing hydrogen from hydrocarbon steam conversion or carboxyl syngas reaction and preparation method thereof | |
| KR101407979B1 (en) | Manufacturing method of metal catalyst for producing alcohol and metal catalyst manufactured by the same | |
| CN102451690A (en) | Preparation method of substitute natural gas | |
| CN101181685A (en) | Catalyst for preparing hydrogen-rich gas by coke oven gas and preparation method thereof | |
| CN106590720B (en) | A method of using coal and oil refinery dry gas as raw material alpha-olefin | |
| CN102039172B (en) | Binderless beta zeolite/MCM-22 symbiotic molecular sieve catalyst and preparation method thereof | |
| CN102133533A (en) | LPG water vapor pre-reforming catalyst and application method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SOUTHWEST RESEARCH + DESIGN INSTITUTE OF CHEMICAL Free format text: FORMER NAME: SOUTHWEST RESEARCH + DESIGN INSTITUTE OF CHEMICAL INDUSTRY |
|
| CP01 | Change in the name or title of a patent holder |
Address after: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Patentee after: SOUTHWEST RESEARCH & DESIGN INSTITUTE OF CHEMICAL INDUSTRY Patentee after: Shanghai Shidongkou Gas Making Co.,Ltd. Address before: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Patentee before: THE SOUTHWEST RESEARCH & DESIGN INSTITUTE OF CHEMICAL INDUSTRY Patentee before: Shanghai Shidongkou Gas Making Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200117 Address after: 611430 No.777, Xinghua 10th Road, dengshuang Town, Xinjin County, Chengdu City, Sichuan Province (Industrial Park) Co-patentee after: Shanghai Shidongkou Gas Making Co.,Ltd. Patentee after: HAO HUA (CHENGDU) TECHNOLOGY Co.,Ltd. Address before: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Co-patentee before: Shanghai Shidongkou Gas Making Co.,Ltd. Patentee before: SOUTHWEST RESEARCH & DESIGN INSTITUTE OF CHEMICAL INDUSTRY |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090225 |