CN101381615B - Catalyst for improving selectivity of synthesis gas conversion and preparation method thereof - Google Patents
Catalyst for improving selectivity of synthesis gas conversion and preparation method thereof Download PDFInfo
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Abstract
The invention provides a catalyst for the conversion of synthesis gases and a method for preparing the same. The catalyst contains iron, copper, potassium and lithium. The catalyst and the method have the advantages that besides the liquid hydrocarbon which is obtained by the catalytic conversion of the synthesis gases and of which the number of carbon chains is 5 to 40, the alcohol which contains a plurality of C2 to C4 alkenes and of which the number of carbon chains is 1 to 6 can also be obtained; and the obtained low-carbon mixing alcohol can be directly doped in gasoline fraction without purification, thereby improving the octane value and further simplifying the processing flow of oil products.
Description
Technical field
The present invention relates to synthetic gas and transform the field, particularly synthetic gas changes into liquid hydrocarbon and uses Catalysts and its preparation method.
Background technology
It is synthetic to be commonly referred to Fascher-Tropsch (FT) by the chemical process of synthetic gas synthetic fluid hydro carbons; Synthetic gas can be produced or produced through gasification by coal by conversion of natural gas; The main purpose product is a generate longer-chain hydrocarbons; When generating hydro carbons, also there is a small amount of oxygen-bearing organic matter to produce as impurity like alcohol, aldehyde, acid.Obtain motor spirits such as vapour, diesel oil after the product refining.Develop this technology and help alleviating the dependency of current energy consumption for oil, help setting up coal, petroleum and natural gas alliance type energy structure, especially meaning is important for China that the relative rich coal is oil-poor.
Synthetic general iron-based or the cobalt-base catalyst of adopting of F-T:
The SMDS technology of Shell Co. Ltd's exploitation adopts SiO
2Be the cobalt-base catalyst of carrier, it consists of 25Co:0.9Zr, Ti or Cr:100 SiO
2, the purpose product is a heavy hydrocarbon, C
5 +Selectivity reach 82%.
Patent CN1695803A discloses a kind of F-T synthesis iron base catalyst, comprises the quality percentage composition and be 50～70% Fe, 0.01～10% Cu, 0.01～8% K
2O, 0.01～8% Na
2O; This catalyzer is converted into C with the synthetic gas highly selective
20 -Hydro carbons contains a large amount of C in the product
2～C
4Alkene, overall selectivity are that 6～8% oxygen-bearing organic matter occurs as the impurity product.
Patent CN1159098C discloses a kind of working method of Fe-series catalyst, and the employing ferrous sulfate is a raw material, has reduced the Preparation of Catalyst cost, C
12 +Selectivity can reach 70%.
Above-mentioned catalyzer purpose product is mainly oil product, can co-producing light olefins although patent CN1695803A is said, and resulting oxygen-bearing organic matter amount is few; Kind is complicated; Be difficult to separate and utilize, oxygen-bearing organic matter needs to be converted into corresponding hydro carbons through hydrogenation process in oil refining process, consumes the hydrogen of some amount simultaneously; Fail to realize the comprehensive full use of product, improved production cost.
The FT synthesis technique economic benefit directly receive the influence of world's crude oil price, in case crude oil price drops, economic benefit will be had a greatly reduced quality.If improve the selectivity of its product, obtain a certain amount of Chemicals, then economic benefit is better.Therefore, the synthetic development direction of F-T is positioned at the production chemical products with high added-value.
Low-carbon alkene such as ethene, propylene is the basic Organic Chemicals that is in great demand, can be in producing multiple Chemicals; Present main source is that price is considerably beyond oil product through refining of petroleum; MAS is meant C
1-C
6The alcohols mixture.Say that from performance MAS is a kind of good gasoline dope, it has high octane value and the blending performance good with gasoline, can replace MTBE as gasoline dope; After MAS separated purification, the methyl alcohol of acquisition and ethanol were important basic Organic Chemicals and energy and materials, C
2 +Alcohol then is the high price product, except that as solvent and the esterifying reagent, also can be used as the raw material of Chemical Manufacture, is widely used in chemical field.
Summary of the invention
The present invention provides a kind of syngas conversion catalyst and preparation method thereof; Purpose is to be liquid hydrocarbon fuel with the synthetic gas catalyzed conversion; When solution is produced the liquid fuel problem by coal or Sweet natural gas; Obtain a certain amount of low-carbon alkene and low-carbon alcohol, product is obtained than the higher added value of simple synthetic fluid hydrocarbon products.
The present invention is achieved in that
Reagent iron nitrate and cupric nitrate are dissolved in the deionized water, or iron powder and copper powder be dissolved in add deionized water behind the concentrated nitric acid and be diluted to desired concn, obtain mixing salt solution.Under agitation in mixing salt solution, add ammonia soln and form the deposition slurries, precipitation temperature is 20～80 ℃, and filtering, use salpeter solution or ammonia soln to regulate endpoint pH is 5～9, with turbid liquid filter the back with the deionized water wash filter cake to remove NH
4 +Ion.
In this filter cake, add the deionized water making beating, saltpetre or lithium nitrate and corresponding additive precursor are mixed with the aqueous solution of mixture, add in the slurries; Behind 20～70 ℃ of stirring certain hours; This dope filtration obtains filter cake, and this filter cake 80～120 ℃ of dryings after 8～12 hours, is obtained required order and counts particle through crushing and screening; 300～500 ℃ of roastings are 1～6 hour in muffle furnace, obtain the catalyzer finished product.
Concrete preparation method of the present invention comprises the steps:
1. reagent iron nitrate and cupric nitrate are dissolved in the deionized water, or iron powder and copper powder are dissolved, dilute with concentrated nitric acid, obtain containing the solution of Fe:10～100g/L, Cu:1～20g/L.Adding concentration is 3%～10% ammoniacal liquor formation deposition slurries in metal salt solution, and precipitation temperature is 20～80 ℃, is preferably 30～50 ℃.Using salpeter solution or ammonia soln to regulate endpoint pH is 5～9, and the pH value is preferably 6～8.
2. obtain the co-precipitation filter cake after filtering, washing.
3. in this co-precipitation filter cake, add the deionized water making beating, this slurry solid content is 8～15%; Be preferably 9～13%; Saltpetre and lithium nitrate are mixed with the aqueous solution, and the content of potassium is 5～50g/L in this aqueous solution, and the content of lithium is 2～20g/L; This solution is added in the slurries, behind 20～70 ℃ of stirring certain hours, obtain catalyst impregnating solution, catalyst impregnating solution is filtered, obtain the macerate filter cake.
With this macerate filter cake 80～120 ℃ of dryings after 8～12 hours, through crushing and screening the particle that obtains order several 240～420,300～500 ℃ of roastings are 1～6 hour in muffle furnace; Maturing temperature is preferably 350～450 ℃, and roasting time is preferably 2～4 hours.Obtain the catalyzer finished product, the consisting of by mass percentage of this catalyzer, it consists of: Fe
2O
3: 75%～97%; CuO:2%～15%; Alkalimetal oxide (K
2O, Li
2O) total amount: 1%～10%; K and Li mass ratio: 1～4.5: 1.
This catalyzer by mass percentage, its preferable consisting of: Fe
2O
3: 80～90%; CuO:4～12%; Alkalimetal oxide total amount: 2～8%; K and Li mass ratio are preferably 1.5～3.0: 1.
Specific surface area of catalyst is 50～100m
2/ g is preferably 60～80m
2/ g.Pore volume is 0.3～0.7ml/g, is preferably 0.4～0.6ml/g.
Catalyzer Fischer-Tropsch synthesis evaluation experimental adopts H at the enterprising row of fixed bed reaction apparatus
2Use after/CO/Ar gas mixture fully reduces, the virgin gas composition is H
2/ CO/Ar gas mixture, H
2/ CO is 1.5～3.5 (volume ratios), is preferably 2.0～2.5; A certain amount of Ar is as interior mark.Air speed is 600～3000 (ml (n))/g-cat./h, is preferably 1000～2000 (ml (n))/g-cat./h; Temperature of reaction is 200～400 ℃, is preferably 250～375 ℃; Reaction pressure is 1.5～8.0MPa, is preferably 2～6MPa.
The analysis test method that the present invention is used:
1. the specific surface area of catalyzer, pore volume and pore size distribution are measured: adopt the U.S. ASAP2020M of Merck & Co., Inc low-temperature nitrogen adsorption method, specific surface area is the BET specific surface area.
2. adopt the thing phase of Japanese D/max-2200PC X-ray diffractometer analysis of catalyst of science.
3. adopt the U.S. Optima2100DV of PE company inductively coupled plasma spectral emissions appearance analysis of catalyst component.
4. adopt the U.S. 6890N of Agilent company gc to combine simulation rectifying assay products to form.
Advantage of the present invention is, is 5 to 40 the liquid hydrocarbon except that the synthetic gas catalyzed conversion being obtained carbochain, also obtains more C
2～C
4Alkene, carbochain is 1～6 alcohols, has significantly improved the price of product, and is worthwhile economically; In addition, gained MAS of the present invention can directly mix in the gasoline fraction without purifying, and can improve its octane value, thereby simplifies the oil product work flow.
Embodiment
Embodiment 1
Iron nitrate crystal and cupric nitrate are dissolved in the deionized water; Solution contains Fe60g/L, Cu1.5g/L; Measuring 500ml solution, is that 5% ammonia soln joins and forms the deposition slurries in iron nitrate, the cupric nitrate mixing solutions through tap funnel with the quality percentage composition, and keeping dripping process temperature is 80 ℃; Dropwising back pH value is 6.4, obtains precipitated filter cakes through filtering, washing.This filter cake is moved into beaker, and it is 380g that the adding deionized water makes filter cake and deionized water gross weight, stirs fast to make it form uniform slurries.A certain amount of lithium nitrate of weighing and saltpetre are dissolved in the deionized water, are made into 50ml solution, and solution contains K:20.6g/L, Li:4.2g/L; Mix above-mentioned solution and slurries, heating slurries to 60 ℃ stirred 60 minutes; After the filtration filter cake is dried down at 110 ℃, fragmentation is sieved, and chooses 240～420 order particles; Be heated to 450 ℃ of roasting 3h, above catalyzer called after A, the catalyzer composition is listed in table 1.
Embodiment 2
Metal iron powder and copper powder are dissolved in the concentrated nitric acid; Solution contains Fe:60g/L, Cu:12g/L; Measuring 400ml solution, is that 3% ammonia soln joins and forms the deposition slurries in iron nitrate, the cupric nitrate mixing solutions through tap funnel with the quality percentage composition, and keeping dripping process temperature is 50 ℃; Dropwising back pH value is 8.0, obtains precipitated filter cakes through filtering, washing.It is 300g that the adding deionized water makes filter cake and deionized water gross weight, stirs fast to make it form uniform slurries, stirs fast to make it form uniform slurries.A certain amount of lithium nitrate of weighing and saltpetre are dissolved in the deionized water, are made into 50ml solution, and solution contains K:50g/L, Li:6g/L; Mix above-mentioned solution and slurries, heating slurries to 55 ℃ stirred 90 minutes; After the filtration filter cake is dried down at 120 ℃, fragmentation is sieved, and chooses 240～420 order particles; Be heated to 300 ℃ of roasting 6h, above catalyzer called after B, the catalyzer composition is listed in table 1.
Embodiment 3
With iron nitrate and cupric nitrate dissolve with deionized water in, solution contains Fe:80g/L, Cu:7g/L; Measure 400ml solution; Is that 10% ammonia soln joins and forms the deposition slurries in iron nitrate, the cupric nitrate mixing solutions through tap funnel with the quality percentage composition; Keeping dripping process temperature is 20 ℃, and dropwising back pH value is 7.2, obtains precipitated filter cakes through filtration, washing the co-precipitation filter cake is moved in the beaker; It is 400g that the adding deionized water makes filter cake and deionized water gross weight, stirs fast to make it form uniform slurries.A certain amount of lithium nitrate of weighing and saltpetre are dissolved in the deionized water, are made into 50ml solution; Solution contains K:20g/L, Li:10g/L, mixes above-mentioned solution and slurries, stirs 30 minutes under the room temperature; After the filtration filter cake is dried down at 120 ℃, fragmentation is sieved, and chooses 240～420 order particles; Be heated to 500 ℃ of roasting 2h, above catalyzer called after C, the catalyzer composition is listed in table 1.
Embodiment 4
With iron nitrate and cupric nitrate dissolve with deionized water in, solution contains Fe:50g/L, Cu:4g/L; Measure 600ml solution; Is that 8% ammonia soln joins and forms the deposition slurries in iron nitrate, the cupric nitrate mixing solutions through tap funnel with the quality percentage composition; Keeping dripping process temperature is 60 ℃, and dropwising back pH value is 7.7, obtains precipitated filter cakes through filtration, washing the co-precipitation filter cake is moved in the beaker; It is 400g that the adding deionized water makes filter cake and deionized water gross weight, stirs fast to make it form uniform slurries.A certain amount of lithium nitrate of weighing and saltpetre are dissolved in the deionized water, are made into 50ml solution, and solution contains K:8g/L, Li:2g/L; Mix above-mentioned solution and slurries, heating slurries to 70 ℃ stirred 50 minutes; After the filtration filter cake is dried down at 90 ℃, fragmentation is sieved, and chooses 240～420 order particles; Be heated to 375 ℃ of roasting 3h, above catalyzer called after D, the catalyzer composition is listed in table 1.
The rerum natura characterization result of catalyzer is listed in table 2.Catalyzer Fischer-Tropsch synthesis evaluation experimental is the enterprising row of fixed bed reaction apparatus in the laboratory, and loaded catalyst is 5g, adopts H
2The reduction of/CO/Ar gas mixture, the virgin gas proportioning is H2/CO=1.5 (volume ratio), and air speed is 1200～1300 (ml (n))/g-cat./h, and temperature of reaction is 280～300 ℃, and reaction pressure is 2.5MPa, evaluation result is listed in table 3.
Table 1 catalyzer is formed
The performance index of table 2 catalyzer
Table 3 evaluating catalyst result
Annotate: selectivity is the selectivity (in carbonatoms) of each component in organic product.
Above data are visible, and catalyzer has reasonably specific surface area, pore volume and pore size distribution.Catalyzer is under above-mentioned reaction conditions; The transformation efficiency that in fixed-bed reactor, has high reaction activity and high and good selectivity: CO is more than 85%; Contain a certain amount of low-carbon alcohol and low-carbon alkene in the product; This shows that this catalyzer is suitable in fixed-bed reactor by products such as synthetic gas synthetic oil product, low-carbon alkene and low-carbon alcohol.
Claims (9)
1. one kind is improved the selectivity of synthesis gas conversion catalyst, it is characterized in that: catalyzer by mass percentage, it consists of: Fe
2O
3: 75%～97%; CuO:2%～15%; The oxide aggregate of K and two kinds of alkali metals of Li: 1%～10%; K and Li mass ratio: 1～4.5:1; Specific surface area of catalyst 50～100m
2/ g; Pore volume is 0.3～0.7ml/g.
2. syngas conversion catalyst as claimed in claim 1 is characterized in that: catalyzer by mass percentage, it consists of: Fe
2O
3: 80～90%; CuO:4～12%; The oxide aggregate of K and two kinds of alkali metals of Li: 2～8%; K and Li mass ratio are 1.5～3.0:1; Specific surface area of catalyst is 60～80m
2/ g; Pore volume is 0.4～0.6ml/g.
3. syngas conversion catalyst as claimed in claim 1, it is characterized in that: the catalyst applications condition is: in the fixed bed reaction apparatus, adopt H
2The reduction of/CO/Ar gas mixture, H
2/ CO volume ratio is 1.5～3.5; A certain amount of Ar is as interior mark; Air speed is 600～3000 (ml (n))/g-cat./h; Temperature of reaction is 200～400 ℃; Reaction pressure is 1.5～8.0MPa.
4. syngas conversion catalyst as claimed in claim 3, it is characterized in that: the catalyst applications condition is: H
2/ CO volume ratio is 2.0～2.5; Air speed is 1000～2000 (ml (n))/g-cat./h; Temperature of reaction is 250～375 ℃; Reaction pressure is 2～6MPa.
5. like the preparation method of described any one syngas conversion catalyst of claim 1～4, it is characterized in that:
A. iron nitrate and cupric nitrate are dissolved in the deionized water; Or with iron powder and copper powder with concentrated nitric acid dissolving, dilution; Obtain containing the solution of Fe:10～100g/L, Cu:1～20g/L, adding concentration is 3%～10% ammoniacal liquor formation deposition slurries in metal salt solution, and precipitation temperature is 20～80 ℃; Using salpeter solution or ammonia soln to regulate endpoint pH is 5～9;
B. obtain the co-precipitation filter cake after filtering, washing;
C. in the co-precipitation filter cake, add the deionized water making beating, slurry solid content is 8～15%; Saltpetre and lithium nitrate are mixed with the aqueous solution, and the content of potassium is 5～50g/L in the aqueous solution, and the content of lithium is 2～20g/L; Solution added in the slurries stir, catalyst impregnating solution is filtered, obtain the macerate filter cake;
D. with the macerate filtration cakes torrefaction,, obtain the catalyzer finished product through pulverizing, screening, roasting.
6. the preparation method of a syngas conversion catalyst as claimed in claim 5, it is characterized in that: among the step a, precipitation temperature is 30～50 ℃; Endpoint pH is 6～8.
7. the preparation method of a syngas conversion catalyst as claimed in claim 5, it is characterized in that: among the step c, slurry solid content is 9～13%.
8. the preparation method of a syngas conversion catalyst as claimed in claim 5 is characterized in that: in the steps d, screening obtains the particle of order several 240～420, and maturing temperature is 300～500 ℃; Roasting time is 1～6 hour, obtains the catalyzer finished product.
9. the preparation method of a syngas conversion catalyst as claimed in claim 8, it is characterized in that: in the steps d, maturing temperature is 350～450 ℃, and roasting time is preferably 2～4 hours.
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| CN101381615B true CN101381615B (en) | 2012-12-26 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0194552A1 (en) * | 1985-03-07 | 1986-09-17 | Air Products And Chemicals, Inc. | Selective conversion of synthesis gas |
| US4617288A (en) * | 1984-12-31 | 1986-10-14 | Mobil Oil Corporation | Low nitrogen iron-containing Fischer-Tropsch catalyst for conversion of synthesis gas and process for preparing the catalyst |
| CN1395993A (en) * | 2001-07-12 | 2003-02-12 | 中国科学院山西煤炭化学研究所 | Fe-base catalyst for Fischer-Tropsch syuthesis and its preparing process |
-
2007
- 2007-09-07 CN CN 200710146032 patent/CN101381615B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617288A (en) * | 1984-12-31 | 1986-10-14 | Mobil Oil Corporation | Low nitrogen iron-containing Fischer-Tropsch catalyst for conversion of synthesis gas and process for preparing the catalyst |
| EP0194552A1 (en) * | 1985-03-07 | 1986-09-17 | Air Products And Chemicals, Inc. | Selective conversion of synthesis gas |
| CN1395993A (en) * | 2001-07-12 | 2003-02-12 | 中国科学院山西煤炭化学研究所 | Fe-base catalyst for Fischer-Tropsch syuthesis and its preparing process |
Non-Patent Citations (1)
| Title |
|---|
| 杨霞珍 等.Fe、Co 基费托合成催化剂助剂研究进展.《化工进展》.2006,第25卷(第8期),867-870. * |
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