CN1014399B - Syngas conversion catalyst production and use thereof - Google Patents
Syngas conversion catalyst production and use thereofInfo
- Publication number
- CN1014399B CN1014399B CN 89102274 CN89102274A CN1014399B CN 1014399 B CN1014399 B CN 1014399B CN 89102274 CN89102274 CN 89102274 CN 89102274 A CN89102274 A CN 89102274A CN 1014399 B CN1014399 B CN 1014399B
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- Prior art keywords
- catalyzer
- synthetics
- zeolite
- synthesis gas
- compound
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Abstract
The present invention relates to a compound used as synthesis gas converted into the catalyst of hydrocarbons with the carbon number of more than 1 after reduction and activation. The compound has the formula of RuaAbCeOx, wherein A is alkali metal, x is a number for satisfying the requirement of other elements for oxygen valency, a is more than 0 and is less than 1 wt%, b is more than 0 and is less than 10 wt% measured by the total weight of the compound, and the remaining part of the compound is composed of Ce and O. The preparation method comprises: (A). soluble ruthenium, cerium salt and carbonate containing alkali metal or ammonium and (or) bicarbonate and (or) the precipitating agent of hydroxide are introduced in solution under the condition that precipitates containing ruthenium and cerium exist in the form of containing compound which can be pyrolyzed into oxide; (B). the precipitates in step (A) are recovered. Catalysts can be combined with zeolite by the method that catalysts produced by the method of the present invention are converted into synthesis gas.
Description
The present invention relates in gasoline boiling range scope, the mixed gas that will contain the mixed gas (hereinafter referred to as synthetic gas) of carbon monoxide and hydrogen changes the method for aliphatic hydrocarbon into.
Utilize Fischer-Tropsch process to convert synthesis gas to hydrocarbon polymer, known by people for many years.But this method only just has the commercialization meaning in the country resemble South Africa.Because in those countries, single economic factors is preponderated.Now, the work of new forms of energy of seeking replaceable coal and Sweet natural gas is increasingly important, and it concentrates on the Fischer-Tropsch process people's interest again.Because Fischer-Tropsch process is a kind of quite attracting research method, it makes people obtain the high-quality fuel that is easy to transport under the condition that environment can allow.
People know that very early the ruthenium in the VIII family metal is one of the most active catalyzer in the synthesis gas conversion reaction.Under middle pressure or high pressure, its product is a high-molecular weight paraffin.Under low pressure then mainly be methane.Several parts of patents such as the patent No. of newly release are 4,042,614; 4,171,320; 4,206,134; 4,413,064; With 4,410, all narrate among 637 United States Patent (USP) and the GB-A 2,119,277 and applied for being under the catalyst action of active constituent with the ruthenium, with the synthesis gas method that raw material is produced different products.
United States Patent (USP) 4,042,614 to have introduced with the synthesis gas be that the synthetic selectively chain length of raw material is C
2～C
10The method of alkene.The carrier of titanium-containing oxide as ruthenium catalyst used in this reaction.Here the titanium-containing oxide carrier of mentioning can be from TiO
2, ZrTiO
4, TiO
2-activated carbon, TiO
2-Al
2O
3, TiO
2-SiO
2, choose in titanates of alkali-earth metals, rare earth metal titanate and their mixture.
United States Patent (USP) 4,171, No. 320 have been introduced with the synthesis gas is the synthetic chain length C of raw material
2～C
5The method of alkene.This reaction uses ruthenium to make catalyzer.Its carrier is from V
2O
3, Nb
2O
5, Ta
2O
5, Al
2O
3-V
2O
3, Al
2O
3-Nb
2O
5, Al
2O
3-Ta
2O
5, SiO
2-V
2O
3, SiO
2-Nb
2O
5, SiO
2-Ta
2O
5, V
2O
3-activated carbon, Nb
2O
5-activated carbon, Ta
2O
5Choose in-activated carbon, alkaline-earth metal-VB family composite oxide of metal, basic metal-VB family composite oxide of metal, IVB family-VB family composite oxide of metal and their mixture.
United States Patent (USP) 4,206, having introduced a kind of employing for No. 134, to be stated from the ruthenium that contains on the Mn oxide carrier be catalyzer, is that raw material is produced C with the synthesis gas
2～C
4Olefin(e) centent is higher and the method for the hydrocarbon polymer that methane content is lower.Wherein, the said Mn oxide carrier that contains can be from MnO, Al
2O
3-MnO, SiO
2Choose in-MnO, MnO-gac, IVB-family metal-manganese composite oxide, VB family metal-manganese composite oxide, rare earth metal-manganese composite oxide and their mixture.
United States Patent (USP) 4,413, No. 064 has been introduced is the senior straight-chain paraffin method that raw material is produced diesel boiling range with the synthesis gas.The catalyzer that is adopted mainly is made up of cobalt, Thorotrast or the lanthanum trioxide and the ruthenium that are stated from the alumina supporter.Here said aluminum oxide is-aluminum oxide ,-aluminum oxide or its mixture.This Preparation of catalysts method is the fine alumina powder
(A) aqueous solution with cobalt salt floods, and
(B) flood with the non-aqueous organic solution of shackles salt and thorium salt or lanthanum salt.
United States Patent (USP) 4,410, having introduced for No. 637 with the synthesis gas to the feedstock production carbon atom quantity is the method for 5～12 hydrocarbon polymer.Contain in the following metal one or more in the catalyzer that this method is used: iron, nickel, cobalt, chromium and (or) ruthenium, and carrier is a magadite-kind multilayer crystalline silicate compound, and it can absorb metal ion or metal-salt by embedding (intercalation).
People such as Kieffer have introduced the reaction on rare earth metal oxide catalyst of carbon monoxide and hydrogen in " Chemical communi-cations, 1983, page 763/764 ".Used Pd-La in the research
2O
3And Pd-Dy
2O
3Catalyzer.The two all is to use immersion process for preparing.
At last, GB-A2 has introduced that a kind of to be used for the mixture of carbon monoxide and hydrogen or the mixture of carbonic acid gas and hydrogen be the raw material catalyzer of synthetic alkene selectively for 119, No. 277.It contains the carboxide that is deposited in the ruthenium on the ceria supports.In example 3, announced and used RuCl
33H
2O(ruthenium content 0.62%(weight ratio)) aqueous solution floods a kind of catalyzer that cerium dioxide is made.Yet when this impregnated catalyst is used for the conversion of synthesis gas, a large amount of unwanted methane (35.7%) have but been generated, to the selectivity but very low (1.6%) of needed alkene.
It is high and low to the selectivity of alkene that we find can to overcome the methane production that shortcoming-catalysis of the impregnated catalyst of prior art produces substantially with the ruthenium-containing catalyst that coprecipitation method is produced.
Therefore, the invention provides a kind of production method that after reduction activation, can be used as the synthetics of catalyzer.This catalyzer is used for synthesis gas and converts to and contain the reaction of carbon number greater than 1 hydrocarbon polymer.This synthetics has following formula:
Ru
aAbCeO
x（Ⅰ）
A is a kind of basic metal in the formula,
X satisfies the number that other element requires the valency of oxygen,
A is greater than 0, less than the 1%(weight ratio), by the gross weight of synthetics,
The value of b is in 0 to 10%(weight ratio) between, by the gross weight of synthetics,
Ce and O constitute the rest part of this synthetics.
This method comprises following step:
(A) but to contain with thermolysis be under the sedimentary condition of the ruthenium that exists of the compound form of corresponding oxide and cerium forming, the soluble salt of metal Ru and cerium and contain basic metal or ammonium carbonate and (or) supercarbonate and (or) the precipitation of hydroxide agent introduces in the solution together.
(B) reclaim the throw out that obtains in (A) step.
Have been found that the difference with catalyzer of the present invention is that its ruthenium content is greater than the 1%(weight ratio) those catalyzer tend to catalysis and produce a large amount of methane.The actual content of methane increases along with the increase of ruthenium content in the catalyzer in the converted product.And shackles content of the present invention is lower than the 1%(weight ratio)-to be lower than the 0.5%(weight ratio) be-catalyzer non-methane hydrocarbon is had activity and selectivity simultaneously, particularly especially true greater than 2 aliphatic hydrocarbon to containing carbon number, C wherein
5+ be its major portion.In addition, different with the catalyzer that ruthenium content is higher, it can remain in the limit of permission the selectivity of unwanted carbonic acid gas.
In formula I, A is a kind of basic metal, with potassium for well.Alkali metal content b with 0 and the 5%(weight ratio) between for well, be more preferably 0 and the 2%(weight ratio) between.
The step of present method (A) is with suitable method ruthenium salt and cerium salt to be introduced the aqueous solution together.Though also can to make on the order the people who is familiar with this area be that conspicuous other changes adding when needing, be added to the aqueous solution in the aqueous solution of water-soluble salt of above-mentioned metal and be advisable a kind of precipitation agent.Yet any solubility ruthenium salt and cerium salt can use, but adopt the shackles (because it has been bought easily from the market) and the cerium (for example cerous nitrate) of nitrate form of chloride form often convenient.Contain some non-Ce rare earth metals in the cerous nitrate that sell in market, also can use when needing.
The precipitation agent that in step (A), uses be a kind of alkali-metal carbonate and (or) supercarbonate and (or) oxyhydroxide.Can replace ready-made carbonate or supercarbonate with the mother liquor of preparation carbonate or supercarbonate, for example use water-soluble salt and carbonic acid gas.Can also use urea, it can pyrolysis become carbonic acid gas and ammonia.In any case, the numerical value of b will be greater than zero in the aforementioned formula I.If desired, this value can or further add alkali metal compound adjustment by washing.In addition, also can with volatile salt and (or) bicarbonate of ammonia and (or) ammonium hydroxide is used as precipitation agent, in the case, the b value will be 0 in the catalyzer that obtains at first, but if desired, after this can adjust this value by adding basic metal.
Can the soluble salt of metal Ru and cerium is miscible together in 0～100 ℃ of temperature range.In a preferred embodiment of the invention, suitable temperature range is 60～100 ℃, with 80～100 ℃ for well.In a further preferred embodiment, temperature being remained on below 50 ℃ be advisable, to remain on below 30 ℃ to well, for example, can be room temperature.
In the solution of metal-salt, add precipitation agent, will the pH value of mixture upwards be increased from initial low value.By requirement of the present invention, in the Preparation of catalysts process, mixture pH value finally should be greater than 6, with in 6～10 scopes for well, at 8～10 scope Nei Gengjia.The interpolation of precipitation agent will make the pH value reach above-mentioned scope and just finish, and can end to add precipitation agent this moment, can stop the pH value further to increase like this.In order to improve the homogeneity of catalyzer, in precipitation process, preferably mix liquid, to be advisable with mechanical stirring.Post precipitation preferably makes mixture keep more than 15 minutes under near the temperature of boiling point, stirs simultaneously so that precipitation is complete.
The amount of ruthenium salt, cerium salt and the precipitation agent that adopts should satisfy the stoichiometric relation of formula I.In preparation process, alkali-metal content can be replenished by adding in the synthetics, also can be reduced by washing.
Step (B) is to reclaim the throw out that obtains in (A) step, and suitable recovery method is to filter.Do not associate and isolate other method of solid (as centrifuging) in the liquid and can use yet.After the recovery, best washing precipitate, to remove unwanted solubility resistates, water promptly is suitable washing composition.Suggestion is preferably in dry sediment under the temperature that is no more than 180 ℃ (for example about 120～150 ℃).
(B) in the throw out that the step reclaims,, the pyrolytic compound that accounts for major portion independently carries out pyrolysis in (C) step but being preferably in one.Can for example in rare gas element (as nitrogen) stream, or in oxygen-containing gas (as air), adopt the method for thermal precipitation thing to carry out pyrolysis aptly in a kind of atmosphere of not having a reductibility, suitable pyrolysis temperature range be 250～600 ℃.
Contain the catalyzer of carbon number for the synthetics that makes formula I is transformed into to can be used for synthesis gas converted to, also need the reduction activation synthetics usually greater than 1 hydrocarbon polymer.Suitable method is under the elevated temperature condition, and it is contacted with reducing gas such as hydrogen, carbon monoxide or its mixture.Reducing gas (as hydrogen) can suitably dilute with rare gas element such as nitrogen.Usually the reduction activation condition is pressure: 1～100 crust, temperature: 150～350 ℃.The reduction activation time can be 24 hours or more longer.Reduction activation can be used as independent step to be carried out before synthetics uses as catalyzer, also it can be merged in the synthesis gas step of converting.
Those skilled in the art that readily understand, under certain conditions, pyrolysis step and reduction activation step can be merged into a step and carry out.
We think: the catalyzer that coprecipitation method obtains and the catalyzer that pickling process obtains are fundamentally said so different, and this species diversity is reflected on their catalytic performance.
It is that raw material production contains the method for carbon number greater than 1 hydro carbons with the synthesis gas that the present invention also provides a kind of.This method comprises: synthesis gas is contacted with the catalyzer of the formula I of process reduction activation, and catalytic condition is: 190～400 ℃ of temperature, pressure 0～100 crust.
The reduction activation of the synthetics of formula I both can be used as an independent step and had carried out outside the synthesis gas conversion reactor, at synthesis gas conversion previous crops is that an independent process carries out in the synthesis gas transmodulator, also can be in the synthesis gas transmodulator, carry out under the switch condition of synthesis gas.
People knew in this area, the main component of synthesis gas was carbon monoxide and hydrogen, may contain a spot of carbonic acid gas, nitrogen and other rare gas element in addition, and this depends primarily on the source and the purity of synthesis gas.In this area, producing the method for synthesis gas and establish, generally is to produce by the incomplete oxidation of this class carbonaceous material of coal.The example of other method has: the water vapor catalyzed conversion by methane is produced synthesis gas.For realizing purpose of the present invention, so that the ratio control of carbon monoxide and hydrogen was advisable between 2: 1 and 1: 6.And in the synthesis gas with method for preparing, the ratio of carbon monoxide and hydrogen ratio therewith may not be inconsistent to some extent.But can carry out suitable adjustment to this ratio, or by so-called conversion reaction adjustment, the understanding those skilled in the art know to this reaction right and wrong Changshu by adding carbon monoxide or hydrogen.
Any of above-mentioned preparation hydrocarbon polymer method improved, and catalyzer can share with inert material such as silicon-dioxide, but to share to good with zeolite.
Zeolite can with the fusion of synthetics physics, form tight mixolimnion, also can separately constitute and separate bed, zeolite is one deck, catalyzer be another layer.When adopting the physics fusion, zeolite can also can carry out thereafter before reduction activation with both mixing of synthetics.Also have a kind of method, promptly when producing the formula I synthetics, (A) Bu co-precipitation can be carried out in the presence of zeolite, especially when precipitation agent be volatile salt and (or) bicarbonate of ammonia and (or) particularly like this during ammonium hydroxide.
MFI type zeolite is as at United States Patent (USP) 3,702, and the ZSM-5 type zeolite of introducing in No. 886 is a kind of suitable zeolite, preferably uses h-type zeolite, and the latter can obtain by acid exchange or method for pyrolysis with ammonium crossover zeolite.The synthetics of alkali-free metal (being b=0 in the formula I) improves its performance for well to use with zeolite facies bonded method.Catalyzer synthetics volume fraction is advisable with 5: 1 to 1: 5 with the ratio of zeolite volume fraction, with about 2: 1 for well.Combine the selectivity that can improve to gasoline boiling range chain hydrocarbon with zeolite.
Temperature is preferably in 250～350 ℃ of scopes and chooses, and pressure is preferably in 10～50 crust scopes and chooses, and air speed (GHSV) is preferably in 100～5000h
-1Choose in the scope.
This process can fixed bed, fluidized-bed or in the suspending phase reactor intermittently or carry out continuously.
Below further specify the present invention by example.
Preparation of Catalyst
(a) high temperature coprecipitation method
Example 1-synthetics A(0.5%Ru/Kx/CeO
2)
With cerous nitrate (68.8 grams; 0.16 mol) be dissolved in the deionized water (300 milliliters), then ruthenium chloride (III) (0.31 gram; 0.001 hot deionized water mol) (30 milliliters) solution is added in the above-mentioned solution, under agitation solution is heated to 80 ℃, and then deionized water (200 milliliters) drips of solution of salt of wormwood (160 gram) is added in the above-mentioned solution, till the pH value reaches 8.3 (about 60 milliliters).With the gained mixture under agitation, under about 90 ℃ of temperature, heat half an hour.Leach the gray precipitate thing that obtains, use deionized water (2 * 500 milliliters) to stir to wash and starch again and wash twice, at last in air, 125 ℃ of dryings 17.0 hours.
Example 2-synthetics B(0.5%Ru/Kx/CeO
2)
Repeat the step of example 1.
Example 3-synthetics C
Prepare 0.5%Ru/Kx/CeO by example 1 step
2Catalyzer adds the 1%(weight ratio in addition in above-mentioned synthetics) potassium.
Example 4～example 6 syntheticss D～synthetics F
Cerous nitrate (68.8 grams, 0.16 mol) is dissolved in the deionized water (200 milliliters), then ruthenium chloride (III) (0.31 gram; 0.001 hot deionized water mol) (300 milliliters) solution is added in the above-mentioned solution, with the solution that obtains under stirring fast, in about 80～85 ℃ of heating, then, again deionized water (1000 milliliters) solution of salt of wormwood (150 gram) speed with 25 milliliters of per minutes is added in the above-mentioned solution, till the pH value reaches 8.5～9.5 (about 225 milliliters).The mixture heating up that obtains is arrived boiling, and kept 12 minutes.Remove thermal source then, continue to stir 20 minutes.The throw out that obtains is stayed in the solution and is kept a night, filters then, then with deionized water (2 * 300 milliliters) it is stirred to wash and starch and washs twice, again in air, in 150 ℃ of dried overnight (17.0 hours).
(b) low-temperature co-precipitation method
Example 7-synthetics G
With cerous nitrate (68.8 grams; 0.16 mol) be dissolved in the deionized water (300 milliliters), then chlorination shackles (III) (0.34 gram, 0.0011 hot deionized water mol) (30 milliliters) solution is added in the above-mentioned solution, under room temperature, violent stirring, be added drop-wise in the above-mentioned solution then deionized water (500 milliliters) solution of salt of wormwood (75 gram), reach till 9.5 up to the pH value, the mixed solution that obtains continues to stir 15 minutes, to guarantee abundant reaction.Leach the gray precipitate thing that obtains, use deionized water (2 * 300 milliliters) to stir to wash and starch then and wash twice, at last in air, 120 ℃ of dryings 17 hours.
(c) pyrolysis, reduction activation are to make catalyzer
(i) catalyst A～G
Corresponding synthetics is carried out pre-treatment as follows:
The catalyzer check
Example 8
Catalyst A is sieved into B.S. specification 8～20 purpose particles and the fixed-bed reactor of packing into.At 225 ℃, in reactor, catalyzer was reduced 17 hours with slow hydrogen stream, then synthesis gas is fed reactor, adjust pressure to 20 crust and begin test.
It is as shown in the table for reaction conditions that adopts and accordingly result.
Example 9
Replace catalyst A with catalyst B, repeat the step of example 8.
Example 10
Replace catalyst A with catalyzer C, repeat the step of example 8.
Example 11
Replace catalyst A with catalyzer D, repeat the step of example 8.
Example 12
Replace catalyst A with catalyzer E, repeat the step of example 8.
Example 13
Replace catalyst A with catalyzer F, repeat the step of example 8.
Example 14
Replace catalyst A with catalyzer G, repeat the step of example 8.
Example 15
Replace catalyst A to separate bed, repeat the step of example 8.This top is the catalyzer by the method preparation for preparing catalyst A (6.0 milliliters), and the bottom is Hydrogen MFI zeolite (4.0 milliliters).
Example 16
Improve temperature, repeat the step of example 15.
Reaction conditions and resulting result that example 8 adopts to the example 16 are as shown in the table:
Claims (7)
1, a kind of is that raw material production contains the method for carbon number greater than 1 hydrocarbon polymer with the synthesis gas that contains carbon monoxide and hydrogen, and this method is included under the pressure of 190-400 ℃ and normal pressure-100 crust, and synthetic gas is contacted with catalysis; This catalyzer contains the composition of the reduction activation with following formula:
RuaAbCeOx (Ⅰ)
Wherein: A is a basic metal,
X satisfies the number that other element requires the valency of oxygen,
A is greater than 0, less than 1% (weight ratio), and by total composition,
The value of b is in 0 to 10% (weight ratio), by total composition,
Ce and O constitute the rest part of said composition, and the composition of described tool formula I is the following steps preparations:
(A) be incorporated into the soluble salt of metal Ru and cerium and the carbonate of alkali metal containing or ammonium and/or the precipitation agent of supercarbonate and/or alkali metal hydroxide in the solution together, up to the final pH value greater than 6, but the precipitation of Xing Chenging contains ruthenium and the cerium compound that thermolysis is an oxide compound thus, (B) recycling step (A) gained precipitation.
2, by the process of claim 1 wherein temperature in 250～350 ℃ of scopes, pressure is in 10～50 crust scopes.
3, by the process of claim 1 wherein before reduction activation or a kind of zeolite being combined with the catalyzer synthetics.
4, by the method for claim 3, its mesolite is a MFI type zeolite.
5, by the method for claim 3, its mesolite is a h-type zeolite.
6, by the method for claim 3, wherein do not contain basic metal in the catalyzer synthetics.
7, by the method for claim 3, wherein the ratio of the volume fraction of the volume fraction of catalyzer synthetics and zeolite is between 5: 1 and 1: 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102274 CN1014399B (en) | 1989-04-14 | 1989-04-14 | Syngas conversion catalyst production and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102274 CN1014399B (en) | 1989-04-14 | 1989-04-14 | Syngas conversion catalyst production and use thereof |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85106510A Division CN1008973B (en) | 1984-07-25 | 1985-08-29 | The preparation method of syngas conversion catalyst |
| CN85106510 Division | 1989-04-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1037889A CN1037889A (en) | 1989-12-13 |
| CN1014399B true CN1014399B (en) | 1991-10-23 |
Family
ID=4854626
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89102274 Expired CN1014399B (en) | 1989-04-14 | 1989-04-14 | Syngas conversion catalyst production and use thereof |
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| CN (1) | CN1014399B (en) |
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| CN102464563B (en) * | 2010-11-17 | 2013-12-04 | 中国石油化工股份有限公司 | Method for producing isopropylbenzene |
| CN103030519B (en) * | 2011-09-29 | 2015-05-13 | 中国石油化工股份有限公司 | Production method for alkylbenzene |
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