CN101646641B - Process for the conversion of syngas to oxygenates - Google Patents
Process for the conversion of syngas to oxygenates Download PDFInfo
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- CN101646641B CN101646641B CN2007800422533A CN200780042253A CN101646641B CN 101646641 B CN101646641 B CN 101646641B CN 2007800422533 A CN2007800422533 A CN 2007800422533A CN 200780042253 A CN200780042253 A CN 200780042253A CN 101646641 B CN101646641 B CN 101646641B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- 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
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- 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
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Abstract
A process for the production of oxygenated hydrocarbons from carbon monoxide and hydrogen in the presence of one or more reduced sulphur compounds, in which a reaction composition comprising carbon monoxide, hydrogen and one or more reduced sulphur compounds is contacted with a catalyst comprising a metal active for the production of oxygenated hydrocarbons from carbon monoxide and hydrogen and an inorganic semiconducting oxide support that is capable of catalysing the oxidation of reduced sulphur compounds, in which the concentration of the one or more reduced sulphur compounds in the reaction composition is greater than 0.5ppm by weight, expressed as elemental sulphur.
Description
The present invention relates to catalytic field, more specifically, relate to a kind of wherein catalyzer to the inactivation due to the sulphur have resistivity catalysis process.
Coal is the fuel that is widely used in generating.But with other fuel, compare as crude oil derived fuel or Sweet natural gas, it often is out of favour, and reason is that its unit weight burning release can be low usually.In addition, coal often contains relatively large sulphur, these sulphur may be usually in the process of using the coal derived feed as the poisonous substance of catalyzer, and may reduce life of catalyst and activity.
As a result, in many cases, must carry out pre-treatment to the high-sulfur raw material, so that sulphur is removed under the admissible level.Such raw materials pretreatment needs sizable investment spending and running cost.In addition, sacrifice for example zinc oxide of sorbent material because desulfurization is adopted usually, so this process has increased the generation of refuse.Therefore, a kind of catalyzer of ability higher amount sulphur is favourable for alleviating and even eliminating this pretreated needs.
Methyl alcohol is a kind of important large commercial chemicals, is produced by synthetic gas (mixture of hydrogen and carbon monoxide) usually.Synthetic gas can be by multiple starting material, particularly for example Sweet natural gas, heavy oil, coal and biomass production of hydrocarbon source.Yet, present catalyzer such as the Cu/ZnO/Al that uses
2O
3Existence to sulphur in the raw material of synthetic gas is extremely sensitive, and even be low to moderate in its amount 0.5ppm sulphur in the presence of, usually also can inactivation.Typical raw material of synthetic gas particularly when being derived by coal, can have the sulfur content in the scope of 10～100ppm.Therefore, still need a kind of method that is used for synthetic gas is changed into oxygenatedchemicals that can restrain oneself the sulphur that exists in the raw material.
According to the present invention, provide a kind of for the method for being produced one or more oxygen-containing hydrocarbons by hydrogen and carbon monoxide, described method comprises makes catalyzer contact under the sufficiency of producing one or more oxygen-containing hydrocarbons with reaction mixture (composition), described reaction mixture comprises carbon monoxide, hydrogen and one or more reduced sulfur compounds, described catalyst pack containing metal and carrier, described metal is active for hydrogen and carbon monoxide are changed into one or more oxygen-containing hydrocarbons, described carrier comprises the semi-conductor inorganic oxide of oxidation that can catalytic reduction attitude sulphur compound, it is characterized in that, by the weight of representing according to elementary sulfur, one or more reduced sulfur compound concentrations in the described reaction mixture are greater than 0.5ppm.
In the present invention, can the concentration of representing according to elementary sulfur greater than 0.5ppm than the high-sulfur environment in, the catalyzer that has carrier by use carries out synthesizing from the carbon monoxide to the oxygen-containing hydrocarbon, described carrier contains the inorganic oxide with semiconductor property, and the reduced sulfur compound oxidation can be become to have the sulphur compound of sulphur of the oxidation state of increase.An example of such sulphur oxidizing reaction is: all be-2 H with the sulphur oxidation value
2S or COS be oxidized to respectively have+4 and sulfurous gas or the sulphur trioxide of+6 oxidation value.
Generally include Cu and support ZnO/Al
2O
3The conventional methanol synthesis catalyst of carrier often may be present in reduced sulfur compound in the raw material of synthetic gas such as organic sulfide, mercaptan, H
2There are rapid deactivation down in S, COS etc.This inactivation is considered to take place with the result any or reaction between two kinds in carrier and/or the catalyst metal as sulphur compound.May cause the sulfuration of catalyst metal like this, thereby cause active the reduction and even complete deactivation.In addition, the sulphur compound of going back ortho states can react with carrier.For example, under the situation of zinc oxide, sulphur is adsorbed in the oxide structure, thereby zinc oxide is converted to zinc sulphide.Cause that like this sulphur concentration around the catalyst metal increases, thereby aggravate any inactivating effect.Because zinc oxide is not easy regeneration under reaction conditions, therefore in addition a spot of sulphur just can impel the foundation of sulphur compound in the structure, the result causes the loss of catalyst activity.
The present invention is head it off by such carrier is provided, and described carrier can typically be oxidized to the reduced sulfur kind and be referred to as SO below one or more
xOxysulfide, for example sulfurous gas or sulphur trioxide.Under the situation that is not subject to any theory, it is believed that the inorganic semiconductor oxide compound can offer lattice oxygen (framework oxygen) sulphur compound of going back ortho states with they oxidations.This can realize that on described oxygen room, oxygenatedchemicals such as oxygen, carbonic acid gas or water that the lattice oxygen that removes then can be existed in the reaction raw materials substitute by the formation in lattice oxygen room; Perhaps as selecting, this can be realized by sulfur by making lattice oxygen, suppressed by vector catalyzed oxidation in the presence of the oxygenatedchemicals that described sulphur subsequently can be in raw material, result's oxide compound of regenerating.In some embodiments of the present invention, with the also Cu/ZnO/Al of rapid deactivation for example even in the presence of the sulphur concentration that is low to moderate 0.5ppm
2O
3The sulphur inactivating effect by contrast, in fact activity of such catalysts can strengthen because of the existence of reduced sulfur.
Described metal can be for being active any metal by hydrogen and carbon monoxide synthesizing oxygen-containing hydrocarbon.In one embodiment of the invention, described metal is selected from one or more among Cu, Cr, Co, Mo, Pt, Pd and the Rh, and is preferably Cu and/or Pd.
The catalyzer that is used for the inventive method can randomly comprise: annexing ingredient, and for example promotor or stabilizer component, it is selected from and for example comprises basic metal, alkaline-earth metal, Sc, Y, La, Nd, Mn, one or more elements in the group of Zn and Al.
Described carrier comprises one or more inorganic semiconductor compounds, and these compounds can will contain reduced sulfur under reaction conditions compound for catalysis is oxidized to oxidation state sulphur compound such as SOx.Randomly, the doped semiconductor inorganic oxide is to give or to improve its semiconductor property or produce the ability in oxygen room.Preferably, described inorganic semiconductor oxide compound is selected from lanthanide oxide, TiO
2, ZrO
2And ThO
2In one or more.Most preferably, carrier comprises and is selected from lanthanide oxide, CeO
2And ZrO
2In one or more, and most preferably, carrier is CeO
2And/or ZrO
2Randomly, can be with one or more semiconductor compounds and one or more non-semiconductor compound, for example CeO
2/ Al
2O
3And ZrO
2/ Al
2O
3Carrier can comprise other component, for example adhesive material extraly.
Inorganic oxide carrier can be by the precipitation path of preparing, and wherein soluble and/or colloid inorganic oxide precursor is processed with the preparation soild oxide.If exist in the carrier more than a kind of oxide compound, then can utilize the co-precipitation route, wherein with the mixture coprecipitation of the solvable of each oxide compound and/or colloid precursor, the soild oxide that mixes with preparation.In another embodiment of the invention, with metal and one or more oxide precursor material coprecipitations, catalyst-loaded to form.By co-precipitation or by a kind of precursor in the oxide compound is deposited on the another kind of oxide compound, can prepare oxide compound compound or that mix.
When the catalyst metal loading on the semi-conductor inorganic oxide was higher than certain threshold value, the life-span of catalyzer in the presence of the reduced sulfur compound can further be prolonged.Usually, catalyst metal (if perhaps there is multiple catalyst metal, then being at least a in the catalyst metal) and the mol ratio of the nonoxygen element of semi-conductor inorganic oxide were greater than 0.09: 1.Usually, the loading of supported catalyst metal surpasses 5 weight %, and more preferably greater than 8 weight %, and most preferably be more than the 10 weight %.When palladium existed, the mol ratio of the nonoxygen element of palladium and semi-conductor inorganic oxide was preferably greater than 0.09: 1, more preferably greater than 0.14: 1.Palladium loading on carrier is preferably greater than 5 weight %, more preferably greater than 8 weight %, and most preferably is more than the 10 weight %.Under the situation that copper exists as only catalyst metal, the copper mol ratio preferably surpasses 0.22: 1, and more preferably more than 0.39: 1.Preferably, the loading of copper on carrier be greater than 8 weight %, and more preferably more than the 10 weight %.
When being used for the method that hydrogen and carbon monoxide change into one or more oxygen-containing hydrocarbons used, catalyzer can use under not pretreated situation, or can optionally reduce, for example in hydrogen stream or hydrogen nitrogen mixed flow, reduce, before use the active catalytic metals component is reduced.The pre-reduction temperature is usually above 100 ℃, to guarantee that any catalyst metal is to effective conversion of going back ortho states or possible hydrogenation structure formation.Preferably be lower than 300 ℃ reduction temperature to improve catalyst activity.The optimum temps of pre-reduction is usually in 220～260 ℃ scope.
In the method for the invention, the reaction mixture that will comprise hydrogen and carbon monoxide contacts with catalyzer, to prepare one or more oxygen-containing hydrocarbons, as alcohol, ester, carboxylic acid and ether.In one embodiment, this method is to produce one or more alcohol by hydrogen and carbon monoxide, and preferably for the production of the method for methyl alcohol and/or dme.The temperature of reaction that adopts is usually at 100～450 ℃, preferably in 170～300 ℃ scope.Usually, increase temperature of reaction and cause the rising of carbon monoxide transformation efficiency, methyl alcohol selectivity to reduce, and the selectivity of carbonic acid gas and light hydrocarbon raises.Usually in 220～280 ℃ temperature range, particularly in 240～260 ℃ scope, obtain best methyl alcohol selectivity and yield.
Reaction pressure is clung to (in 0.1～10MPa) the scope at 1-100 usually.Although the hydrocarbon yield also increases with pressure, higher pressure often causes the methyl alcohol selectivity and the carbon monoxide transformation efficiency that improve.The carbonic acid gas yield often increases with pressure and reduces.Pressure is preferably at 10～60 bar (in 1～6MPa) the scope.
Synthetic gas is a kind of carbon monoxide that conveniently is easy to get and hydrogen resource.Synthetic gas can be by for example Sweet natural gas, liquid hydrocarbon, coal or the biomass preparation of multiple material.Sulfur resistant catalyst of the present invention is particularly suitable for containing the synthetic gas of higher sulfur content, the synthetic gas when for example being derived by coal.Catalyzer ability of the present invention surpasses 0.5ppm (representing according to elementary sulfur), for example more than the 3ppm, or the above sulfur content of 10ppm.Preferably, this catalyzer ability is up to the sulfur content of 100ppm.
Carbon monoxide in reaction mixture and hydrogen (CO: H
2) mol ratio usually in 10: 1 to 1: 10 scope, and preferably in 5: 1 to 1: 5 scope, for example in 3: 1 to 1: 3 scope.Preferably, this ratio is in 1: 1 to 1: 3 scope.
Gas hourly space velocity (GHSV) increase causes methyl alcohol and hydrocarbon yield to reduce usually, and the carbon monoxide transformation efficiency reduces, and the carbonic acid gas yield often increases, and described gas hourly space velocity per hour is expressed as the volume of gas (under standard temperature and pressure (STP)) on the per volume of catalyst.Yet, if GHSV is low excessively, also may cause the methyl alcohol selectivity to reduce.GHSV preferably is maintained at 500～5000h
-1Scope in, more preferably at 500～2000h
-1Scope in value.
Reaction mixture can additionally comprise oxygen source, as water, oxygen or carbonic acid gas.In one embodiment of the invention, in the synthetic gas that can supply to process system, there is molecular oxygen.In a selectivity embodiment, wittingly oxygen is joined in the reaction mixture.Oxygen with molecular oxygen or oxygenatedchemicals for example water or form of carbon dioxide to exist be favourable because it can promote the formation of SOx, and can remove oxide compound room in the carrier, thereby promote the anti-sulphur of catalyzer.Therefore, can be conducive to catalytic activity and life-span like this.Oxygen source can be accompanied by hydrogen and carbon monoxide is supplied in the process system continuously.As selection, when catalytic activity and/or product yield begin to descend, can supply with oxygen source off and on to improve transformation efficiency.
Add no matter be present in the raw material or have a mind to, the concentration of molecular oxygen is usually at 1 weight % at the most, for example at the most in the scope of 0.5 weight %.Preferably, molecule keto concentration＞10ppm.
Carbonic acid gas can be present in the reaction mixture with one or more the composition form in the feed composition (for example, synthetic gas), perhaps prepares in reaction process, perhaps joins in the reaction mixture individually.Carbonic acid gas can also help the reduced sulfur compound to the conversion of oxidation state sulphur compound, and helps inorganic oxide is reoxidized.When existing, its concentration in reaction mixture can be at 15 weight % at the most, for example at the most in the scope of 10 weight %, and usually above 10ppm.
Now will be in the following example and the present invention is described with reference to the accompanying drawings, in the accompanying drawings:
Fig. 1 has shown one of reaction scheme of the catalyst deactivation under the inhibition sulphur existence of advising.
Fig. 2 shown the catalyst deactivation of the inhibition sulphur of suggestion under existing reaction scheme two.
Fig. 3 is at 3ppm H
2Produced in the process of methyl alcohol Pd/Al under the existence of S by hydrogen and carbon monoxide
2O
3The graphic representation of the catalytic activity of catalyzer;
Fig. 4 is at 3ppm H
2Produced in the process of methyl alcohol Pd/CeO under the existence of S by hydrogen and carbon monoxide
2The graphic representation of the catalytic activity of catalyzer;
Fig. 5 is at 11ppm H
2Produced in the process of methyl alcohol by hydrogen and carbon monoxide under the existence of S, have the Pd/CeO of different palladium loadings
2The graphic representation of the carbon monoxide transformation efficiency of catalyzer;
Fig. 6 is at 11ppm H
2Produced in the process of methyl alcohol by hydrogen and carbon monoxide under the existence of S, have the Pd/CeO of different palladium loadings
2The methyl alcohol of catalyzer is graphic representation optionally;
Fig. 7 is at 2.2ppm COS and 0.8ppm H
2Produced in the process of methyl alcohol Pd/CeO under the existence of S by hydrogen and carbon monoxide
2The graphic representation of the catalytic activity of catalyzer;
Fig. 8 is at 30ppm H
2Produced in the process of methyl alcohol Pd/CeO under the existence of S by hydrogen and carbon monoxide
2The graphic representation of the catalytic activity of catalyzer;
Fig. 9 is at 36ppm H
2Produced in the process of methyl alcohol Pd/ZrO under the existence of S by hydrogen and carbon monoxide
2The graphic representation of the catalytic activity of catalyzer;
Figure 10 is at 36ppm H
2Produced in the process of methyl alcohol the graphic representation of the catalytic activity of Cu/ZnO catalyzer under the existence of S by hydrogen and carbon monoxide;
Figure 11 is at 30ppm H
2Produced in the process of methyl alcohol Cu/CeO under the existence of S by hydrogen and carbon monoxide
2The graphic representation of the catalytic activity of catalyzer;
Figure 12 is at 36ppm H
2Produced in the process of methyl alcohol Cu/ZrO under the existence of S by hydrogen and carbon monoxide
2The graphic representation of the catalytic activity of catalyzer;
Figure 13 is at 36ppm H
2Under the existence of S, Cu/ZrO
2The carbon monoxide transformation efficiency of catalyzer is with respect to the graphic representation of copper loading;
Figure 14 is at 11ppm H
2Produced in the process of methyl alcohol Pd/CeO under the existence of S by hydrogen and carbon monoxide
2/ Al
2O
3The graphic representation of the catalytic activity of catalyzer;
Figure 15 is at 2.2ppm COS and 0.8ppm H
2Produced in the process of methyl alcohol Pd-Cu/CeO under the existence of S by hydrogen and carbon monoxide
2The graphic representation of the catalytic activity of catalyzer;
Figure 16 is having and is not having 30ppm H
2Produced in the process of methyl alcohol Pd/CeO under the situation of S by hydrogen and carbon monoxide
2The graphic representation of the catalytic activity of catalyzer;
Figure 17 is having and is not having 30ppm H
2Under the situation of S, Pd/CeO
2The graphic representation of the methyl alcohol of catalyzer and dme (DME) yield;
Figure 18 is having and is not having 30ppm H
2Under the situation of S, Pd/CeO
2The graphic representation of the carbonic acid gas yield of catalyzer;
Figure 19 is having and is not having 30ppm H
2Under the situation of S, Pd/CeO
2The graphic representation of the light hydrocarbon yield of catalyzer;
Figure 20 is to use Pd/CeO
2The carbon monoxide transformation efficiency of catalyzer under differing temps and the optionally comparison diagram of methyl alcohol, carbonic acid gas and light hydrocarbon;
Figure 21 is to use Pd/CeO
2The carbon monoxide transformation efficiency of catalyzer under different pressures and the optionally comparison diagram of methyl alcohol, carbonic acid gas and light hydrocarbon;
Figure 22 is to use Pd/CeO
2The carbon monoxide transformation efficiency of catalyzer under different gas hourly space velocities and the optionally comparison diagram of methyl alcohol, carbonic acid gas and light hydrocarbon.
Reaction scheme shown in Figure 1 has shown forward reaction 1, and backward reaction 2, and catalyzer 3 comprises to be supported on and is called MO
xSemi-conductor inorganic oxide carrier 5 on metal E 4, described metal E 4 is active for hydrogen and carbon monoxide to the conversion of oxygen-containing hydrocarbon.In forward reaction, H
2The reaction of S and inorganic oxide, thus cause sulphur combined 6 and enter carrier (MO
xAnd discharge water outlet S).In backward reaction, sulphur is by being removed with the oxygen reaction that is present in the reaction mixture, thereby causes SO
xRelease and MO
xThe regeneration of carrier.
The reaction scheme of Fig. 2 is presented at and has generated oxygen room (MO in the oxide compound
x) 7, but not form the inorganic oxide that vulcanizes.Therefore, not from carrier, to discharge water, but from carrier, obtain oxygen to form SO
x, the room is by being removed with the oxygen reaction.
Embodiment 1-Pd/Al
2O
3
Prepare catalyzer by following steps: by adopting 25gNa
2CO
3Solution in 60ml water is handled 22.5ml and is comprised Palladous chloride (II) (every milliliter has 20mg Pd) and 18.765gAl (NO as precipitation agent
3)
39H
2The aqueous solution of O.The pH value of maintenance 8～9 and 55 ℃ temperature.With aging 2 hours of the throw out that forms, filter, use distilled water wash afterwards, 120 ℃ of dried overnight, and roasting 6 hours in 360 ℃ of air.The Pd of catalyzer: the Al mol ratio is 0.08: 1, thereby produces the palladium loading of 15 weight %.
Because aluminum oxide is not conductor oxidate, therefore adopts the method for this catalyzer and do not meet the present invention.
Embodiment 2-4-Pd/CeO
2
Except using Ce (NO
3)
36H
2O replaces beyond the aluminum nitrate, uses the step identical with embodiment 1 to prepare these catalyzer.The amount of material therefor is listed in the table 1.20gNa
2CO
3Solution in 60ml water also is used to each embodiment.In embodiment 2, the Pd of catalyzer: the Ce mol ratio is 0.29: 1. Embodiment 3 and 4 mol ratio are respectively 0.18: 1 and 0.09: 1.These produce the palladium loading of 15 weight %, 10 weight % and 5 weight % respectively.
Because palladium is active for synthetic gas to the synthetic of oxygen-containing hydrocarbon, and cerium dioxide be can the oxidation of catalytic reduction attitude sulphur compound conductor oxidate, therefore adopt any method in these catalyzer can meet the present invention.
Table 1: the amount of the material that in embodiment 2-4, adopts
| Embodiment | Pd amount of solution (ml) | Ce(NO 3) 3·6H 2O(g) |
| 2 | 22.5 | 6.450 |
| 3 | 15.0 | 6.813 |
| 4 | 7.5 | 7.191 |
Embodiment 5-Pd/ZrO
2
Except the palladium solution and the 20gNa that use 30ml
2CO
3Beyond the solution in 40ml water, use the step identical with embodiment 1 to prepare catalyzer.In addition, use 11.846g Zr (NO
3)
45H
2O replaces aluminum nitrate.The Pd of catalyzer: the Zr mol ratio is 0.20: 1, thereby produces the palladium loading of 15 weight %.
Because palladium is active for synthetic gas to the synthetic of oxygen-containing hydrocarbon, and zirconium white be can the oxidation of catalytic reduction attitude sulphur compound conductor oxidate, therefore adopt the method for this catalyzer can meet the present invention.
Embodiment 6-Cu/ZnO
With 13.904g Cu (NO
3)
23H
2O and 8.559g Zn (NO
3)
26H
2O is dissolved in the 50ml deionized water, and with 20g Na
2CO
3Solution in 50ml water mixes.Mixture was stirred 2 hours, and keep 8～9 pH value, and 55 ℃ temperature.With aging 2 hours of the throw out that forms, filter, use distilled water wash afterwards, 120 ℃ of dried overnight, and roasting 6 hours in 360 ℃ of air.The Cu of catalyzer: the Zn mol ratio is 2: 1, thereby produces the copper loading of 56.6 weight %.
Because therefore the not oxidation of catalytic reduction attitude sulphur compound of zinc oxide adopts the method for this catalyzer not meet the present invention.
Embodiment 7-Cu/CeO
2
Except using 9.479g Cu (NO
3)
23H
2O and 20g Na
2CO
3Beyond the solution in 40ml water, use the step identical with embodiment 6.In addition, use 8.521g Ce (NO
3)
36H
2O replaces zinc nitrate.The Cu of catalyzer: the Ce mol ratio is 2: 1, thereby produces the copper loading of 42.5 weight %.
Because copper is active for synthetic gas to the synthetic of oxygen-containing hydrocarbon, and cerium dioxide be can the oxidation of catalytic reduction attitude sulphur compound conductor oxidate, therefore adopt the method for this catalyzer can meet the present invention.
Embodiment 8-Cu/ZrO
2
Except using 11.580g Cu (NO
3)
23H
2O and 25g Na
2CO
3Beyond the solution in 60ml water, use the step identical with embodiment 6.In addition, use 10.304g Zr (NO
3)
45H
2O replaces zinc nitrate.The Cu of catalyzer: the Zr mol ratio is 2: 1, thereby produces the copper loading of 50.7 weight %.
Because copper is active for synthetic gas to the synthetic of oxygen-containing hydrocarbon, and zirconium white be can the oxidation of catalytic reduction attitude sulphur compound conductor oxidate, therefore adopt the method for this catalyzer can meet the present invention.
Embodiment 9-15-Cu/ZrO
2
Except using the quantity of material list in the table 2, use the step identical with embodiment 8.
With embodiment 8, because copper is active for synthetic gas to the synthetic of oxygen-containing hydrocarbon, and zirconium white and cupric oxide be can the oxidation of catalytic reduction attitude sulphur compound conductor oxidate, therefore adopt any method in these catalyzer can meet the present invention.
Table 2: the amount of the salt that in embodiment 9-15, adopts
Embodiment 16-Pd/CeO
2/ Al
2O
3
Except using 45ml palladium solution, 30g Na
2CO
3Solution in 50ml water and 11.206gCe (NO
3)
36H
2Beyond the O, use the step identical with embodiment 2.In addition, with 4.841gAl (NO
3)
39H
2O adds in this solution.The Pd of catalyzer: Ce: the Al mol ratio is 0.33: 1: 0.5.Produced the CeO of 15 weight % like this
2/ Al
2O
3On the Pd loading.
Because palladium is active for synthetic gas to the synthetic of oxygen-containing hydrocarbon, and carrier contains the cerium dioxide as conductor oxidate that can the oxidation of catalytic reduction attitude sulphur compound, therefore adopts the method for this catalyzer can meet the present invention.
Embodiment 17-Pd-Cu/CeO
2
Except using 19.6ml palladium solution, 20g Na
2CO
3Solution in 50ml water and 6.45gCe (NO
3)
36H
2Beyond the O, use the step identical with embodiment 2.In addition, with 0.222gCu (NO
3)
23H
2O adds in this solution.The Pd of catalyzer: Cu: the Ce mol ratio is 0.25: 0.06: 1.Produce the CeO of 13.1 weight % like this
2On the Pd loading, and the CeO of 1.9 weight %
2On the copper loading.
With embodiment 2-4 and 7, adopt the method for this catalyzer can meet the present invention.
All catalyzer compositions of summarizing are listed in the table 3.
Table 3: catalyzer is formed
| Embodiment | Catalyst metal | Inorganic oxide carrier | Mol ratio | Catalyst metal, |
| 1 | Pd | Al 2O 3 | Pd∶Al＝0.08∶1 | 15.0 |
| 2 | Pd | CeO 2 | Pd∶Ce＝0.29∶1 | 15.0 |
| 3 | Pd | CeO 2 | Pd∶Ce＝0.18∶1 | 10.0 |
| 4 | Pd | CeO 2 | Pd∶Ce＝0.09∶1 | 5.0 |
| 5 | Pd | ZrO 2 | Pd∶Zr＝0.20∶1 | 15.0 |
| 6 | Cu | ZnO | Cu∶Zn＝2.00∶1 | 56.6 |
| 7 | Cu | CeO 2 | Cu∶Ce＝2.00∶1 | 42.5 |
| 8 | Cu | ZrO 2 | Cu∶Zr＝2.00∶1 | 50.7 |
| 9 | Cu | ZrO 2 | Cu∶Zr＝0.39∶1 | 10.3 |
| 10 | Cu | ZrO 2 | Cu∶Zr＝0.85∶1 | 30.6 |
| 11 | Cu | ZrO 2 | Cu∶Zr＝1.33∶1 | 40.7 |
| 12 | Cu | ZrO 2 | Cu∶Zr＝2.99∶1 | 60.7 |
| 13 | Cu | ZrO 2 | Cu∶Zr＝4.65∶1 | 70.6 |
| 14 | Cu | ZrO 2 | Cu∶Zr＝17.95∶1 | 90.3 |
| 15 | Cu | CuO | - | - |
| 16 | Pd | CeO 2/Al 2O 3 | Pd∶Ce∶Al＝ 0.33∶1∶0.5 | 15.1 |
| 17 | Pd Cu | CeO 2 | Pd∶Cu∶Ce＝ 0.25∶0.06∶1 | 13.2/1.9a |
aPd (weight %)/Cu (weight %)
Evaluating catalyst
The powder catalyst sample is at 20MPa pressure lower sheeting, broken then, and screening is to obtain 20～40 purpose granularities.With the screening particle of 0.4g with the quartzy sand grains dilution of 1.0g, and be loaded into long 140mm, internal diameter is in the stainless steel fixed-bed tube reactor of 14mm.The catalyst bed height that produces is about 5mm.Catalyzer was being reduced 8 hours in 100% hydrogen stream (6.67ml/min) under the temperature of appointment.To contain CO: H then
2Mol ratio is that the reaction mixture of 1: 2 hydrogen and carbon monoxide is at the temperature of reaction of appointment, absolute pressure and the 1000h of 3.0MPa
-1GHSV (gas hourly space velocity) under be supplied to catalyzer.Unstripped gas also comprises 5 volume %CO
2With 2.3 volume %N
2Sulphur is also with the H of different concns
2S or COS and H
2The array configuration of S is present in the unstripped gas.
Adopt online gas-chromatography and the high-pure helium carrier gas of the carbonaceous molecular sieve pillar that is equipped with long 1.5m to measure from the quantity of methyl alcohol in the product stream of tubular reactor.
Pd/Al with embodiment 1
2O
3Catalyzer is at 300 ℃ of pre-reduction.It is to adopt to contain 3ppmH
2The raw material of S is studied under 240 ℃ temperature of reaction.Also with O
2Concentration with 0.5 volume % adds in the raw material.Fig. 3 has shown optionally result of CO transformation efficiency during 100 hours and methyl alcohol.CO transformation efficiency and methyl alcohol selectivity all reduce in time, thereby show catalyst deactivation.This is not the method according to this invention, because aluminum oxide is not conductor oxidate.
Pd/CeO with embodiment 2
2Catalyzer is at 300 ℃ of pre-reduction.It is to adopt to contain 3ppmH
2The raw material of S is studied under 240 ℃ temperature of reaction.Also with O
2Concentration with 0.5 volume % adds in the raw material.Fig. 4 has shown optionally result of CO transformation efficiency during 100 hours and methyl alcohol.After 20 hours initial amphibolia, two parameters all flatten in initial reaction, and beginning increases in time.This shows to have CeO
2The Pd catalyzer of carrier is the sulphur that ability exists.
Pd/CeO with embodiment 2～4
2Catalyzer is at 240 ℃ of pre-reduction, and employing contains 11ppm H under 240 ℃ temperature of reaction
2The raw material of S is studied.Also with O
2Concentration with 0.5 volume % adds in the raw material.Embodiment 3 and 4 is during 100 hours, and the results are shown among Fig. 5 of the CO transformation efficiency of embodiment 2 during 72 hours, and the methyl alcohol selectivity is shown among Fig. 6.The result shows, after going into operation 100 hours, with Pd/Al
2O
3Catalyzer is compared, and the methyl alcohol selectivity is higher.It also shows as palladium and CeO
2The mol ratio of carrier was greater than 0.09 o'clock, even the sulphur concentration in the raw material is higher, carbon monoxide transformation efficiency also higher and inactivation rate reduces.As by this result is found out obviously that with the comparison as a result of experiment 2 embodiment 2 this result shows that further even when sulphur content is higher, the carbon monoxide transformation efficiency of preprocessed catalyst is also higher under 240 ℃ lesser temps in hydrogen.
Pd/CeO with embodiment 2
2Catalyzer is at 300 ℃ of pre-reduction.It is to adopt to contain 0.8ppm H
2The raw material of S and 2.2ppm COS is studied under 240 ℃ temperature of reaction.Also with O
2Concentration with 0.5 volume % adds in the raw material.Fig. 7 has shown optionally result of CO transformation efficiency during 100 hours and methyl alcohol.After 20 hours initial activity reduction phase, active beginning increases in time in initial reaction.This experiment shows, Pd/CeO
2The different sulphur compounds that the catalyzer ability exists.
Pd/CeO with embodiment 2
2Catalyzer is at 240 ℃ of pre-reduction.It is to adopt to contain 30ppm H
2The raw material of S is studied under 240 ℃ temperature of reaction.Molecular oxygen is not added in the reactor.Fig. 8 has shown optionally result of CO transformation efficiency during 100 hours and methyl alcohol.After 20 hours initial activity reduction phase, active beginning increases in time in initial reaction.This experiment shows, Pd/CeO
2The catalyzer ability is present in the high density sulphur in the raw material.
Pd/ZrO with embodiment 5
2Catalyzer is at 240 ℃ of pre-reduction.It is to adopt to contain 36ppmH
2The raw material of S is studied under 240 ℃ temperature of reaction.Molecular oxygen is not added in the reactor.Fig. 9 has shown optionally result of CO transformation efficiency during 10 hours and methyl alcohol.Demonstrated high CO transformation efficiency.This experiment shows, ZrO
2It also is a kind of effective carrier of energy resisting high-concentration sulphur.
Experiment 7
With the Cu/ZnO catalyzer of embodiment 6 at 220 ℃ of pre-reduction.It is to adopt to contain 36ppmH
2The raw material of S is studied under 220 ℃ temperature of reaction.Molecular oxygen is not added in the reactor.Figure 10 has shown optionally result of CO transformation efficiency during 7 hours and methyl alcohol.The loss fast of active experience shows the not sulphur of ability a large amount of Cu/ZnO.
Cu/CeO with embodiment 7
2Catalyzer is at 220 ℃ of pre-reduction, and containing 30ppmH
2Under the existence of the raw material of S, test is 8 hours under 220 ℃ temperature of reaction, then 240 ℃ of tests 7 hours.Molecular oxygen is not added in the reactor.Figure 11 has shown optionally result of CO transformation efficiency during 15 hours and methyl alcohol.Do not observe loss of activity, and active increase under higher reaction temperatures.This experiment shows, even under high sulphur concentration, and Cu/CeO
2Catalyzer also has resistivity to the inactivation due to the sulphur.
Cu/ZrO with embodiment 8
2Catalyzer is at 220 ℃ of pre-reduction, and containing 36ppmH
2Under the existence of the raw material of S, test under 240 ℃ temperature of reaction, the time is 100 hours.Molecular oxygen is not added in the reactor.Figure 12 has shown optionally result of CO transformation efficiency during 100 hours and methyl alcohol.The active maintenance, stablize, and only observes the inactivation of not half.This experiment shows, even under high sulphur concentration, and Cu/ZrO
2Catalyzer also has resistivity to the inactivation due to the sulphur.
Cu/ZrO with embodiment 8～15
2Catalyzer is at 220 ℃ of pre-reduction, and containing 36ppm H
2Under the existence of the raw material of S, test under 220 ℃ temperature of reaction, the time is 10 hours.Molecular oxygen is not added in the reactor.Figure 13 has shown result's (data point markers is represented the embodiment numbering of catalyst system therefor) of the CO transformation efficiency of every kind of catalyzer after 10 hours.This experiment shows, Cu: the Zr mol ratio is greater than 1.33 and less than 17.95 ZrO
2Catalyst-loadedly show the highest activity, corresponding copper loading is greater than 40.7 weight % and less than 90.3 weight %.
Pd/CeO with embodiment 16
2/ Al
2O
3Catalyzer is at 300 ℃ of pre-reduction, and at 11ppmH
2Under the existence of S, test under 240 ℃ temperature of reaction, the time is 27 hours.Also with O
2Concentration with 0.5 volume % adds in the raw material.Figure 14 has shown optionally result of CO transformation efficiency during 27 hours and methyl alcohol.This result shows that the catalyzer with the carrier that contains conductor oxidate and non-semiconductor oxide compound still can anti-sulphur.
Pd-Cu/CeO with embodiment 17
2Catalyzer is at 300 ℃ of pre-reduction, and at 0.8ppmH
2Under the existence of S and 2.2ppm COS, test under 240 ℃ temperature of reaction, the time is 29 hours.Also with O
2Concentration with 0.5 volume % adds in the raw material.Figure 15 has shown optionally result of CO transformation efficiency during 29 hours and methyl alcohol.This result shows, the catalyzer that has not only contained the Pd catalyst metal but also contained the Cu catalyst metal also is active, and the sulphur concentration greater than 0.5ppm is had resistivity.
Containing 30ppm H
2Go into operation in the atmosphere of S and react 100 hours before with afterwards, with the Pd/Al of embodiment 1 and 2
2O
3And Pd/CeO
2Catalyzer is analyzed by X-ray diffraction and XRF respectively.The results are shown in the table 4.
Aluminum oxide after the use is catalyst-loaded to be had than the remarkable higher sulfur content of cerium dioxide-bound catalyzer, shows in the cerium dioxide-bound catalyzer lower by the poisoning of catalyst level due to the sulphur.
Table 4:XRD analyzes
aMeasured by X-ray diffraction
bThe S content (being 0 weight % before the use) of the catalyzer of being measured by XRF.
There is not H except in the raw material
2Beyond the S, with the Pd/CeO of embodiment 2
2Catalyzer is contacting with carbon monoxide with hydrogen under the 5 described identical conditions with experiment.This is not the method according to this invention, because sulphur concentration is not more than 0.5ppm.
Catalytic activity during 100 hours the results are shown among Figure 16,17,18 and 19, and compares with the result who tests 5.
There is not H
2Under the situation of S, the methyl alcohol selectivity descends rapidly in initial 2 hours of reaction, but increases to 83% gradually after 100 hours.The carbon monoxide transformation efficiency is down to 20% after 100 hours from 27.5% initial value, thereby causes after 100 hours 16.6% methyl alcohol yield.Carbonic acid gas is also shown generation, and concentration is from dropping to about 1.5% after 100 hours near 4% maximum value.In addition, the yield of the output of light hydrocarbon (C1～C5 hydrocarbon) from 4～5% drops to about 1% after 100 hours.
In experiment 5, under the sulphur of 30ppm was present in situation in the raw material, the CO transformation efficiency was lower, but the methyl alcohol selectivity is higher, and meaning is that the methyl alcohol yield is equivalent to there be not H
2Methyl alcohol yield under the S situation.The output of carbonic acid gas is lower, from drop to about 0.5% after 100 hours near 2% maximum value.Equally, generate very a spot of C1～C5 hydrocarbon.
Described experiment shows that also when sulphur was present in the raw material, the output of carbonic acid gas and hydrocarbon byproduct was lower.
Pd/CeO with embodiment 2
2Catalyzer is at pressure, the 1000h of 30 bar (3MPa)
-1GHSV under, adopt and to contain 3.3ppm H
2The raw material of the oxygen of S and 0.4 volume % is estimated.Under the temperature of 220 ℃, 240 ℃, 260 ℃ and 280 ℃, catalyzer is studied.The results are shown among Figure 20.
The methyl alcohol selectivity is improved between 220～240 ℃, then descends.Carbon dioxide selectivity descends between 220～240 ℃, then increases.The carbon monoxide transformation efficiency increases with the increase of temperature.The light hydrocarbon selectivity increases with the increase of temperature.
Pd/CeO with embodiment 2
2Catalyzer is at 240 ℃ temperature, 1000h
-1GHSV under, adopt and test raw material identical described in 15 and estimate.The pressure of employing 1,2,3,4 and 5MPa.The results are shown among Figure 21.
Generally, methyl alcohol selectivity and light hydrocarbon selectivity increase with pressure, and carbon dioxide selectivity increases with pressure and descends, and the carbon monoxide transformation efficiency increases with pressure.
Experiment 17
Pd/CeO with embodiment 2
2Catalyzer adopts the raw material identical with embodiment 15 to estimate under the pressure of 240 ℃ temperature, 3MPa.Employing is at 500～5000h
-1Between GHSV.The results are shown among Figure 22.
Generally, the selectivity that generates methyl alcohol and light hydrocarbon reduces with the increase of GHSV, and carbon monoxide transformation efficiency and carbon dioxide selectivity increase with the increase of GHSV.
Claims (15)
1. one kind is used for the method for producing one or more oxygen-containing hydrocarbons by hydrogen and carbon monoxide, described method comprises makes catalyzer contact under the condition of 100 to 450 ℃ the temperature of reaction of producing one or more oxygen-containing hydrocarbons and the reaction pressure of 1 to 100 bar with reaction mixture, described reaction mixture comprises carbon monoxide, hydrogen and one or more reduced sulfur compounds, described catalyst pack containing metal and carrier, described metal is active for hydrogen and carbon monoxide are changed into one or more oxygen-containing hydrocarbons, described carrier comprises the semi-conductor inorganic oxide of oxidation that can catalytic reduction attitude sulphur compound, it is characterized in that, by the weight of representing according to elementary sulfur, described one or more reduced sulfur compound concentrations in the described reaction mixture are greater than 0.5ppm.
2. the method for claim 1, wherein said is that active metal is selected from one or more among Cu, Cr, Co, Mo, Pt, Pd and the Rh for hydrogen and carbon monoxide are changed into one or more oxygen-containing hydrocarbons.
3. method as claimed in claim 2, wherein said metal is Pd and/or Cu.
4. as each described method in the claim 1 to 3, wherein the mol ratio of the nonoxygen element of at least a catalyst metal and described semi-conductor inorganic oxide was greater than 0.09: 1.
5. as each described method in the claim 1 to 4, the semi-conductor inorganic oxide of wherein said oxidation that can catalytic reduction attitude sulphur compound is selected from lanthanide oxide, TiO
2, ZrO
2And ThO
2In one or more.
6. method as claimed in claim 5, wherein said semi-conductor inorganic oxide is ZrO
2And/or CeO
2
7. as each described method in the claim 1 to 6, wherein said catalyzer also comprises promotor, and described promotor is selected from the group that comprises basic metal, alkaline-earth metal, Sc, Y, La, Nd, Mn, Zn and Al.
8. as each described method in the claim 1 to 7, wherein the reduced sulfur compound exists with the concentration more than the 3ppm.
9. as each described method, wherein carbon monoxide/hydrogen (CO:H in the claim 1 to 8
2) mol ratio in 3: 1 to 1: 3 scope.
10. as each described method in the claim 1 to 9, wherein the source of carbon monoxide and hydrogen is synthetic gas.
11. as each described method in the claim 1 to 10, wherein said method is for the production of methyl alcohol and/or dme.
12. as each described method in the claim 1 to 11, the oxygen source that wherein is in one or more forms in molecular oxygen, carbonic acid gas and the water is present in the described reaction mixture.
13. method as claimed in claim 12, wherein oxygen is present in the described reaction mixture with the concentration of 1 weight % at the most.
14. as claim 12 or the described method of claim 13, wherein carbonic acid gas is present in the described reaction mixture with the concentration of 15 weight % at the most.
15. as each described method in the claim 1 to 14, wherein gas hourly space velocity is remained on 500 to 5000h
-1Value in the scope.
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| CNPCT/CN2006/003064 | 2006-11-14 | ||
| PCT/GB2007/004243 WO2008059208A1 (en) | 2006-11-14 | 2007-11-08 | Process for the conversion of syngas to oxygenates |
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| CN111569888B (en) * | 2020-06-02 | 2023-03-28 | 瓮福（集团）有限责任公司 | Preparation method of sulfur-resistant and high-temperature-resistant methanol catalyst with hollow core-shell structure |
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| US1681753A (en) * | 1927-06-04 | 1928-08-21 | Roessler & Hasslacher Chemical | Synthesis of methanol |
| JPS5543003A (en) * | 1978-09-20 | 1980-03-26 | Sagami Chem Res Center | Preparation of methanol |
| CN1065816A (en) * | 1992-05-29 | 1992-11-04 | 天津大学 | Sulfur-resistant catalst for synthesis of methanol |
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| Title |
|---|
| Keiichi Tomishige,et al..syngas production by biomass gasification using Rh/CeO2/SiO2catalyst and fluidized bed reactor.《catalysis today》.2004,第89卷 * |
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