CN109772329A - Catalyst, preparation method and its application in the synthetic reaction of low carbon alcohol by synthetic gas - Google Patents
Catalyst, preparation method and its application in the synthetic reaction of low carbon alcohol by synthetic gas Download PDFInfo
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Abstract
The present invention provides a kind of catalyst, preparation method and its applications in the synthetic reaction of low carbon alcohol by synthetic gas.The catalyst includes active component and silica, and wherein the composition of catalyst is indicated with general formula (I): CuaFebZrcOd/(SiO2), in general formula (I), the molal quantity of a, b, c, d successively representative element Cu, Fe, Zr and O, wherein a=1, b are that 0.1~5, c is 0.05~3, CuaFebZrcOdWhole chemical valence be 0, and silica accounts for the 0.5~40% of total catalyst weight.Catalyst made from the application has many advantages, such as reaction temperature and reaction pressure is low, carbon dioxide selectivity is low and long service life.
Description
Technical field
The present invention relates to low carbon alcohol by synthetic gas field, in particular to a kind of catalyst, preparation method and its
Application in the synthetic reaction of low carbon alcohol by synthetic gas.
Background technique
Low carbon mixed alcohol (C1~C6Alcohol-based mixtures) clean gasoline additive both may be used as due to its high-octane rating,
The dimethyl tertiary butyl ether (MTBE) with carcinogenesis is substituted, can also be used as excellent clean vehicle fuel and for oil product,
And it has huge economic value as chemicals itself or large Chemical Manufacture raw material.Therefore, it is developed by source of coal
Methanol fuel is substituted, it is highly selective to produce mixed alcohol (especially C2Above higher alcohol), with high economic benefit and again
The strategic importance wanted.
According to literature survey, Cu-Fe base higher alcohols synthesis catalyst is considered as the catalytic body of most prospects for commercial application
System.Since Fe has the ability of dissociation CO, adsorbs and form methylene etc. after CO dissociation plus hydrogen thereon and make C chain growth, and Cu
It is the active component of synthesizing methanol, there is CO insertions function.The synergistic effect of the two eventually leads to the generation of low-carbon alcohols.Cu-Fe
Base catalyst has preferable activity to synthesis of low-carbon alcohol reaction, and required operating condition is more mild, catalyst raw material
It is cheap and easy to get.In addition, can effectively improve the stability of catalyst after adding suitable carrier and auxiliary agent to catalyst.Cu-
Fe alloying pellet is formed in synthesis of low-carbon alcohol becoming apparent from for the synergistic effect performance for making iron-copper bi-metal, and it is low to promote synthesis
The progress of carbon alcohol reaction.Zirconium oxide has good stability as carrier, can stablize in high temperature, strongly reducing atmosphere and deposit
Cu-Fe alloying pellet is being supported to the surface of Zirconia carrier, restrained effectively sintering and the group of Cu-Fe alloying pellet
It is poly-, improve the stability of catalyst；Furthermore Zirconia carrier itself has certain catalytic effect to synthesis of low-carbon alcohol reaction, has
Conducive to the activity and C for improving reaction2+The selectivity of alcohol.
And since low carbon alcohol by synthetic gas is exothermic, volume-diminished reversible reaction, adjoint many in synthesis process
Side reaction such as generates various alkane, the reaction of alkene and water gas shift reaction, belongs to strong exothermal reaction.Due to reaction
Process thermal discharge is big, using the hot-spot for unavoidably causing catalyst when fixed bed reactors, cause catalyst activity and
Selectivity of product reduces, and catalyst carbon deposit is caused even to block reactor bed, with the amplification of unit scale, this phenomenon
It is particularly evident, and can not be replaced online after fixed bed reactor catalyst failure, and stop and replace time-consuming and laborious, serious shadow
Ring production.Therefore, fixed bed has the shortcomings that inevitable, and slurry bed system can effectively solve this problem.And it applies and is starching
Catalyst in state bed is just proposed some new requirements to catalyst, is catalyzed due to its more harsh use environment
The anti-physical polishing machine of agent is exactly a bit mostly important, affects service performance and the service life of catalyst.Improve catalyst
Wear resistance need to add the binders such as silica to realize, if experimental condition and process conditions can be reached
Whether lower required abrasion index, be able to achieve the application performance of slurry bed catalyst in this catalyst system of low-carbon alcohols,
This two broad aspect requires largely to test to be explored, be found and be improved.
Existing document provides a kind of preparation method of copper cobalt-based low carbon alcohol by synthetic gas catalyst, and this method uses colloidal sol
Gel method prepares catalyst Precursors, and then catalyst coat is supported in ball-type heat-resistant carriers, to reduce catalyst anti-
Fuel factor during answering.This kind of method is only 2~6 hours dry at 100 DEG C after catalyst load, catalyst coat and load
Not by the combination of high-temperature roasting between body, thus it is easy to fall off during the reaction；And the nothing in loading process
Method solves the problem of that the homogeneity question of load can not still solve to be easy to reunite between active component particle.
Existing document provides the copper and iron nucleocapsid catalyst and preparation method of a kind of synthesis of low-carbon alcohol, which only has
The activity of the characteristics of structure novel, catalyst are poor, and the conversion per pass of CO is most of 20% or so.And this catalyst
As fixed bed catalyst, have the shortcomings that the inevitable of the mild inconvenient operation of Workflow in industrialized application.
Summary of the invention
The main purpose of the present invention is to provide a kind of catalyst, preparation method and its in the conjunction of low carbon alcohol by synthetic gas
At the application in reaction, it is poor that there are catalytic activity to solve the problems, such as existing higher alcohols synthesis catalyst.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of catalyst, the catalyst include living
Property component and silica, wherein the composition of catalyst is indicated with general formula (I): CuaFebZrcOd/(SiO2), in general formula (I), a,
B, the molal quantity of c, d successively representative element Cu, Fe, Zr and O, wherein a=1, b are that 0.1~5, c is 0.05~3, CuaFebZrcOd
Whole chemical valence be 0, and silica accounts for the 0.5~40% of total catalyst weight.
Further, a=1 in the catalyst that general formula (I) indicates, b is that 0.3~3.5, c is 0.08~2.
Further, silica accounts for the 5~30% of total catalyst weight.
Further, the average grain diameter of catalyst is 50~150 μm.
The another aspect of the application additionally provides a kind of preparation method of above-mentioned catalyst, which includes: that will contain
The mixture progress precipitation reaction of copper soluble-salt, iron content soluble-salt, soluble-salt containing zirconium and precipitating reagent, after filtering, obtains
Filter cake；And filter cake and water are formed into slurries, and after slurries are mixed with binder, through drying, roasts and obtain catalyst；Wherein,
Binder is selected from silica solution and/or siliceous soluble-salt.
Further, binder is the silica solution that pH value is 1~5, and the weight concentration of silica solution is 15~35%；It is preferred that
Ground, binder is the silica solution of pH value 2~4, and the weight concentration of silica solution is 20~30%.
Further, the slurries that binder and temperature are room temperature~100 DEG C are subjected to mixing step, it is preferable that through mixing
After step, the temperature of the mixed liquor of binder and slurries is 30~80 DEG C；It is highly preferred that the temperature of the mixed liquor of binder and slurries
Degree is 50~70 DEG C.
Further, the temperature of precipitation reaction is 30~80 DEG C, and the reaction time is 0.5~3h；Preferably, precipitation reaction
Temperature is 50 DEG C~70 DEG C；Reaction time is 0.5~2h.
Further, it in dry step, is carried out using press spray drying device or atomizer drying device
It is dry；Preferably, when being dried using press spray drying device, using in drying steps, atomisation pressure is 1.0~
2.0MPa, inlet air temperature are 220~260 DEG C, and leaving air temp is 90~130 DEG C, and nozzle diameter is 0.5~2mm；
It is highly preferred that atomisation pressure be 1.6~1.9MPa, inlet air temperature be 230~250 DEG C, leaving air temp be 100~
120 DEG C, nozzle diameter is 0.7~1.2mm.
Further, in the step of roasting, maturing temperature is 300~500 DEG C, it is preferable that maturing temperature is 350~450
℃；Calcining time is 4~12h, preferably 6~10h.
Further, cupric soluble-salt is selected from one of copper nitrate, copper chloride and copper sulphate or a variety of；It is preferred that iron content
Soluble-salt is selected from one of ferric nitrate, iron chloride and ferric sulfate or a variety of；It is preferred that soluble-salt containing zirconium is selected from zirconium nitrate, chlorine
Change one of zirconium and zirconium sulfate or a variety of；It is preferred that siliceous soluble-salt is selected from one of potassium silicate, sodium metasilicate and ammonium silicate
Or it is a variety of；
It is preferred that precipitating reagent is selected from one of soluble carbonate salt, bicarbonate and phosphate or a variety of.
The another aspect of the application additionally provides a kind of above-mentioned catalyst answering in the synthetic reaction of low carbon alcohol by synthetic gas
With.
It applies the technical scheme of the present invention, due to Fe3O4For the active phase of Water gas shift/WGS, CO will lead to2Generation, and
Catalyst provided by the present application by by the limited proportion of copper and ferro element in specific proportional region so that the two
More collaboration generates alcohol, generates ferroso-ferric oxide without extra ferro element, this inhibits CO to a certain extent2Life
It produces.The addition of element zirconium simultaneously is conducive to the selectivity of catalyst and the yield of low-carbon alcohols during raising catalyst, together
When also advantageously improve the physical strength and stability of catalyst, the loss of inhibitory activity component, to improve making for catalyst
Use the service life.In conclusion catalyst made from the application there is reaction temperature and reaction pressure is low, carbon dioxide selectivity is low and
The advantages that long service life.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As described in background technique, existing higher alcohols synthesis catalyst has that catalytic activity is poor.For
Solution above-mentioned technical problem, this application provides a kind of catalyst, which includes active component and silica, wherein
The composition of catalyst is indicated with general formula (I): CuaFebZrcOd/(SiO2), wherein a, b, c, d successively representative element Cu, Fe, Zr and O
Atomic molar number, wherein a=1, b are that 0.1~5, c is 0.05~3, CuaFebZrcOdWhole chemical valence be 0, and titanium dioxide
Silicon accounts for the 0.5~40% of total catalyst weight.
Due to Fe3O4For the active phase of Water gas shift/WGS, CO will lead to2Generation, and catalyst provided by the present application passes through
By the limited proportion of copper and ferro element in specific proportional region, so that the two, which more cooperates with, generates alcohol, and do not have
There is extra ferro element to generate ferroso-ferric oxide, this inhibits CO to a certain extent2Production.The addition of element zirconium has simultaneously
Conducive to the selectivity of catalyst and the yield of low-carbon alcohols in raising catalytic process, while the physics for also advantageously improving catalyst is strong
Degree and stability, the loss of inhibitory activity component, to improve the service life of catalyst.In conclusion made from the application
Catalyst has many advantages, such as reaction temperature and reaction pressure is low, carbon dioxide selectivity is low and long service life.
Catalyst provided by the present application is low with reaction temperature and reaction pressure, carbon dioxide selectivity is low and service life
The advantages that long.In order to further increase the comprehensive performance of catalyst, it is preferable that a=1 in the catalyst that general formula (I) indicates, b are
0.3~3.5, c are 0.08~2.
Preferably, silica accounts for the 5~30% of total catalyst weight.The weight percentage of silica includes but not
It is limited to above range, and is limited the dispersibility and service life for being conducive to further increase catalyst within the above range.
Preferably, the average grain diameter of catalyst is 50~150 μm.The partial size of catalyst includes but is not limited to above range,
And limited the catalyst performance for being conducive to further increase catalyst within the above range.
On the other hand the application in order to better understand, the application provide a kind of preparation method of above-mentioned catalyst, should
Preparation method includes: to precipitate the mixture of cupric soluble-salt, iron content soluble-salt, soluble-salt containing zirconium and precipitating reagent
Reaction, after filtering, obtains filter cake；And filter cake and water are formed into slurries, and after above-mentioned slurries are mixed with binder, through drying,
Roasting obtains catalyst；Wherein, binder is selected from silica solution and/or siliceous soluble-salt.
Catalyst provided by the present application by by the limited proportion of copper and ferro element in specific proportional region, thus
So that the two, which more cooperates with, generates alcohol, ferroso-ferric oxide is generated without extra ferro element, this inhibits to a certain extent
CO2Production.The addition of element zirconium simultaneously is conducive to the selectivity and low-carbon alcohols of catalyst during raising catalyst
Yield, while also advantageously improving the physical strength and stability of catalyst, the loss of inhibitory activity component is urged to improve
The service life of agent.In conclusion catalyst made from the application is low with reaction temperature and reaction pressure, carbon dioxide choosing
The advantages that selecting property is low and long service life.
In a preferred embodiment, when binder is silica solution, binder is the silica solution of pH value 1~5, and
The weight concentration of silica solution is 15~35%.The silica solution being added within the scope of above-mentioned pH is conducive to inhibit precipitated product in slurries
It decomposes, to be conducive to be transferred to more active metallic elements in catalyst, improves the catalytic activity of catalyst；Silicon is molten
The weight percentage of glue limits living in the stability for being conducive to further increase catalyst within the above range and catalyst
The dispersibility of property metallic element.
In order to further increase the comprehensive performance of catalyst, it is highly preferred that silica solution of the binder for pH value 2~4, and silicon
The weight concentration of colloidal sol is 20~30%.
In a preferred embodiment, binder and the slurries lower than 100 DEG C are subjected to mixing step.By slurries
Limit temperature is conducive to improve within the above range the adhesion strength of precipitated product in binder and slurries, to be conducive to improve
The intensity of catalyst, and then improve the service life of catalyst.In order to further increase the stability and service life of catalyst,
It is highly preferred that the temperature of the mixed liquor of binder and slurries is 30~80 DEG C after mixing step；It is further preferred that bonding
The temperature of the mixed liquor of agent and slurries is 50~70 DEG C.
In a preferred embodiment, the temperature of precipitation reaction is 30~80 DEG C, and the reaction time is 0.5~3h.It is heavy
The temperature and time reacted that forms sediment includes but is not limited to above range, and is limited and be conducive to make precipitation reaction within the above range
It carries out more abundant, is precipitated to make more active components in the form that precipitates, improves the utilization rate of raw material.More preferably
Ground, the temperature of precipitation reaction are 50 DEG C~70 DEG C, and the reaction time is 0.5~2h.
In a preferred embodiment, precipitation reaction process further includes that will precipitate abundant filtration washing, until detection
The conductivity of cleaning solution is in 100 μm/cm or less.This is conducive to the content for further decreasing Impurities In Catalyst ion, to mention
The yield and purity of high catalyst.
Above-mentioned preparation method can be dried by the way of commonly used in the art.In a preferred embodiment,
In dry step, it is dried using press spray drying device or atomizer drying device.
In order to further increase drying effect, it is preferable that when being dried using press spray drying device, use
In drying steps, atomisation pressure is 1.0~2.0MPa, and inlet air temperature is 220~260 DEG C, and leaving air temp is 90~130 DEG C, spray
Outspoken diameter is 0.5~2mm.It is highly preferred that atomisation pressure is 1.6~1.9MPa；Inlet air temperature is 230~250 DEG C, nozzle diameter
For 0.7~1.2mm；Leaving air temp is 100~120 DEG C.
In above-mentioned preparation method, maturing temperature and calcining time can choose parameter area commonly used in the art.In one kind
In preferred embodiment, the step of roasting in, maturing temperature is 300~500 DEG C, it is preferable that maturing temperature is 350~450
℃；Calcining time is 4~12h, preferably 6~10h.It include but is not limited to above range by maturing temperature and calcining time, and
Limited the decomposition efficiency for being conducive to improve carbonate obtained in precipitation reaction within the above range.
In above-mentioned preparation method, those skilled in the art can choose the type of raw material.In a kind of preferred embodiment
In, cupric soluble-salt includes but is not limited to one of copper nitrate, copper chloride and copper sulphate or a variety of；It is preferred that iron content is soluble
Salt includes but is not limited to one of ferric nitrate, iron chloride and ferric sulfate or a variety of；It is preferred that soluble-salt containing zirconium includes but unlimited
In one of zirconium nitrate, zirconium chloride and zirconium sulfate or a variety of；It is preferred that siliceous soluble-salt includes but is not limited to potassium silicate, silicic acid
One of sodium and ammonium silicate are a variety of；It is preferred that precipitating reagent includes but is not limited to soluble carbonate salt, bicarbonate and phosphate
One of or it is a variety of.Above-mentioned a few class compounds are soluble-salt, as precipitation reaction raw material be conducive to improve it is heavy
Form sediment the reaction effect reacted, improves the utilization rate of raw material.Cost is relatively low for above-mentioned a few class compounds simultaneously, selects it as raw material
Also help reduction process costs.
The another aspect of the application additionally provides a kind of above-mentioned catalyst answering in the synthetic reaction of low carbon alcohol by synthetic gas
With.
Since the catalyst with above-mentioned composition has, reaction temperature and pressure are low, carbon dioxide selectivity is low and use the longevity
It orders the advantages that long, thus is conducive to improve as catalyst using above-mentioned catalyst in the synthetic reaction of low carbon alcohol by synthetic gas
The yield of the conversion ratio of carbon monoxide and total alcohol.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
Embodiment 1
It is Cu:Fe:Zr=1:0.7:0.3 according to simple substance molar ratio, weighs the Cu (NO of corresponding weight3)2·3H2O、Fe
(NO3)3·9H2O and Zr (NO3)4·5H2O is added in appropriate amount of deionized water and is mixed evenly；Precipitating reagent uses weight percent
The solution of potassium carbonate that content is 8.24% is reacted at being 70 DEG C in precipitation temperature, after reaction in synthermal stirring shape
Aging 2h under state；Abundant filtration washing will be precipitated, until the conductivity of detection cleaning solution is in 100 μm/cm or less.By gained filter cake
It is beaten again, slurry temperature control is 60 DEG C, and the 12.6g commercial acid silica solution that dropwise addition PH is 3 thereto, concentration is 25% is extremely
It stirs evenly, aging 1h is then carried out under synthermal not stirring；Filter press is used continuously to be washed after the completion of aging,
Until with the conductivity of conductivity meter detection cleaning solution in 100us/cm or less.
By the filter cake after washing with deionized water be diluted to concentration be 15%, use pressure spray drying tower, diameter for
The nozzle of 1mm carries out slurries spray drying forming, spray condition setting are as follows: atomisation pressure 1.8MPa, inlet air temperature 240
DEG C, leaving air temp is 110 DEG C.Catalyst after molding roasts 8h at 400 DEG C, obtains finished catalyst particle.Its silicone content
The 15wt% of finished catalyst is accounted for, attrition of catalyst rate the results are shown in Table 1.
In 1L gas one way by the way that 500mL atoleine is added in stirred tank evaluating apparatus, 15g spray drying is then added
Then catalyst seals reactor.Under normal pressure, the catalyst after reductase 12 4h at 300 DEG C is activated, in reaction temperature
For 260 DEG C, pressure 6.0Mpa, air speed 4000h-1, agitator speed 1000rpm, hydrogen-carbon ratio carry out under conditions of being 2:1
Higher alcohols synthesis reaction.Long-term operation 500h with this condition, acquired by catalyst activity (CO conversion ratio) fall off rate
Evaluation results are shown in Table 1.
Embodiment 2
It is Cu:Fe:Zr=1:0.7:0.05 according to simple substance molar ratio, weighs the Cu (NO of corresponding weight3)2·3H2O、Fe
(NO3)3·9H2O and Zr (NO3)4·5H2O, remaining condition is same as Example 1, gained attrition of catalyst rate result and catalysis
Agent activity (CO conversion ratio) fall off rate the results are shown in Table 1.
Embodiment 3
In catalyst, the weight of silica accounts for the 30% of finished catalyst total weight, remaining condition with 1 phase of embodiment
Together, gained attrition of catalyst rate result and catalyst activity (CO conversion ratio) fall off rate the results are shown in Table 1.
Embodiment 4
The pH value of the commercially available silica solution used is 5, concentration 15wt%, remaining condition is same as Example 1, and gained is urged
Agent rate of wear result and Evaluation results are shown in Table 1.
Embodiment 5
It is 5wt% that filter cake after washing, which is diluted to concentration with deionized water, use pressure spray drying tower, diameter for
The nozzle of 0.7mm carries out slurries spray drying forming, spray condition setting are as follows: atomisation pressure 2.0MPa, inlet air temperature 230
DEG C, leaving air temp is 90 DEG C.Remaining condition is same as Example 1, gained attrition of catalyst rate result and catalyst activity (CO
Conversion ratio) fall off rate the results are shown in Table 1.
Embodiment 6
It is 20wt% that filter cake after washing, which is diluted to concentration with deionized water, using pressure spray drying tower, diameter
Slurries spray drying forming, spray condition setting are as follows: atomisation pressure 1.6MPa, inlet air temperature are are carried out for the nozzle of 1.5mm
250 DEG C, leaving air temp is 120 DEG C.Remaining condition is same as Example 1, and gained attrition of catalyst rate result and catalyst are living
Property (CO conversion ratio) fall off rate the results are shown in Table 1.
Table 1
| Embodiment | Attrition of catalyst rate %/h | Active rate of descent (%/h) |
| Embodiment 1 | 1.84 | 0.0005 |
| Embodiment 2 | 1.95 | 0.0038 |
| Embodiment 3 | 1.93 | 0.0042 |
| Embodiment 4 | 2.41 | 0.0025 |
| Embodiment 5 | 3.93 | 0.0019 |
| Embodiment 6 | 4.52 | 0.0026 |
It can be seen from the above description that the above embodiments of the present invention realized the following chievements: the application system
Catalyst have many advantages, such as reaction temperature and reaction pressure is low, carbon dioxide selectivity is low and long service life.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (12)
1. a kind of catalyst, which is characterized in that the catalyst includes active component and silica, wherein the catalyst
Composition is indicated with general formula (I): CuaFebZrcOd/(SiO2),
In the general formula (I), the molal quantity of a, b, c, d successively representative element Cu, Fe, Zr and O, wherein a=1, b are 0.1~5, c
For 0.05~3, CuaFebZrcOdWhole chemical valence be 0, and the silica account for the total catalyst weight 0.5~
40%.
2. catalyst according to claim 1, which is characterized in that a=1 in the catalyst that the general formula (I) indicates, b are
0.3~3.5, c are 0.08~2.
3. catalyst according to claim 1 or 2, which is characterized in that the silica accounts for the total catalyst weight
5~30%.
4. catalyst according to any one of claim 1 to 3, which is characterized in that the average grain diameter of the catalyst is
50~150 μm.
5. a kind of preparation method of catalyst described in any one of Claims 1-4, which is characterized in that the preparation method
Include:
The mixture of cupric soluble-salt, iron content soluble-salt, soluble-salt containing zirconium and precipitating reagent is subjected to precipitation reaction, filtering
Afterwards, filter cake is obtained；And
The filter cake and water are formed into slurries, and after the slurries are mixed with binder, through drying, roasts and obtain the catalysis
Agent；
Wherein, the binder is selected from silica solution and/or siliceous soluble-salt.
6. preparation method according to claim 5, which is characterized in that the binder is the silica solution that pH value is 1~5,
And the weight concentration of the silica solution is 15~35%；
Preferably, the binder is the silica solution of pH value 2~4, and the weight concentration of the silica solution is 20~30%.
7. preparation method according to claim 5, which is characterized in that by the binder and temperature be room temperature~100 DEG C
The slurries carry out the mixing step,
Preferably, after the mixing step, the temperature of the mixed liquor of the binder and the slurries is 30~80 DEG C；
It is highly preferred that the temperature of the mixed liquor of the binder and the slurries is 50~70 DEG C.
8. preparation method according to claim 5, which is characterized in that the temperature of the precipitation reaction is 30~80 DEG C, instead
It is 0.5~3h between seasonable；Preferably, the temperature of the precipitation reaction is 50 DEG C~70 DEG C；The reaction time is 0.5~2h.
9. the preparation method according to any one of claim 5 to 8, which is characterized in that in the step of the drying, use
Press spray drying device or atomizer drying device are dried；
Preferably, when being dried using press spray drying device, using in the drying steps, atomisation pressure is
1.0~2.0MPa, inlet air temperature are 220~260 DEG C, and leaving air temp is 90~130 DEG C, and nozzle diameter is 0.5~2mm；
It is highly preferred that the atomisation pressure is 1.6~1.9MPa, the inlet air temperature is 230~250 DEG C, the leaving air temp
It is 100~120 DEG C, the nozzle diameter is 0.7~1.2mm.
10. preparation method according to claim 9, which is characterized in that in the step of the roasting, maturing temperature 300
~500 DEG C, it is preferable that the maturing temperature is 350~450 DEG C；Calcining time is 4~12h, preferably 6~10h.
11. the preparation method according to any one of claim 5 to 10, which is characterized in that
The cupric soluble-salt is selected from one of copper nitrate, copper chloride and copper sulphate or a variety of；
It is preferred that the iron content soluble-salt is selected from one of ferric nitrate, iron chloride and ferric sulfate or a variety of；
It is preferred that the soluble-salt containing zirconium is selected from one of zirconium nitrate, zirconium chloride and zirconium sulfate or a variety of；
It is preferred that the siliceous soluble-salt is selected from one of potassium silicate, sodium metasilicate and ammonium silicate or a variety of；
It is preferred that the precipitating reagent is selected from one of soluble carbonate salt, bicarbonate and phosphate or a variety of.
12. a kind of catalyst described in any one of Claims 1-4 answering in the synthetic reaction of low carbon alcohol by synthetic gas
With.
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| CN110152675A (en) * | 2019-05-22 | 2019-08-23 | 国家能源投资集团有限责任公司 | The method of low carbon alcohol by synthetic gas catalyst, preparation method and low carbon alcohol by synthetic gas |
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