CN106582269B - Use the method for modification sections catalyst ethane oxidation - Google Patents
Use the method for modification sections catalyst ethane oxidation Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01D2255/00—Catalysts
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- B01D2255/207—Transition metals
- B01D2255/20738—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
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- B01D2257/7025—Methane
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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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- Y02C20/20—Capture or disposal of greenhouse gases of methane
Abstract
The invention belongs to Industrial Catalysis and field of environment protection, provide a kind of method using modification sections catalyst ethane oxidation.This method includes modifying the preparation of sections catalyst, and the reaction system of modification sections catalyst ethane oxidation prepares and the reaction condition of ethane catalysis oxidation controls three parts.The preparation process for wherein modifying iron catalyst includes following steps: Step 1: raw material preparation；Step 2: the first mixed liquid dipping；Step 3: alkali catalyzed hydrolysis；Step 4: catalyst roasts；Step 5: multiple circulate operation.The reaction system for modifying sections catalyst ethane oxidation prepares, and uses ethane oxidation fixed-bed reactor.It is controlled by the reaction condition of ethane catalysis oxidation, the conversion ratio of ethane can be 90% or more.For ethane oxidation, sections catalyst is modified compared with unmodified iron catalyst, may be significantly the ethane conversion of raising and the yield of complete oxidation product carbon dioxide.
Description
Technical field
The invention belongs to Industrial Catalysis and field of environment protection, are related to a kind of method of ethane oxidation；In particular it relates to
A method of using modification sections catalyst ethane oxidation, the preparation method comprising catalyst, and catalysis were reacted
Process control method.
Background technique
Small molecule alkane, such as methane, ethane, propane are the gas of a kind of strong greenhouse effects.Such as the greenhouse effect of methane
It should be 25 times or so of carbon dioxide.The discharge of small molecule alkane will cause biggish atmosphere pollution.Small molecule alkane is due to it
Chemical structure saturability, chemical property torpescence, carries out chemical conversion to it and usually requires higher cost under normal conditions.From
It is said on principles of chemical kinetics, the chemical conversion of small molecule alkane usually requires biggish activation energy.It therefore will be in temperate condition
Under, small molecule alkane is removed by the method for oxidation, needs the catalyst of high catalytic activity.Loaded catalyst is industrially to pass through
A kind of catalyst type being often used.
Since the widely distributed property of elemental iron is with inexpensively, iron usually is paid the utmost attention to be used as by Industrial Catalysis field technical staff
Catalytically-active metals component or in which a kind of active component.Since the general activity and preparation means of catalyst are closely related, because
It is one lasting Scientific And Technical Problems of catalytic field technical staff that this, which develops new method for preparing catalyst,.It is catalyzed about loading type iron
The preparation of agent and the report of catalytic performance are very more, however for the effect after the method for modifying of loaded catalyst, and modification
Fruit research is considerably less.
Patent CN1431048A describe a kind of load typed iron catalyst preparation method and its possess oxidation of alkanes
Effect.The presoma of the presoma of Fe component and auxiliary agent is made into the solution that concentration is 0.1~6mol/L by its inventor respectively, is pressed
Ratio is by active carbon or γ-Al2O3It is impregnated into the solution of Fe presoma and auxiliary agent presoma, stands 18~36 hours after dipping,
110~120 DEG C drying 4~6 hours, under nitrogen protection in 450~650 DEG C, roast 4~5 hours, enter drier.The invention
Preparation process contain only the load of ferrous metal component, without including subsequent modification process.Catalyst is in practical alkane oxygen
During change, temperature is higher, and active component is in continuous oxidation and reduction circulation, causes active component to be easy existing in catalysis
Field aggregation is substantially reduced catalytic activity and even inactivates.
Document [Luyao Xu et al., Alumina-supported Fe catalyst prepared by vapor
deposition and its catalytic performance for oxidative dehydrogenation of
Ethane, Materials Research Bulletin, 59 (2014) 254-260.] it reports a kind of loading type iron and urges
The gas-phase deposition process for preparing of agent.Iron component can be improved for conventional methods such as infusion processes in this method read fortune from principle
Degree of scatter is expected to the improvement for having on catalytic performance for reactions such as catalysis oxidation of alkanes.The document is found for ethane oxidation
For, iron catalyst and the catalyst of identical iron content prepared by infusion process of vapour deposition process preparation, catalyzed conversion is active
Improve about 4 times.However the document does not still contain the report for modification process after the load of iron component.
In conclusion there is also the technical needs of further Development of Novel iron catalyst method of modifying for this field, and need
Further explore its application prospect in oxidation of alkanes.
Summary of the invention
In the presence of overcoming the shortcomings of the prior art, the present invention provides a kind of using modification sections catalyst second
The method of alkoxide.Technical solution of the present invention makes every effort to avoid using noxious material and expensive device, so that entire technique side
Method is a low cost, has operated, environmental-friendly method.
The present invention uses following proposal:
A method of using modification sections catalyst ethane oxidation, the preparation including modifying sections catalyst is repaired
The reaction system for adoring sections catalyst ethane oxidation prepares and the reaction condition of ethane catalysis oxidation controls three portions
Point.The preparation process for wherein modifying iron catalyst includes following steps:
Step 1: raw material preparation；
Step 2: the first mixed liquid dipping；
Step 3: alkali catalyzed hydrolysis；
Step 4: catalyst roasts；
Step 5: multiple circulate operation；
The reaction system for modifying sections catalyst ethane oxidation prepares, using ethane oxidation fixed-bed reactor,
It include: main reactor tube, main reactor tube has main reactor tube air inlet, main reactor tube gas outlet；Oxygen source provides purity oxygen；
Ethane gas source provides pure ethane gas；Noble gas source provides N2One or more of gas, He gas, Ar gas gas
Mixture；Oxygen source, ethane gas source, noble gas source flow pass through first flow controller, second flow control respectively
Device processed and third flow controller control；Oxygen source by after first flow controller, ethane gas source pass through second flow
After controller, noble gas source is by being merged into the unstripped gas for becoming ethane oxidation all the way after third flow controller；Raw material
Gas flows into main reactor tube air inlet, flows out from main reactor tube gas outlet；Catalyst, which can be filled in main reactor tube, forms catalyst
Bed；All gases for flowing through catalyst bed are finally all flowed out from main reactor tube gas outlet, form product gas.
Above-mentioned " modification sections catalyst " is filled in main reactor tube and forms catalyst bed, catalyst bed is full of master
The section of reaction tube.
The reaction condition of ethane catalysis oxidation controls, and the specific method is as follows:
Oxygen source, ethane gas source and noble gas source are opened, and is controlled by first flow controller, second flow
Device and third flow controller control the flow velocity of oxygen, ethane and inert gas respectively；Control the temperature of catalyst bed.Work as institute
When the temperature of some gas flow rates and catalyst bed reaches setting value, the reaction condition control of ethane oxidation is finished, and starts to connect
Continuous production.
Using the method for above-mentioned modification sections catalyst ethane oxidation, the present invention is it was discovered by researchers that ethane turns
Rate can be 85% or more.
Beneficial effects of the present invention are as follows:
(1), for load typed iron catalyst, the present invention provides the preparation of modification sections catalyst and it is used for second
The whole set process process of alkoxide, gives more considerable ethane conversion under the conditions of relatively mild.
(2), in conjunction with the embodiments with comparative example the result shows that, for ethane oxidation, modify and sections catalyst and do not repair
The iron catalyst of decorations is compared, and may be significantly the ethane conversion of raising and the yield of complete oxidation product carbon dioxide.
(3) each step operation of the invention is fairly simple, and involved equipment belongs to conventional equipment, related each object
Matter belongs to environmental-friendly substance, and implementing operation and environmental protection of the invention, cost is relatively low, while safe operation, personnel protection cost
It is lower, it is suitable for large-scale production and industrial applications.
Detailed description of the invention
Fig. 1 is ethane oxidation fixed-bed reactor structural schematic diagram.
In figure, 1, main reactor tube；2, main reactor tube air inlet；3, main reactor tube gas outlet；4, oxygen source；5, ethane gas
Source；6, noble gas source；7, first flow controller；8, second flow controller；9, third flow controller；10, raw material
Gas；11, product gas；12, catalyst bed；Thick-line arrow represents the flow direction of gas.
Specific embodiment
A method of using modification sections catalyst ethane oxidation, the preparation including modifying sections catalyst is repaired
The reaction system for adoring sections catalyst ethane oxidation prepares and the reaction condition of ethane catalysis oxidation controls three portions
Point.The preparation process for wherein modifying iron catalyst includes following steps:
Step 1: raw material preparation；Including following raw material:
Initial load sections catalyst, contains catalyst carrier and active metal component；The chemical component of catalyst carrier
For aluminium oxide；Active metal component is iron or ferriferous oxide；The load capacity of iron is 0.5 ~ 10 in initial load sections catalyst
wt%；The specific surface area of initial load sections catalyst is greater than 100 m2/g；Initial load sections catalyst is graininess, particle
Magnitude range is within 10 ~ 200 mesh；
First mixed liquor, specific preparation method are to mix alcohol with positive two substance of esters of silicon acis, the quality of the latter one
It is the former 0.2 ~ 15 times；Wherein positive esters of silicon acis refers to methyl orthosilicate, ethyl orthosilicate, one in positive silicic acid propyl ester three
A or their arbitrary proportion mixture；Wherein alcohol refers to methanol, ethyl alcohol, 1- propyl alcohol, one in 2- propyl alcohol, or
Their arbitrary proportion mixture；Obtained mixed liquor is known as the first mixed liquor；
Ammonium hydroxide is referred to containing NH3Mass percent is more than 3% aqueous solution；
First roasting gas source, refers specifically to compressed air, oxygen, nitrogen, argon gas, helium or these above-mentioned gases
Arbitrary proportion gaseous mixture.
Step 2: the first mixed liquid dipping；The specific method is as follows:
Initial load sections catalyst described in step 1 is completely soaked in the first mixed liquor；Being completely soaked the time is
20 min ~ 48 h；It impregnates after completing, the first extra mixed liquor is filtered out, load typed iron catalyst particle is left.
Step 3: alkali catalyzed hydrolysis；The specific method is as follows:
Prepare two containers, is referred to as the first container and second container；The first container is an open container；Second
Container is a closed container with cover, can hold entire the first container under air-tight state；Under second container opening-wide state,
It is put into a certain amount of ammonium hydroxide, quality is 5 ~ 1000 times of initial load sections catalyst quality；It will complete obtained by step 2
Load typed iron catalyst be put into the first container, and the first container is put into second container；Wherein ammonium hydroxide is put with the first container
The time sequencing for entering second container is random order；It covers the lid of second container to form closed container；After closeing the lid, protect
Hold 4 ~ 48h；Take out the load typed iron catalyst in the first container.
Step 4: catalyst roasts；The specific method is as follows:
Obtained load typed iron catalyst exposure will be handled by step 3 in air, or be exposed to the first roasting
Gas source is formed by under atmosphere and roasts；Calcining time is the h of 30 min ~ 24, and maturing temperature is 200 ~ 750oC。
Step 5: multiple circulate operation；The specific method is as follows:
Using the obtained load typed iron catalyst of step 4 is completed, described in alternative steps one " raw material preparation " " just
Beginning load typed iron catalyst " raw material carries out new one cycle operation；Wherein refer to step 1 to step per " one cycle operation "
All operationss described in rapid four；The total degree that circulate operation executes is 1 ~ 15 time.
In step 5, liquid composition involved in any primary new circulate operation, gas composition, maturing temperature,
The operating parameters such as calcining time, soaking time, can be identical as the parameter of its preceding circulate operation, can also be different；Parameter
Selection is fallen in range described by above-mentioned steps one to step 4.
" specific surface area " described in above-mentioned steps one is a term in catalyst and surface chemistry field, is referred to
The product of microcosmic surface possessed by the catalyst of unit mass.In the art, the most common measuring method of specific surface area is
Brunauer-Emmett-Teller (BET) method passes through N under measurement low temperature2Adsorption desorption curve on a catalyst calculates
It arrives.What " specific surface area " mentioned in the present invention referred to is also the numerical value measured by BET method.
" being completely soaked " in above-mentioned steps two refers in the institute's having time terminated since timing to timing, solid
Particle is immersed in liquid always.
After above-mentioned steps one to step 5, " initial load sections catalysis described in step 1 " raw material preparation "
Agent " is turned into " modification sections catalyst ".
The reaction system for modifying sections catalyst ethane oxidation prepares, using ethane oxidation fixed-bed reactor,
As shown in Figure 1, comprising: main reactor tube 1, main reactor tube 1 have main reactor tube air inlet 2, main reactor tube gas outlet 3；Oxygen gas
Source 4, provides purity oxygen；Ethane gas source 5 provides pure ethane gas；Noble gas source 6, provides N2Gas, He gas, in Ar gas
The mixture of one or more kinds of gases；Oxygen source 4, ethane gas source 5, noble gas source 6 flow pass through first respectively
Flow controller 7, second flow controller 8 and third flow controller 9 control；Oxygen source 4 is controlled by first flow
After device 7, ethane gas source 5 by after second flow controller 8, noble gas source 6 is after third flow controller 9 by being merged into
All the way, become the unstripped gas 10 of ethane oxidation；Unstripped gas 10 flows into main reactor tube air inlet 2, flows from main reactor tube gas outlet 3
Out；Catalyst, which can be filled in main reactor tube 1, forms catalyst bed 12；All gases for flowing through catalyst bed 12 are finally all
It is flowed out from main reactor tube gas outlet 3, forms product gas 11.
Above-mentioned " modification sections catalyst " is filled in main reactor tube 1 and forms catalyst bed 12, catalyst bed 12
Section full of main reactor tube 1；The modification sections catalyst gross mass of filling is denoted as mcat。
The reaction condition of ethane catalysis oxidation controls, and the specific method is as follows:
Oxygen source 4, ethane gas source 5 and noble gas source 6 are opened, and passes through first flow controller 7, second flow
Controller 8 and third flow controller 9 control the flow velocity of oxygen, ethane and inert gas respectively；The quality stream of ethane is taken down in short-hand
For F (C2H6), the mass velocity of oxygen is denoted as F (O2), the mass velocity of inert gas is denoted as F (Inert)；Control F (C2H6)
0.07 ~3 mcat*h-1In range；Control F (O2) it is F (C2H6) 2 ~ 8 times；Controlling F (Inert) is F (C2H6) 1 ~ 50
Times；The temperature of catalyst bed 12 is controlled 300 ~ 750oA target value between C.
Above-mentioned " mass velocity " refers to the gaseous mass for flowing through any one flow controller per hour.
When the temperature of all gas flow rates and catalyst bed 12 reaches setting value, the reaction item of ethane catalysis oxidation
Part control finishes, and starts continuous production.
Technical staff can be sampled simultaneously quantitative analysis to product gas 11, calculate ethane after continuous production starts
Conversion ratio and yield of carbon dioxide.For use the reaction-ure conversion-age that reaction is catalyzed in fixed bed reactors, object yield,
Object is selectively measured and is calculated, and is a routine operation content of catalytic field, not within protection scope of the present invention.
In this field, a way for being easier to realize is to analyze the unstripped gas 10 of ethane oxidation respectively by on-line gas chromatography
And the gas composition of product gas 11, and it is calculate by the following formula ethane conversion (XC2%) with the yield of carbon dioxide (Y%):
,
；
Wherein [C 2 H 6]0Respectively represent the concentration of ethane and oxygen in unstripped gas 10；[C 2 H 6]1[CO 2]1Respectively represent second
The concentration of alkane and carbon dioxide in product gas 11.
Using the method for above-mentioned modification sections catalyst ethane oxidation, the present invention is it was discovered by researchers that ethane turns
Rate can be 85% or more.
Embodiment one,
A method of using modification sections catalyst ethane oxidation, the preparation including modifying sections catalyst is repaired
The reaction system for adoring sections catalyst ethane oxidation prepares and the reaction condition of ethane catalysis oxidation controls three portions
Point.The preparation process for wherein modifying iron catalyst includes following steps:
Step 1: raw material preparation；Including following raw material:
Initial load sections catalyst, contains catalyst carrier and active metal component；The chemical component of catalyst carrier
For aluminium oxide；Active metal component is iron or ferriferous oxide；The load capacity of iron is 3.5 in initial load sections catalyst
wt%；The specific surface area of initial load sections catalyst is 260 m2/g；Initial load sections catalyst is graininess, and particle is big
Small range is between 20 ~ 40 mesh；Initial load sections catalyst gross mass is 4.0 g；
First mixed liquor, specific preparation method are to mix alcohol with positive two substance of esters of silicon acis, the quality of the latter one
It is the former 0.7 times；Wherein positive esters of silicon acis refers to that ethyl orthosilicate, alcohol refer to ethyl alcohol；
Ammonium hydroxide is referred to containing NH3The aqueous solution that mass percent is about 18%；
First roasting gas source, refers specifically to oxygen and helium mix gas, and the volume ratio that wherein oxygen accounts for is 4.9%.
Step 2: the first mixed liquid dipping；The specific method is as follows:
Initial load sections catalyst described in step 1 is completely soaked in the first mixed liquor；Being completely soaked the time is
24 h；It impregnates after completing, the first extra mixed liquor is filtered out, load typed iron catalyst particle is left.
Step 3: alkali catalyzed hydrolysis；The specific method is as follows:
Prepare the first container and second container；Second container is opened wide, the quality for being put into ammonium hydroxide is about that initial load sections is urged
25 times of agent quality；It will complete the obtained load typed iron catalyst of step 2 to be put into the first container, and by the first container
It is put into second container；It covers the lid of second container to form closed container；After closeing the lid, 24 h are kept；First is taken out to hold
Load typed iron catalyst in device.
Step 4: catalyst roasts；The specific method is as follows:
The first roasting gas source will be exposed to by the obtained load typed iron catalyst of step 3 processing be formed by atmosphere
Lower roasting；Calcining time is 6 h, maturing temperature 650oC。
Step 5: multiple circulate operation；The specific method is as follows:
Using the obtained load typed iron catalyst of step 4 is completed, described in alternative steps one " raw material preparation " " just
Beginning load typed iron catalyst " raw material carries out new one cycle operation；The total degree that circulate operation executes is 6 times.
In step 5, liquid composition involved in any primary new circulate operation, gas composition, maturing temperature,
The operating parameters such as calcining time, soaking time are identical as the parameter of its preceding circulate operation.
Obtained product is known as " modification sections catalyst ".
The reaction system for modifying sections catalyst ethane oxidation prepares, using ethane oxidation fixed-bed reactor,
As shown in Figure 1, wherein main reactor tube 1 is a cylindrical pipe, internal diameter is 11 mm, and length is 60 cm；Wherein indifferent gas
Body gas source 6, which provides, contains N2The gaseous mixture of gas 9.8%, He gas 90.2%；" modification sections catalyst " made from the above process is loaded
In forming catalyst bed 12 in main reactor tube 1, catalyst bed 12 is full of the section of main reactor tube 1；The modification sections of filling
The gross mass m of catalystcat = 0.5 g。
The reaction condition of ethane catalysis oxidation controls, and the specific method is as follows:
Oxygen source 4, ethane gas source 5 and noble gas source 6 are opened, and passes through first flow controller 7, second flow
Controller 8 and third flow controller 9 control the flow velocity of oxygen, ethane and inert gas respectively；Control the mass velocity F of ethane
(C2H6) = 0.48 mcat*h-1, control the mass velocity F (O of oxygen2) it is F (C2H6) 3.6 times, control the matter of inert gas
Measuring flow rate F (Inert) is F (C2H6) 20 times；The temperature for controlling catalyst bed 12 is 600oC。
When the temperature of all gas flow rates and catalyst bed 12 reaches setting value, the reaction item of ethane catalysis oxidation
Part control finishes, and starts continuous production.
After continuous production starts, the conversion ratio X of the ethane of the present embodiment is calculated by online gas chromatographic analysisC2%
=100%, the yield of carbon dioxideY% = 70.5%。
Embodiment two,
This example is comparative example, it is therefore an objective to verify one of good effect of the invention.Specific practice is:
Preparation without " modified iron catalyst "；
The reaction system of load typed iron catalyst catalysis ethane oxidation prepares: " modifying sections catalyst to urge with embodiment 1
The reaction system for changing ethane oxidation prepares ", difference is, " modification sections catalyst " therein is substituted for " initial load type
Iron catalyst ", and be filled in the catalyst bed of ethane oxidation fixed-bed reactor；The initial load sections of filling is catalyzed
The gross mass m of agentcat = 0.5 g。
The reaction condition of ethane catalysis oxidation controls, with embodiment one.
When the temperature of all gas flow rates and catalyst bed 12 reaches setting value, the reaction item of ethane catalysis oxidation
Part control finishes, and starts continuous production.
After continuous production starts, the conversion ratio X of the ethane of the present embodiment is calculated by online gas chromatographic analysisC2%
=63.2%, the yield of carbon dioxideY% = 58.2%。
One, two result is it can be found that using the sections catalyst original negative more unmodified than using is modified in conjunction with the embodiments
Sections catalyst is carried, can more completely be converted ethane under the conditions of same process, and complete oxidation produces in conversion process
Object is more.That is, the former has the performance for preferably removing small molecule alkane.
Embodiment three,
It is other to be as in the first embodiment, distinguishing:
For modifying the preparation process of sections catalyst, in " raw material preparation " of step 1, the first mixed liquor is specifically matched
Method processed is to mix alcohol with positive two substance of esters of silicon acis, and the quality of the latter one is the former 0.41 times；Wherein positive esters of silicon acis
Refer to that ethyl orthosilicate, alcohol refer to ethyl alcohol；In " the multiple circulate operation " of step 5, the total degree that circulate operation executes is
9 times.
After continuous production starts, by online gas chromatographic analysis be calculated the ethane of the present embodiment conversion ratio, two
The yield of carbonoxide is almost consistent in error range.
Example IV,
It is other to be as in the first embodiment, distinguishing:
For modifying the preparation process of sections catalyst, in " the multiple circulate operation " of step 5, what circulate operation executed
Total degree is 2 times.
Reaction condition control for ethane catalysis oxidation, the temperature of control catalyst bed 12 are 570oC。
After continuous production starts, the conversion ratio X of the ethane of the present embodiment is calculated by online gas chromatographic analysisC2%
= 88.9%。
Embodiment five,
It is other to be as in the first embodiment, distinguishing:
For modifying the preparation process of sections catalyst, in " the multiple circulate operation " of step 5, what circulate operation executed
Total degree is 5 times；Wherein, in the 1-3 times circulate operation, liquid group involved in any primary new circulate operation
Parameter phase at, operating parameters such as gas composition, maturing temperature, calcining time, soaking time, with its preceding circulate operation
Together；The 4-5 times is recycled, is with the operating parameter difference that the 1-3 times recycles:
" the catalyst roasting " of step 4, maturing temperature 400oC, the atmosphere of exposure is air when roasting.
After continuous production starts, the conversion ratio X of the ethane of the present embodiment is calculated by online gas chromatographic analysisC2%
= 98.0%。
Embodiment six,
It is other to be as in the first embodiment, distinguishing:
The reaction system for modifying sections catalyst ethane oxidation prepares, using ethane oxidation fixed-bed reactor,
As shown in Figure 1, wherein main reactor tube 1 is a cylindrical pipe, internal diameter is 18 mm, and length is 72 cm；It " is repaired by made from
Decorations sections catalyst ", which is filled in main reactor tube 1, forms catalyst bed 12, and catalyst bed 12 is cut full of main reactor tube 1
Face；The gross mass m of the modification sections catalyst of fillingcat = 2.0 g。
The reaction condition of ethane catalysis oxidation controls, and the specific method is as follows:
Control the mass velocity F (C of ethane2H6) = 0.12 mcat*h-1, control the mass velocity F (O of oxygen2) it is F
(C2H6) 4.0 times, control inert gas mass velocity F (Inert) be F (C2H6) 25 times；Control catalyst bed 12
Temperature is 570oC。
When the temperature of all gas flow rates and catalyst bed 12 reaches setting value, the reaction item of ethane catalysis oxidation
Part control finishes, and starts continuous production.
After continuous production starts, the conversion ratio X of the ethane of the present embodiment is calculated by online gas chromatographic analysisC2%
= 100%。
Claims (5)
1. a kind of method using modification sections catalyst ethane oxidation, which is characterized in that including modifying sections catalyst
Preparation, modification sections catalyst ethane oxidation reaction system prepare and ethane catalysis oxidation reaction condition control
Make three parts；The preparation process for wherein modifying iron catalyst includes following steps:
Step 1: raw material preparation；Including following raw material:
Initial load sections catalyst, contains catalyst carrier and active metal component；The chemical component of catalyst carrier is oxygen
Change aluminium；Active metal component is iron or ferriferous oxide；In initial load sections catalyst the load capacity of iron be 0.5~
10wt%；The specific surface area of initial load sections catalyst is greater than 100m2/g；Initial load sections catalyst is graininess,
Grain magnitude range is within 10~200 mesh；
First mixed liquor, specific preparation method is to mix alcohol with positive two substance of esters of silicon acis, before the quality of the latter one is
0.2~15 times of person；Wherein positive esters of silicon acis refers to methyl orthosilicate, ethyl orthosilicate, one in positive silicic acid propyl ester three,
Or their arbitrary proportion mixture；Wherein alcohol refer to methanol, ethyl alcohol, 1- propyl alcohol, one in 2- propyl alcohol or they
Arbitrary proportion mixture；Obtained mixed liquor is known as the first mixed liquor；
Ammonium hydroxide is referred to containing NH3Mass percent is more than 3% aqueous solution；
First roasting gas source, it is any to refer specifically to compressed air, oxygen, nitrogen, argon gas, helium or these above-mentioned gases
Ratio gaseous mixture；
Step 2: the first mixed liquid dipping；The specific method is as follows:
Initial load sections catalyst described in step 1 is completely soaked in the first mixed liquor；Being completely soaked the time is
20min~48h；It impregnates after completing, the first extra mixed liquor is filtered out, load typed iron catalyst particle is left；
Step 3: alkali catalyzed hydrolysis；The specific method is as follows:
Prepare two containers, is referred to as the first container and second container；The first container is an open container；Second container
For a closed container with cover, entire the first container can be held under air-tight state；Under second container opening-wide state, it is put into
A certain amount of ammonium hydroxide, quality are 5~1000 times of initial load sections catalyst quality；It is obtained negative will to complete step 2
It carries sections catalyst to be put into the first container, and the first container is put into second container；Wherein ammonium hydroxide and the first container are put into the
The time sequencing of two containers is random order；It covers the lid of second container to form closed container；After closeing the lid, 4 are kept
~48h；Take out the load typed iron catalyst in the first container；
Step 4: catalyst roasts；The specific method is as follows:
Obtained load typed iron catalyst exposure will be handled by step 3 in air, or be exposed to the first roasting gas source
It is formed by under atmosphere and roasts；Calcining time is 30min~for 24 hours, and maturing temperature is 200~750 DEG C；
Step 5: multiple circulate operation.
2. the method according to claim 1 using modification sections catalyst ethane oxidation, which is characterized in that modification
The step of iron catalyst preparation process five, the specific method is as follows:
Using the completion obtained load typed iron catalyst of step 4, " original negative described in alternative steps one " raw material preparation "
Carry sections catalyst " raw material, carry out new one cycle operation；Wherein refer to step 1 to step 4 per " one cycle operation "
The all operationss；The total degree that circulate operation executes is 1~15 time；
In step 5, liquid composition, gas composition, maturing temperature, roasting involved in any primary new circulate operation
Time, soaking time these operating parameters, can be identical as the parameter of its preceding circulate operation, it can also be different；Parameter choosing
It selects and falls in range described by above-mentioned steps one to step 4；
After above-mentioned steps one to step 5, " initial load sections catalyst " described in step 1 " raw material preparation " becomes
As " modification sections catalyst ".
3. the method according to claim 1 using modification sections catalyst ethane oxidation, which is characterized in that wherein
The reaction system for modifying sections catalyst ethane oxidation prepares, and uses ethane oxidation fixed-bed reactor, comprising: main anti-
Ying Guan, main reactor tube have main reactor tube air inlet, main reactor tube gas outlet；Oxygen source provides purity oxygen；Ethane gas source,
Pure ethane gas is provided；Noble gas source provides N2The mixture of one or more of gas, He gas, Ar gas gas；Oxygen
Gas gas source, ethane gas source, noble gas source flow pass through first flow controller, second flow controller and third respectively
Flow controller controls；Oxygen source pass through first flow controller after, ethane gas source by after second flow controller, it is lazy
Property gas source by being merged into the unstripped gas for becoming ethane oxidation all the way after third flow controller；Flow of feed gas is become owner of instead
Should pipe air inlet, from main reactor tube gas outlet flow out；Catalyst, which can be filled in main reactor tube, forms catalyst bed；All streams
Gas through catalyst bed is finally all flowed out from main reactor tube gas outlet, forms product gas；
Above-mentioned " modification sections catalyst " is filled in main reactor tube and forms catalyst bed, catalyst bed is full of main reaction
The section of pipe；The modification sections catalyst gross mass of filling is denoted as mcat。
4. the method according to claim 1 using modification sections catalyst ethane oxidation, which is characterized in that wherein
The reaction condition of ethane catalysis oxidation controls, and the specific method is as follows:
Open oxygen source, ethane gas source and noble gas source, and by first flow controller, second flow controller and
Third flow controller controls the flow velocity of oxygen, ethane and inert gas respectively；The mass velocity of ethane is denoted as F (C2H6), oxygen
The mass velocity of gas is denoted as F (O2), the mass velocity of inert gas is denoted as F (Inert)；Control F (C2H6) in 0.07~3mcat*
h-1In range；Control F (O2) it is F (C2H6) 2~8 times；Controlling F (Inert) is F (C2H6) 1~50 times；Control catalyst
A target value of the temperature of bed between 300~750 DEG C.
5. the method according to claim 1 using modification sections catalyst ethane oxidation, which is characterized in that ethane
Conversion ratio 85% or more.
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