CN108728151A - The production method and a kind of alpha-olefin production system of a kind of alpha-olefin - Google Patents

The production method and a kind of alpha-olefin production system of a kind of alpha-olefin Download PDF

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CN108728151A
CN108728151A CN201710256681.1A CN201710256681A CN108728151A CN 108728151 A CN108728151 A CN 108728151A CN 201710256681 A CN201710256681 A CN 201710256681A CN 108728151 A CN108728151 A CN 108728151A
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gas
fischer
metallic element
methane
temperature
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CN108728151B (en
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晋超
吴玉
张荣俊
侯朝鹏
孙霞
阎振楠
夏国富
李明丰
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of production method of alpha-olefin and production system, the production method is included under the conditions of steam reforming reaction, and methane is contacted with water, obtains steam reforming synthesis gas；Under dry reforming reaction condition, by methane and carbon dioxide exposure, dry reforming synthesis gas is obtained；Steam reforming synthesis gas and dry reforming synthesis gas are mixed, Fischer-Tropsch synthesis charging is obtained to prepare, Fischer-Tropsch synthesis charging is contacted under the reaction temperature of production alpha-olefin with fischer-tropsch synthetic catalyst, obtain Fischer-Tropsch synthetic logistics, isolate the methane and carbon dioxide in Fischer-Tropsch synthetic logistics, methane is sent into steam reforming step and/or dry reforming step, carbon dioxide is sent into dry reforming step.The production method of alpha-olefin according to the present invention can be effectively reduced the discharge capacity of system energy consumption and greenhouse gases (such as carbon dioxide).

Description

The production method and a kind of alpha-olefin production system of a kind of alpha-olefin
Technical field
The present invention relates to a kind of production methods of alpha-olefin, and the invention further relates to a kind of alpha-olefin production systems.
Background technology
Linear alpha-olefin is a kind of important Organic Ingredients and intermediate, is widely used in production comonomer, lubrication oil base Plinth oil, surfactant, vistanex, plasticizer, dyestuff, pharmaceutical preparation etc..South Africa Sasol companies are completed a set of from expense Separation 1- amylenes in support (F-T) sintetics (be rich in alpha-olefin), 1- hexenes process units and successfully go into operation, the technique is maximum Advantage is using coal as raw material, and using 1- amylenes, 1- hexenes as by-product recovery, industrial production cost is low, can be obtained higher Income.
The method of most widely used production alpha-olefin is olefin(e) oligomerization method at present, but this method production cost is excessively high, and And the linear alpha-alkene that the same carbon number with market value is odd number cannot be produced.South Africa Sasol companies are taken using high temperature F-T The cost that support synthetic technology extracts linear 1- hexenes from crude product is less than Philips companies using ethylene trimer method production line Property 1- hexene costs one third, while based on the F-T synthetic product Anderson-Schulz-Flory regularities of distribution (chain increase The long molar distribution with exponential decrease), the high added values such as 1- amylenes and the 1- heptene of odd number carbon number also can be obtained in high temperature F-T synthesis Product.Therefore, isolated alpha-olefin has important commercial value from Fischer-Tropsch synthetic.
China's energy is in the resource distribution situation of rich coal, more natural gases, oil starvation, will be between coal or natural gas by F-T synthesis Switch through that turn to clean, highly effective liquid fuel be the importance for rationally utilizing resource, China's oil imbalance between supply and demand can be alleviated Major Technology.In recent years in China's coal chemical technology, coal emerges rapidly through methanol alpha-olefin, and coal is direct through synthesis gas Alpha-olefin (FTO techniques) processed is another coal alpha-olefin technique.The manufacturing process converts coal or natural gas to synthesis first Gas (CO and H2), the process of alpha-olefin is directly made using F-T synthesis.
Fig. 1, including sequentially connected water-coal-slurry preparation unit I, coal are shown in the technological process that alpha-olefin is prepared using FTO techniques Gasification unit II, WGS unit III, purified synthesis gas unit IV, F- T synthesis unit V and alpha-olefin separative element VI, detailed process are that water-coal-slurry C is made in water-coal-slurry preparation unit I in fine coal A and water B, and water-coal-slurry C is delivered into coal gas Change unit II, is reacted with oxygen D and generate coal gasification crude synthesis gas E, coal gasification crude synthesis gas E through WGS unit III tune The molar ratio of whole hydrogen and carbon monoxide becomes crude synthesis gas F after the transformation of the requirement for meeting Fischer-Tropsch synthesis, transformation Crude synthesis gas F is purified synthesis gas J through synthesis gas clean unit IV removing sour gas and sulfide M afterwards, net by what is obtained It is combined to gas J and is conveyed into F- T synthesis unit V progress Fischer-Tropsch synthesis, generate the fischer-tropsch reaction product N of olefin-containing, Fischer-Tropsch is anti- Product N is answered to isolate alpha-olefin K through alpha-olefin separative element VI, the carbon dioxide H and methane G that F- T synthesis unit V is generated are then Outer row, a part of unreacted synthesis gas Y are recycled back to F- T synthesis unit V, and the unreacted synthesis gas of another part, which is used as, speeds to put Gas Z discharge systems.
The above-mentioned main problem using FTO techniques is：1, high energy consumption, carbon atom utilization rate are low；2, CO2 emission Amount is 5-6 times of conventional petroleum route；3, it is limited by Anderson-Schulz-Flory rules since Fischer-Tropsch synthetic is distributed System, and be limited by a large amount of methane, carbon dioxide caused by the strongly exothermic property of reaction and generate, FTO technique entirety efficiencies are relatively low, serious shadow Ring the process of industrialization of FTO techniques.The a large amount of cooling water of FTO techniques and externally discharged waste water keep water consume high.
Therefore, it is necessary to optimize, FTO techniques, a kind of efficiency of selection be high, system of GHG emissions mitigation.
Invention content
The purpose of the present invention is to provide a kind of production method of alpha-olefin, this method can be effectively reduced system energy consumption with And the discharge capacity of greenhouse gases.
According to the first aspect of the invention, the present invention provides a kind of production method of alpha-olefin, this method include with Lower step：
S11, under the conditions of steam reforming reaction, methane is contacted with vapor, obtains steam reforming synthesis gas；
S21, under dry reforming reaction condition, by methane and carbon dioxide exposure, obtain dry reforming synthesis gas；
S31, will at least partly steam reforming synthesis gas and at least partly dry reforming synthesis gas mix, with prepare obtain expense Synthetic reaction charging is held in the palm, Fischer-Tropsch synthesis charging is connect under the reaction temperature of production alpha-olefin with fischer-tropsch synthetic catalyst It touches, obtains Fischer-Tropsch synthetic logistics；
S41, alpha-olefin, methane and carbon dioxide are isolated from the Fischer-Tropsch synthetic logistics, the first that will be isolated Alkane be sent into one of S11 and S21, or both in, will the carbon dioxide that isolated be sent into S21 in.
According to the second aspect of the invention, the present invention provides a kind of alpha-olefin production system, which includes that water steams Gas reforming reaction unit, dry reforming reaction member, synthesis gas mixed cell, Fischer-Tropsch synthesis unit, Fischer-Tropsch synthesis production Object separative element and cycling element,
The steam reforming reaction unit carries out steam reforming reaction, obtains for contacting methane with vapor Steam reforming synthesis gas；
The dry reforming reaction member is used to, by methane and carbon dioxide exposure, carry out dry reforming reaction, obtain dry reforming Synthesis gas；
The synthesis gas mixed cell is matched for mixing the steam reforming synthesis gas with the dry reforming synthesis gas It is made for Fischer-Tropsch synthesis charging, and the Fischer-Tropsch synthesis is fed in the Fischer-Tropsch synthesis unit；
The Fischer-Tropsch synthesis unit is provided with Fischer-Tropsch synthesis device, for by the Fischer-Tropsch synthesis charging with Fischer-tropsch synthetic catalyst contacts under the reaction temperature of production alpha-olefin, obtains the Fischer-Tropsch synthetic logistics containing alpha-olefin；
The Fischer-Tropsch synthesis product separative element obtains first for detaching the Fischer-Tropsch synthetic logistics Alkane, carbon dioxide, alpha-olefin, optional hydrogen and optional carbon monoxide；
The methane cycle that the cycling element is used to isolate Fischer-Tropsch synthesis product separative element is sent into vapor One of reforming reaction unit and dry reforming reaction member, or both in, by Fischer-Tropsch synthesis product separative element detach The carbon dioxide recycle gone out is sent into dry reforming reaction member, the hydrogen that Fischer-Tropsch synthesis product separative element is isolated And/or carbon monoxide cycle is sent into Fischer-Tropsch synthesis unit.
The production method and system of alpha-olefin according to the present invention, can be effectively reduced system energy consumption and greenhouse gases The discharge capacity of (such as carbon dioxide).
Description of the drawings
Fig. 1 is for illustrating that existing coal directly prepares the typical process flow of alpha-olefin (FTO techniques) through synthesis gas.
Fig. 2 is for illustrating alpha-olefin preparation method and system according to the present invention.
Fig. 3 is θ-Al prepared by preparation example 12O3X-ray diffraction spectrogram.
Fig. 1 reference signs
I：Water-coal-slurry preparation unit II：Coal gasification unit II：WGS unit
IV：Purified synthesis gas unit V：F- T synthesis unit VI：Alpha-olefin separative element
A：Fine coal B：Water C：Water-coal-slurry
D：Oxygen E：Coal gasification crude synthesis gas F：Crude synthesis gas after transformation
G：Methane H：Carbon dioxide K：Alpha-olefin
M：Sour gas and sulfide N：Fischer-tropsch reaction product Y：Unreacted synthesis gas
Z：Periodic off-gases J：Decontaminating syngas
Fig. 2 reference signs
I：Unstripped gas separative element II：Steam reforming reaction unit III：Dry reforming reaction member
IV：Fischer-Tropsch synthesis unit V：Fischer-Tropsch synthetic separative element A：Unstripped gas
B：Methane C：Vapor D：Carbon dioxide
E：Steam reforming synthesis gas F：Dry reforming synthesis gas G：Fischer-Tropsch synthesis is fed
H：Fischer-Tropsch synthetic logistics L：Hydrogen and carbon monoxide K for cycle：Alpha-olefin
M：Methane N：Carbon dioxide Z：Periodic off-gases
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of production method of alpha-olefin, this method include with Lower step：
S11, under the conditions of steam reforming reaction, methane is contacted with water, obtains steam reforming synthesis gas；
S21, under dry reforming reaction condition, by methane and carbon dioxide exposure, obtain dry reforming synthesis gas；
S31, will at least partly steam reforming synthesis gas and at least partly dry reforming synthesis gas mix, with prepare obtain expense Synthetic reaction charging is held in the palm, Fischer-Tropsch synthesis charging is connect under the reaction temperature of production alpha-olefin with fischer-tropsch synthetic catalyst It touches, obtains Fischer-Tropsch synthetic logistics；
S41, alpha-olefin, methane and carbon dioxide are isolated from the Fischer-Tropsch synthetic logistics, the first that will be isolated Alkane be sent into one of S11 and S21, or both in, will the carbon dioxide that isolated be sent into S21 in.
In step S11, the molar ratio of methane and vapor can be 1：0.5-4, preferably 1：1-3.Can by methane with Vapor is contacted at a temperature of 700-950 DEG C, preferably 800-900 DEG C.The reactor that methane is contacted with vapor Interior pressure can be 0.1-5MPa, and preferably 1-3MPa, the pressure is gauge pressure.The steam reforming reaction can be normal It is carried out in the reactor seen.Preferably, the steam reforming reaction carries out in fixed bed reactors.With methane and vapor Total amount meter, volume space velocity can be 10000-100000 hours when the gas of charging-1, preferably 50000-100000 hours-1。
In step S11, the various steam reformings suitable for steam reforming reaction commonly used in the art may be used and urge Agent.As an example, the steam reforming catalyst contains the active component of carrier and load on the carrier. The carrier can be the combination of one or more of aluminium oxide, silica, zirconium oxide and silicon carbide.Preferably, institute It is aluminium oxide to state carrier, is specifically as follows γ-Al2O3、θ-Al2O3、δ-Al2O3With α-Al2O3One or more of.Institute It can be group VIII metallic element, preferably group VIII non-noble metal j element to state active component, such as one in Fe, Co and Ni Kind is two or more.It is highly preferred that the active component is Ni.Load capacity of the active component on carrier can be conventional Selection.Usually, on the basis of the total amount of catalyst, based on the element, the content of the active component can be 1-30 weight %, Preferably 5-25 weight %, more preferably 10-15 weight %.
In step S21, the molar ratio of methane and carbon dioxide can be 1：0.5-5, preferably 1：0.8-3, more preferably 1：1-2.Methane can be contacted with carbon dioxide at a temperature of 600-800 DEG C, preferably 650-750 DEG C.Methane and dioxy The pressure changed in the reactor that carbon is contacted can be 0.1-5MPa, and preferably 1-3MPa, the pressure is in terms of gauge pressure.It is described Dry reforming reaction can carry out in common reactor.Preferably, the dry reforming reaction carries out in fixed bed reactors. In terms of the total amount of methane and carbon dioxide, volume space velocity can be 10000-100000 hours when the gas of charging-1, preferably 50000-100000 hours-1。
In step S21, the various dry reforming catalyst suitable for dry reforming reaction commonly used in the art may be used.As One example, the dry reforming catalyst contain the active component of carrier and load on the carrier.The carrier can be with For the combination of one or more of aluminium oxide, silica, zirconium oxide and silicon carbide.Preferably, the carrier is oxidation Aluminium is specifically as follows γ-Al2O3、θ-Al2O3、δ-Al2O3With α-Al2O3One or more of.The active component can Think group VIII metallic element, preferably group VIII non-noble metal j element, as one or both of Fe, Co and Ni with On.It is highly preferred that the active component is Ni.Load capacity of the active component on carrier can be conventional selection.Generally Ground, on the basis of the total amount of catalyst, based on the element, the content of the active component can be 1-30 weight %, preferably 5- 25 weight %, more preferably 10-15 weight %.
The production method of alpha-olefin according to the present invention, one of the raw material as methane vapor reforming and methane dry reforming Methane, can be various sources methane, the methane preferably isolated from the unstripped gas rich in methane.At this point, according to The production method of the alpha-olefin of the present invention, further includes step S10, in S10, first is isolated from the unstripped gas containing methane Alkane.The unstripped gas can be the common mixture rich in methane.Specifically, the unstripped gas can be selected from shale gas, One or more of coal bed gas, natural gas, refinery gas and oven gas.
Conventional method may be used and isolate methane from the unstripped gas, such as use pressure swing adsorption method from the unstripped gas In isolate methane.As an example, methane is isolated from unstripped gas by condensation at low temperature.The condensation at low temperature is The method for isolating and purifying methane using boiling-point difference according to the boiling point determination of each component in unstripped gas is obtained from gas phase Methane, or methane is obtained from liquid phase.
The production method of alpha-olefin according to the present invention, methane as one of steam reforming and the raw material of dry reforming Purity is generally 90 weight % or more.In methane as one of steam reforming and the raw material of dry reforming, the quality of element sulphur Content be generally 20ppm hereinafter, preferably 10ppm hereinafter, more preferably 5ppm hereinafter, further preferably 1ppm or less.
The production method of alpha-olefin according to the present invention, according to the reaction property and Fischer-Tropsch of steam reforming and dry reforming The amount of the requirement of synthetic reaction charging, the methane that can be sent into step S11 and step S21 by control is further increased according to this The raw material availability of the method for invention.Preferably, the weight of the methane used in step S11 and the methane used in step S21 Than being 1：0.5-2.5.
The production method of alpha-olefin according to the present invention will at least partly steam reforming synthesis gas and extremely in step S31 Small part dry reforming synthesis gas mixes, and preparation obtains meeting F- T synthesis charging hydrogen-carbon ratio (that is, mole of hydrogen and carbon monoxide Than) Fischer-Tropsch synthesis charging.From improve alpha-olefin selectivity angle, Fischer-Tropsch synthesis charging in, hydrogen and The molar ratio of carbon monoxide is preferably 0.4-3：1, more preferably 0.6-2.8：1, further preferably 0.8-2.6：1, more into one Step is preferably 1.5-2.5：1.
The production method of alpha-olefin according to the present invention in step S31, Fischer-Tropsch synthesis is fed and is urged with F- T synthesis Agent contacts, and carries out Fischer-Tropsch synthesis, obtains Fischer-Tropsch synthetic logistics.
The fischer-tropsch synthetic catalyst can be conventional to catalyst of the Fischer-Tropsch synthesis with catalytic action.One In kind preferred embodiment, the fischer-tropsch synthetic catalyst contains the first metal member of carrier and load on the carrier Element, the second metallic element and optional third metallic element.
According to the fischer-tropsch synthetic catalyst of the preferred embodiment, the carrier is aluminium oxide, and specific example can be with Including but not limited to：γ-Al2O3、θ-Al2O3、δ-Al2O3With α-Al2O3One or more of.It can be according to aluminium oxide Concrete type the parameters such as its specific surface area, average pore size and particle diameter distribution are optimized, to further increase catalyst Catalytic performance.As an example, for γ-Al2O3, Kong Rongke is with for 0.6-1mL/g, preferably 0.65-0.9mL/g is more excellent It is selected as 0.65-0.85mL/g；Average pore size can be 8-35nm, preferably 12-30nm, more preferably 15-20nm；Grain size exists The content of particle in 70-150 μ ms can be 80 volume % or more, preferably 85 volume % or more, more preferably 90 bodies Product % or more；Specific surface area can be 100-300m2/ g, preferably 120-250m2/ g, more preferably 150-200m2/g.As Another example, for θ-Al2O3, Kong Rongke is with for 0.3-0.8mL/g, preferably 0.35-0.7mL/g, more preferably 0.4- 0.6mL/g；Average pore size can be 12-40nm, preferably 15-35nm, more preferably 18-25nm；Grain size is in 70-150 μm of model The content of particle in enclosing can be 80 volume % or more, preferably 85 volume % or more, more preferably 90 volume % or more；Than Surface area can be 50-200m2/ g, preferably 60-150m2/ g, more preferably 65-100m2/g。
Preferably, the carrier contains θ-Al2O3.By introducing θ-Al in the carrier2O3So that fischer-tropsch synthetic catalyst Higher catalytic activity can be obtained.Usually, on the basis of the total amount of aluminium oxide in catalyst, the content of θ-aluminium oxide can be 10 weight % or more, preferably 20 weight % or more, more preferably 30 weight % or more, further preferably 40 weight % with On, it is still more preferably 50 weight % or more.It is particularly preferred that the carrier is θ-aluminium oxide.
θ-the Al2O3It is commercially available, it can also be by by γ-Al2O3It is roasted and is obtained.It specifically, can be with By γ-Al2O3It is roasted at a temperature of 700-1050 DEG C, preferably 780-1050 DEG C.The duration of the roasting can root It is selected according to the temperature of roasting, to be enough γ-Al2O3It is converted into θ-Al2O3Subject to.Usually, the roasting it is lasting when Between can be 0.5-5 hours, preferably 1-4 hours.The roasting carries out in air atmosphere.
According to the fischer-tropsch synthetic catalyst of the preferred embodiment, the group VIII metallic element is as catalyst Active component can be group VIII noble metals element, or group VIII non-noble metal j element can also be Section VIII The combination of race's precious metal element and group VIII non-noble metal j element.In a preferred embodiment, the group VIII Metallic element is group VIII non-noble metal j element, specific example can include but is not limited to one kind in Fe, Co and Ni or It is two or more.It is highly preferred that the group VIII metallic element is Fe.
Valence state according to the fischer-tropsch synthetic catalyst of the preferred embodiment, at least partly group VIII metallic element is Less than the highest oxidation valence state of the metallic element.Usually, with the total amount of group VIII metallic element in fischer-tropsch synthetic catalyst On the basis of, based on the element, valence state is that the content of the group VIII metallic element less than its highest oxidation valence state can be 40 weights % or more, preferably 50 weight % or more, more preferably 55 weight % or more, further preferably 60 weight % or more are measured, more Further preferably 70 weight % or more.On the basis of the total amount of group VIII metallic element in catalyst, based on the element, valence state Content highest for the group VIII metallic element less than its highest oxidation valence state can be 100 weight %, such as can be 95 Weight %, 90 weight %, 85 weight %.According to the preferred embodiment, the fischer-tropsch synthetic catalyst is used directly for Catalysis reaction, without carrying out additional reduction activation.In the present invention, term " highest oxidation valence state " refers to the metallic element quilt Chemical valence when complete oxidation, by taking Fe as an example, highest oxidation valence state refers to iron oxide (Fe2O3) in ferro element chemical valence, be+3 Valence.In the present invention, group VIII metallic element and its content with different valence state are measured using X-ray photoelectron spectroscopy.
According to the fischer-tropsch synthetic catalyst of the preferred embodiment, in a particularly preferred example, described Group VIII metal element is Fe, in the x-ray photoelectron spectroscopy spectrogram of the fischer-tropsch synthetic catalyst, is existed corresponding to FeO's Spectral peak (typically occurring at 711.9eV and 724.4eV) and correspond to Fe5C2Spectral peak (typically occurring at 717.9eV). There is more excellent catalytic performance according to the fischer-tropsch synthetic catalyst of the particularly preferred example.In the particularly preferred example In, based on the element, by the content of Fe that is determined corresponding to the spectral peak of FeO with by corresponding to Fe5C2Spectral peak determine Fe content Ratio can be 8-25：1.From the angle for the catalytic activity and catalytic stability for further increasing catalyst, by right It should be in the content for the Fe that the spectral peak of FeO determines and by corresponding to Fe5C2The ratio of content of Fe that determines of spectral peak be preferably 8.5- 20：1, more preferably 9-18：1, further preferably 9.5-16：1, particularly preferably 9.5-12：1.It is particularly preferred according to this The fischer-tropsch synthetic catalyst of example, from the angle for further increasing catalytic activity, based on the element, with by x-ray photoelectron Power spectrum determine Fe total amount on the basis of, by corresponding to FeO spectral peak and correspond to Fe5C2The content of Fe that determines of spectral peak can Think 40 weight % or more, preferably 50 weight % or more, more preferably 55 weight % or more, further preferably 60 weight % More than, it is still more preferably 70 weight % or more.On the basis of the total amount of the Fe determined by x-ray photoelectron spectroscopy, by right It should be in the spectral peak of FeO and corresponding to Fe5C2Spectral peak determine Fe content highest can be 100 weight %, such as can be 95 Weight %, 90 weight %, 85 weight %.
In the present invention, x-ray photoelectron spectroscopy is in Thermo Scientific companies equipped with Thermo It is tested on the ESCALab250 type x-ray photoelectron spectroscopies of Avantage V5.926 softwares, excitaton source is monochromatization Al K α X-rays, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, base vacuum when analysis test It is 6.5 × 10-10Mbar, the peaks C1s (284.6eV) correction of electron binding energy simple substance carbon, in Thermo Avantage softwares Upper carry out data processing carries out quantitative analysis in analysis module using sensitivity factor method.
According to the fischer-tropsch synthetic catalyst of the preferred embodiment, the content of the group VIII metallic element can be Conventional selection.Usually, on the basis of the total amount of fischer-tropsch synthetic catalyst, based on the element, the group VIII metallic element Content can be 3-30 weight %, preferably 5-25 weight %, more preferably 8-20 weight %, further preferably 10-15 weights Measure %.In the present invention, the type and content of each metallic element are used according to RIPP 132- in catalyst and catalyst precarsor 92(《Petrochemical analysis method (RIPP experimental methods)》, Yang Cui is surely equal to be compiled, Science Press, nineteen ninety September the 1st edition, the 371-379 pages) specified in X-ray fluorescence spectra analysis method measure.
According to the fischer-tropsch synthetic catalyst of the preferred embodiment, containing carrier and load on the carrier While group VIII metallic element, also contain the second metallic element and the optional third gold loaded on the carrier Belong to element.Catalyst containing second metallic element and optional third metallic element shows more excellent catalysis Activity.In the present invention, it is " optional " indicate with or without.
Second metallic element is selected from one or more of V Group IIB metallic element.Preferably, described Second metallic element is Mn.Preferably, on the basis of the total amount of catalyst, based on the element, the content of second metallic element Can be 0.1-10 weight %, preferably 1-8 weight %, more preferably 2-6 weight %, further preferably 2.5-4 weight %.
The third metallic element is one in alkali metal element, alkali earth metal and group ivb metallic element Kind is two or more.The specific example of the third metallic element can include but is not limited to：Li, Na, K, Mg, Ca, Zr and Ti One or more of.Preferably, the third metallic element is one or more of Li, K, Mg and Zr.More Preferably, the third metallic element is K and/or Zr.It is further preferred that the third metallic element is K and Zr, at this point, On the basis of the total amount of third metallic element, the content of Zr is preferably 40-70 weight %, more preferably 50-65 weight %.To urge On the basis of the total amount of agent, based on the element, the content of the third metallic element can be 0.1-15 weight %, preferably 1-12 Weight %, more preferably 2-11 weight %, further preferably 4-9 weight %.
From the angle for the catalytic activity for further increasing catalyst, according to the F- T synthesis of the preferred embodiment Catalyst preferably comprises the second metallic element and the third metallic element loaded on the carrier.Contain simultaneously in the catalyst When having the second metallic element and third metallic element, second metallic element is more preferably Mn, and the third metallic element is more Preferably one or more of Mg, K, Li and Zr, further preferably K and/Zr, are still more preferably K and Zr, this Sample can obtain more excellent catalytic activity.
CO2- TPD is (that is, temperature programmed desorption CO2) it can be used for characterizing desorption performance of the catalyst for hydrocarbon molecules, CO2In-TPD spectrograms, the temperature for desorption peaks occur is higher, illustrates that catalyst is conducive to the desorption of hydrocarbon molecules, for same There are multiple catalyst of desorption peaks in position, and the bigger catalyst of peak area is stronger to the desorption ability of hydrocarbon molecules.According to this The fischer-tropsch synthetic catalyst of preferred embodiment shows unique CO2Spectrogram is desorbed in-TPD, at 300-600 DEG C, preferably 350- 500 DEG C, there are desorption peaks (which herein, to be known as CO in more preferable 380-450 DEG C of temperature range2Elevated temperature desorption Peak).The CO2The peak area at elevated temperature desorption peak is generally 0.5-4a.u. (arbitrary unit), and preferably 1-3a.u. is (arbitrary single Position).According to the CO of the fischer-tropsch synthetic catalyst of the preferred embodiment2- TPD be desorbed spectrogram in, 90-200 DEG C, preferably There is also another desorption peaks (which herein, to be known as CO in 140-180 DEG C of temperature range2Low temperature desorption peaks).Institute State CO2The peak area of low temperature desorption peaks is generally 1-4.5a.u. (arbitrary unit), preferably 2-4a.u. (arbitrary unit).
CO-TPD (that is, temperature programmed desorption CO) can be used for characterizing catalyst for the dissociation capability of CO, and it is de- CO occur The temperature at attached peak is higher, shows that the activity of catalyst is higher, is conducive to improve olefine selective.It is de- for existing in same position Multiple catalyst at attached peak, the bigger catalyst of peak area are more conducive to CO dissociation.It is closed according to the Fischer-Tropsch of the preferred embodiment At catalyst CO-TPD desorption figure in, 300-700 DEG C, preferably 320-650 DEG C, it is 450-600 DEG C more preferable, further preferably There are desorption peaks (which herein, is known as CO low temperature desorption peaks) in 480-560 DEG C of temperature range.The CO low temperature The peak area of desorption peaks is generally 1-8a.u. (arbitrary unit), preferably 3-7a.u. (arbitrary unit).According to the preferred implementation In the CO-TPD desorption spectrograms of the fischer-tropsch synthetic catalyst of mode, in 350-720 DEG C, preferably 550-700 DEG C of temperature range It is interior that there is also another desorption peaks (which herein, is known as CO elevated temperature desorptions peak).The peak face at CO elevated temperature desorptions peak Product is generally 0.5-4a.u. (arbitrary unit), preferably 1.5-3.5a.u. (arbitrary unit).The peak of the CO low temperature desorption peaks Position is less than the peak position at CO elevated temperature desorptions peak.
In the present invention, CO2- TPD and CO-TPD is all made of Mike's chemical adsorption instrument, using OMistar mass spectrographs as detection Device on-line checking measures, wherein CO2The signal that-TPD is 44 by mass spectrograph record nucleocytoplasmic ratio, CO-TPD record core by mass spectrograph Matter is than the signal for 28.In the present invention, the position of desorption peaks is the peak position of desorption peaks.
The production method of alpha-olefin according to the present invention, the fischer-tropsch synthetic catalyst can be by the way that F- T synthesis to be catalyzed Agent precursor carries out reduction activation and obtains, and the reduction activation includes the following steps：
(1) fischer-tropsch synthetic catalyst precursor in first gas is subjected to prereduction, obtains catalyst pre-reduction；
(2) catalyst pre-reduction in second gas is subjected to reduction activation, obtains reduction activation catalyst.
The fischer-tropsch synthetic catalyst precursor contains carrier and load the first metallic element on the carrier, second Metallic element and optional third metallic element.The carrier, the first metallic element and the second metallic element type and Content may refer to previously described fischer-tropsch synthetic catalyst, no longer be described in detail herein.
In the fischer-tropsch synthetic catalyst precursor, the group VIII metallic element is supported on described in the form of the oxide The valence state of group VIII metallic element on carrier, and in the oxide is highest oxidation valence state (this paper of the metallic element In, the valence state of the metallic element in metal oxide is also referred to as full oxide for the oxide of highest oxidation valence state).It is described to take The representative instance of Tropsch synthesis catalyst precursor is that dry and roasting is undergone in preparation process (that is, carrying out heat in oxygen atmosphere Processing) and the catalyst precarsor of reduction treatment is not carried out.Group VIII metallic element existing in the form of full oxide needs Reduction activation is carried out, just there is the catalytic performance for meeting requirement.
In the reduction activation, the first gas be hydrogen or be hydrogen and inert gas gaseous mixture.It is described Inert gas can be selected from one or more of nitrogen and group 0 element gas, the group 0 element as carrier gas Gas for example can be argon gas.Preferably, the inert gas is nitrogen and/or argon gas.The first gas be hydrogen with When the gaseous mixture of inert gas, the molar ratio of the inert gas and the hydrogen can be 1-200：1, preferably 1-100：1, More preferably 2-50：1, further preferably 5-20：1.
Institute's F- T synthesis states catalyst precarsor with the Contact Temperature of the first gas can make fischer-tropsch synthetic catalyst The group VIII metallic element in highest oxidation valence state is reduced subject to (that is, valence state reduction) in precursor.
Specifically, the fischer-tropsch synthetic catalyst precursor can be at 200-600 DEG C, preferably 300- with the first gas 550 DEG C, it is 400-500 DEG C more preferable at a temperature of contacted.The volume space velocity of the first gas (in terms of hydrogen) can be 5000-30000 hours-1, preferably 10000-20000 hours-1.In terms of gauge pressure, the pressure in reactor can be 0-3MPa, Preferably 0.1-1MPa.The duration of the prereduction can carry out according to the temperature of prereduction and the pressure of first gas Selection.Usually, the duration of the prereduction can be 1-20 hours, and preferably 2-15 hours, more preferably 4-10 was small When.
The second gas is to be gaseous hydrocarbon at a temperature of reduction activation or is gaseous at a temperature of reduction activation The gaseous mixture of hydrocarbon and inert gas.Described is that gaseous hydrocarbon can be for selected from a temperature of reduction activation at a temperature of reduction activation It is one or more of gaseous alkene for gaseous alkane and at a temperature of reduction activation, such as can is choosing From C1-C4Alkane and C2-C4One or more of alkene.Described is the specific of gaseous hydrocarbon at a temperature of reduction activation Example can include but is not limited to one or more of methane, ethane, ethylene, propylene, propane, butane and butylene.From The angle for further increasing the catalytic activity of the catalyst finally prepared is set out, and described is gaseous hydrocarbon at a temperature of reduction activation It is one or more of gaseous alkane to be preferably selected from a temperature of reduction activation, is more preferably selected from C1-C4Alkane One or more of, further preferably ethane.The inert gas can be selected from nitrogen and zero group as carrier gas One or more of elemental gas, the group 0 element gas for example can be argon gas.Preferably, the inert gas For nitrogen and/or argon gas.The second gas be in reduction activation at a temperature of be gaseous hydrocarbon and inert gas gaseous mixture When, the inert gas be the molar ratio of gaseous hydrocarbon at a temperature of reduction activation can be 1-200：1, preferably 1-100： 1, more preferably 2-50：1, further preferably 5-20：1.
In the reduction activation method, the reduction activation can 150-500 DEG C, preferably 180-400 DEG C, more preferably It is carried out at a temperature of 200-350 DEG C.The volume space velocity of the second gas (to be in terms of gaseous hydrocarbon at a temperature of reduction activation) It can be 1000-30000 hours-1, preferably 2000-10000 hours-1.During carrying out reduction activation, in terms of gauge pressure, Pressure in reactor can be 0-3MPa, preferably 0.1-1MPa.The duration of the reduction activation can be according to reduction The temperature of activation and the pressure of second gas are selected.Usually, the duration of the reduction activation can be 1-20 Hour, preferably 2-15 hours, more preferably 3-8 hours.
In the reduction activation method, method comprising the following steps may be used in the fischer-tropsch synthetic catalyst precursor It prepares：Will load have group VIII metallic element oxide and/or group VIII metallic element oxide precursor, with And the carrier of the compound containing auxiliary element is roasted, and catalyst precarsor is obtained, the carrier is aluminium oxide.
The preparation method of catalyst according to the invention precursor, the aluminium oxide can not load additional modifying element and It is directly used as carrier (that is, using pure aluminium oxide as carrier), is used as carrier after can also being modified.A kind of preferred Embodiment in, at least partly aluminium oxide be the aluminium oxide containing modifying element.Usually, on the basis of the total amount of carrier, The content of aluminium oxide containing modifying element can be 10 weight % or more, preferably 30 weight % or more, more preferably 50 weights % or more, further preferably 70 weight % or more are measured, are still more preferably 90 weight % or more.It is particularly preferred that described Carrier is the aluminium oxide containing modifying element.
The modifying element be one kind in alkali metal element, alkali earth metal and group ivb metallic element or It is two or more.The specific example of the modifying element can include but is not limited to one kind in Li, Na, K, Mg, Ca, Zr and Ti or It is two or more.It is highly preferred that the modifying element is one or more of K, Mg and Zr.It is further preferred that described Modifying element is Mg and/or Zr.
From the angle for the catalytic activity for further increasing the catalyst finally prepared, on the basis of the total amount of carrier, Based on the element, the content of the modifying element can be 0.1-10 weight %, preferably 1-8 weight %, more preferably 2-6 weight Measure %.
Conventional method may be used and obtain the aluminium oxide containing modifying element.It can be during preparing aluminium oxide, it will Modifying element loads on alumina, such as by co-precipitation, while preparing aluminium oxide, modifying element is supported on oxidation On aluminium.
In a preferred example, there can be the aluminium oxide of the compound containing modifying element to roast load, from And obtain the aluminium oxide containing modifying element.The roasting can carry out under normal conditions, and usually, the roasting can be It is carried out at a temperature of 300-900 DEG C, preferably 300-800 DEG C, the duration of the roasting can carry out according to the temperature of roasting Selection, typically 0.5-12 hours, preferably 1-8 hours.The roasting carries out in air atmosphere.It specifically, can be with By way of dipping on alumina by modifying element load.By way of dipping on alumina by modifying element load When, the maceration extract oxide impregnation aluminium containing the compound containing modifying element can be used, the aluminium oxide of maceration extract will be adsorbed with successively It is dried and roasts, to obtain the aluminium oxide containing modifying element.
In the preferred example, the compound containing modifying element can be water soluble salt containing modifying element and/ Or water-soluble alkali, specific example can include but is not limited to：Nitrate, oxalates, acetate, chloride, hydroxide, carbon One or more of hydrochlorate, bicarbonate and phosphate.
In the preferred example, conventional impregnation methods may be used in the dipping, such as saturation dipping or excessive dipping. The dipping can carry out at ambient temperature.
In the preferred example, it can be enough to remove the volatile materials (master being adsorbed in the aluminium oxide of maceration extract To be the solvent in maceration extract) under conditions of, it is dried.Specifically, the drying can be at 50-300 DEG C, preferably 100- It is carried out at a temperature of 300 DEG C, the drying can carry out under normal pressure (that is, 1 standard atmospheric pressure, similarly hereinafter), can also reduce It is carried out under conditions of pressure.The duration of the drying can be selected according to dry temperature and dry pressure, and one As can be 1-20 hours, preferably 2-12 hours.The drying can carry out in air atmosphere.
Oxidation of the conventional method by the oxide of group VIII metallic element and/or group VIII metallic element may be used The precursor of object is supported on carrier.For example, the method that co-precipitation may be used, is preparing aluminium oxide (alternatively, containing modified member The aluminium oxide of element) during, by the oxide carried on carrier of group VIII metallic element.
In a kind of more preferably embodiment, with oxide and/or Section VIII containing group VIII metallic element The maceration extract impregnated carrier of the precursor of the oxide of race's metallic element, and the carrier for being adsorbed with the maceration extract is done It is dry, there are the oxide and/or the carrier of the precursor to obtain load.
The type of the precursor of the oxide of the group VIII metallic element can be selected according to the solvent of maceration extract Select so that subject to the precursor of the oxide of group VIII metallic element can be dissolved in the solvent, such as can be selected from The oxalates of group VIII metallic element, the nitrate of group VIII metallic element, the sulfate of group VIII metallic element, The acetate of group VIII metal element, the chloride of group VIII metallic element, the carbonate of group VIII metallic element, The phosphoric acid of the subcarbonate of group VIII metal element, the hydroxide of group VIII metallic element, group VIII metallic element The water of salt, the molybdate of group VIII metallic element, the tungstates of group VIII metallic element and group VIII metallic element One or more of dissolubility compound.The specific example of the precursor of the oxide of the group VIII metallic element can To include but not limited to：Ferric nitrate, ferric sulfate, ferric acetate, nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, sulphur One or more of sour cobalt, cobalt acetate, basic cobaltous carbonate, cobalt chloride, nickel chloride and ferric citrate.
The carrier for being adsorbed with the maceration extract can be dried under normal conditions, it is molten in maceration extract to remove Agent has oxide and/or the carrier of precursor to obtain load.Usually, the drying can 50-300 DEG C, preferably It is carried out at a temperature of 100-300 DEG C, the drying can carry out under normal pressure, can also be carried out under conditions of reducing pressure. The duration of the drying can be selected according to dry temperature and dry pressure, generally can be 1-20 hours, Preferably 2-12 hours.The drying can carry out in air atmosphere.
Can there are the oxide and/or the carrier of the precursor to roast under normal conditions load, to Obtain catalyst precarsor.In the catalyst precarsor, group VIII metallic element is substantially at its highest oxidation valence state.Generally Ground, the roasting can carry out at a temperature of 300-900 DEG C, preferably 300-800 DEG C, and the duration of the roasting can root It is selected according to the temperature of roasting, typically 0.5-12 hours, preferably 1-8 hours.The roasting is in air atmosphere It carries out.
Further include being helped in supported on carriers from the angle for the catalytic activity for further increasing the catalyst finally prepared Agent element, the auxiliary element be V Group IIB metallic element or the auxiliary element be V Group IIB metallic element and Alkali metal element.The V Group IIB metallic element is preferably Mn.The alkali metal element is preferably one kind in Li, Na and K Or two or more, more preferably Li and/or K.Preferably, the auxiliary element is Mn and one kind in Li and K or two Kind.
The auxiliary element is on the basis of the load capacity on carrier can make by the total amount of catalyst precarsor, with element Meter, the content of the auxiliary element can be 0.1-10 weight %, preferably 1-8 weight %, more preferably 4-7 weight %.? When the auxiliary element is V Group IIB metallic element and alkali metal element, on the basis of the total amount of auxiliary element, with element The content of meter, V Group IIB metallic element is preferably 10-90 weight %, preferably 20-85 weight %, more preferably 30-80 weights Measure %, more preferably 40-75 weight %.
Conventional method may be used auxiliary element is supported on carrier, such as infusion process.It can be by auxiliary element and Group VIII metal element is supported on carrier simultaneously, auxiliary element and group VIII metallic element may not be synchronize be supported On carrier.Preferably, auxiliary element and group VIII metallic element are supported on carrier simultaneously, at this point it is possible to using containing There is the precursor of the oxide of group VIII metallic element and/or the oxide of group VIII metallic element and contains auxiliary agent The maceration extract impregnated carrier of the compound of element, and the carrier for being adsorbed with maceration extract is dried and is roasted successively, to To catalyst precarsor.
The compound containing auxiliary element can be the common substance being dispersed in maceration extract that can dissolve, such as Can be nitrate, chloride, sulfate, acetate, oxalates, carbonate, bicarbonate and hydroxide in one kind or It is two or more.The specific example of the compound containing auxiliary element can include but is not limited to：Sodium nitrate, sodium chloride, sulphur Sour sodium, sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate, lithium nitrate, lithium carbonate, lithium chloride, potassium nitrate, potassium chloride, potassium sulfate, One or more of potassium acetate, potassium oxalate, potassium carbonate, saleratus, manganese nitrate and manganese chloride.
When group VIII metallic element and auxiliary element are supported on carrier by the way of dipping, the dipping Number can be primary, or more than twice.From the angle for the catalytic activity for further increasing the catalyst finally prepared Degree sets out, and is preferably impregnated more than twice.When being impregnated more than twice, every time after dipping, it will preferably be adsorbed with leaching The carrier of stain liquid is dried and roasts successively.
The production method of alpha-olefin according to the present invention in step S31, can carry out under conditions of routinely producing alpha-olefin Fischer-Tropsch synthesis.Preferably, Fischer-Tropsch synthesis charging can be at 200-380 DEG C, preferably 250- with fischer-tropsch synthetic catalyst It is contacted at a temperature of 350 DEG C.Fischer-Tropsch synthesis feeds the pressure contacted with fischer-tropsch synthetic catalyst 0.8-3MPa, preferably 1-2.8MPa, the pressure is in terms of gauge pressure.
The production method of alpha-olefin according to the present invention, Fischer-Tropsch synthesis can be connect in fixed bed reactors It touches, can also be contacted in a fluidized bed reactor, it can also be in the combination of fixed bed reactors and fluidized-bed reactor It is contacted.Preferably, hydrogen and carbon monoxide are contacted with fischer-tropsch synthetic catalyst in fixed bed reactors.Solid In fixed bed reactor, when hydrogen and carbon monoxide are contacted with fischer-tropsch synthetic catalyst, the volume of Fischer-Tropsch synthesis charging is empty Speed can be 2000-50000 hours-1, preferably 5000-40000 hours-1, preferably 10000-30000 hours-1。
The production method of alpha-olefin according to the present invention may be used conventional method and produced from F- T synthesis in step S41 Alpha-olefin, methane and carbon dioxide are isolated in object logistics.As an example, condensation at low temperature may be used, Fischer-Tropsch is closed It is detached at product stream, to respectively obtain alpha-olefin, methane and carbon dioxide.
The methane isolated from Fischer-Tropsch synthetic logistics is sent into and is walked by the production method of alpha-olefin according to the present invention In rapid S11 and/or step S21, as steam reforming reaction and/or the raw material of dry reforming reaction.It will be from Fischer-Tropsch synthetic The carbon dioxide isolated in logistics is made to be sent into step S21, the charging as dry reforming reaction.Alpha-olefin according to the present invention Production method, by the way that steam reforming and dry reforming to be applied in combination, and will isolate from Fischer-Tropsch synthetic logistics Methane and carbon dioxide recycles, and effectively increases raw material availability, and significantly reduce GHG carbon dioxide Discharge capacity.
The production method of alpha-olefin according to the present invention, from the angle for further increasing raw material availability, preferably also Including isolating unreacted hydrogen and/or carbon monoxide from Fischer-Tropsch synthetic logistics, and will at least partly hydrogen and/or At least partly carbon monoxide is sent into step S31, for preparing Fischer-Tropsch synthesis charging.Preferably, it will be produced from F- T synthesis The hydrogen partial and/or part carbon monoxide cycle isolated in object logistics are sent into step S31, anti-for preparing F- T synthesis It should feed, and using remainder hydrogen and/or remainder carbon monoxide as periodic off-gases, outer discharge system.Usually, with from On the basis of the total amount of the hydrogen and carbon monoxide isolated in Fischer-Tropsch synthetic logistics, hydrogen and carbon monoxide for cycle Amount can be 10-98%, preferably 15-98%.
According to the second aspect of the invention, the present invention provides a kind of alpha-olefin production system, which includes that water steams Gas reforming reaction unit, dry reforming reaction member, synthesis gas mixed cell, Fischer-Tropsch synthesis unit, Fischer-Tropsch synthesis production Object separative element and cycling element.
The steam reforming reaction unit carries out steam reforming reaction, obtains for contacting methane with vapor Steam reforming synthesis gas.Conventional steam reforming reaction device and corresponding can be arranged in the steam reforming reaction unit Feed pieces, outlet member and control unit so that methane and vapor can carry out reforming reaction, obtain with hydrogen and Carbon monoxide makees steam reforming synthesis gas as main component.
The dry reforming reaction member is used to, by methane and carbon dioxide exposure, carry out dry reforming reaction, obtain dry reforming Synthesis gas.Conventional dry reforming reactor and corresponding feed pieces, discharging portion can be arranged in the dry reforming reaction member Part and control unit so that methane can carry out reforming reaction with carbon dioxide, obtain using hydrogen and carbon monoxide as mainly The dry reforming synthesis gas of ingredient.
The synthesis gas mixed cell respectively with the steam reforming synthesis gas output port of steam reforming unit and The dry reforming synthesis gas output port of dry reforming reaction member is connected to, and is used for the steam reforming synthesis gas and the dry weight It is integrated into gas mixing, preparing, which becomes Fischer-Tropsch synthesis, feeds, and the Fischer-Tropsch synthesis is fed to the Fischer-Tropsch and is closed At in reaction member.The synthesis gas mixed cell can be arranged for accommodating and mixing steam reforming synthesis gas and dry reforming The container of synthesis gas in a reservoir mixes steam reforming synthesis gas with dry reforming synthesis gas, to obtain F- T synthesis into Material.Pipe-line mixer can also be used, vapor is directly lived again into synthesis gas and dry reforming synthesis gas carries out in conveyance conduit Mixing, to obtain Fischer-Tropsch synthesis charging.Common various control devices can be arranged in the synthesis gas mixed cell, use In the mixed proportion of control steam reforming synthesis gas and dry reforming synthesis gas, to obtain meeting Fischer-Tropsch synthesis hydrogen-carbon ratio Fischer-Tropsch synthesis charging.
The Fischer-Tropsch synthesis unit is provided with Fischer-Tropsch synthesis device, anti-with the F- T synthesis of synthesis gas mixed cell Feed outlet port is answered to be connected to, for the Fischer-Tropsch synthesis to be fed to the reaction temperature with fischer-tropsch synthetic catalyst in production alpha-olefin Lower contact obtains the Fischer-Tropsch synthetic logistics containing alpha-olefin.The Fischer-Tropsch synthesis device can be common various anti- Device form is answered, specifically, the Fischer-Tropsch synthesis device can be fixed bed reactors, or fluidized-bed reactor, also It can be the combination of fixed bed reactors and fluidized-bed reactor.Preferably, the Fischer-Tropsch synthesis device is fixed bed reaction Device.
The Fischer-Tropsch synthesis unit is preferably additionally provided with reduction activation subelement, and the reduction activation subelement is used for Fischer-tropsch synthetic catalyst precursor is subjected to reduction activation, fischer-tropsch synthetic catalyst precursor is transformed into catalytic activity Fischer-tropsch synthetic catalyst.The reduction activation subelement can be by connecing fischer-tropsch synthetic catalyst precursor with reducibility gas It touches, thus by fischer-tropsch synthetic catalyst precursor reduction activation.
In a preferred embodiment, the reduction activation subelement includes first gas storing and conveying device, Two gas storing and conveying devices, reducing gas control device and reduction activation reactor.
The first gas storing and conveying device is sent into reduction activation reaction for storing first gas, and by first gas In device.The first gas is the gaseous mixture of hydrogen or hydrogen and inert gas.The first gas storing and conveying device quilt It is set as being enough to store and conveys first gas.It can instruct according to prior art first gas storage conveying dress is arranged It sets, can store and convey first gas.
The second gas storing and conveying device is sent into reduction activation reaction for storing second gas, and by second gas In device, the second gas is to be gaseous hydrocarbon under reduction temperature or is gaseous hydrocarbon and indifferent gas under reduction temperature The gaseous mixture of body.Detailed description has been carried out above for the type of the first gas and the second gas, herein not It is described in detail again.
The reducing gas control device is used to control the feeding of the gas type and gas of being sent into reduction activation reactor Amount.Specifically, when the reduction activation subelement is run, the reducing gas control device is arranged to first anti-to reduction activation It answers and inputs first gas in device, so that fischer-tropsch synthetic catalyst precursor is contacted with first gas carries out prereduction reaction, obtain pre- Then reducing catalyst inputs second gas into reduction activation reactor, so that the catalyst pre-reduction and second gas Contact carries out reduction reaction.Conventional control element, such as various control valves may be used in the reducing gas control device, The gas type of reduction reactor and the feeding amount of gas are sent into control.
The reduction reactor for accommodating fischer-tropsch synthetic catalyst precursor, and with first gas storing and conveying device and the Two gas storing and conveying devices are connected to, so that fischer-tropsch synthetic catalyst precursor is contacted with first gas and second gas successively, Reduction activation is carried out, the catalyst with F- T synthesis catalytic activity is obtained.
The reduction activation reactor can be same reactor with Fischer-Tropsch synthesis device, i.e., in Fischer-Tropsch synthesis device The interior reduction activation for carrying out fischer-tropsch synthetic catalyst precursor.
The reduction activation reactor may not be same reactor, i.e. Fischer-Tropsch synthesis with Fischer-Tropsch synthesis device Device and reduction activation reactor are respective self-existent reactor.At this point, the reduction activation of the reduction activation reactor is urged Agent output port is set as being connected to the catalyst input port of the Fischer-Tropsch synthesis device, by reduction activation reactor The reduction activation catalyst of output is sent into the Fischer-Tropsch synthesis device.The reduction activation of reduction activation reactor can be urged Agent output port is connected to the catalyst input port of the Fischer-Tropsch synthesis device using transfer pipeline, and in transfer pipeline Upper setting control valve, when reduction activation reactor exports reduction activation catalyst, opening controlling valve, by reduction activation reactor Reduction activation catalyst output port be connected to the catalyst input port of Fischer-Tropsch synthesis device, by reduction activation catalyst It is sent into Fischer-Tropsch synthesis device.
Alpha-olefin production system according to the present invention, the cycling element are used for Fischer-Tropsch synthesis product separative element The methane cycle isolated be sent into one of steam reforming reaction unit and dry reforming reaction member, or both in, will take The carbon dioxide recycle that support synthetic reaction product separative element is isolated is sent into dry reforming reaction member, by Fischer-Tropsch synthesis The hydrogen and/or carbon monoxide cycle that product separative element is isolated are sent into Fischer-Tropsch synthesis unit.
The cycling element, which can be arranged, is respectively used to connection Fischer-Tropsch synthesis product separative element and vapor weight The methane transfer pipeline of whole reaction member and dry reforming reaction member and the control valve being arranged on the methane transfer pipeline, It is respectively fed to steam reforming reaction unit with the methane for isolating Fischer-Tropsch synthesis product separative element and dry reforming is anti- It answers in unit.The cycling element can be arranged single for being connected to Fischer-Tropsch synthesis product separative element and dry reforming reaction The carbon dioxide transfer pipeline of member and the control valve being arranged on the carbon dioxide transfer pipeline, by Fischer-Tropsch synthesis The carbon dioxide of product separative element output is sent into dry reforming reaction member.
When Fischer-Tropsch synthesis product separative element also isolates hydrogen and carbon monoxide, the cycling element is preferably set It sets the transfer pipeline for being connected to Fischer-Tropsch synthesis product separative element and Fischer-Tropsch synthesis unit and is arranged in institute The control valve on transfer pipeline is stated, the hydrogen and carbon monoxide that Fischer-Tropsch synthesis product separative element is isolated are sent into In Fischer-Tropsch synthesis unit.Hydrogen and carbon monoxide can be sent into Fischer-Tropsch synthesis unit by same transfer pipeline In, hydrogen and carbon monoxide can also be respectively fed to by different transfer pipelines in Fischer-Tropsch synthesis unit, at this time may be used Be respectively set hydrogen delivery tube road and the control valve that is arranged on hydrogen delivery tube road and with carbon monoxide transfer pipeline With the control valve being arranged on carbon monoxide transfer pipeline.
Alpha-olefin production system according to the present invention preferably further includes unstripped gas separative element, and the unstripped gas separation is single Member for isolating methane from the unstripped gas containing methane, the methane output port of the unstripped gas separative element respectively with it is described The methane feed input port of the methane feed input port of steam reforming reaction unit and the dry reforming reaction member Connection, the methane isolated is respectively fed in steam reforming reaction unit and the dry reforming reaction member.
Conventional separation method may be used in the unstripped gas separative element, and methane is isolated from unstripped gas.In one kind In embodiment, the unstripped gas separative element isolates methane using pressure swing adsorption method from unstripped gas.A kind of more excellent In the embodiment of choosing, the unstripped gas separative element isolates methane using condensation at low temperature from unstripped gas.This more In preferred embodiment, can low-temperature condenser be set in unstripped gas separative element, unstripped gas is condensed, with separation Go out the methane in the unstripped gas.The low-temperature condenser can be conventional condenser, be not particularly limited.
Fig. 2 shows a kind of preferred embodiments of alpha-olefin production system according to the present invention, are carried out below in conjunction with Fig. 2 It is described in detail.As shown in Fig. 2, the alpha-olefin production system includes unstripped gas separative element I, steam reforming reaction unit II, dry reforming reaction member III, Fischer-Tropsch synthesis unit IV, Fischer-Tropsch synthetic separative element V and cycling element.
Unstripped gas A, which enters in unstripped gas separative element I, to be detached, and methane B is obtained.Methane B is respectively fed to vapor In reforming reaction unit II and dry reforming reaction member III, while vapor C is sent into steam reforming reaction unit II, So that methane carries out reforming reaction with vapor, steam reforming synthesis gas E is obtained.It is sent into dry reforming reaction member III Enter carbon dioxide D, so that methane carries out reforming reaction with carbon dioxide, obtains dry reforming synthesis gas F.Steam reforming synthesizes Gas E and dry reforming synthesis gas F mixing (preferably using pipe-line mixer), prepare the expense for becoming and meeting Fischer-Tropsch synthesis hydrogen-carbon ratio Synthetic reaction is ask to feed G.Fischer-Tropsch synthesis charging G enters in Fischer-Tropsch synthesis unit IV, is connect with fischer-tropsch synthetic catalyst It touches, carries out Fischer-Tropsch synthesis.Fischer-Tropsch synthesis device in Fischer-Tropsch synthesis unit IV is transported at a temperature of producing alpha-olefin Row.The Fischer-Tropsch synthetic logistics H of Fischer-Tropsch synthesis unit IV outputs, which enters in Fischer-Tropsch synthetic separative element V, to be divided From obtaining alpha-olefin K, unreacted hydrogen and carbon monoxide, methane M and carbon dioxide N.Wherein, alpha-olefin K transmitting systems.
The hydrogen and carbon monoxide isolated can be recycled for preparing Fischer-Tropsch synthesis charging, can also be discharged outside and are System can also be part cycle for preparing Fischer-Tropsch synthesis charging, the outer discharge system of remainder.Preferably, such as Fig. 2 Shown, hydrogen and carbon monoxide L for cycle are mixed with steam reforming synthesis gas E and dry reforming synthesis gas F, for preparing Fischer-Tropsch synthesis feeds G；Remainder hydrogen and carbon monoxide are as the outer discharge systems of periodic off-gases Z.
The carbon dioxide N isolated is sent into dry reforming reaction member III, one of raw material as dry reforming reaction cycle It uses.The methane M isolated is respectively fed in steam reforming reaction unit II and dry reforming reaction member III anti-as reforming One of raw material answered recycles.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment, preparation example and comparative example, if not otherwise specified, pressure is gauge pressure.
In following embodiment, preparation example and comparative example, the conversion ratio (X of COCO)、C5-C15Selectivity (the S of alpha-olefinAlpha-olefin) And C5(C above5+) hydro carbons selectivityIt is calculated by the following formula to obtain respectively：
Wherein, V1、V2Be illustrated respectively under the status of criterion, enter in certain period the unstripped gas of reaction system volume and Flow out the exhaust gas volumes of reaction system；
C1,CO、C2,COMole containing for CO in the unstripped gas of reaction system and the tail gas of outflow reaction system is indicated entry into respectively Amount；
nconTo participate in the molal quantity of the CO reacted；
To generate CO2Molal quantity；
nAlpha-olefinFor the molal quantity of the alpha-olefin of generation；
For the CH of generation4、C2Hydrocarbon, C3Hydrocarbon and C4The sum of molal quantity of hydrocarbon.
Preparation example 1-21 is used to prepare fischer-tropsch synthetic catalyst and evaluates its performance.
In following preparation example, specific surface area, hole hold and average pore size is measured according to nitrogen adsorption methods, specifically Ground, using N2Adsorption isotherm is measured under 77K constant temperature, is then pressed BET formula and is calculated specific surface area and Kong Rong, and presses the side BJH Method calculates average pore size distribution；Particle diameter distribution is measured using laser particle analyzer.
In following preparation example, the type and content of each metallic element use basis in catalyst and catalyst precarsor RIPP 132-92(《Petrochemical analysis method (RIPP experimental methods)》, Yang Cui is surely equal to be compiled, Science Press, nineteen ninety September 1st edition, the 371-379 pages) specified in X-ray fluorescence spectra analysis method measure.When catalyst is measured, catalyst Sample is stored in argon gas atmosphere.
In following preparation example, CO2- TPD and CO-TPD is all made of Mike's chemical adsorption instrument, using OMistar mass spectrographs as Detector on-line checking measures, wherein CO2The signal that-TPD is 44 by mass spectrograph record nucleocytoplasmic ratio, CO-TPD are remembered by mass spectrograph Record the signal that nucleocytoplasmic ratio is 28.
In following preparation example, X-ray photoelectron spectroscopic analysis is in Thermo Scientific companies equipped with Thermo It is tested on the ESCALab250 type x-ray photoelectron spectroscopies of Avantage V5.926 softwares, excitaton source is monochromatization Al K α X-rays, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, base vacuum when analysis test It is 6.5 × 10-10Mbar, the peaks C1s (284.6eV) correction of electron binding energy simple substance carbon, in Thermo Avantage softwares Upper carry out data processing carries out quantitative analysis in analysis module using sensitivity factor method.
Preparation example 1
(1) preparation of carrier
Take γ-Al2O3(Sasol products, specific surface area, Kong Rong, average pore size and particle diameter distribution are as shown in table 1) 200g, It is roasted 2 hours in 980 DEG C of air atmospheres, product of roasting is subjected to X-ray diffraction analysis (as shown in Figure 1), what determination obtained It is θ-Al2O3, specific surface area, Kong Rong, average pore size and particle diameter distribution are as shown in table 1.
Five water zirconium nitrates are dissolved in 43g deionized waters, modified zirconium solution is made, 100.0g systems are added to modified zirconium solution Standby obtained θ-Al2O3, impregnated 2 hours in 25 DEG C of saturations.Then, the mixture that dipping obtains is placed in baking oven, in 120 DEG C And it is 5 hours dry in air atmosphere under normal pressure (1 standard atmospheric pressure, similarly hereinafter).By the substance being dried to obtain in 400 DEG C of air atmospheres Middle roasting 3 hours, obtains carrier.The carrier of preparation is subjected to X-ray fluorescence spectra analysis, is determined using the total amount of carrier as base Standard, based on the element, the content of Zr is 5 weight %.
(2) preparation of catalyst precarsor
Ferric citrate, potassium carbonate and six water manganese nitrates are added in 12mL deionized waters, are heated in 50 DEG C of water-baths It is uniformly mixed, obtains maceration extract.
The maceration extract for taking 50 volume % adds 15g carriers into maceration extract, in environment temperature (for 25 DEG C) saturation dipping 1 Hour.Then, the mixture that dipping obtains is placed in baking oven, it is 5 hours dry in air atmosphere under 120 DEG C and normal pressure.It will It is dried to obtain substance to roast 3 hours in 400 DEG C of air atmospheres, obtains a leaching rear catalyst.
One leaching rear catalyst is added in remaining maceration extract, is impregnated 1 hour in environment temperature (for 25 DEG C) saturation.So Afterwards, the mixture that dipping obtains is placed in baking oven, it is 5 hours dry in air atmosphere under 120 DEG C and normal pressure.It will be dried to obtain Substance roasts 3 hours in 400 DEG C of air atmospheres, obtains catalyst precarsor.
(3) reduction activation of catalyst precarsor
Catalyst precarsor is fitted into fixed bed reactors, H is passed through into reactor2, adjusting reactor pressure is The volume space velocity of 0.1MPa, hydrogen are 10000 hours-1, the temperature of reactor is increased to 400 DEG C by 25 DEG C, and in the temperature Lower constant temperature 8 hours.Then, reactor is cooled to 200 DEG C, hydrogen is switched to ethane, and the volume space velocity of ethane is 2000 Hour-1, after maintaining 4 hours, fischer-tropsch synthetic catalyst is obtained, the composition of the catalyst is shown in table 2 and table 4, CO2- TPD and CO-TPD test results are listed in table 3.
(4) preparation of alpha-olefin
After reduction activation, synthesis gas is passed through into reactor, and the temperature of reactor is warming up to 310 DEG C and carries out expense Hold in the palm synthetic reaction, wherein the volume space velocity of synthesis gas is 10000 hours-1, pressure is 1.5MPa (in terms of gauge pressure), synthesis gas Group becomes H2：CO=50：50 (molar ratios).In reaction process, the reaction exported to reactor using on-line gas chromatography is mixed The composition for closing gas is analyzed, and 50 hours results measured of reaction are listed in table 5.
Preparation example 2
Catalyst is prepared using method identical with preparation example 1 and prepares alpha-olefin, unlike, in step (1), γ- Al2O3Without roasting, but saturation dipping directly is carried out with modified zirconium solution, to prepare carrier, wherein with the total of carrier On the basis of amount, based on the element, the content of Zr is 5 weight %.
Preparation example 3
Catalyst is prepared using method identical with preparation example 1 and prepares alpha-olefin, unlike, in step (1), θ- Al2O3It is not contacted with modified zirconium solution, but is directly used in step (2) and prepares catalyst precarsor.
Preparation example 4
Catalyst is prepared using method identical with preparation example 1 and prepares alpha-olefin, unlike, in step (2), with Six water manganese nitrates are not used when maceration extract processed.
Preparation example 5
Catalyst is prepared using method identical with preparation example 1 and prepares alpha-olefin, unlike, in step (2), dipping For single-steeping, and impregnate, dry and roasting condition it is identical with preparation example 1, that is, use 6mL maceration extracts saturation impregnated carrier, and The mixture that dipping obtains is dried and is roasted successively, to obtain catalyst precarsor.
Preparation example 6
Catalyst is prepared using method identical with preparation example 1 and prepares alpha-olefin, unlike, in step (3), ethane It is replaced with isometric ethylene.
Preparation example 7
Catalyst is prepared using method identical with preparation example 1 and prepares alpha-olefin, unlike, in step (1), and change Property zirconium solution contact be by γ-Al2O3With θ-Al2O3According to weight ratio 1：1 mixture being mixed to get.
Preparation example 8
Catalyst is prepared using method identical with preparation example 1 and prepares alpha-olefin, unlike, in step (3), lead to hydrogen After gas, do not continue to be passed through ethane, but directly carry out step (4), i.e., reduction activation is only with hydrogen, without using ethane.
Preparation example 9
Catalyst is prepared using method identical with preparation example 1 and prepares alpha-olefin, unlike, in step (3), ethane It is replaced, that is, is passed through after the completion of the prereduction of hydrogen with isometric CO, reactor is cooled to 200 DEG C, hydrogen is switched to CO, And the volume space velocity of CO is 2000 hours-1, maintain 4 hours.
Preparation example 10
Catalyst is prepared using method identical with preparation example 1 and prepares alpha-olefin, unlike, in step (3), ethane It is replaced, that is, is passed through after the completion of the prereduction of hydrogen with the gaseous mixture of CO and nitrogen, reactor is cooled to 200 DEG C, hydrogen is cut It is changed to the gaseous mixture of CO and nitrogen, and the molar ratio of CO and nitrogen is 1：1, CO and nitrogen gaseous mixture volume space velocity be 2000 Hour-1, maintain 4 hours.
Preparation example 11
Catalyst is prepared using method identical with preparation example 1 and prepares alpha-olefin, unlike, in step (3), not into The operation of the logical hydrogen of row, but lead to ethane directly into reactor, i.e., catalyst is fitted into fixed bed reactors, to reactor In be passed through ethane, adjustment reactor pressure is 0.1MPa, the temperature of reactor is increased to 200 DEG C by 25 DEG C, and in the temperature Lower constant temperature 4 hours, wherein the volume space velocity of ethane is 2000 hours-1。
Preparation example 12
Catalyst is prepared using method identical with preparation example 2 and prepares alpha-olefin, unlike, in step (3), lead to hydrogen After gas, do not continue to be passed through ethane, but directly carry out step (4), i.e., reduction activation is only with hydrogen, without using ethane.
Preparation example 13
Catalyst is prepared using method identical with preparation example 2 and prepares alpha-olefin, unlike, in step (3), ethane It is replaced, that is, is passed through after the completion of the prereduction of hydrogen with CO, reactor is cooled to 200 DEG C, hydrogen is switched to CO, and the body of CO Product air speed is 2000 hours-1, maintain 4 hours.
Preparation example 14
(1) preparation of carrier
Take γ-Al2O3(Sasol products, specific surface area, Kong Rong, average pore size and particle diameter distribution are as shown in table 1) 200g, It is roasted 1 hour in 1050 DEG C of air atmospheres, product of roasting is subjected to X-ray diffraction analysis, that determination obtains is θ-Al2O3, Specific surface area, Kong Rong, average pore size and particle diameter distribution are as shown in table 1.
Five water zirconium nitrates are dissolved in 41g deionized waters, modified zirconium solution is made, 100.0g systems are added to modified zirconium solution Standby obtained θ-Al2O3, impregnated 2 hours in 25 DEG C of saturations.Then, the mixture that dipping obtains is placed in baking oven, in 200 DEG C And it is 3 hours dry under normal pressure.The substance being dried to obtain is roasted 1 hour in 800 DEG C of air atmospheres, obtains carrier.It will prepare Carrier carry out X-ray fluorescence spectra analysis, determine on the basis of the total amount of carrier, based on the element, the content of Zr is 2.5 weights Measure %.
(2) preparation of catalyst precarsor
Ferric nitrate, potassium carbonate and six water manganese nitrates are added in 12mL deionized waters, the heating stirring in 50 DEG C of water-baths It is uniformly mixed, obtains maceration extract.
The maceration extract for taking 50 volume % adds 15g carriers into maceration extract, in environment temperature (for 25 DEG C) saturation dipping 1 Hour.Then, the mixture that dipping obtains is placed in baking oven, it is 3 hours dry in air atmosphere under 200 DEG C and normal pressure.It will It is dried to obtain substance to roast 1 hour in 800 DEG C of air atmospheres, obtains a leaching rear catalyst.
One leaching rear catalyst is added in remaining maceration extract, is impregnated 1 hour in environment temperature (for 25 DEG C) saturation.So Afterwards, the mixture that dipping obtains is placed in baking oven, it is 3 hours dry in air atmosphere under 200 DEG C and normal pressure.It will be dried to obtain Substance roasts 1 hour in 800 DEG C of air atmospheres, obtains catalyst precarsor.
(3) reduction activation of catalyst precarsor
Catalyst precarsor is fitted into fixed bed reactors, H is passed through into reactor2, adjusting reactor pressure is The volume space velocity of 0.1MPa, hydrogen are 20000 hours-1, the temperature of reactor is increased to 500 DEG C by 25 DEG C, and in the temperature Lower constant temperature 6 hours.Then, reactor is cooled to 250 DEG C, hydrogen is switched to ethane, and the volume space velocity of ethane is 10000 Hour-1, after maintaining 5 hours, fischer-tropsch synthetic catalyst is obtained, the composition of the catalyst is shown in table 2 and table 4, CO2- TPD and CO-TPD test results are listed in table 3.
(4) preparation of alpha-olefin
After reduction activation, synthesis gas is passed through into reactor, and the temperature of reactor is adjusted to 310 DEG C and carries out expense Hold in the palm synthetic reaction, wherein the volume space velocity of synthesis gas is 10000 hours-1, pressure 1.5MPa, the group of synthesis gas is as H2：CO =60：40 (molar ratios).In reaction process, the composition of the reaction mixture gas that reactor is exported using on-line gas chromatography into Row analysis, 50 hours results measured of reaction are listed in table 5.
Preparation example 15
Catalyst is prepared using method identical with preparation example 14 and prepares alpha-olefin, unlike, in step (1), γ- Al2O3Without roasting, but saturation dipping directly is carried out with modified zirconium solution, to prepare carrier, wherein with the total of carrier On the basis of amount, based on the element, the content of Zr is 2.5 weight %.
Preparation example 16
(1) preparation of carrier
Take γ-Al2O3(Sasol products, specific surface area, Kong Rong, average pore size and particle diameter distribution are as shown in table 1) 200g, It is roasted 4 hours in 780 DEG C of air atmospheres, product of roasting is subjected to X-ray diffraction analysis, that determination obtains is θ-Al2O3, Specific surface area, Kong Rong, average pore size and particle diameter distribution are as shown in table 1.
Five water zirconium nitrates are dissolved in 53g deionized waters, modified zirconium solution is made, 100.0g systems are added to modified zirconium solution Standby obtained θ-Al2O3, impregnated 2 hours in 25 DEG C of saturations.Then, the mixture that dipping obtains is placed in baking oven, in 300 DEG C And it is 2 hours dry in air atmosphere under normal pressure.The substance being dried to obtain is roasted 6 hours in 500 DEG C of air atmospheres, is carried Body.The carrier of preparation is subjected to X-ray fluorescence spectra analysis, is determined on the basis of the total amount of carrier, based on the element, the content of Zr For 6 weight %.
(2) preparation of catalyst precarsor
Ferric nitrate, potassium carbonate and six water manganese nitrates are added in 12mL deionized waters, the heating stirring in 50 DEG C of water-baths It is uniformly mixed, obtains maceration extract.
The maceration extract for taking 50 volume % adds 15g carriers into maceration extract, in environment temperature (for 25 DEG C) saturation dipping 1 Hour.Then, the mixture that dipping obtains is placed in baking oven, it is 2 hours dry in air atmosphere under 300 DEG C and normal pressure.It will It is dried to obtain substance to roast 6 hours in 500 DEG C of air atmospheres, obtains a leaching rear catalyst.
One leaching rear catalyst is added in remaining maceration extract, is impregnated 1 hour in environment temperature (for 25 DEG C) saturation.So Afterwards, the mixture that dipping obtains is placed in baking oven, it is 2 hours dry in air atmosphere under 300 DEG C and normal pressure.It will be dried to obtain Substance roasts 6 hours in 500 DEG C of air atmospheres, obtains catalyst precarsor.
(3) reduction activation of catalyst precarsor
Catalyst precarsor is fitted into fixed bed reactors, H is passed through into reactor2With gaseous mixture (wherein, the argon of argon gas The molar ratio of gas and hydrogen is 15：1), adjustment reactor pressure is 0.15MPa, and the volume space velocity of hydrogen is 20000 hours-1, will The temperature of reactor is increased to 450 DEG C, and constant temperature 10 hours at such a temperature by 25 DEG C.Then, reactor is cooled to 250 DEG C, hydrogen is switched to ethane, and the volume space velocity of ethane is 8000 hours-1, after maintaining 8 hours, obtain F- T synthesis catalysis The composition of agent, the catalyst shows in table 2 and table 4, CO2- TPD and CO-TPD test results are listed in table 3.
(4) preparation of alpha-olefin
After reduction activation, synthesis gas is passed through into reactor, and the temperature of reactor is adjusted to 315 DEG C and carries out expense Hold in the palm synthetic reaction, wherein the volume space velocity of synthesis gas is 12000 hours-1, pressure 1.2MPa, the group of synthesis gas is as H2：CO =50：50 (molar ratios).In reaction process, the composition of the reaction mixture gas that reactor is exported using on-line gas chromatography into Row analysis, 50 hours results measured of reaction are listed in table 5.
Preparation example 17
(1) preparation of carrier
θ-Al are prepared using method identical with preparation example 12O3。
Magnesium nitrate is dissolved in 43g deionized waters, modified magnesium solution is made, 100.0g, which is added, to modified magnesium solution is prepared into θ-the Al arrived2O3, impregnated 2 hours in 25 DEG C of saturations.Then, the mixture that dipping obtains is placed in baking oven, in 100 DEG C and often It depresses 12 hours dry in air atmosphere.The substance being dried to obtain is roasted 8 hours in 300 DEG C of air atmospheres, obtains carrier. The carrier of preparation is subjected to X-ray fluorescence spectra analysis, is determined on the basis of the total amount of carrier, based on the element, the content of Mg is 5 Weight %.
(2) preparation of catalyst precarsor
Ferric nitrate, lithium carbonate and six water manganese nitrates are added in 12mL deionized waters, heats and stirs in 50 DEG C of water-baths It mixes uniformly mixed, obtains maceration extract.
The maceration extract for taking 50 volume % adds 15g carriers into maceration extract, in environment temperature (for 25 DEG C) saturation dipping 1 Hour.Then, the mixture that dipping obtains is placed in baking oven, it is 12 hours dry in air atmosphere under 100 DEG C and normal pressure.It will It is dried to obtain substance to roast 8 hours in 300 DEG C of air atmospheres, obtains a leaching rear catalyst.
One leaching rear catalyst is added in remaining maceration extract, is impregnated 1 hour in environment temperature (for 25 DEG C) saturation.So Afterwards, the mixture that dipping obtains is placed in baking oven, it is 12 hours dry in air atmosphere under 100 DEG C and normal pressure.It will be dry It is roasted 8 hours in 300 DEG C of air atmospheres to substance, obtains catalyst precarsor.
(3) reduction activation of catalyst precarsor
Catalyst precarsor is fitted into fixed bed reactors, H is passed through into reactor2, adjusting reactor pressure is The volume space velocity of 0.1MPa, hydrogen are 20000 hours-1, the temperature of reactor is increased to 500 DEG C by 25 DEG C, and in the temperature Lower constant temperature 4 hours.Then, reactor is cooled to 350 DEG C, hydrogen is switched to gaseous mixture (wherein, the argon gas of ethane and argon gas Molar ratio with ethane is 10：1), and the volume space velocity of ethane is 10000 hours-1, after maintaining 3 hours, obtain F- T synthesis and urge The composition of agent, the catalyst shows in table 2 and table 4, CO2- TPD and CO-TPD test results are listed in table 3.
(4) preparation of alpha-olefin
After reduction activation, synthesis gas is passed through into reactor, and the temperature of reactor is adjusted to 305 DEG C and carries out expense Hold in the palm synthetic reaction, wherein the volume space velocity of synthesis gas is 8000 hours-1, pressure 2MPa, the group of synthesis gas is as H2：CO= 50：50 (molar ratios).In reaction process, the composition progress for the reaction mixture gas that on-line gas chromatography exports reactor is utilized Analysis, 50 hours results measured of reaction are listed in table 5.
Preparation example 18
(1) preparation of carrier
θ-Al are prepared using method identical with preparation example 142O3。
Potassium nitrate is dissolved in 41g deionized waters, modified potassium solution is made, 100.0g, which is added, to modified potassium solution is prepared into θ-the Al arrived2O3, impregnated 2 hours in 25 DEG C of saturations.Then, the mixture that dipping obtains is placed in baking oven, in 120 DEG C and often It depresses 5 hours dry in air atmosphere.The substance being dried to obtain is roasted 3 hours in 400 DEG C of air atmospheres, obtains carrier. The carrier of preparation is subjected to X-ray fluorescence spectra analysis, is determined on the basis of the total amount of carrier, based on the element, the content of K is 5 Weight %.
(2) preparation of catalyst precarsor
Ferric nitrate, potassium carbonate and six water manganese nitrates are added in 11mL deionized waters, heats and stirs in 50 DEG C of water-baths It mixes uniformly mixed, obtains maceration extract.
The maceration extract for taking 50 volume % adds 15g carriers into maceration extract, in environment temperature (for 25 DEG C) saturation dipping 1 Hour.Then, the mixture that dipping obtains is placed in baking oven, it is 5 hours dry in air atmosphere under 120 DEG C and normal pressure.It will It is dried to obtain substance to roast 8 hours in 500 DEG C of air atmospheres, obtains a leaching rear catalyst.
One leaching rear catalyst is added in remaining maceration extract, is impregnated 1 hour in environment temperature (for 25 DEG C) saturation.So Afterwards, the mixture that dipping obtains is placed in baking oven, it is 5 hours dry in air atmosphere under 120 DEG C and normal pressure.It will be dried to obtain Substance roasts 8 hours in 500 DEG C of air atmospheres, obtains catalyst precarsor.
(3) reduction activation of catalyst precarsor
Catalyst precarsor is fitted into fixed bed reactors, and H is passed through into reactor2With gaseous mixture (wherein, the argon gas of argon gas And H2Molar ratio be 5：1), adjustment reactor pressure is 0.1MPa, and the volume space velocity of hydrogen is 20000 hours-1, by reactor Temperature be increased to 400 DEG C, and constant temperature 8 hours at such a temperature by 25 DEG C.Then, reactor is cooled to 250 DEG C, by hydrogen Being switched to the gaseous mixture of ethane and argon gas, (wherein, the molar ratio of argon gas and ethane is 20：1), and the volume space velocity of ethane is 10000 hours-1, after maintaining 4 hours, fischer-tropsch synthetic catalyst is obtained, the composition of the catalyst is shown in table 2 and table 4, CO2- TPD and CO-TPD test results are listed in table 3.
(4) preparation of alpha-olefin
After reduction activation, synthesis gas is passed through into reactor, and the temperature of reactor is adjusted to 320 DEG C and carries out expense Hold in the palm synthetic reaction, wherein the volume space velocity of synthesis gas is 15000 hours-1, pressure 1MPa, the group of synthesis gas is as H2：CO= 50：50 (molar ratios).In reaction process, the composition progress for the reaction mixture gas that on-line gas chromatography exports reactor is utilized Analysis, 50 hours results measured of reaction are listed in table 5.
Preparation example 19
Catalyst is prepared using method identical with preparation example 18 and prepares alpha-olefin, unlike, unlike, step (2) in, ferric nitrate is replaced with cobalt nitrate.
Preparation example 20
Catalyst is prepared using method identical with preparation example 18 and prepares alpha-olefin, unlike, unlike, step (2) in, ferric nitrate is replaced with nickel nitrate.
Preparation example 21
Catalyst is prepared using method identical with preparation example 18 and prepares alpha-olefin, unlike, in step (2), no Using potassium carbonate, but accordingly increase the dosage of six water manganese nitrates.
Table 1
Table 2 (on the basis of the total amount of catalyst)
Table 3
Table 4
1：Fe is not detected5C2 2：FeO and Fe is not detected5C2
Table 5
Preparation example 1 and preparation example 8-11 and preparation example 2 are compared with preparation example 12 and 13 as can be seen that will urge After the hydrogen prereduction of agent precursor, then at a temperature of the reduction activation it is gaseous hydrocarbon reduction activation, can significantly improves final The catalytic activity of the reduction activation catalyst of formation can especially significantly improve the selectivity for alpha-olefin.By preparation example 1 with Preparation example 2, preparation example 14 are compared with preparation example 15 as can be seen that using θ-Al2O3Fischer-tropsch synthetic catalyst can be significantly improved Catalytic activity.
Embodiment 1-7 is used to illustrate the alpha-olefin production method and production system of the present invention.
Embodiment 1
The present embodiment use Fig. 2 shows alpha-olefin production system, including unstripped gas separative element I, steam reforming be anti- Answer unit II, dry reforming reaction member III, Fischer-Tropsch synthesis unit IV, Fischer-Tropsch synthetic separative element V and cycle Unit.Concrete technology flow process is as follows.
(1) it is 220kmol/h using flow and shale gas that pressure is 2.0MPa is sent into unstripped gas separation as unstripped gas A Cryogenic condensation separation, removing sulphur, carbon and other impurity are carried out in unit I, the mass content for obtaining sulphur is less than 1ppm methane B.
Methane B is divided into two strands through current divider, is respectively fed to steam reforming reaction unit II and dry reforming reaction member In III.
(2) by first strand of methane and flow is 120kmol/h, temperature is 370 DEG C and pressure is 3MPa middle pressure vapor C After mixing, it is 600 DEG C that the temperature of mixture, which is increased, subsequently into the fixed bed reactors of steam reforming reaction unit II In, reforming reaction is carried out, steam reforming synthesis gas E is obtained.Wherein, the molar ratio of methane and vapor is 1：3, in reactor The catalyst of filling is Ni/Al2O3(on the basis of the total amount of catalyst, based on the element, the content of Ni is 10 weight %, Al2O3 For α-Al2O3), the temperature in catalyst bed is 900 DEG C, and the pressure in reactor is 3MPa, with the total amount of methane and vapor Meter, volume space velocity is 50000h when gas-1。
(3) second strand of methane is mixed with flow is 100kmol/h, temperature is 370 DEG C and pressure is 2MPa carbon dioxide D It after conjunction, exchanges heat with heat exchanger, it is 600 DEG C that the temperature of mixture, which is increased, subsequently into consolidating for dry reforming reaction member III In fixed bed reactor, reforming reaction is carried out, dry reforming synthesis gas F is obtained.Wherein, the molar ratio of methane and carbon dioxide is 1：1, The catalyst loaded in reactor is Ni/Al2O3(on the basis of the total amount of catalyst, based on the element, the content of Ni is 10 weights Measure %, Al2O3For α-Al2O3), the temperature in catalyst bed is 750 DEG C, and the pressure in reactor is 2MPa, with methane and water The total amount meter of steam, volume space velocity is 80000h when gas-1。
(4) steam reforming synthesis gas E and dry reforming synthesis gas F are mixed, it is 2.1 to prepare as hydrogen-carbon ratio is met：1 Fischer-Tropsch synthesis feeds G.
The Fischer-Tropsch synthesis device that Fischer-Tropsch synthesis charging G is sent into Fischer-Tropsch synthesis unit IV is (anti-for fixed bed Answer device) in, it is contacted with fischer-tropsch synthetic catalyst (catalyst prepared for preparation example 1), carries out Fischer-Tropsch synthesis.Wherein, instead It is 320 DEG C to answer temperature in device, and the pressure in reactor is 1.5MPa, on the basis of the total amount of synthesis gas, volume space velocity when gas For 15000h-1。
(5) the Fischer-Tropsch synthetic logistics H of Fischer-Tropsch synthesis unit IV outputs is sent into Fischer-Tropsch synthetic separation list It is detached in first V.The flow of separation is：Gas-liquid separation is carried out first, obtains alpha-olefin K and gaseous product；Then, make gas Product is by cryogenic separation, to remove carbon dioxide therein；Then, the gaseous product for having isolated carbon dioxide is carried out deep Cold separation obtains methane and unreacted hydrogen and carbon monoxide.
By discharge system outside alpha-olefin K；The carbon dioxide N cycles isolated are sent into dry reforming reaction member III；It will The methane M isolated is respectively fed in steam reforming reaction unit II and dry reforming reaction member III；The hydrogen that will be isolated It is sent into Fischer-Tropsch synthesis unit IV with a part of L cycles of carbon monoxide, remainder is discharged outside as periodic off-gases Z is System, wherein on the basis of the total amount of the hydrogen and carbon monoxide isolated, the hydrogen of cycle and the amount of carbon monoxide L are 98%.
In reaction process, using on-line gas chromatography to the gas-phase product of the reactor discharge of Fischer-Tropsch synthesis unit The composition of logistics is analyzed, and 50 hours results measured of reaction are listed in table 7.System totality water consume, CO2 emission Amount and energy efficiency are listed in table 8.
Comparative example 1
This comparative example use system shown in FIG. 1, including sequentially connected water-coal-slurry preparation unit I, coal gasification unit II, WGS unit III, purified synthesis gas unit IV, F- T synthesis unit V and alpha-olefin separative element VI.Concrete technology stream Journey is as follows.
By fine coal A (for by solid material coal (Inner Mongol production lignite), through fine coal obtained from crushing and screening, (grain size is Water-coal-slurry C 10mm)) is made in water-coal-slurry preparation unit I for the water B of 360t/h with the flow of 360t/h and flow, by water coal Slurry C delivers into coal gasification unit II, under conditions of temperature is 1300 DEG C and pressure is 3MPa, is reacted with oxygen D and generates coal Gasify crude synthesis gas E.
Molar ratios of the coal gasification crude synthesis gas E through WGS unit III adjustment hydrogen and carbon monoxide is 2：1, then Through synthesis gas clean unit IV removing sour gas and sulfide, it is purified the synthesis gas (molar ratio of hydrogen and carbon monoxide It is 2.1：1).
It is anti-that obtained decontaminating syngas is conveyed into F- T synthesis unit V the progress F- T synthesis in fixed bed reactors (catalyst prepared using preparation example 1) is answered, the fischer-tropsch reaction product N of olefin-containing is generated.Wherein, the temperature in reactor is 320 DEG C, pressure in reactor is 1.5MPa, and on the basis of the total amount of synthesis gas, volume space velocity is 15000h when gas-1。
Fischer-tropsch reaction product N isolates alpha-olefin K, the dioxy that F- T synthesis unit V is generated through alpha-olefin separative element VI Change carbon H and methane G then outer rows, (on the basis of the total amount for the synthesis gas isolated, content is a part of unreacted synthesis gas 98%) Y is recycled back to F- T synthesis unit V, and the unreacted synthesis gas of another part is as periodic off-gases Z discharge systems.
In reaction process, the composition for the gas-phase product logistics that Fischer-Tropsch synthesis device is discharged in on-line gas chromatography is utilized It is analyzed, 50 hours results measured of reaction are listed in table 7.System totality water consume, CO2 emissions and energy Efficiency is listed in table 8.
Comparative example 2
Alpha-olefin is prepared using method same as Example 1, unlike, it is not provided with dry reforming reaction member III, first Alkane (including fresh methane and cycle methane), which fully enters in steam reforming reaction unit II, carries out reforming reaction.
Comparative example 3
Alpha-olefin is prepared using method same as Example 1, unlike, it is not provided with steam reforming reaction unit II, methane (including fresh methane and cycle methane), which fully enters in dry reforming reaction member III, carries out reforming reaction.
Embodiment 2
Alpha-olefin is prepared using method same as Example 1, unlike, the fischer-tropsch synthetic catalyst used is preparation Fischer-tropsch synthetic catalyst prepared by example 2.
Embodiment 3
Alpha-olefin is prepared using method same as Example 1, unlike, the fischer-tropsch synthetic catalyst used is preparation Fischer-tropsch synthetic catalyst prepared by example 8.
Embodiment 4
The present embodiment uses reaction system shown in Fig. 2, concrete technology flow process as follows.
(1) it is 500kmol/h using flow and oven gas gas that pressure is 3.0MPa is sent into raw material qi leel as unstripped gas A From cryogenic condensation separation, removing sulphur, carbon and other impurity is carried out in unit I, the mass content for obtaining sulphur is less than 1ppm methane B.
Methane B is divided into two strands through current divider, is respectively fed to steam reforming reaction unit II and dry reforming reaction member In III.
(2) by first strand of methane and flow is 240kmol/h, temperature is 370 DEG C and pressure is 3MPa middle pressure vapor C After mixing, it is 700 DEG C that the temperature of mixture, which is increased, subsequently into the fixed bed reactors of steam reforming reaction unit II In, reforming reaction is carried out, steam reforming synthesis gas E is obtained.Wherein, the molar ratio of methane and vapor is 1：2, in reactor The catalyst of filling is Ni/Al2O3(on the basis of the total amount of catalyst, based on the element, the content of Ni is 10 weight %, Al2O3 For α-Al2O3), the temperature in catalyst bed is 900 DEG C, and the pressure in reactor is 3MPa, with the total amount of methane and vapor Meter, volume space velocity is 50000h when gas-1。
(3) second strand of methane is mixed with flow is 200kmol/h, temperature is 370 DEG C and pressure is 2MPa carbon dioxide D It after conjunction, exchanges heat with heat transferring medium, it is 600 DEG C that the temperature of mixture, which is increased, subsequently into dry reforming reaction member III's In fixed bed reactors, reforming reaction is carried out, dry reforming synthesis gas F is obtained.Wherein, the molar ratio of methane and carbon dioxide is 1： 1.5, the catalyst loaded in reactor is Ni/Al2O3(on the basis of the total amount of catalyst, based on the element, the content of Ni is 10 Weight %, Al2O3For α-Al2O3), the temperature in catalyst bed is 750 DEG C, and the pressure in reactor is 2MPa, with methane and The total amount meter of vapor, volume space velocity is 100000h when gas-1。
(4) steam reforming synthesis gas E and dry reforming synthesis gas F are mixed, it is 2.5 to prepare as hydrogen-carbon ratio is met：1 Fischer-Tropsch synthesis feeds G.Fischer-Tropsch synthesis charging G is sent into the Fischer-Tropsch synthesis device of Fischer-Tropsch synthesis unit IV In (for fixed bed reactors), is contacted with fischer-tropsch synthetic catalyst (catalyst prepared for preparation example 14), carry out F- T synthesis Reaction.Wherein, the temperature in reactor is 310 DEG C, and the pressure in reactor is 1.5MPa, on the basis of the total amount of synthesis gas, Volume space velocity is 10000h when gas-1。
(5) the Fischer-Tropsch synthetic logistics H of Fischer-Tropsch synthesis unit IV outputs is sent into Fischer-Tropsch synthetic separation list It is detached in first V.The flow of separation is：Gas-liquid separation is carried out first, obtains alpha-olefin K and gaseous product；Then, make gas Product is by cryogenic separation, to remove carbon dioxide therein；Then, the gaseous product for having isolated carbon dioxide is carried out deep Cold separation obtains methane and unreacted hydrogen and carbon monoxide.
By discharge system outside alpha-olefin K；The carbon dioxide N cycles isolated are sent into dry reforming reaction member III；It will The methane M isolated is respectively fed in steam reforming reaction unit II and dry reforming reaction member III；The hydrogen that will be isolated It is sent into Fischer-Tropsch synthesis unit IV with a part of L cycles of carbon monoxide, remainder is discharged outside as periodic off-gases Z is System, wherein on the basis of the total amount of the hydrogen and carbon monoxide isolated, the hydrogen of cycle and the amount of carbon monoxide L are 20%.
In reaction process, tail gas composition is analyzed using on-line gas chromatography, reacts 50 hours results measured It is listed in table 7.Device totality water consume, CO2 emissions and energy efficiency are listed in table 8.
Embodiment 5
The present embodiment uses reaction system shown in Fig. 2, concrete technology flow process as follows.
(1) it is 150kmol/h using flow and oven gas gas that pressure is 1MPa is sent into unstripped gas separation as unstripped gas A Cryogenic condensation separation, removing sulphur, carbon and other impurity are carried out in unit I, the mass content for obtaining sulphur is less than 1ppm methane B.
Methane B is divided into two strands through current divider, is respectively fed to steam reforming reaction unit II and dry reforming reaction member In III.
(2) by first strand of methane and flow is 300kmol/h, temperature is 450 DEG C and pressure is 3MPa middle pressure vapor C It after mixing, exchanges heat with heat exchanger, it is 700 DEG C that the temperature of mixture, which is increased, subsequently into steam reforming reaction unit In the fixed bed reactors of II, reforming reaction is carried out, steam reforming synthesis gas E is obtained.Wherein, mole of methane and vapor Than being 1：1, the catalyst loaded in reactor is Ni/Al2O3(on the basis of the total amount of catalyst, based on the element, the content of Ni For 15 weight %, Al2O3For α-Al2O3), the temperature in catalyst bed is 860 DEG C, and the pressure in reactor is 1MPa, with first The total amount meter of alkane and vapor, volume space velocity is 100000h when gas-1。
(3) second strand of methane is mixed with flow is 150kmol/h, temperature is 450 DEG C and pressure is 3MPa carbon dioxide D It after conjunction, exchanges heat with heat transferring medium, it is 700 DEG C that the temperature of mixture, which is increased, subsequently into dry reforming reaction member III's In fixed bed reactors, reforming reaction is carried out, dry reforming synthesis gas F is obtained.Wherein, the molar ratio of methane and carbon dioxide is 1： 1, the catalyst loaded in reactor is Ni/Al2O3(on the basis of the total amount of catalyst, based on the element, the content of Ni is 12 weights Measure %, Al2O3For α-Al2O3), the temperature in catalyst bed is 650 DEG C, and the pressure in reactor is 1.5MPa, with methane and The total amount meter of vapor, volume space velocity is 60000h when gas-1。
(4) steam reforming synthesis gas E and dry reforming synthesis gas F are mixed, it is 1.5 to prepare as hydrogen-carbon ratio is met：1 Fischer-Tropsch synthesis feeds G.Fischer-Tropsch synthesis charging G is sent into the Fischer-Tropsch synthesis device of Fischer-Tropsch synthesis unit IV In (for fixed bed reactors), is contacted with fischer-tropsch synthetic catalyst (catalyst prepared for preparation example 16), carry out F- T synthesis Reaction.Wherein, the temperature in reactor is 290 DEG C, and the pressure in reactor is 2.5MPa, on the basis of the total amount of synthesis gas, Volume space velocity is 20000h when gas-1。
(5) the Fischer-Tropsch synthetic logistics H of Fischer-Tropsch synthesis unit IV outputs is sent into Fischer-Tropsch synthetic separation list It is detached in first V.The flow of separation is：Gas-liquid separation is carried out first, obtains alpha-olefin K and gaseous product；Then, make gas Product is by cryogenic separation, to remove carbon dioxide therein；Then, the gaseous product for having isolated carbon dioxide is carried out deep Cold separation obtains methane and unreacted hydrogen and carbon monoxide.
By discharge system outside alpha-olefin K；The carbon dioxide N cycles isolated are sent into dry reforming reaction member III；It will The methane M isolated is respectively fed in steam reforming reaction unit II and dry reforming reaction member III；The hydrogen that will be isolated It is sent into Fischer-Tropsch synthesis unit IV with a part of L cycles of carbon monoxide, remainder is discharged outside as periodic off-gases Z is System, wherein on the basis of the total amount of the hydrogen and carbon monoxide isolated, the hydrogen of cycle and the amount of carbon monoxide L are 15%.
In reaction process, tail gas composition is analyzed using on-line gas chromatography, reacts 50 hours results measured It is listed in table 7.Device totality water consume, CO2 emissions and energy efficiency are listed in table 8.
Embodiment 6
Alpha-olefin is produced using system and method same as Example 5, unlike, fischer-tropsch synthetic catalyst is to prepare Fischer-tropsch synthetic catalyst prepared by example 17, and the temperature in Fischer-Tropsch synthesis device is 330 DEG C, the pressure in reactor is 1.5MPa, on the basis of the total amount of synthesis gas, volume space velocity is 30000h when gas-1。
Embodiment 7
Alpha-olefin is produced using system and method same as Example 5, unlike, fischer-tropsch synthetic catalyst is to prepare Fischer-tropsch synthetic catalyst prepared by example 18, and the temperature in Fischer-Tropsch synthesis device is 280 DEG C, the pressure in reactor is 1.5MPa, on the basis of the total amount of synthesis gas, volume space velocity is 30000h when gas-1。
Table 7
Table 8
Number Water consume (t/tAlpha-olefin) CO2 emission (t/tAlpha-olefin) Energy efficiency (%)
Embodiment 1 14 0.6 55
Comparative example 1 21 6.8 34
Comparative example 2 19 2.3 36
Comparative example 3 26 0.8 45
Embodiment 4 15 0.9 52
Embodiment 5 15 1.0 50
Embodiment 6 16 1.1 49
Embodiment 7 18 1.3 44
Note：The calorific value of the alpha-olefin of energy efficiency=finally go out device/into the coal electricity vapor catalyst solvent etc. of device The sum of calorific value of raw material, the i.e. calorific value of gained alpha-olefin/produce comprehensive energy consumption needed for these alpha-olefins.Wherein, comprehensive energy consumption Including raw material calorific value and public work energy consumption, include mainly：Bunker coal and feed coal calorific value, device technique motor pump are consumed Electric energy, the indirect energy consumptions such as recirculated cooling water, boiler feedwater, plant air, instrument air, fresh water.
Table 8 the result shows that, the present invention is by combining methane vapor reforming technique and methane dry reforming technique, to dioxy Change carbon and methane both greenhouse gases are used simultaneously, is allowed to be changed into the product with high added value, reduces greenhouse Gas discharges, and significantly improves resource, the energy utilization rate of integrated artistic.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to Protection scope of the present invention.

Claims (35)

1. a kind of production method of alpha-olefin, this approach includes the following steps：
S11, under the conditions of steam reforming reaction, methane is contacted with vapor, obtains steam reforming synthesis gas；
S21, under dry reforming reaction condition, by methane and carbon dioxide exposure, obtain dry reforming synthesis gas；
S31, will at least partly steam reforming synthesis gas and at least partly dry reforming synthesis gas mix, with prepare obtain Fischer-Tropsch close At reaction feed, Fischer-Tropsch synthesis charging is contacted under the reaction temperature of production alpha-olefin with fischer-tropsch synthetic catalyst, Obtain Fischer-Tropsch synthetic logistics；
S41, alpha-olefin, methane and carbon dioxide are isolated from the Fischer-Tropsch synthetic logistics, the methane isolated is sent Enter one of S11 and S21, or both in, will the carbon dioxide that isolated be sent into S21 in.
2. according to the method described in claim 1, wherein, in S11, the molar ratio of methane and vapor is 1：0.5-4；
Preferably, methane is contacted with vapor under conditions of temperature is 700-950 DEG C and pressure is 0.1-5MPa, institute Pressure is stated in terms of gauge pressure；
It is highly preferred that the steam reforming reaction carries out in fixed bed reactors, in terms of the total amount of methane and vapor, into Volume space velocity is preferably 10000-100000 hours when the gas of material-1。
3. method according to claim 1 or 2, wherein in S21, the molar ratio of methane and carbon dioxide is 1：0.5-5；
Preferably, methane is contacted with carbon dioxide under conditions of temperature is 600-800 DEG C and pressure is 0.1-5MPa, The pressure is in terms of gauge pressure；
It is highly preferred that the dry reforming reaction carries out in fixed bed reactors, and in terms of the total amount of methane and carbon dioxide, charging Gas when volume space velocity be 10000-100000 hours-1。
4. according to the method described in any one of claim 1-3, wherein the Fischer-Tropsch synthesis temperature for producing alpha-olefin is 200-380 DEG C, preferably 250-250 DEG C；
Preferably, in S31, Fischer-Tropsch synthesis feeds the pressure in 0.8-3MPa, preferably 1-2.8MPa with fischer-tropsch synthetic catalyst It is contacted under power, the pressure is in terms of gauge pressure；
Preferably, in S31, the contact carries out in fixed bed reactors, Fischer-Tropsch synthesis charging gas when volume space velocity Preferably 2000-50000 hours-1, more preferably 5000-40000 hours-1；
Preferably, in the Fischer-Tropsch synthesis charging, the molar ratio of hydrogen and carbon monoxide is 0.4-3：1, preferably 1.5- 2.5：1.
5. method according to claim 1 or 4, wherein the fischer-tropsch synthetic catalyst contains carrier and is supported on institute The first metallic element, the second metallic element and the optional third metallic element on carrier are stated, first metallic element is It is described selected from one or more of group VIII metallic element, preferably one or more of Fe, Co and Ni Second metallic element is selected from one or more of V Group IIB metallic element, and the third metallic element is selected from alkali One or more of metallic element, alkali earth metal and group ivb metallic element, the carrier are aluminium oxide, until The valence state of small part group VIII metallic element is the highest oxidation valence state less than the metallic element.
6. according to the method described in claim 5, wherein, the CO of the fischer-tropsch synthetic catalyst2- TPD is desorbed in figure, in 300- 600 DEG C, preferably 350-500 DEG C, there are CO in more preferable 380-450 DEG C of temperature range2Elevated temperature desorption peak；
Preferably, the CO of the fischer-tropsch synthetic catalyst2- TPD is desorbed in spectrogram, in 90-200 DEG C, preferably 140-180 DEG C of temperature There is also CO in degree section2Low temperature desorption peaks；
It is highly preferred that in the CO-TPD desorption figures of the fischer-tropsch synthetic catalyst, in 350-720 DEG C, preferably 550-700 DEG C of temperature There are CO elevated temperature desorptions peaks in degree section；
It is further preferred that in the CO-TPD desorption figures of the fischer-tropsch synthetic catalyst, at 300-700 DEG C, preferably 450-600 DEG C, there is also CO low temperature desorption peaks, the peak position of the CO low temperature desorption peaks to be less than institute in more preferable 480-560 DEG C of temperature range State the peak position at CO elevated temperature desorptions peak.
7. method according to claim 5 or 6, wherein the group VIII metallic element is Fe, and the F- T synthesis is urged In the x-ray photoelectron spectroscopy spectrogram of agent, there is the spectral peak corresponding to FeO and correspond to Fe5C2Spectral peak；
Preferably, based on the element, by the Fe contents that are determined corresponding to the spectral peak of FeO with by corresponding to Fe5C2Spectral peak determine Fe The ratio of content is 8-25：1, preferably 9.5-16：1, more preferably 9.5-12：1；
Preferably, based on the element, on the basis of the total amount of the Fe determined by x-ray photoelectron spectroscopy, by the spectral peak corresponding to FeO With corresponding to Fe5C2Spectral peak determine Fe content be 40% or more, preferably 55-95%, more preferably 60-90 weight %.
8. according to the method described in any one of claim 5-7, wherein in catalyst group VIII metallic element it is total On the basis of amount, based on the element, valence state is that the content of the group VIII metallic element less than its highest oxidation valence state is 40 weight % More than, preferably 50 weight % or more, further preferably 60 weight % or more.
9. according to the method described in any one of claim 5-8, wherein second metallic element is Mn；
Preferably, on the basis of the total amount of fischer-tropsch synthetic catalyst, based on the element, the content of second metallic element is 0.1- 10 weight %, preferably 2.5-4 weight %.
10. according to the method described in any one of claim 5-9, wherein the third metallic element be selected from Li, Na, K, one or more of Mg, Ca, Zr and Ti, preferably one or more of Li, K, Mg and Zr, more preferably K and Zr；
Preferably, on the basis of the total amount of fischer-tropsch synthetic catalyst, based on the element, the content of the third metallic element is 0.1- 15 weight %, preferably 4-9 weight %.
11. according to the method described in any one of claim 5-10, wherein using the total amount of fischer-tropsch synthetic catalyst as base Standard, based on the element, the content of the group VIII metallic element is 3-30 weight %, preferably 8-20 weight %, more preferably 10-15 weight %.
12. according to the method described in any one of claim 1 and 5-11, wherein the fischer-tropsch synthetic catalyst is to pass through Obtained from catalyst precarsor is carried out reduction activation, the method for the reduction activation includes：
(1) catalyst precarsor is carried out to prereduction in first gas, obtains catalyst pre-reduction, the first gas is hydrogen Gas or gaseous mixture for hydrogen and inert gas, the catalyst precarsor contain carrier and load on the carrier First metallic element, the second metallic element and optional third metallic element, first metallic element are selected from Section VIII One or more of race's metallic element, preferably one or more of Fe, Co and Ni, more preferably Fe, institute The first metallic element is stated to load in the form of the oxide on the carrier, the group VIII metallic element in the oxide Valence state is the highest oxidation valence state of the metallic element, and the carrier is aluminium oxide, and second metallic element is selected from Section VII B One or more of race's metallic element, the third metallic element be selected from alkali metal element, alkali earth metal and One or more of group ivb metallic element；
(2) catalyst pre-reduction in second gas is subjected to reduction activation, obtains reduction activation catalyst, described second Gas is to be gaseous hydrocarbon at a temperature of reduction activation or be the mixed of gaseous hydrocarbon and inert gas at a temperature of reduction activation Gas is closed, the reduction activation carries out at a temperature of 150-500 DEG C.
13. according to the method for claim 12, wherein the prereduction carries out at a temperature of 200-600 DEG C, preferably exists It is carried out at a temperature of 300-550 DEG C；
Preferably, in terms of hydrogen, the volume space velocity of the first gas is 5000-30000 hours-1；
It is highly preferred that in terms of gauge pressure, it is 0-3MPa, preferably 0.1-1MPa to carry out the pressure in the reactor of prereduction；
It is further preferred that the duration of the prereduction is 1-20 hours, preferably 2-15 hours.
14. method according to claim 12 or 13, wherein it is gaseous state that the second gas, which is at a temperature of reduction activation, Hydrocarbon and inert gas gaseous mixture；
Preferably, the inert gas be the molar ratio of gaseous hydrocarbon at a temperature of reduction activation be 1-200：1, preferably 5- 20：1.
15. according to the method described in any one of claim 12-14, wherein described is gaseous state at a temperature of reduction activation Hydrocarbon be selected from be at a temperature of reduction activation gaseous alkane and at a temperature of reduction activation be in gaseous alkene one Kind is two or more, is preferably selected from C1-C4Alkane and C2-C4One or more of alkene, be more preferably selected from One or more of methane, ethane, ethylene, propylene, propane, butane and butylene.
16. according to the method described in any one of claim 12-15, wherein the reduction activation 180-400 DEG C, it is excellent It is carried out at a temperature of selecting 200-350 DEG C；
Preferably, to be in terms of gaseous hydrocarbon at a temperature of reduction activation, the volume space velocity of the second gas is 1000-30000 Hour-1；
Preferably, in terms of gauge pressure, it is 0-3MPa, preferably 0.1-1MPa to carry out the pressure in the reactor of reduction activation；
It is highly preferred that the duration of the reduction activation is 1-20 hours, preferably 2-15 hours.
17. according to the method described in any one of claim 12-16, wherein the first gas and the second gas In inert gas it is identical or different, respectively be selected from one or more of nitrogen and group 0 element gas, preferably respectively From for nitrogen and/or argon gas.
18. according to the method described in any one of claim 12-17, wherein on the basis of the total amount of catalyst precarsor, with The content of element meter, the group VIII metallic element is 3-30 weight %, preferably 8-20 weight %, more preferably 10-15 Weight %.
19. according to the method described in any one of claim 12-18, wherein second metallic element is Mn；
Preferably, on the basis of the total amount of catalyst precarsor, based on the element, the content of second metallic element is 0.1-10 weights Measure %, preferably 2.5-4 weight %.
20. according to the method described in any one of claim 12-19, wherein the third metallic element be selected from Li, One or more of Na, K, Mg, Ca, Zr and Ti, preferably one or more of Li, K, Mg and Zr, it is more excellent It is selected as K and Zr；
Preferably, on the basis of the total amount of catalyst precarsor, based on the element, the content of the third metallic element is 0.1-15 weights Measure %, preferably 4-9 weight %.
21. according to the method described in any one of claim 12-20, wherein it includes following that the catalyst precarsor, which uses, It is prepared by the method for step：Load is had to the oxide of group VIII metallic element and/or the oxide of group VIII metallic element Precursor and the carrier of compound containing auxiliary element roasted, the carrier is aluminium oxide, described to contain group VIII The compound of metallic element is the predecessor of the oxide of group VIII metallic element and/or the oxide of group VIII metallic element Object, the auxiliary element be V Group IIB metallic element or be V Group IIB metallic element and alkali metal element, preferably Mn or for Mn and one or more of selected from Li, Na and K；
Preferably, the compound containing auxiliary element and the group VIII metallic element are supported on the carrier simultaneously On；
Preferably, the roasting carries out at a temperature of 300-900 DEG C, and the duration of the roasting is preferably 0.5-12 small When.
22. according to the method for claim 21, wherein at least partly aluminium oxide is the aluminium oxide containing modifying element, institute State modifying element be selected from one or more of alkali metal element, alkali earth metal and group ivb metallic element, it is excellent Be selected as one or more of Li, Na, K, Mg, Ca, Zr and Ti, more preferably one or both of K, Mg and Zr with On；
Preferably, on the basis of the total amount of the carrier, based on the element, the content of the modifying element is 0.1-10 weight %, Preferably 2-6 weight %.
23. according to the method for claim 22, wherein the preparation method of the aluminium oxide containing modifying element includes：It will bear The aluminium oxide for being loaded with the compound containing modifying element is roasted, and the aluminium oxide containing modifying element is obtained, and the roasting is preferred It is carried out at a temperature of 300-900 DEG C, the duration of the roasting is preferably 0.5-12 hours.
24. according to the method described in any one of claim 5-23, wherein the aluminium oxide contains θ-aluminium oxide；
Preferably, on the basis of the total amount of aluminium oxide in fischer-tropsch synthetic catalyst, the content of the θ-aluminium oxide is 50 weight % More than；
It is highly preferred that the aluminium oxide is θ-aluminium oxide.
25. according to the method described in any one of claim 5-24, wherein what the aluminium oxide use included the following steps It is prepared by method：By γ-Al2O3At a temperature of 700-1050 DEG C, roasted in air atmosphere, the roasting it is lasting when Between preferably 0.5-5 hours.
26. according to the method described in claim 1, wherein, this method further includes being isolated not from Fischer-Tropsch synthetic logistics The hydrogen and/or carbon monoxide of reaction, will at least partly hydrogen and/or at least partly carbon monoxide cycle for prepare Fischer-Tropsch conjunction At reaction feed.
27. according to the method described in claim 1, wherein, this method further includes S10, in S10, from the raw material containing methane The methane isolated in gas, the unstripped gas are preferably selected from shale gas, coal bed gas, natural gas, refinery gas and oven gas It is one or more kinds of；
Preferably, methane is isolated from the unstripped gas using condensation at low temperature.
28. according to the method described in any one of claim 1,26 and 27, wherein adopted in the methane and S21 that are used in S11 The weight ratio of methane is 1：0.5-2.5.
29. a kind of alpha-olefin production system, which includes steam reforming reaction unit, dry reforming reaction member, synthesis gas Mixed cell, Fischer-Tropsch synthesis unit, Fischer-Tropsch synthesis product separative element and cycling element,
The steam reforming reaction unit carries out steam reforming reaction, obtains water steaming for contacting methane with vapor Gas reformed syngas；
The dry reforming reaction member is used to, by methane and carbon dioxide exposure, carry out dry reforming reaction, obtain dry weight and be integrated into Gas；
The synthesis gas mixed cell is configured to for mixing the steam reforming synthesis gas with the dry reforming synthesis gas It is fed for Fischer-Tropsch synthesis, and the Fischer-Tropsch synthesis is fed in the Fischer-Tropsch synthesis unit；
The Fischer-Tropsch synthesis unit is provided with Fischer-Tropsch synthesis device, for feeding and Fischer-Tropsch the Fischer-Tropsch synthesis Synthetic catalyst contacts under the reaction temperature of production alpha-olefin, obtains the Fischer-Tropsch synthetic logistics containing alpha-olefin；
The Fischer-Tropsch synthesis product separative element for the Fischer-Tropsch synthetic logistics to be detached, obtain methane, Carbon dioxide, alpha-olefin, optional hydrogen and optional carbon monoxide；
The methane cycle that the cycling element is used to isolate Fischer-Tropsch synthesis product separative element is sent into steam reforming One of reaction member and dry reforming reaction member, or both in, Fischer-Tropsch synthesis product separative element is isolated Carbon dioxide recycle is sent into dry reforming reaction member, the hydrogen for optionally isolating Fischer-Tropsch synthesis product separative element And/or carbon monoxide cycle is sent into Fischer-Tropsch synthesis unit.
30. system according to claim 29, wherein the system further includes unstripped gas separative element, the raw material qi leel From unit for isolating methane from the unstripped gas containing methane, the methane output port of the unstripped gas separative element respectively with The methane feed of the methane feed input port of the steam reforming reaction unit and the dry reforming reaction member inputs Port is connected to, and the methane isolated is respectively fed in steam reforming reaction unit and the dry reforming reaction member；
Preferably, the unstripped gas separative element is provided with low-temperature condenser, for being condensed to the unstripped gas, with separation Go out the methane in the unstripped gas.
31. the system according to claim 29 or 30, wherein the Fischer-Tropsch synthesis unit further includes reduction activation Unit, the reduction activation subelement are used for the fischer-tropsch synthetic catalyst precursor reduction activation.
32. system according to claim 31, wherein the reduction activation subelement includes first gas storage conveying dress It sets, second gas storing and conveying device, reducing gas control device and reduction activation reactor,
The first gas storing and conveying device is sent into reduction activation reactor for storing first gas, and by first gas In, the first gas is the gaseous mixture of hydrogen or hydrogen and inert gas,
The second gas storing and conveying device is sent into reduction activation reactor for storing second gas, and by second gas In, the second gas is to be gaseous hydrocarbon under reduction temperature or is gaseous hydrocarbon and inert gas under reduction temperature Gaseous mixture,
The reducing gas control device is used to control the feeding amount of the gas type and gas of being sent into reduction activation reactor, When reduction activation subelement operation, the reducing gas control device is arranged to first to input the into reduction activation reactor One gas so that fischer-tropsch synthetic catalyst precursor contacted with hydrogen carry out prereduction reaction, obtain catalyst pre-reduction, then to Second gas is inputted in reduction activation reactor, so that the catalyst pre-reduction is contacted with second gas, carries out reduction reaction.
33. system according to claim 32, wherein it is described be at a temperature of reduction activation gaseous hydrocarbon be selected from also Under former activation temperature it is gaseous alkane and is one or more of gaseous alkene at a temperature of reduction activation, Preferably gaseous hydrocarbon is selected from C1-C4Alkane and C2-C4One or more of alkene, be more preferably selected from first One or more of alkane, ethane, ethylene, propylene, propane, butane and butylene；
Preferably, the inert gas in the first gas and the second gas is identical or different, respectively be selected from nitrogen and One or more of group 0 element gas, preferably respectively nitrogen and/or argon gas.
34. the system according to claim 32 or 33, wherein the reduction activation reactor is with Fischer-Tropsch synthesis device Same reactor, or
The reduction reactor and Fischer-Tropsch synthesis device are not same reactors, the reduction activation of the reduction activation reactor Catalyst output port is connected to the catalyst input port of the Fischer-Tropsch synthesis device, and reduction activation reactor is exported Reduction activation catalyst be sent into the Fischer-Tropsch synthesis device.
35. according to the system described in any one of claim 29-34, wherein the Fischer-Tropsch synthesis device is fixed bed Reactor.
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