CN108728152A - The production method and a kind of synthetic oil production system of a kind of synthetic oil - Google Patents

The production method and a kind of synthetic oil production system of a kind of synthetic oil Download PDF

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CN108728152A
CN108728152A CN201710256682.6A CN201710256682A CN108728152A CN 108728152 A CN108728152 A CN 108728152A CN 201710256682 A CN201710256682 A CN 201710256682A CN 108728152 A CN108728152 A CN 108728152A
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gas
fischer
tropsch
methane
catalyst
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CN108728152B (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
    • 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

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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)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of production method of synthetic oil and production system, the preparation 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 synthetic oil 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 synthetic oil 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 synthetic oil production system of a kind of synthetic oil
Technical field
The present invention relates to a kind of production methods of synthetic oil, and the invention further relates to a kind of synthetic oil production systems.
Background technology
China's energy is in the resource distribution situation of rich coal, more natural gases, oil starvation, is synthesized coal or day by Fischer-Tropsch (F-T) Right gas indirect reformer is clean, highly effective liquid fuel is the importance for rationally utilizing resource, can alleviate China's oil supply and demand Contradictory Major Technology.Coal converts coal or natural gas to synthesis gas first through synthesis gas clear gusoline technique directly processed (CO and H2), liquid fuel is directly made using F-T synthesis.It is not to synthesize the most important advantage of synthetic oil obtained by F-T The undesirable components such as sulfur-bearing, nitrogen and aromatic hydrocarbons, belong to clean fuel, comply fully with the strict demand of Modern Engine and increasingly harsh Environmental legislation.
Currently, industrial generally use ferrum-based catalyst, using slurry bed system or fixed-bed process and serial hydrocracking device Product high-carbon hydrocarbon-wax product is cracked into the related liquids fuels and chemicals such as gasoline, diesel oil or lubricating oil.The technique system synthesizes Fig. 1 is shown in oily technological process, 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 synthetic oil separative element VI.Detailed process is by fine coal A and water B in water coal Water-coal-slurry C is made in slurry preparation unit I, water-coal-slurry C is delivered into coal gasification unit II, is reacted with oxygen D and generates coal gasification The molar ratio of crude synthesis gas E, coal gasification crude synthesis gas E through WGS unit III adjustment hydrogen and carbon monoxide makes its symbol Crude synthesis gas F after the requirement of conjunction Fischer-Tropsch synthesis is converted, crude synthesis gas F is removed through synthesis gas clean unit IV after transformation Sour gas and sulfide M are purified synthesis gas J, and obtained decontaminating syngas J, which is conveyed into F- T synthesis unit V, to carry out Fischer-Tropsch synthesis, fischer-tropsch reaction the product N, fischer-tropsch reaction product N for generating olefin-containing are detached through low-carbon alkene separative element VI Go out synthetic oil K, then outer row, a part of unreacted synthesis gas Y are recycled the carbon dioxide H and methane G that F- T synthesis unit V is generated F- T synthesis unit V is returned, the unreacted synthesis gas of another part is as periodic off-gases Z discharge systems.
The main problem of above-mentioned technique is：1, high energy consumption, carbon atom utilization rate are low；2, CO2 emissions are tradition 5-6 times of petroleum path；3, since by Anderson-Schulz-Flory rules, (chain growth is according to finger for Fischer-Tropsch synthetic distribution The molar distributions successively decreased of number) limitation, and be limited by a large amount of methane, carbon dioxide caused by the strongly exothermic property of reaction and generate, the work Skill entirety efficiency is relatively low, seriously affects the process of industrialization of F-T synthesis technologies.The a large amount of cooling water of coal gasifying process and outer row Sewage keeps water consume high.
Therefore, it is necessary to optimize, F-T 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 synthetic oil, 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 synthetic oil, 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 synthetic oil with fischer-tropsch synthetic catalyst It touches, obtains Fischer-Tropsch synthetic logistics；
S41, synthetic oil, 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 synthetic oil 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 synthetic oil, obtains the Fischer-Tropsch synthetic logistics containing synthetic oil；
The Fischer-Tropsch synthesis product separative element obtains first for detaching the Fischer-Tropsch synthetic logistics Alkane, carbon dioxide, synthetic oil, 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, optionally isolates Fischer-Tropsch synthesis product separative element Hydrogen and/or carbon monoxide cycle are sent into Fischer-Tropsch synthesis unit.
The production method and system of synthetic oil 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 synthetic oil (FTO techniques) through synthesis gas.
Fig. 2 is for illustrating synthetic oil preparation method and system according to the present invention.
Fig. 1 reference signs
I：Water-coal-slurry preparation unit II：Coal gasification unit
III：WGS unit IV：Purified synthesis gas unit
V：F- T synthesis unit VI：Synthetic oil 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：Synthetic oil 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：Water D：Carbon dioxide
E：Steam reforming synthesis gas F：Dry reforming synthesis gas
G：Fischer-Tropsch synthesis feeds H：Fischer-Tropsch synthetic logistics
L：Hydrogen and carbon monoxide K for cycle：Synthetic oil
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.
In the present invention, term " synthetic oil " refers to C5-C30Component.
According to the first aspect of the invention, the present invention provides a kind of production method of synthetic oil, 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 synthetic oil with fischer-tropsch synthetic catalyst It touches, obtains Fischer-Tropsch synthetic logistics；
S41, synthetic oil, 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 synthetic oil 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 synthetic oil 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 can be isolated from unstripped gas by the method for condensation at low temperature.It is described Condensation at low temperature is the method to isolate and purify methane using boiling-point difference, can be according to the boiling point determination of each component in unstripped gas Methane is obtained from gas phase, or methane is obtained from liquid phase.
The production method of synthetic oil 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 synthetic oil 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 synthetic oil according to the present invention, in step S31, will at least partly steam reforming synthesis gas and At least partly dry reforming synthesis gas mixes, and obtains meeting F- T synthesis charging hydrogen-carbon ratio (that is, hydrogen and carbon monoxide to prepare Molar ratio) Fischer-Tropsch synthesis charging.From the angle for the selectivity for improving synthetic oil, Fischer-Tropsch synthesis charging, The molar ratio of hydrogen and carbon monoxide is preferably 0.4-3：1, more preferably 0.6-2.8：1, further preferably 0.8-2.6：1, Still more preferably it is 1.5-2.5：1.
The production method of synthetic oil 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 and the second 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.Preferably, the carrier For γ-Al2O3。
The parameters such as its specific surface area, average pore size and particle diameter distribution can be carried out according to the concrete type of aluminium oxide excellent Change, to further increase the catalytic performance of catalyst.As an example, for γ-Al2O3, Kong Rongke with for 0.6-1mL/g, Preferably 0.65-0.9mL/g, more preferably 0.65-0.85mL/g；Average pore size can be 8-35nm, preferably 12-30nm, More preferably 15-20nm；The content of particle of the grain size in 70-150 μ ms can be 80 volume % or more, preferably 85 bodies Product % or more, more preferably 90 volume % or more；Specific surface area can be 100-300m2/ g, preferably 120-250m2/ g, it is more excellent It is selected as 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；The content of particle of the grain size in 70-150 μ ms can be 80 volume % or more, preferably 85 volume % or more, more Preferably 90 volume % or more；Specific surface area can be 50-200m2/ g, preferably 60-150m2/ g, more preferably 65-100m2/ g。
According to the fischer-tropsch synthetic catalyst of the preferred embodiment, first metallic element is selected from group VIII gold Belong to one or more of element.Active component of the group VIII metallic element as catalyst can be the VIII group precious metal element, or group VIII non-noble metal j element can also be group VIII noble metals element and the The combination of VIII group non-noble metal j element.In a preferred embodiment, the group VIII metallic element is Section VIII Race's non-noble metal j element, specific example can include but is not limited to one or more of Fe, Co and Ni.More preferably Ground, the group VIII metallic element are 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 30 weights % or more, preferably 40 weight % or more, more preferably 50 weight % or more (such as 55 weight % or more) are measured, further preferably 60 weight % or more.On the basis of the total amount of group VIII metallic element in fischer-tropsch synthetic catalyst, based on the element, valence state is low In its highest oxidation valence state group VIII metallic element highest content can be 100 weight %, such as：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 that the metallic element is fully oxidized When chemical valence, by taking Fe as an example, highest oxidation valence state refers to iron oxide (Fe2O3) in ferro element chemical valence, for+trivalent.This hair In bright, 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 8-20：1.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 10- 15：1.According to the fischer-tropsch synthetic catalyst of the particularly preferred example, from the angle for further increasing catalytic activity, with member Element meter, on the basis of the total amount of the Fe determined by x-ray photoelectron spectroscopy, by corresponding to FeO spectral peak and correspond to Fe5C2's The content for the Fe that spectral peak determines can be 30 weight % or more, preferably 40 weight % or more, more preferably 50 weight % or more (such as 55 weight % or more), further preferably 60 weight % or more.By corresponding to FeO spectral peak and correspond to Fe5C2Spectral peak The content of determining Fe is generally not higher than 95 weight %, preferably not higher than 90 weight %, more preferably not above 85 weights Measure %.
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 6-20 weight %, further preferably 8-15 weights Measure %.In the present invention, the type and content of each metallic element are used according to RIPP 132-92 in catalyst and catalyst precarsor (《Petrochemical analysis method (RIPP experimental methods)》, Yang Cui is surely equal to be compiled, Science Press, nineteen ninety September the 1st edition, 371- Page 379) 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 of load on the carrier.Contain second metal The catalyst of element shows more excellent catalytic activity.
Second metallic element is selected from group ivb metallic element, optional alkali metal element and optional alkaline earth One or more of metallic element.The group ivb metallic element is preferably Zr and/or Ti.The alkali metal element Preferably one or more of Li, Na and K, more preferably Li and/or K.The alkali earth metal be preferably Mg and/ Or Ca, more preferably Mg.On the basis of the total amount of catalyst, based on the element, the content of second metallic element can be 0.5-10 weight %, preferably 1-8 weight %, more preferably 2-6 weight %.
In a preferred embodiment, second metallic element is for group ivb metallic element and selected from alkali gold Belong to one or more of element and alkali earth metal, better catalytic effect can be obtained in this way.In the preferred reality It applies in mode, on the basis of the total amount of the second metallic element, the content of group ivb metallic element is preferably 10-60 weight %, more Preferably 20-55 weight %, further preferably 30-50 weight %.It is highly preferred that second metallic element is group ivb Metallic element and alkali earth metal.It is further preferred that second metallic element is Zr and Mg.
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 300-500 DEG C, preferably 320- There are desorption peaks (which herein, to be known as CO in 400 DEG C of temperature range2Elevated temperature desorption peak).The CO2High temperature is de- The peak area at attached peak is generally 0.3-2.5a.u. (arbitrary unit), preferably 0.5-2a.u. (arbitrary unit).Preferably according to this The CO of the fischer-tropsch synthetic catalyst of embodiment2- TPD is desorbed in spectrogram, 100-200 DEG C, preferably 140-180 DEG C of humidity province It is interior that there is also another desorption peaks (which herein, to be known as CO2Low temperature desorption peaks).The CO2The peak of low temperature desorption peaks Area is generally 0.5-3.5a.u. (arbitrary unit), preferably 1-2a.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 in the CO-TPD desorption spectrograms of catalyst, there are desorption peaks (these in 300-600 DEG C, preferably 400-500 DEG C of temperature range The desorption peaks are known as CO elevated temperature desorptions peak by Wen Zhong).It is (arbitrary single that the peak area at CO elevated temperature desorptions peak is generally 1-5a.u. Position), preferably 2-4a.u. (arbitrary unit).It is desorbed and is composed according to the CO-TPD of the fischer-tropsch synthetic catalyst of the preferred embodiment In figure, there is also another desorption peaks (herein, by the desorption peaks in 100-200 DEG C, preferably 160-180 DEG C of temperature range Referred to as CO low temperature desorption peaks).The peak area of the CO low temperature desorption peaks is generally 0.5-2a.u. (arbitrary unit).
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 location of peak value.
The production method of synthetic oil 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 contain carrier and load the first metallic element on the carrier and Second metallic element.The type and content of the carrier, the first metallic element and the second metallic element may refer to institute above The fischer-tropsch synthetic catalyst stated, and will not be described here in detail.
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, and the group 0 element gas for example may be used Think argon gas.Preferably, the inert gas is nitrogen and/or argon gas.It is hydrogen and inert gas in the first gas When gaseous mixture, the molar ratio of the inert gas and the hydrogen can be 1-30：1.
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 It is contacted at a temperature of 500 DEG C.The volume space velocity of the first gas (in terms of hydrogen) can be 1000-20000 hours-1, Preferably 2000-10000 hours-1.In terms of gauge pressure, it can be 0-3MPa to carry out the pressure in the reactor of prereduction, preferably 0.1-1MPa.The duration of the prereduction can be selected according to the temperature of prereduction.Usually, the prereduction Duration can be 1-20 hours, preferably 2-15 hours, more preferably 4-10 hours.
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 group 0 element gas One or more of, the group 0 element gas for example can be argon gas.Preferably, the inert gas is nitrogen And/or argon gas.It is described when being the gaseous mixture of gaseous hydrocarbon and inert gas at a temperature of the second gas is in reduction activation Inert gas be the molar ratio of gaseous hydrocarbon at a temperature of reduction activation can be 1-200：1, preferably 1-100：1, it is more excellent It is selected as 5-50：1, further preferably 10-30：1.
In the reduction activation method, the reduction activation can 150-500 DEG C, preferably 180-450 DEG C, more preferably It is carried out at a temperature of 200-400 DEG C, further preferred 200-300 DEG C.The second gas (using at a temperature of reduction activation as gas The hydrocarbon meter of state) volume space velocity can be 1000-10000 hours-1, preferably 2000-8000 hours-1.Carrying out reduction activation During, in terms of gauge pressure, it can be 0-3MPa, preferably 0.1-1MPa to carry out the pressure in the reactor of reduction activation.Institute Stating the duration of reduction activation can be selected according to the temperature of reduction activation.Usually, the reduction activation continues Time can be 1-20 hours, preferably 2-8 hours, more preferably 4-6 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 the second metallic element is roasted, and catalyst precarsor is obtained.
Second metallic element can be supported on together with group VIII metallic element on carrier, can also be in load regulation After group VIII metal element, the second metallic element is supported on carrier.
In a preferred embodiment, oxidation of second metallic element prior to the group VIII metallic element The precursor of the oxide of object and group VIII metallic element is loaded on carrier, can significantly improve the catalyst of preparation in this way Catalytic activity.
In the preferred embodiment, conventional method may be used and obtain the aluminium oxide containing the second metallic element.? It, can be during preparing aluminium oxide, on alumina by the load of the second metallic element, such as by coprecipitated in one example It forms sediment, while preparing aluminium oxide, on alumina by the load of the second metallic element.
In another example, the aluminium oxide of the compound containing the second metallic element roasts load, to To the aluminium oxide containing the second metallic element.The roasting can carry out under normal conditions, and usually, the roasting can be 300-900 DEG C, preferably 320-800 DEG C, it is 350-700 DEG C more preferable at a temperature of carry out, the duration of the roasting can root It is selected according to the temperature of roasting, typically 1-8 hours, preferably 1.5-6 hours.It is described roasting in air atmosphere into Row.
The second metallic element can be loaded on alumina by way of dipping.By the second gold medal by way of dipping When belonging to element load on alumina, the maceration extract oxide impregnation aluminium containing the compound containing the second metallic element can be used, it will The aluminium oxide for being adsorbed with maceration extract is dried and roasts successively, to obtain the aluminium oxide containing the second metallic element.
The compound for containing the second metallic element can be water soluble salt and/or water solubility containing the second metallic element Alkali, specific example can include but is not limited to：Nitrate, oxalates, acetate, chloride, hydroxide, carbonate, carbon One or more of sour hydrogen salt and phosphate.
In this example, conventional impregnation methods may be used in the dipping, such as saturation dipping or excessive dipping.The leaching Stain can carry out at ambient temperature.
In this example, it (can predominantly be soaked being enough to remove the volatile materials being adsorbed in the aluminium oxide of maceration extract Solvent in stain liquid) under conditions of, it is dried.Specifically, the drying can 50-300 DEG C, preferably 80-250 DEG C, more It is preferred that being carried out at a temperature of 100-200 DEG C, the drying can carry out under normal pressure (that is, 1 standard atmospheric pressure, similarly hereinafter), also may be used To be carried out under conditions of reducing pressure.The duration of the drying can carry out according to dry temperature and dry pressure Selection generally can be 1-15 hours, preferably 3-12 hours.The drying can carry out in air atmosphere.
According to the preferred embodiment, the carrier for load regulation group VIII metal element all can contain second The aluminium oxide that the aluminium oxide of metallic element can also be the aluminium oxide containing the second metallic element and be free of the second metallic element Mixture.Usually, on the basis of the total amount of carrier, the content of the aluminium oxide containing the second metallic element can be 10 weight % More than, preferably 30 weight % or more, more preferably 50 weight % or more, further preferably 70 weight % or more.It is especially excellent Selection of land is used for all aluminium oxide containing the second metallic element of carrier of load regulation group VIII metal element.
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 Salt, the molybdate of group VIII metallic element, the tungstates of group VIII metallic element and group VIII metallic element it is water-soluble One or more of property compound.The specific example of the precursor of the oxide of the group VIII metallic element can be with Including but not limited to：Ferric nitrate, ferric sulfate, ferric acetate, nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, sulfuric acid One or more of 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 80-250 DEG C, it is 100-200 DEG C more preferable at a temperature of carry out, the drying can carry out under normal pressure, can also reduce press It is carried out under conditions of power.The duration of the drying can be selected according to dry temperature and dry pressure, generally It can be 1-15 hours, preferably 4-12 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 300-700 DEG C, and the duration of the roasting can root It is selected according to the temperature of roasting, typically 1-12 hours, preferably 2-8 hours.It is described roasting in air atmosphere into Row.
The production method of synthetic oil according to the present invention in step S31, can carry out under conditions of routinely producing synthetic oil Fischer-Tropsch synthesis.Preferably, Fischer-Tropsch synthesis charging can be at 200-300 DEG C with fischer-tropsch synthetic catalyst, preferably 220- 280 DEG C, it is 250-260 DEG C more preferable at a temperature of contacted.Fischer-Tropsch synthesis charging is connect with fischer-tropsch synthetic catalyst Tactile pressure can be 0.8-3MPa, and preferably 1-2.8MPa, the pressure is in terms of gauge pressure.
The production method of synthetic oil 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 catalyst in fixed bed reactors.In fixed bed reaction In device, when hydrogen and carbon monoxide are contacted with fischer-tropsch synthetic catalyst, the volume space velocity of Fischer-Tropsch synthesis charging can be 2000-30000 hours-1, preferably 4000-20000 hours-1。
The production method of synthetic oil according to the present invention may be used conventional method and produced from F- T synthesis in step S41 Synthetic oil, 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 synthetic oil, methane and carbon dioxide.
The methane isolated from Fischer-Tropsch synthetic logistics is sent into and is walked by the production method of synthetic oil 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.Synthetic oil 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 is effectively improved raw material availability, and significantly reduce GHG carbon dioxide Discharge capacity.
The production method of synthetic oil 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 synthetic oil 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 are obtained using hydrogen and carbon monoxide as leading so that methane and carbon dioxide can carry out reforming reaction Want 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 synthetic oil Lower contact obtains the Fischer-Tropsch synthetic logistics containing synthetic oil.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 reactor for storing hydrogen, and by first gas In.The first gas is the gaseous mixture of hydrogen or hydrogen and inert gas.The first gas storing and conveying device is set It is set to and is enough to store and conveys first gas.It can instruct according to prior art first gas storing and conveying device is arranged, 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 hydrogen carries out prereduction reaction, obtain prereduction Then catalyst inputs second gas into reduction activation reactor, so that the catalyst pre-reduction is contacted with second gas, Carry out reduction reaction.Conventional control element may be used in the reducing gas control device, such as various control valves, control are sent Enter the gas type of reduction reactor and the feeding amount of gas.
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.
Synthetic oil 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.
Synthetic oil 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 synthetic oil 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 synthetic oil production system include 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 synthetic oil 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 synthetic oil K, unreacted hydrogen and carbon monoxide, methane M and carbon dioxide N.Wherein, synthetic oil 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), diesel component (C9-C18) selectivity (SDiesel component), the selectivity (S of isomery diesel oilIsomery diesel oil) and synthetic oil (that is, C5-C30Component) hydro carbons selectivityPoint It is not calculated by the following formula to obtain：
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；
nDiesel componentFor the molal quantity of the diesel component of generation；
nIsomery diesel oilFor the molal quantity of the isomery diesel oil of generation；
For the CH of generation4、C2Hydrocarbon, C3Hydrocarbon and C4The sum of molal quantity of hydrocarbon.
Preparation example 1-19 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
Five water zirconium nitrates are dissolved in 75g deionized waters, modified zirconium solution is made, 100.0g γ-are added to modified zirconium solution Al2O3(its nature parameters is listed in table 1) impregnates 2 hours in 25 DEG C of saturations.Then, the mixture that dipping obtains is placed in baking It is 5 hours dry in air atmosphere under 120 DEG C and normal pressure (1 standard atmospheric pressure, similarly hereinafter) in case.The substance being dried to obtain is existed It 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 to carry On the basis of the total amount of body, based on the element, the content of Zr is 6 weight %.
(2) preparation of catalyst precarsor
Ferric citrate is added in 17mL deionized waters, heating stirring is uniformly mixed in 50 DEG C of water-baths, is soaked Stain liquid.24g carriers are added into maceration extract, are impregnated 1 hour in environment temperature (for 25 DEG C) saturation.Then, dipping is obtained Mixture is placed in baking oven, 6 hours dry in air atmosphere under 150 DEG C and normal pressure.Substance will be dried to obtain in 420 DEG C of air It is roasted 5 hours in atmosphere, 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 2000 hours-1, the temperature of reactor is increased to 400 DEG C by 25 DEG C, and at such a temperature 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 small When-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 synthetic oil
After reduction activation, it is passed through synthesis gas, and adjusting reactor to 260 DEG C into reactor, carries out Fischer-Tropsch Synthetic reaction, wherein the volume space velocity of synthesis gas is 6000 hours-1, pressure 1.5MPa, the group of synthesis gas is as H2：CO= 50：50 (molar ratios).In reaction process, the composition progress for the admixture of gas that on-line gas chromatography exports reactor is utilized Analysis, 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 synthetic oil, unlike, in step (1), γ- Al2O3It is added in maceration extract after being roasted 2 hours in 980 DEG C.Wherein, product of roasting is subjected to X-ray diffraction analysis, determining To be θ-Al2O3, nature parameters are as shown in table 1.
Preparation example 3
Catalyst is prepared using method identical with preparation example 1 and prepares synthetic oil, unlike, without step (1), γ-Al2O3It 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 synthetic oil, unlike, without step (1), In step (2), will with five water zirconium nitrates of the weight such as 1 step of preparation example (1) together with ferric citrate for configuring maceration extract, The maceration extract for being used for impregnated carrier is dispersed with five water zirconium nitrates and ferric citrate, to obtain catalyst precarsor.
Preparation example 5
Catalyst is prepared using method identical with preparation example 1 and prepares synthetic oil, unlike, in step (3), ethane It is replaced with isometric ethylene.
Preparation example 6
Catalyst is prepared using method identical with preparation example 1 and prepares synthetic oil, 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 7
Catalyst is prepared using method identical with preparation example 1 and prepares synthetic oil, 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 8
Catalyst is prepared using method identical with preparation example 1 and prepares synthetic oil, 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 volume ratio of the gaseous mixture of CO and nitrogen is 1：1, CO and nitrogen gaseous mixture volume it is empty Speed is 2000 hours-1, maintain 4 hours.
Preparation example 9
Catalyst is prepared using method identical with preparation example 1 and prepares synthetic oil, 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 10
Catalyst is prepared using method identical with preparation example 2 and prepares synthetic oil, 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 11
Catalyst is prepared using method identical with preparation example 2 and prepares synthetic oil, 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 12
(1) preparation of carrier
Five water zirconium nitrates are dissolved in 68g deionized waters, modified zirconium solution is made, 100.0g γ-are added to modified zirconium solution Al2O3(its nature parameters is listed in table 1) impregnates 2 hours in 25 DEG C of saturations.Then, the mixture that dipping obtains is placed in baking It is 3 hours dry in air atmosphere under 200 DEG C and normal pressure in case.The substance being dried to obtain is roasted in 700 DEG C of air atmospheres 1.5 hours, obtain carrier.The carrier of preparation is subjected to X-ray fluorescence spectra analysis, is determined on the basis of the total amount of carrier, with The content of element meter, Zr is 3 weight %.
(2) preparation of catalyst precarsor
Ferric citrate is added in 15mL deionized waters, heating stirring is uniformly mixed in 50 DEG C of water-baths, is soaked Stain liquid.24g carriers are added into maceration extract, are impregnated 1 hour in environment temperature (for 25 DEG C) saturation.Then, dipping is obtained Mixture is placed in baking oven, 4 hours dry in air atmosphere under 180 DEG C and normal pressure.Substance will be dried to obtain in 700 DEG C of air It is roasted 2 hours in atmosphere, 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 2000 hours-1, the temperature of reactor is increased to 450 DEG C by 25 DEG C, and at such a temperature 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 5000 small When-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 synthetic oil
After reduction activation, it is passed through synthesis gas, and adjusting reactor to 240 DEG C into reactor, carries out Fischer-Tropsch Synthetic reaction, wherein the volume space velocity of synthesis gas is 5000 hours-1, pressure 1.5MPa, the group of synthesis gas is as H2：CO= 55：45 (molar ratios).In reaction process, the composition progress for the admixture of gas that on-line gas chromatography exports reactor is utilized Analysis, 50 hours results measured of reaction are listed in table 5.
Preparation example 13
(1) preparation of carrier
Five water zirconium nitrates and potassium nitrate are dissolved in 81g deionized waters, modified solution is made, is added to modified solution 100.0gγ-Al2O3(its nature parameters is listed in table 1) impregnates 2 hours in 25 DEG C of saturations.Then, dipping is obtained mixed Object is closed to be placed in baking oven, it is 12 hours dry in air atmosphere under 100 DEG C and normal pressure.By the substance being dried to obtain in 350 DEG C of skies It is roasted 6 hours in gas atmosphere, obtains carrier.The carrier of preparation is subjected to X-ray fluorescence spectra analysis, determines the total amount with carrier On the basis of, based on the element, the content that the content of Zr is 3 weight %, K is 3 weight %.
(2) preparation of catalyst precarsor
Ferric citrate is added in 18mL deionized waters, heating stirring is uniformly mixed in 50 DEG C of water-baths, is soaked Stain liquid.24g carriers are added into maceration extract, are impregnated 1 hour in environment temperature (for 25 DEG C) saturation.Then, dipping is obtained Mixture is placed in baking oven, 12 hours dry in air atmosphere under 100 DEG C and normal pressure.Substance will be dried to obtain in 300 DEG C of skies It is roasted 8 hours in gas atmosphere, 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 5000 hours-1, the temperature of reactor is increased to 480 DEG C by 25 DEG C, and at such a temperature Constant temperature 4 hours.Then, reactor is cooled to 260 DEG C, by hydrogen be switched to ethane and argon gas gaseous mixture (wherein, ethane with The molar ratio of argon gas is 1：20), and the volume space velocity of ethane is 8000 hours-1, after maintaining 6 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 synthetic oil
After reduction activation, it is passed through synthesis gas, and adjusting reactor to 260 DEG C into reactor, carries out Fischer-Tropsch Synthetic reaction, wherein the volume space velocity of synthesis gas is 5000 hours-1, pressure 1MPa, the group of synthesis gas is as H2：CO=60： 40 (molar ratios).In reaction process, the composition of the admixture of gas exported to reactor using on-line gas chromatography is divided Analysis, 50 hours results measured of reaction are listed in table 5.
Preparation example 14
Catalyst is prepared using method identical with preparation example 13 and prepares synthetic oil, unlike, step does not make in (1) With five water zirconium nitrates.
Preparation example 15
Catalyst is prepared using method identical with preparation example 13 and prepares synthetic oil, unlike, step does not make in (1) Use potassium nitrate.
Preparation example 16
(1) preparation of carrier
Five water zirconium nitrates and magnesium nitrate are dissolved in 81g deionized waters, modified solution is made, is added to modified solution 100.0gγ-Al2O3(with embodiment 6) impregnates 2 hours in 25 DEG C of saturations.Then, the mixture that dipping obtains is placed in baking oven In, it is 5 hours dry in air atmosphere under 120 DEG C and normal pressure.The substance being dried to obtain is roasted 3 in 460 DEG C of air atmospheres Hour, obtain carrier.The carrier of preparation is subjected to X-ray fluorescence spectra analysis, is determined on the basis of the total amount of carrier, with element Meter, the content that the content of Zr is 3 weight %, Mg is 3 weight %.
(2) preparation of catalyst precarsor
Ferric citrate is added in 18mL deionized waters, heating stirring is uniformly mixed in 50 DEG C of water-baths, is soaked Stain liquid.24g carriers are added into maceration extract, are impregnated 1 hour in environment temperature (for 25 DEG C) saturation.Then, dipping is obtained Mixture is placed in baking oven, 5 hours dry in air atmosphere under 120 DEG C and normal pressure.Substance will be dried to obtain in 400 DEG C of air It is roasted 5 hours in atmosphere, 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 10：1), adjustment reactor pressure is 0.15MPa, and the volume space velocity of hydrogen is 6000 hours-1, will The temperature of reactor is increased to 350 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 the gaseous mixture of ethane and argon gas, and (wherein, the molar ratio of ethane and argon gas is 1：, and the volume of ethane 10) Air speed is 4000 hours-1, after maintaining 6 hours, fischer-tropsch synthetic catalyst is obtained, the composition of the catalyst shows in table 2 and table 4 Go out, CO2- TPD and CO-TPD test results are listed in table 3.
(4) preparation of synthetic oil
After reduction activation, it is passed through synthesis gas, and adjusting reactor to 260 DEG C into reactor, carries out Fischer-Tropsch Synthetic reaction, wherein the volume space velocity of synthesis gas is 5000 hours-1, pressure 1.5MPa, the group of synthesis gas is as H2：CO= 50：50 (molar ratios).In reaction process, the composition progress for the admixture of gas that on-line gas chromatography exports reactor is utilized Analysis, 50 hours results measured of reaction are listed in table 5.
Preparation example 17
Catalyst is prepared using method identical with preparation example 16 and prepares synthetic oil, unlike, step does not make in (1) With five water zirconium nitrates.
Preparation example 18
Catalyst is prepared using method identical with preparation example 16 and prepares synthetic oil, unlike, step does not make in (1) Use magnesium nitrate.
Preparation example 19
(1) preparation of carrier
Carrier is prepared using method identical with preparation example 1.
(2) preparation of catalyst precarsor
Cabaltous nitrate hexahydrate is added in 18mL deionized waters, heating stirring is uniformly mixed in 50 DEG C of water-baths, is obtained Maceration extract.24g carriers are added into maceration extract, are impregnated 1 hour in environment temperature (for 25 DEG C) saturation.Then, dipping is obtained Mixture be placed in baking oven, under 120 DEG C and normal pressure dry 5 hours in air atmosphere.Substance will be dried to obtain in 400 DEG C of skies It is roasted 3 hours in gas atmosphere, obtains catalyst precarsor.
(3) reduction activation of catalyst precarsor
The catalyst precarsor reduction activation for being prepared step (2) using method same as Example 1, to F- T synthesis The composition of catalyst, the catalyst shows in table 2 and table 4, CO2- TPD and CO-TPD test results are listed in table 3.
(4) preparation of synthetic oil
After reduction activation, it is passed through synthesis gas, and adjusting reactor to 280 DEG C into reactor, carries out Fischer-Tropsch Synthetic reaction, wherein the volume space velocity of synthesis gas is 1000 hours-1, pressure 5MPa, the group of synthesis gas is as H2：CO=40： 60 (molar ratios).In reaction process, the composition of the admixture of gas exported to reactor using on-line gas chromatography is divided Analysis, 50 hours results measured of reaction are listed in table 5.
Table 1
Table 2 (on the basis of the total amount of catalyst)
Number Group VIII metallic element/content (wt%) Second metallic element/content (wt%) Alumina type
Preparation example 1 Fe/8 Zr/5.5 γ-Al2O3
Preparation example 2 Fe/8 Zr/5.5 θ-Al2O3
Preparation example 3 Fe/8 Nothing γ-Al2O3
Preparation example 4 Fe/8 Zr/5.5 γ-Al2O3
Preparation example 5 Fe/8 Zr/5.5 γ-Al2O3
Preparation example 6 Fe/8 Zr/5.5 γ-Al2O3
Preparation example 7 Fe/8 Zr/5.5 γ-Al2O3
Preparation example 8 Fe/8 Zr/5.5 γ-Al2O3
Preparation example 9 Fe/8 Zr/5.5 γ-Al2O3
Preparation example 10 Fe/8 Zr/5.5 θ-Al2O3
Preparation example 11 Fe/8 Zr/5.5 θ-Al2O3
Preparation example 12 Fe/11 Zr/2.7 γ-Al2O3
Preparation example 13 Fe/12 Zr/2.6+K/2.6 γ-Al2O3
Preparation example 14 Fe/12 K/2.6 γ-Al2O3
Preparation example 15 Fe/12 Zr/2.6 γ-Al2O3
Preparation example 16 Fe/13 Zr/2.6+Mg/2.6 γ-Al2O3
Preparation example 17 Fe/13 Mg/2.6 γ-Al2O3
Preparation example 18 Fe/13 Zr/2.6 γ-Al2O3
Preparation example 19 Co/11 Zr/5.3 γ-Al2O3
Table 3
Table 4
1：Fe is not detected5C2 2：FeO and Fe is not detected5C2
Table 5
1：Diesel component includes n-alkane, isoparaffin and alkene, and isomery diesel oil refers to the isomeric alkane in diesel component Hydrocarbon.
Preparation example 1 and preparation example 6-9 and preparation example 2 are compared with preparation example 10 and 11 as can be seen that will catalysis After agent precursor carries out prereduction with hydrogen, then at a temperature of the reduction activation it is that gaseous hydrocarbon carries out reduction activation, can obviously carries The catalytic activity of high finally formed reduction activation catalyst, can be significantly improved for diesel component, particularly isomery diesel oil Selectivity.Preparation example 1 and preparation example 2 are compared as can be seen that using θ-Al2O3F- T synthesis catalysis can be significantly improved The catalytic activity of agent.
Embodiment 1-6 is used to illustrate the synthesis oil producing method and production system of the present invention.
Embodiment 1
The present embodiment use Fig. 2 shows synthetic oil 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 15 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 After conjunction, it is 600 DEG C that the temperature of mixture, which is increased, subsequently into the fixed bed reactors of dry reforming reaction member III, is carried out Reforming reaction obtains dry reforming synthesis gas F.Wherein, the molar ratio of methane and carbon dioxide is 1：1, that loads in reactor urges Agent 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, in terms of the total amount of methane and vapor, 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 250 DEG C to answer temperature in device, and the pressure in reactor is 2.0MPa, on the basis of the total amount of synthesis gas, volume space velocity when gas For 4000h-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 synthetic oil 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 synthetic oil 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 synthetic oil 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 be 2：1, then through synthesis gas clean unit IV removing sour gas and sulfide, it is purified synthesis gas, wherein hydrogen and an oxidation The molar ratio of carbon is 2.1：1.Obtained decontaminating syngas is conveyed into F- T synthesis unit V and is carried out in fixed bed reactors Fischer-Tropsch synthesis (catalyst prepared using preparation example 1), generates the fischer-tropsch reaction product N of olefin-containing.Wherein, in reactor Temperature be 250 DEG C, pressure in reactor is 2.0MPa, and on the basis of the total amount of synthesis gas, volume space velocity is when gas 4000h-1.Fischer-tropsch reaction product N isolates synthetic oil K, the titanium dioxide that F- T synthesis unit V is generated through synthesizing oil separation unit VI Carbon H and methane G is then outer to be arranged, and (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.
Comparative example 2
Synthetic oil 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
Synthetic oil 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
Synthetic oil is prepared using method same as Example 1, unlike, the fischer-tropsch synthetic catalyst used is preparation Fischer-tropsch synthetic catalyst prepared by example 3.
Embodiment 3
Synthetic oil is prepared using method same as Example 1, unlike, the fischer-tropsch synthetic catalyst used is preparation Fischer-tropsch synthetic catalyst prepared by example 6.
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 850 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 After conjunction, it is 600 DEG C that the temperature of mixture, which is increased, subsequently into the fixed bed reactors of dry reforming reaction member III, is carried out Reforming reaction obtains dry reforming synthesis gas F.Wherein, the molar ratio of methane and carbon dioxide is 1：1.5, it loads in reactor Catalyst is Ni/Al2O3(on the basis of the total amount of catalyst, based on the element, the content of Ni is 15 weight %, Al2O3For α- Al2O3), the temperature in catalyst bed is 700 DEG C, and the pressure in reactor is 2MPa, in terms of the total amount of methane and 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 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 12), carry out F- T synthesis Reaction.Wherein, the temperature in reactor is 260 DEG C, and the pressure in reactor is 2.5MPa, 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 synthetic oil 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 synthetic oil 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 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 1：1, 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 12 weight %, Al2O3 For α-Al2O3), the temperature in catalyst bed is 900 DEG C, and the pressure in reactor is 1MPa, with the total amount of methane and vapor Meter, 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 After conjunction, it is 700 DEG C that the temperature of mixture, which is increased, subsequently into the fixed bed reactors of dry reforming reaction member III, is carried out Reforming reaction obtains dry reforming synthesis gas F.Wherein, the molar ratio of methane and carbon dioxide is 1：1, that loads in reactor urges Agent is Ni/Al2O3(on the basis of the total amount of catalyst, based on the element, the content of Ni is 12 weight %, Al2O3For α- Al2O3), the temperature in catalyst bed is 750 DEG C, and the pressure in reactor is 2MPa, in terms of the total amount of methane and 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 13), carry out F- T synthesis Reaction.Wherein, the temperature in reactor is 240 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 synthetic oil 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 synthetic oil 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
Synthetic oil 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 16, and the temperature in Fischer-Tropsch synthesis device is 240 DEG C, 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。
Table 7
1：Diesel component includes n-alkane, isoparaffin and alkene, and isomery diesel oil refers to the isomeric alkane in diesel component Hydrocarbon calculates isomery diesel oil selectivity on the basis of the total amount of diesel component.
Table 8
Water consume (ton/tonSynthetic oil) CO2 emission (ton/tonSynthetic oil) Energy efficiency (%)
Embodiment 1 12 0.7 59
Comparative example 1 22 6.4 35
Comparative example 2 18 2.5 35
Comparative example 3 25 0.7 43
Embodiment 4 15 1.1 51
Embodiment 5 14 1.0 55
Embodiment 6 13 0.9 53
Note：The calorific value of the synthetic oil 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 synthetic oil/produce comprehensive energy consumption needed for these synthetic oils.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.
Embodiment 1 and comparative example 1 are compared as can be seen that the present invention by combine methane vapor reforming technique and Methane dry reforming technique is used simultaneously to carbon dioxide and methane both greenhouse gases, is allowed to be changed into high attached Value added product, reduces greenhouse gas emission, 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 (31)

1. a kind of production method of synthetic oil, 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 synthetic oil with fischer-tropsch synthetic catalyst, Obtain Fischer-Tropsch synthetic logistics；
S41, synthetic oil, 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 synthetic oil is 200-300 DEG C, preferably 220-280 DEG C；
Preferably, in S31, the contact carries out in fixed bed reactors, Fischer-Tropsch synthesis charging gas when volume space velocity Preferably 2000-30000 hours-1, more preferably 4000-20000 hours-1；
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 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 and the second metallic element on carrier are stated, first metallic element is selected from group VIII metal member One or more of element, preferably one or more of Fe, Co and Ni, more preferably Fe, second gold medal Belong to element be one kind in group ivb metallic element, optional alkali metal element and optional alkali earth metal or Two or more, the carrier is aluminium oxide, and at least partly the valence state of group VIII metallic element is most less than the metallic element High oxidation valence state.
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- There are CO in 500 DEG C, preferably 320-400 DEG C of temperature range2Elevated temperature desorption peak；
Preferably, the CO of the fischer-tropsch synthetic catalyst2- TPD is desorbed in spectrogram, in 100-200 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 spectrograms of the fischer-tropsch synthetic catalyst, at 300-600 DEG C, preferably 400-500 DEG C There are CO elevated temperature desorptions peaks in temperature range；
It is further preferred that in the CO-TPD desorption spectrograms of the fischer-tropsch synthetic catalyst, at 100-200 DEG C, preferably 160-180 DEG C temperature range in there is also CO low temperature desorption peaks.
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 8-20：1, preferably 10-15：1；
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 30% or more, preferably 60% or more.
8. according to the method described in any one of claim 5-7, wherein with group VIII metal in fischer-tropsch synthetic catalyst On the basis of the total amount of element, based on the element, valence state is that the content of the group VIII metallic element less than its highest oxidation valence state is 30% or more, preferably 60% or more.
9. according to the method described in any one of claim 5-8, wherein the group ivb metallic element be Zr and/or Ti；
Preferably, the alkali metal element is one or more of Li, Na and K, preferably Li and/or K；
Preferably, the alkali earth metal is Mg and/or Ca, preferably Mg；
It is further preferred that second metallic element is for group ivb metallic element and selected from alkali metal element and alkaline earth gold Belong to one or more of element.
10. according to the method described in any one of claim 5-9, wherein on the basis of the total amount of fischer-tropsch synthetic catalyst, Based on the element, the content of second metallic element is 0.5-10 weight %, preferably 1-8 weight %, more preferably 2-6 weight Measure %.
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 6-20 weight %, more preferably 8-15 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 and the second metallic element, first metallic element are one kind in group VIII metallic element Or two or more, preferably one or more of Fe, Co and Ni, more preferably Fe, first metallic element is with oxygen On the carrier, the valence state of the group VIII metallic element in the oxide is the metallic element for the form load of compound Highest oxidation valence state, the carrier are aluminium oxide, and second metallic element is selected from group ivb metallic element, optional alkali One or more of metallic element and optional alkali earth metal；
(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 300-500 DEG C；
In terms of hydrogen, the volume space velocity of the first gas is 1000-20000 hours-1, preferably 2000-10000 hours-1；
Preferably, 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 highly preferred that the duration of the prereduction is 1-20 hours, preferably 4-10 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 10-30：1.
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 180-450 DEG C, it is excellent Select 200-400 DEG C, it is 200-300 DEG C more preferable at a temperature of carry out；
Preferably, to be in terms of gaseous hydrocarbon at a temperature of reduction activation, the volume space velocity of the second gas is 1000-10000 Hour-1, preferably 2000-8000 hours-1；
Preferably, in terms of gauge pressure, the pressure in the reactor is 0-3MPa, preferably 0.1-1MPa；
It is highly preferred that the duration of the reduction activation is 1-20 hours, preferably 2-8 hours, more preferably 4-6 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 6-20 weight %, more preferably 8-15 weight Measure %.
19. according to the method described in any one of claim 12-18, wherein the group ivb metallic element be Zr and/ Or Ti；
Preferably, the alkali metal element is one or more of Li, Na and K, preferably Li and/or K；
Preferably, the alkali earth metal is Mg and/or Ca, preferably Mg；
It is further preferred that second metallic element is for group ivb metallic element and selected from alkali metal element and alkaline earth gold Belong to one or more of element；
Preferably, on the basis of the total amount of catalyst precarsor, based on the element, the content of second metallic element is 0.5-10 weights Measure %, preferably 1-8 weight %, more preferably 2-6 weight %.
20. according to the method described in any one of claim 12-19, 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 the second metallic element roasted, obtain catalyst precarsor, the carrier is oxygen Change aluminium；
Preferably, oxide and group VIII metallic element of second metallic element prior to the group VIII metallic element The precursor of oxide be loaded on carrier；
Preferably, the roasting carries out at a temperature of 300-900 DEG C, and the duration of the roasting is preferably 1-12 hours.
21. according to the method for claim 20, wherein include by the method for the second metallic element load on alumina： There is the compound oxidation aluminium containing the second metallic element to roast load, the roasting is preferably at a temperature of 300-900 DEG C It carries out, the duration of the roasting is preferably 1-8 hours.
22. 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.
23. 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.
24. according to the method described in any one of claim 1,22 and 23, wherein adopted in the methane and S21 that are used in S11 The weight ratio of methane is 1：0.5-2.5.
25. a kind of synthetic oil 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 synthetic oil, obtains the Fischer-Tropsch synthetic logistics containing synthetic oil；
The Fischer-Tropsch synthesis product separative element for the Fischer-Tropsch synthetic logistics to be detached, obtain methane, Carbon dioxide, synthetic oil, 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.
26. system according to claim 25, 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.
27. the system according to claim 25 or 26, 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.
28. system according to claim 27, 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 activation Reaction.
29. system according to claim 28, 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.
30. the system according to claim 28 or 29, 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.
31. according to the system described in any one of claim 25-30, wherein the Fischer-Tropsch synthesis device is fixed bed Reactor.
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