CN105622309B - A kind of method for producing low-carbon alkene - Google Patents
A kind of method for producing low-carbon alkene Download PDFInfo
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Abstract
The invention provides a kind of method for producing low-carbon alkene, this method comprises the following steps：(1) liquefied petroleum gas is isolated from the gas-phase product of Fischer-Tropsch synthesis；(2) liquefied petroleum gas is subjected to hydrogenation reaction so that the alkene in the liquefied petroleum gas is changed into alkane substantially, obtains hydrogenation products；(3) hydrogenation products are subjected to steam cracking reaction.Higher low-carbon alkene total recovery can be obtained using method provided by the invention.
Description
Technical field
The present invention relates to a kind of method for producing low-carbon alkene.
Background technology
Low-carbon alkene mainly includes ethene, propylene, butadiene, is most important basic organic chemical raw material.Ethene can use
In production polyethylene from high pressure process, low-pressure polyethylene, LLDPE, polyvinyl chloride, oxirane, ethylene glycol, ethanol, benzene
The products such as ethene, acetaldehyde, acetic acid, alpha-olefin, polyvinyl alcohol, EP rubbers.Propylene can be used for production polypropylene, acrylonitrile, benzene
The product such as phenol, acetone, butanol, octanol, isopropanol, acrylic acid and its lipid, expoxy propane, epoxychloropropane, polypropylene fibre.Butadiene
Available for production butadiene rubber, butadiene-styrene rubber, butyl rubber, neoprene, polybutadiene, SBS resins, ABS resin etc..With low
Carbon olefin is that the product of raw material production has been widely used in the every field of national economy, can promote and promote national economy
Development.
At present, the ethene in China 98% is produced with steam cracking process.Propylene is mainly by steam cracking process, oil refining work
Skill, MTO (MTP), dehydrogenating propane technique productions, wherein more than 50% propylene is mainly by steam cracking process production.Fourth
Diene is mainly by steam cracking process and butylene oxidation-dehydrogenation technique productions, wherein more than 92% butadiene is by steam cracking
Technique productions.Steam cracking process produce ethene while, can by-product propylene, butylene, butadiene, aromatic hydrocarbons (benzene, toluene,
Dimethylbenzene), turn into the main source of petro chemical industry basic material.Therefore, ethylene industry is to weigh a countries and regions
The horizontal mark of petrochemical industry.
The raw material of steam cracking process is essentially from petroleum resources, and China's petroleum resources is few, and crude oil relies on import, every year
The crude oil of import is more than half of demand.In recent years, the emergence with Middle East ethylene industry and the big rule of North America shale gas
It is honest and clean to occupy raw material based on cheap ethane and propane in international competition for the ethylene industry of the exploitation of mould, the Middle East and North America
The advantage of valency, huge impact certainly will be caused to China's ethene and propylene industry.Rich coal resources in China, sent out by coal and water
Raw water gas reaction generation carbon monoxide and hydrogen, carbon monoxide and hydrogen by different catalytic reactions can generate methanol,
Acetic acid, gasoline, diesel oil, liquefied petroleum gas (abbreviation LPG), naphtha, day hot gas, wax etc., especially China is based on coal chemical industry
Methanol-to-olefins (MTO) and the booming competition for exacerbating propylene industry of preparing propylene from methanol (MTP) industry, are made indirectly with coal
Oil tech (F- T synthesis technology) has obtained commercial Application in the company such as Shanxi coalification institute of the Chinese Academy of Sciences of China and South Africa Sha Suo, obtains
Preferable economic benefit.And produced by main resource of lighter hydrocarbons or coal the product of low-carbon alkene mainly using ethene or propylene as
It is main, without producing butadiene and aromatic hydrocarbons.The domestic needs to low-carbon alkene are huge at present, how to overcome and prepared using steam cracking
The coal resources production low-carbon alkene that the defects of petroleum resources is in short supply in the technique of low-carbon alkene and utilization are enriched is that China is current
The problem of in the urgent need to address.
The content of the invention
The invention aims to overcome to use existing steam cracking process to need with oil gas when preparing low-carbon alkene
The defects of resource is cracking stock, scarcity of resources, and provide it is a kind of not using petroleum resources as initiation material and can obtain compared with
The method of the production low-carbon alkene of high yield of light olefins.
The invention provides a kind of method for producing low-carbon alkene, this method comprises the following steps：
(1) liquefied petroleum gas is isolated from the gas-phase product of Fischer-Tropsch synthesis；
(2) liquefied petroleum gas is subjected to hydrogenation reaction so that the alkene in the liquefied petroleum gas is changed into substantially
Alkane, obtain hydrogenation products；
(3) hydrogenation products are subjected to steam cracking reaction.
Fischer-Tropsch synthesis is dexterously combined by the present invention with steam cracking reaction, and is introduced and carried out liquefied petroleum gas
The step of hydrogenation reaction, it is achieved thereby that (can not be former by starting of abundant coal resources by initiation material of petroleum resources
Material) and the purpose of higher yield of light olefins can be obtained, opened up a new way for production low-carbon alkene.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The method of production low-carbon alkene provided by the invention comprises the following steps：
(1) liquefied petroleum gas is isolated from the gas-phase product of Fischer-Tropsch synthesis；
(2) liquefied petroleum gas is subjected to hydrogenation reaction so that the alkene in the liquefied petroleum gas is changed into substantially
Alkane, obtain hydrogenation products；
(3) hydrogenation products are subjected to steam cracking reaction.
In the present invention, described " alkene is changed into alkane substantially " refers to that at least 95 weight % above alkene are changed into alkane
Hydrocarbon.
As a rule, it is gentle to include solid product, oil-phase product, water-phase product for the reaction product of the Fischer-Tropsch synthesis
Phase product.The component of the liquefied petroleum gas is known to the skilled person, and in the present invention, the liquefied petroleum gas refers to
CO, H are removed from the gas-phase product of the Fischer-Tropsch synthesis2、CO2With remaining product after methane.In actual mechanical process
In, the method that the method for liquefied petroleum gas is isolated from the gas-phase product of Fischer-Tropsch synthesis to use this area conventional is entered
OK, refined for example, the gas-phase product of the Fischer-Tropsch synthesis can be passed through in existing various domethanizing columns, it is described
The concrete structure and purification condition of domethanizing column are known to the skilled person, and therefore not to repeat here.
The Fischer-Tropsch synthesis usually requires to carry out in the presence of fischer-tropsch synthetic catalyst, the F- T synthesis catalysis
The species of agent can be the conventional selection of this area, for example, the fischer-tropsch synthetic catalyst includes first vector and is supported on
The first active component in the first vector, first active component are VIII group 4 transition metal component, the first vector
One or more in metal oxide, molecular sieve and carbon material.In addition, the gross weight with the fischer-tropsch synthetic catalyst
On the basis of, the content of the first vector can be 65-92 weight %, preferably 75-90 weight %；Described in terms of oxide
The content of first active component can be 8-35 weight %, preferably 10-25 weight %.
Specifically, the example of the VIII group 4 transition metal component includes but is not limited to：Iron (Fe), cobalt (Co), nickel (Ni), ruthenium
(Ru), rhodium (Rh), palladium (Pd), platinum (Pt) etc., particularly preferably cobalt (Co), the liquefied petroleum gas so enabled to are more applicable
In production low-carbon alkene, so as to obtain higher yield of light olefins.In addition, the first active component (i.e. VIII race transition gold
Belong to component) exist generally in the form of its oxide.
In the fischer-tropsch synthetic catalyst carrier, the example of the metal oxide includes but is not limited to：Aluminum oxide, oxygen
One or more in SiClx, titanium oxide etc..The example of the molecular sieve includes but is not limited to：One kind in ZSM, MCM etc. or
It is a variety of.The example of the carbon material includes but is not limited to：In activated carbon, CNT, carbon nano-fiber, mesoporous carbon molecular sieve etc.
One or more.
In addition, rare-earth additive can also be contained in the fischer-tropsch synthetic catalyst.The rare-earth additive is described in preparation
Formed during fischer-tropsch synthetic catalyst by additionally adding rare earth chloride.In the fischer-tropsch synthetic catalyst, institute
Rare-earth additive is stated generally with rare earth oxide (RE2O3) form exist.Using the butt weight of the fischer-tropsch synthetic catalyst as base
Standard, the content of the rare-earth additive in terms of rare earth element can be 0.5-5 weight %.Wherein, it is dilute in the rare-earth additive
Earth elements refer to the various conventional rare earth elements being related in fischer-tropsch synthetic catalyst field, for example, can be lanthanum, cerium, praseodymium, neodymium,
One or more in promethium, samarium, europium etc..
The fischer-tropsch synthetic catalyst can be prepared according to well known to a person skilled in the art various methods, for example,
It can be prepared using infusion process.Specifically, by the first vector be immersed in the compound containing the first active component with
And in solution of the selectivity containing rare earth chloride, then it is dried and is calcined again.Wherein, the chemical combination of first active component
The species for the first active component that thing should obtain as needed is selected, as described above, first active component is VIII
Group 4 transition metal component, it is chosen in particular from iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt) etc.
One or more, therefore, correspondingly, the compound of first active component is selected from iron containing compoundses, cobalt compound, nickeliferous
Compound, containing the one or more in ruthenium compound, rhodium-containing compound, containing palladium compound, compound containing platinum etc..Specifically, institute
It can be ferric nitrate and/or ferric sulfate to state iron containing compoundses.The cobalt compound can be cobalt nitrate and/or cobaltous sulfate.Institute
It can be the one or more in basic nickel carbonate, nickel nitrate, nickel sulfate etc. to state nickel compound containing.It is described can be with containing ruthenium compound
For nitric acid ruthenium and/or ruthenium sulfate.The rhodium-containing compound can be rhodium nitrate and/or rhodium sulfate.The containing palladium compound can be with
For palladium nitrate and/or palladium sulfate.The compound containing platinum can be platinum nitrate and/or cyclohexyl diamine platinic sulfate.It is in addition, described
The compound of first active component and the dosage of first vector are so that first vector in obtained fischer-tropsch synthetic catalyst to be contained
Amount controls in 65-92 weight %, is preferably controlled in 75-90 weight %, the content of first active component in terms of oxide
Control in 8-35 weight %, be preferably controlled in 10-25 weight % and be defined, therefore not to repeat here.
The present invention is not particularly limited to the condition dried described in fischer-tropsch synthetic catalyst preparation process, as long as will
The solvent being attached to after dipping on carrier removes, and as a rule, the condition of the drying includes：Drying temperature can be with
For 45-160 DEG C, preferably 65-120 DEG C；Drying time can be 2-40 hours, preferably 3-24 hours.
The present invention is not particularly limited to the condition being calcined described in fischer-tropsch synthetic catalyst preparation process, as long as will
The compound of first active component is converted into corresponding oxide, and as a rule, the condition of the roasting includes：Roasting
It can be 300-550 DEG C, preferably 350-480 DEG C to burn temperature；Roasting time can be 1-20 hours, preferably 2-12 hours.
The present invention is not particularly limited to the condition of the Fischer-Tropsch synthesis, it is preferable that the Fischer-Tropsch synthesis
Condition include：Temperature is 200-450 DEG C, pressure 1-15MPa, and volume space velocity is 500-1500h during the gas of raw material-1, hydrogen
Volume ratio with carbon monoxide is 0.5-2.5：1；It is highly preferred that the condition of the Fischer-Tropsch synthesis includes：Temperature is 200-
300 DEG C, pressure 2-8MPa, volume space velocity is 800-1500h during the gas of raw material-1, the volume ratio of hydrogen and carbon monoxide is
1.5-2.5：1, the liquefied petroleum gas so enabled to is more suitable for producing low-carbon alkene, so as to obtain higher low-carbon alkene
The total recovery of hydrocarbon.In the present invention, volume space velocity refers to that the catalyst of unit volume handles phase feed per hour during the gas
Volume.The pressure refers both to gauge pressure.
Alkene is usually contained in the liquefied petroleum gas separated from the gas-phase product of Fischer-Tropsch synthesis, when this is contained into alkene
When the liquefied petroleum gas of hydrocarbon is directly used in steam cracking reaction, tube cracking furnace convection section meeting coking, particularly when the liquefaction
When the content of alkene is more than 2 weight % in oil gas, convection section coking is more serious, so as to influence the normal life of tube cracking furnace
Production operation.Therefore, it is necessary to which liquefied petroleum gas is first carried out into hydrogenation reaction before steam cracking reaction.
According to the method for production low-carbon alkene provided by the invention, in the hydrogenation products, the content of n-alkane is preferably extremely
It is 90 weight %, more preferably at least 95 weight % less.Because for each component in cracking stock, n-alkane is production
The high-quality cracking stock of low-carbon alkene, the content of n-alkane is higher in the cracking stock, and the total recovery of low-carbon alkene is got over
Height, conversely, the content of n-alkane is lower in the cracking stock, the total recovery of low-carbon alkene is lower, therefore, controls Fischer-Tropsch
The content of n-alkane controls within the above range in the hydrogenation products that the condition of synthetic reaction and hydrogenation reaction makes to obtain, can
Obtain the total recovery of higher low-carbon alkene.
The hydrogenation reaction usually requires to carry out in the presence of hydrogenation catalyst, and the species of the hydrogenation catalyst can be with
For the conventional selection of this area, for example, the hydrogenation catalyst includes Second support and be supported on the Second support the
Two active components, the Second support are heat-resistant inorganic oxide and/or molecular sieve, and second active component contains VIII
Race's metal component and/or the VIIth B races metal component.In addition, on the basis of the gross weight of the hydrogenation catalyst, described second carries
The content of body can be 20-99.8 weight %, more preferably preferably 80-99.5 weight %, 98-99.5 weight %；With oxidation
The content of second active component of thing meter can be 0.2-80 weight %, preferably 0.5-20 weight %, be more preferably
0.5-2 weight %.Specifically, the example of VIII race metal component includes but is not limited to：Iron (Fe), cobalt (Co), nickel (Ni), ruthenium
(Ru), rhodium (Rh), palladium (Pd), platinum (Pt) etc..VIIth B races metal component is particularly preferably manganese (Mn).The group VIII
Metal component and/or the VIIth B races metal component exist generally in the form of its oxide.
In the hydrogenation catalyst, it is preferable that second active component generally includes main active component and helps activity
Component, wherein, the main active component is platinum and/or palladium, it is described help active component be in copper, silver, lead, nickel, cobalt and manganese extremely
Few one kind.Preferably, weight ratio of the main active component in terms of oxide with helping active component described in terms of oxide
For 1-16：1, most preferably 2-9：1.
In the hydrogenation catalyst, the heat-resistant inorganic oxide can be in aluminum oxide, silica, titanium oxide etc.
It is one or more.The molecular sieve can be ZSM and/or MCM.
The hydrogenation catalyst can be prepared according to well known to a person skilled in the art various methods, for example, can be with
It is prepared using infusion process.Specifically, Second support is immersed in the solution of the compound containing the second component, Ran Houjin
Row is dried and roasting.Wherein, the kind for the second active component that the compound of second active component should obtain as needed
Class is selected, as described above, second active component includes main active component and helps active component, the main active component
It is described to help active component as the one or more in copper, silver, lead, nickel, cobalt and manganese for platinum and/or palladium.Therefore, correspondingly, it is described
The compound of second active component includes the compound of main active component and helps the compound of active component.The main active component
Compound be compound containing platinum and/or containing palladium compound.Wherein, the compound containing platinum can be platinum nitrate and/or hexamethylene
Base diamines platinic sulfate.The containing palladium compound can be palladium nitrate and/or palladium sulfate.The compound for helping active component can be with
For copper-containing compound, Ag-containing compound, lead-containing compounds, nickel compound containing, cobalt compound and containing one kind in manganese compound
It is or a variety of.Wherein, the copper-containing compound can be copper nitrate and/or copper sulphate.The Ag-containing compound can be silver nitrate.
The lead-containing compounds can be plumbi nitras and/or ceruse.The nickel compound containing can be nickel nitrate and/or nickel sulfate.
The cobalt compound can be cobalt nitrate and/or cobaltous sulfate.The manganese compound that contains can be potassium permanganate, manganese nitrate, alkali
One or more in formula manganese carbonate etc..In addition, in actual fabrication process, Second support can be impregnated at the same time containing master
The compound of active component and help in the solution of compound of active component, be then dried and be calcined again；Can also first by
Second support is immersed in the solution of the compound containing main active component, is then dried and is calcined, afterwards again will load
The Second support for having main active component is immersed in the solution containing the compound for helping active component, is then dried and is roasted again
Burn；First Second support can also be immersed in the solution containing the compound for helping active component, then be dried and be calcined,
The Second support that load is helped to active component again afterwards is immersed in the solution of the compound containing main active component, Ran Houzai
It is dried and is calcined.
In addition, in the preparation process of the hydrogenation catalyst, the dosage of each material is with by obtained hydrogenation catalyst
The content control of Second support in 20-99.8 weight %, be preferably controlled in 80-99.5 weight %, more preferably control in 98-99.5
Weight %, the content of second active component in terms of oxide control in 0.2-80 weight %, are preferably controlled in 5-20 weights
Amount %, more preferably control and be defined in 0.5-2 weight %.In addition, change of the compound of the main active component with helping active component
The dosage of compound preferably so as to hydrogenation catalyst in, the main active component in terms of oxide and the institute in terms of oxide
It is 1-16 to state and help the weight ratio of active component：1, most preferably 2-9：1.
The present invention is not particularly limited to the condition dried described in hydrogenation catalyst preparation process, as long as will be through leaching
The solvent being attached to after stain on carrier removes, and as a rule, the condition of the drying includes：Drying temperature can be
45-160 DEG C, preferably 65-120 DEG C；Drying time can be 2-40 hours, preferably 4-24 hours.
The present invention is not particularly limited to the condition being calcined described in hydrogenation catalyst preparation process, as long as by described in
The compound of second active component is converted into corresponding oxide, and as a rule, the condition of the roasting includes：Roasting temperature
Degree can be 300-550 DEG C, preferably 350-480 DEG C；Roasting time can be 1-20 hours, preferably 2-12 hours.
The hydrogenation reaction is generally carried out in hydrogenation reaction device.The condition of the hydrogenation reaction can be this area
Conventional selection, it is preferable that the condition of the hydrogenation reaction includes：The inlet temperature of hydrogenation reaction device is 50-250 DEG C, reaction
Pressure is 0.1-6MPa, and volume space velocity is 0.5-30h during the liquid of raw material-1, mole of hydrogen and alkene in the liquefied petroleum gas
Than for 1-20：1；It is highly preferred that the condition of the hydrogenation reaction includes：The inlet temperature of hydrogenation reaction device is 60-230 DEG C,
Reaction pressure is 0.5-3MPa, and volume space velocity is 15-25h during the liquid of raw material-1, hydrogen rubs with alkene in the liquefied petroleum gas
Your ratio is 1-5：1, can be more effectively so alkane by the Olefin conversion in the liquefied petroleum gas, and improve n-alkane
Content, so as to obtain higher yield of light olefins.In the present invention, volume space velocity refers to urging for unit volume during the liquid
Agent handles the volume of liquid phase feed per hour.
According to the method for production low-carbon alkene provided by the invention, the separation of the steam cracking reaction and pyrolysis product exists
Carried out in cracker.The cracker includes pyrolysis furnace and separator.The pyrolysis furnace can be that this area routinely makes
The pyrolysis furnace of steam cracking producing light olefins.The pyrolysis furnace generally mainly include convection section, radiant section, quenching boiler and
Gas burning system.In the pyrolysis furnace, the hydrogenation products are heated to high temperature in pyrolysis furnace and steam cracking reaction life occur
Into the cracking gas (pyrolysis product) rich in low-carbon alkene.Preferably, the pyrolysis furnace is tube cracking furnace.The tube cracking furnace
Including convection section, radiant section, quenching boiler and gas burning system, cracking stock enters radiant section in convection section；In radiant section,
Cracking stock generates the cracking gas containing low-carbon alkene with being steam heated to generation steam cracking reaction；Cracking gas is from radiant section
Enter quenching boiler after out, in quenching boiler, cracking gas is cooled to 300-600 DEG C, so that cracking gas does not crack
Reaction, while reclaim heat；Fuel system is used to provide heat to steam cracking reaction process.The separator is used to split
Vent one's spleen and be separated into the hydrocarbon of different carbon numbers.Cracking gas forms Organic Chemicals by the separation and purification of separator and other are former
Material, such as hydrogen, fuel gas, ethene, propylene, C 4 fraction (including butane, butylene, butadiene), drippolene (containing aromatic hydrocarbons), split
Solve diesel oil, Pyrolysis fuel oil PFO etc..In separator, although processing flow sequence is not disclosed in different patent applications or document
Together, the order separation process such as LUMMUS, LINDE front-end deethanization flow, S＆W predepropanization process, but be all finally
What the carbon number according to hydrocarbon was separated and purified.As a rule, the separator mainly includes：Oil scrubber, water scrubber, compression
Machine, ice chest, domethanizing column, dethanizer, ethylene rectifying column, depropanizing tower, propylene rectification tower, debutanizing tower, C2 and C3 hydrogenation
Device etc..The implementation of the separator is known to those skilled in the art, will not be repeated here.Cracking gas part
Component forms raw material by the separating-purifying of separator, such as hydrogen, ethene, propylene, C 4 fraction (including butane, butylene, fourth two
Alkene etc.), drippolene (containing aromatic hydrocarbons), constituent part is consumed or recycles, as carbon monoxide by methanation device at
Reason forms fuel gas, and methane generates fuel gas by domethanizing column, and the fuel that fuel gas is used as pyrolysis furnace is consumed；Titanium dioxide
Carbon is absorbed by caustic wash tower；Acetylene, propine and allene are by hydrogenation reactor generation ethene and ethane, propylene and propane；Ethane,
Propane forms cycle ethane, recycled propane after ethylene rectifying column, propylene rectification tower purification；Cycle ethane and recycled propane
Pyrolysis furnace is returned as cracking stock；Pyrolysis gas oil and Pyrolysis fuel oil PFO form fuel oil by oil scrubber.
In the case that the steam cracking reaction is carried out in tube cracking furnace, in the steam cracking reaction process
In, the coil outlet temperature of the tube cracking furnace is preferably 840-890 DEG C, more preferably 850-890 DEG C.In addition, described
During steam cracking reaction, the other conditions parameter of the pyrolysis furnace can be the conventional selection of this area, to this this area
Known in technical staff, therefore not to repeat here.
According to the method for production low-carbon alkene provided by the invention, the low-carbon alkene can be selected from ethene, propylene and fourth
One or more in diene.
According to the method for production low-carbon alkene provided by the invention, the raw material of the Fischer-Tropsch synthesis is carbon monoxide
And hydrogen (H (CO)2).The present invention is not particularly limited to the source of both raw materials, but because coal resources in China is rich
It is rich, it is preferable that the raw material of the Fischer-Tropsch synthesis is obtained by coal through water gas reaction, prepares Fischer-Tropsch synthesis raw material
Specific course of reaction is as follows：C+H2O=CO+H2, so low-carbon alkene effectively can be produced by initiation material of coal resources,
So as to be opened up a new way for production low-carbon alkene.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, yield of light olefins calculates according to below equation：
The weight of ethene/steam cracking reaction product is total in the yield (weight %) of ethene=steam cracking reaction product
Weight × 100%；
The weight of propylene/steam cracking reaction product is total in the yield (weight %) of propylene=steam cracking reaction product
Weight × 100%；
The weight of butadiene/steam cracking reaction product in the yield (weight %) of butadiene=steam cracking reaction product
Gross weight × 100%；
The yield of yield+butadiene of yield+propylene of total recovery (weight %)=ethene.
Preparation example 1
The preparation example is used for the preparation method for illustrating fischer-tropsch synthetic catalyst provided by the invention.
100g is weighed by boehmite and HZSM-5 molecular sieves by 7：The carrier that 3 parts by weight mixing aftershaping obtains,
The specific surface area of the carrier is 195m2/ g, aperture are distributed in three-level, average pore size 12nm, pore volume 1.10mL/g.By 90g
Cobalt nitrate hexahydrate heating is water-soluble to 150mL, obtains the solution containing cobalt nitrate.The above-mentioned solution 110mL containing cobalt nitrate is taken to pour into load
Dry 3 hours at 120 DEG C after being impregnated 2 hours in body, be then calcined in moisture vapor 5vol% air stream at 450 DEG C
2 hours, obtain fischer-tropsch synthetic catalyst, numbering cat-1.In the fischer-tropsch synthetic catalyst cat-1, closed with the Fischer-Tropsch
Into on the basis of catalyst cat-1 gross weight, the content of carrier is 84.5 weight %, and the active component cobalt in terms of oxide contains
Measure as 15.5 weight %.
100g is weighed by boehmite and H-beta molecular sieves by 9：The carrier that 1 parts by weight mixing aftershaping obtains,
The specific surface area of the carrier is 225m2/ g, aperture are distributed in two level, average pore size 17nm, pore volume 0.9mL/g.By 90g six
Water cobalt nitrate and the heating of 40g ferric nitrates are water-soluble to 150mL, obtain the solution containing cobalt nitrate and ferric nitrate.Take and above-mentioned contain cobalt nitrate
Pour into carrier with the solution 90mL of ferric nitrate after impregnating 2 hours and dried 3 hours at 120 DEG C, then in moisture vapor
It is calcined 2 hours at 450 DEG C in 5vol% air stream, obtains fischer-tropsch synthetic catalyst, numbering cat-2.In the Fischer-Tropsch
In synthetic catalyst cat-2, on the basis of the gross weight of the fischer-tropsch synthetic catalyst cat-2, the content of carrier is 81.6 weights
% is measured, the content for the active component cobalt counted using oxide is as 12.0 weight %, the content of the active component iron in terms of oxide
6.4 weight %.
100g is weighed by Al2O3, violet cyanines stone and lanthanum chloride form obtained carrier, wherein, Al2O3With the weight of violet cyanines stone
Than for 8:2, the content for the lanthanum auxiliary agent counted using La elements in carrier is 1 weight %.The specific surface area of the carrier is 145m2/ g, put down
Equal aperture is 18nm, pore volume 0.80mL/g.The heating of 100g cobalt nitrate hexahydrates is water-soluble to 140mL, obtain containing the molten of cobalt nitrate
Liquid.Take the above-mentioned solution 80mL containing cobalt nitrate pour into carrier impregnate 2 hours after at 120 DEG C dry 3 hours, then aqueous
It is calcined 2 hours at 450 DEG C in steam 5vol% air stream, obtains black sample.In the remaining solution containing cobalt nitrate
8mL nitric acid ruthenium solution (ruthenium content is 0.005 weight %) is added, it is molten that the black sample after roasting then is imported into above-mentioned mixing
Impregnate 2 hours, then dried 3 hours at 120 DEG C, then in moisture vapor 10vol% air stream at 450 DEG C in liquid
Roasting 2 hours, obtains fischer-tropsch synthetic catalyst, numbering cat-3.In the fischer-tropsch synthetic catalyst cat-3, taken with described
On the basis of Tropsch synthesis catalyst cat-3 gross weight, the content of carrier is 78.3 weight %, the active component cobalt in terms of oxide
Content be 13.9 weight %, the content for the active component ruthenium counted using oxide is 0.02 weight %, the auxiliary agent in terms of oxide
Content be 0.8 weight %.
Preparation example 2
The preparation example is used for the preparation method for illustrating hydrogenation catalyst provided by the invention.
The main active component of the hydrogenation catalyst is platinum, and helping active component, carrier is aluminum oxide for silver, wherein, with oxidation
The content of the platinum of thing meter is 0.6 weight %, and using the silver-colored content that oxide is counted as 0.3 weight %, the content of carrier is 99.1 weights
Measure %.The hydrogenation catalyst is prepared as follows to obtain：A diameter of Φ 3-4mm of 100 parts by weight alumina globule is existed
It is calcined 6 hours at 1000 DEG C, the pH value of the salpeter solution for the platinum nitrate that platinum content is 1.33 weight % is adjusted to 5 with ammoniacal liquor,
Then the alumina globule after roasting is immersed in the salpeter solution for the platinum nitrate that the above-mentioned pH value of 45 parts by weight is 5, and will leaching
Alumina globule after stain is dried 8 hours at 120 DEG C, is then calcined 8 hours at 300 DEG C；It is 0.67 weight by silver content
The pH value for measuring the salpeter solution of % silver nitrate is adjusted to 5, then by the above-mentioned aluminum oxide for having loaded main active component with ammoniacal liquor
Bead is immersed in the salpeter solution for the silver nitrate that the above-mentioned pH value of 45 parts by weight is 5, and by the alumina globule after dipping 120
Dried 8 hours at DEG C, be then calcined 8 hours at 300 DEG C, obtain hydrogenation catalyst cat-4.
Embodiment 1
The embodiment is used for the method for illustrating production low-carbon alkene provided by the invention.
(1) Fischer-Tropsch (FT) reaction evaluating：
By the above-mentioned Co based Fischer-Tropsch synthesis catalyst cat-1 quartz sands of 40mL according to 1:1 weight after dilution than loading
In 25mm reactors, it is 2.8MPa to control reaction pressure, and reactor inlet temperature is 200 DEG C, and volume space velocity is during the gas of raw material
800h-1, it is passed through H2It is 2 with CO volume ratios:1 synthesis gas, it is at room temperature after two-stage gas-liquid separation and phase separator
Wax phase product, oil-phase product, water-phase product and the gas-phase product of solid.Then gas-phase product is divided in domethanizing column
From removing CO, H2、CO2It is liquefied petroleum gas LPG1 with remaining product after methane, its composition refers to table 1.
(2) hydrogenation reaction：
Liquefied petroleum gas LPG1 is passed through the hydrogenation reactor including two sections of fixed bed reactors and (is purchased from Haian County's Petroleum Section
Grind Instrument Ltd., model ZR-2, similarly hereinafter) in carry out hydrogenation reaction, hydrogenation catalyst cat-4 loadings are 30mL,
It is 3.0 that raw material and product circulation ratio are controlled in hydrogenation process:1, reactor inlet temperature is 200 DEG C, and reaction pressure is
2MPa, volume space velocity is 20h during the liquid of raw material-1, the mol ratio of alkene is 1.05 in hydrogen and liquefied petroleum gas LPG1:1, obtain
Hydrogenation products 1 of the content of saturated alkane more than 99.9 weight %, the property of hydrogenation products 1 refer to table 2.
(3) steam cracking：
The hydrogenation products 1 that step (2) obtains are sent into SL-I pyrolysis furnaces and carry out steam cracking, the condition of steam cracking is detailed
4 are shown in Table, yield of light olefins refers to table 5.
Embodiment 2-3
Embodiment 2-3 is used for the method for illustrating production low-carbon alkene provided by the invention.
Low-carbon alkene is produced according to the method for embodiment 1, unlike, cracking furnace tube outlet temperature is different, specific temperature
The yield of degree and low-carbon alkene is shown in Table 5.
Embodiment 4
The embodiment is used for the method for illustrating production low-carbon alkene provided by the invention.
(1) Fischer-Tropsch (FT) reaction evaluating：
The above-mentioned Co based Fischer-Tropsch synthesis catalyst cat-2 of 40mL are fitted into 25mm reactors, control the reaction pressure to be
3.0MPa, reactor inlet temperature are 220 DEG C, and volume space velocity is 1500h during the gas of raw material-1, it is passed through H2It is with CO volume ratios
2.1:1 synthesis gas, obtained after two-stage gas-liquid separation and phase separator at room temperature as the wax phase product of solid, oil phase production
Thing, water-phase product and gas-phase product.Then gas-phase product is separated in domethanizing column, removes CO, H2、CO2After methane
Remaining product is liquefied petroleum gas LPG2, and its composition refers to table 1.
(2) hydrogenation reaction：
Liquefied petroleum gas LPG2 is passed through in the hydrogenation reactor including two sections of fixed bed reactors and carries out hydrogenation reaction, is added
Hydrogen catalyst cat-4 loadings are 25mL, and it is 2 that raw material and product circulation ratio are controlled in hydrogenation process:1, reactor enters
Mouthful temperature is 210 DEG C, reaction pressure 3MPa, and volume space velocity is 10h during the liquid of raw material-1, in hydrogen and liquefied petroleum gas LPG2
The mol ratio of alkene is 5:1, hydrogenation products 2 of the content more than 99.9 weight % of saturated alkane are obtained, the property of hydrogenation products 2 is detailed
It is shown in Table 2.
(3) steam cracking：
The hydrogenation products 2 that step (2) obtains are sent into SL-I pyrolysis furnaces and carry out steam cracking, the condition of steam cracking is detailed
4 are shown in Table, yield of light olefins refers to table 5.
Embodiment 5
The embodiment is used for the method for illustrating production low-carbon alkene provided by the invention.
(1) Fischer-Tropsch (FT) reaction evaluating：
By the above-mentioned Co based Fischer-Tropsch synthesis catalyst cat-3 quartz sands of 40mL according to 1:1 weight after dilution than loading
In 25mm reactors, it is 2.5MPa to control reaction pressure, and reactor inlet temperature is 205 DEG C, and volume space velocity is during the gas of raw material
1250h-1, it is passed through H2It is 1.8 with CO volume ratios:1 synthesis gas, obtained at room temperature after two-stage gas-liquid separation and phase separator
For wax phase product, oil-phase product, water-phase product and the gas-phase product of solid.Then gas-phase product is divided in domethanizing column
From removing CO, H2、CO2It is liquefied petroleum gas LPG3 with remaining product after methane, its composition refers to table 1.
(2) hydrogenation reaction：
Liquefied petroleum gas LPG3 is passed through in the hydrogenation reactor including two sections of fixed bed reactors and carries out hydrogenation reaction, is added
Hydrogen catalyst cat-4 loadings are 30mL, and it is 3 that raw material and product circulation ratio are controlled in hydrogenation process:1, reactor enters
Mouthful temperature is 220 DEG C, reaction pressure 3MPa, and volume space velocity is 15h during the liquid of raw material-1, in hydrogen and liquefied petroleum gas LPG3
The mol ratio of alkene is 8:1, hydrogenation products 3 of the content more than 99.9 weight % of saturated alkane are obtained, the property of hydrogenation products 3 is detailed
It is shown in Table 2.
(3) steam cracking：
The hydrogenation products 3 that step (2) obtains are sent into SL-I pyrolysis furnaces and carry out steam cracking, the condition of steam cracking is detailed
4 are shown in Table, yield of light olefins refers to table 5.
Comparative example 1
The comparative example is used for the method for the production low-carbon alkene for illustrating reference.
The liquefied petroleum gas LPG4 (property is shown in Table 3) of reference in oil refining process is sent into SL-I type pyrolysis furnaces and steamed
Vapour cracks, and the condition of steam cracking refers to table 4, and yield of light olefins refers to table 5.
Table 1
Table 2
Table 3
| LPG4 components | Content (weight %) |
| Ethane | 1.74 |
| Propane | 21.36 |
| Normal butane | 44.65 |
| Iso-butane | 28.77 |
| Light dydrocarbon | 2.49 |
| Alkene | 0.98 |
| Alkane | 99.02 |
| N-alkane | 69.01 |
Table 4
| Raw material | LPG |
| Inventory (t/h) | 39.817 |
| Dilution steam generation flow (DS, t/h) | 20.011 |
| Water-oil factor (wt/wt) | 0.503 |
Table 5
Note：In table 5, COT refers to cracking furnace pipe outlet temperature.
From the results shown in Table 5, higher low-carbon alkene total recovery can be obtained using method provided by the invention.
In addition, expense can be passed through using abundant coal resources as initiation material by using the method for production low-carbon alkene provided by the invention
Coal resources and steam cracking process are combined production low-carbon alkene by support synthetic technology, so as to be opened up for production low-carbon alkene
One new approach.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (13)
1. a kind of method for producing low-carbon alkene, this method comprise the following steps：
(1) liquefied petroleum gas is isolated from the gas-phase product of Fischer-Tropsch synthesis；
(2) liquefied petroleum gas being subjected to hydrogenation reaction so that the alkene in the liquefied petroleum gas is changed into alkane substantially,
Obtain hydrogenation products；Wherein, the mol ratio of hydrogen and alkene in the liquefied petroleum gas is 1-20：1；And the hydrogenation products
The content of middle n-alkane is at least 90 weight %；
(3) hydrogenation products are subjected to steam cracking reaction；
Wherein, the Fischer-Tropsch synthesis is carried out in the presence of fischer-tropsch synthetic catalyst, and the fischer-tropsch synthetic catalyst includes
First vector and the first active component being supported in the first vector, first active component are VIII group 4 transition metal
Component, one or more of the first vector in metal oxide, molecular sieve and carbon material；
Wherein, on the basis of the gross weight of the fischer-tropsch synthetic catalyst, the content of the first vector is 65-92 weight %,
The content for first active component counted using oxide is 8-35 weight %；
Wherein, the hydrogenation reaction is carried out in the presence of hydrogenation catalyst, and the hydrogenation catalyst includes Second support and born
The second active component being loaded on the Second support, the Second support are heat-resistant inorganic oxide and/or molecular sieve, described
Second active component contains group VIII metal component and/or the VIIth B races metal component；
Wherein, second active component includes main active component and helps active component, the main active component be platinum and/or
Palladium, it is described to help active component as the one or more in copper, silver, lead, nickel, cobalt and manganese；
Wherein, the main active component counted using oxide with to help the weight ratio of active component as 1- described in oxide is counted
16：1.
2. according to the method for claim 1, wherein, the content of n-alkane is at least 95 weights in the hydrogenation products
Measure %.
3. according to the method for claim 1, wherein, on the basis of the gross weight of the fischer-tropsch synthetic catalyst, described the
The content of one carrier is 75-90 weight %, and the content for first active component counted using oxide is 10-25 weight %.
4. according to the method for claim 1, wherein, first active component is cobalt.
5. according to the method described in any one in claim 1-4, wherein, the condition of the Fischer-Tropsch synthesis includes：Temperature
Spend for 200-450 DEG C, pressure 1-15MPa, volume space velocity is 500-1500h during the gas of raw material-1, the body of hydrogen and carbon monoxide
Product ratio is 0.5-2.5：1.
6. according to the method for claim 5, wherein, the condition of the Fischer-Tropsch synthesis includes：Temperature is 200-300
DEG C, pressure 2-8MPa, volume space velocity is 800-1500h during the gas of raw material-1, the volume ratio of hydrogen and carbon monoxide is 1.5-
2.5：1.
7. according to the method for claim 1, wherein, on the basis of the gross weight of the hydrogenation catalyst, described second carries
The content of body is 20-99.8 weight %, and the content for second active component counted using oxide is 0.2-80 weight %.
8. according to the method for claim 7, wherein, on the basis of the gross weight of the hydrogenation catalyst, described second carries
The content of body is 80-99.5 weight %, and the content for second active component counted using oxide is 0.5-20 weight %.
9. the method according to claim 11, wherein, the main active component in terms of oxide and the institute in terms of oxide
It is 2-9 to state and help the weight ratio of active component：1.
10. according to the method for claim 1, wherein, the condition of the hydrogenation reaction includes：The entrance of hydrogenation reaction device
Temperature is 50-250 DEG C, reaction pressure 0.1-6MPa, and volume space velocity is 0.5-30h during the liquid of raw material-1。
11. according to the method for claim 10, wherein, the condition of the hydrogenation reaction includes：Hydrogenation reaction device enters
Mouthful temperature is 60-230 DEG C, reaction pressure 0.5-3MPa, and volume space velocity is 15-25h during the liquid of raw material-1, hydrogen and the liquid
The mol ratio of alkene is 1-5 in liquefied oil gas：1.
12. according to the method for claim 1, wherein, the steam cracking reaction is carried out in tube cracking furnace, and in institute
During stating steam cracking reaction, the coil outlet temperature of the tube cracking furnace is 840-890 DEG C.
13. the method according to claim 11, wherein, the one kind of the low-carbon alkene in ethene, propylene and butadiene
It is or a variety of.
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| CN101993319A (en) * | 2009-08-11 | 2011-03-30 | 亚申科技研发中心（上海）有限公司 | Transportable modularized compact Fischer-Tropsch synthesis device |
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