CN103086821B - A kind of production method of low-carbon alkene - Google Patents
A kind of production method of low-carbon alkene Download PDFInfo
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- CN103086821B CN103086821B CN201110335539.9A CN201110335539A CN103086821B CN 103086821 B CN103086821 B CN 103086821B CN 201110335539 A CN201110335539 A CN 201110335539A CN 103086821 B CN103086821 B CN 103086821B
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Abstract
The invention discloses a kind of production method of low-carbon alkene, the method comprises the following steps: Naphtha solvent is carried out steam cracking by (1), obtains splitting gas; (2) under oxidative dehydrogenation condition, lighter hydrocarbons are contacted with oxy-dehydrogenation catalyst with the gas of oxygen with containing nitrogen, obtains the oxydehydrogenation logistics being rich in ethene; (3) Separation and Recovery together with oxydehydrogenation logistics step (1) gained splitting gas and step (2) gained being rich in ethene, obtains the circulation lighter hydrocarbons and the low-carbon alkene product that contain ethane and/or propane.Present invention also offers a kind of production method of low-carbon alkene, the method is carried out in Ethylene vapor cracking system, and described cracking of ethylene system comprises at least one the oxydehydrogenation equipment be arranged at outside Naphtha solvent pyrolyzer body of heater.The present invention significantly reduces energy consumption and the cost of existing steam cracking system.
Description
Technical field
The present invention relates to a kind of production method of low-carbon alkene.
Background technology
Ethene is important basic chemical raw materials, has the title of " mother of petrochemical industry ".The ethene of 90% is produced by steam cracking (i.e. thermo-cracking) method in the world.In modern petrochemical enterprise, Ethylene vapor cracking system is made up of multiple stage Naphtha solvent pyrolyzer and a gaseous light hydrocarbons pyrolyzer usually, and Naphtha solvent pyrolyzer generally includes naphtha cracking stove and multiple stage heavy oit pyrolysis stove.Steam cracking is produced in the process of ethene, the splitting gas that Naphtha solvent pyrolyzer and gas hydro carbons pyrolyzer produce is aggregated in splitting gas house steward, split product is fractionation purification in follow-up Separation and Recovery equipment after gasoline splitter oil wash and water wash column washing, obtain the cut of different carbonatoms, then isolate ethene, propylene product from carbon two, C3 fraction.The raw material of Ethylene vapor cracking is generally containing the gaseous state lighter hydrocarbons of at least one in ethane, propane and butane, liquid petroleum naphtha, hydrogenation tail oil and solar oil etc., wherein, the gaseous state lighter hydrocarbons of Ethylene vapor cracking system are generally originated two portions, the circulation lighter hydrocarbons such as the pure ethane that the by product that a part produces from Naphtha solvent pyrolyzer obtains after Separation and Recovery or pure propane, ethane after Separation and Recovery or propane send into gaseous light hydrocarbons pyrolyzer usually respectively, also can mix rear feeding gaseous light hydrocarbons pyrolyzer.Another part is from one or more in the ethane be purchased, propane, butane.
Although steam-cracking process is the most effective existing ethylene production technique, this process is also that whole chemical industry consumes energy maximum technological process, accounts for greatly 8% of the total primary energy consumption of whole chemical industry.Fig. 1 is the schematic diagram of current Ethylene vapor cracking system, and Ethylene vapor cracking system comprises Naphtha solvent pyrolyzer 1, the quenching boiler 10 of Naphtha solvent pyrolyzer and gas light hydrocarbon cracking stove 8, the quenching boiler 80 of gaseous light hydrocarbons pyrolyzer, splitting gas house steward 2, gasoline splitter 6, water wash column 7 and Separation and Recovery equipment 3.Naphtha solvent 100 produces splitting gas after Naphtha solvent pyrolyzer 1 cracking, splitting gas sends into splitting gas house steward 2 after quenching boiler 10 heat exchange of Naphtha solvent pyrolyzer 1, carry out oil wash through gasoline splitter 6 to isolate cracking solar oil and Pyrolysis fuel oil PFO, carry out sending into Separation and Recovery equipment 3 after pyrolysis gasoline is isolated in washing through water wash column 7 and carry out Separation and Recovery, be separated and obtain ethene, propylene product and the circulation lighter hydrocarbons 200 containing ethane and/or propane.Circulation lighter hydrocarbons 200 containing ethane and/or propane send into light hydrocarbon cracking stove 8 through ngl pipeline 5, the lighter hydrocarbons 200 containing ethane and/or propane from Separation and Recovery equipment 3 send into splitting gas house steward 2 with the splitting gas of external lighter hydrocarbons logistics as produced after light hydrocarbon cracking stove 8 cracking from the lighter hydrocarbons 300 of refinery after quenching boiler 80 heat exchange of light hydrocarbon cracking stove 8, send into Separation and Recovery equipment 3 separation obtain ethene, propylene product through gasoline splitter 6, water wash column 7.In above-mentioned Ethylene vapor cracking process, Pintsch process operation is the operation that in whole Ethylene vapor cracking production process, energy consumption is the highest.In sum, how to reduce the energy consumption of Ethylene vapor cracking system, especially the energy consumption of Pintsch process operation has become the ultimate challenge faced by project planner of current Ethylene vapor cracking system.
At present, the tube furnace used in Ethylene vapor cracking system, through the development of decades, its room for improvement is more and more little.By comparison, new ethylene then develops very fast, wherein the most noticeable with oxydehydrogenation.Oxydehydrogenation starts from twentieth century sixties, and before this, the Catalytic Oxidation of alkane is mainly combustion reactions.In recent years, have more research to report the process of making ethylene from ethane oxidative dehydrogenation both at home and abroad, main what pay close attention to is heterogeneous reaction under catalyzer exists.Union carbide corporation of the U.S. and domestic Lan Hua company etc. all have studied oxidative dehydrogenation of ethane process under low temperature, adopt the transition metal oxide of easily reduction, as the metal oxide of molybdenum, vanadium, the ethane conversion of 45-70% and the ethylene selectivity of 70-80% can be obtained in 300-400 DEG C.Rare-earth oxide and oxychloride usually and basic metal or alkaline-earth metal compound, are used for the oxidative dehydrogenation of catalysis ethane, as Li/Dy/Mg/O, Sr/La/Nd/O, Sm/Na/P/O, Ba/La/O, Sr/Er/O, La/Sr/Fe/Cl/O, La/Sr/Cu/Cl/O, Y/Ba/Cu/Cl/O.These catalyzer need to realize katalysis at relatively high temperatures, and its catalytic mechanism is not conventional redox, which includes relevant homogeneous reaction.When the oxychlorination thing of rare earth metal is as catalyzer, the yield of ethene can than slightly higher during oxide catalyst, as consisted of La
1.85sr
0.15cuO
3.930cl
0.053catalyzer, at 660 DEG C, C
2h
6/ O
2/ N
2time=2/1/3.7 (volume ratio), the ethane conversion of 82.4% and the ethylene selectivity of 73.6% can be obtained.But the high-temperature stability of this catalyzer has much room for improvement, and the HCl in product has certain corrodibility to equipment.
The formation of alkanes oxidative dehydrogenation water in products makes this reaction thermodynamically quite favourable, because water is stable.Oxydehydrogenation does not limit by thermodynamic(al)equilibrium, can react at a lower temperature, reduce carbon deposit simultaneously, and can successive reaction, and technique simplifies greatly, and exothermic heat of reaction, can save energy.Compared with steam cracking furnace, oxidative dehydrogenation process has potential energy-saving and cost-reducing and environment-friendly advantage.If adopt the method for oxydehydrogenation to carry out alternative light hydrocarbon cracking stove steam cracking prepare low-carbon alkene, the high energy consumption of pyrolyzer Pintsch process effectively can be reduced.Although the research of making ethylene from ethane oxidative dehydrogenation is a lot of at present, but these researchs all rest on the stage of the mixed gas prepared containing ethene at present, there is no the mixed gas separation synthesis pure ethylene product that technology will produce after oxydehydrogenation containing ethene, and these experiments all rest on the lab scale stage, low-carbon alkanes oxydehydrogenation is prepared low-carbon alkene and is applied in suitability for industrialized production by nobody, the technology more not having technology low-carbon alkene to be prepared by low-carbon alkanes oxydehydrogenation is applied to steam cracking and produces in the system of ethene, separation and recovery method in conjunction with steam cracking prepares pure ethylene, the report of the low-carbon alkenes such as propylene product.
Summary of the invention
The object of the invention is to overcome in prior art, the lighter hydrocarbons steam cracking producing light olefins in Ethylene vapor cracking system needs high temperature thus the shortcoming causing energy consumption high, provides a kind of method of low-carbon alkene of less energy-consumption.
The present inventor finds through research, the lighter hydrocarbons steam cracking in original steam cracking system is replaced with oxidative dehydrogenation, due in the oxidative dehydrogenation process of lighter hydrocarbons, only can generate water, ethene, methane, oxycarbide and a small amount of carbon more than three hydro carbons, not containing organic oxygen compounds such as acid, ester and alcohol, its constituent species is similar to steam cracking product, so, the oxydehydrogenation logistics of lighter hydrocarbons can send into the Separation and Recovery equipment of steam cracking device, carries out follow-up process for separating and recovering together with the splitting gas in the splitting gas that liquid hydrocarbon pyrolyzer produces.
On the basis of above-mentioned research, the invention provides a kind of production method of low-carbon alkene, the method comprises the following steps:
(1) Naphtha solvent is carried out steam cracking, obtain splitting gas;
(2) under oxidative dehydrogenation condition, lighter hydrocarbons are contacted with oxy-dehydrogenation catalyst with the gas of oxygen with containing nitrogen, obtains the oxydehydrogenation logistics being rich in ethene;
(3) Separation and Recovery together with oxydehydrogenation logistics step (1) gained splitting gas and step (2) gained being rich in ethene, obtains the circulation lighter hydrocarbons and the low-carbon alkene product that contain ethane and/or propane.
The present invention also provides a kind of production method of low-carbon alkene, the method is carried out in Ethylene vapor cracking system, described Ethylene vapor cracking system comprises at least one the Naphtha solvent pyrolyzer be communicated with successively according to flow direction of material, splitting gas house steward, gasoline splitter, water wash column and Separation and Recovery equipment, it is characterized in that, this cracking system also comprises at least one the oxydehydrogenation equipment be arranged at outside Naphtha solvent pyrolyzer body of heater, the discharge port of described oxydehydrogenation equipment and splitting gas house steward, gasoline splitter, water wash column is connected with at least one in Separation and Recovery equipment, said method comprising the steps of:
(1) Naphtha solvent is carried out steam cracking in Naphtha solvent pyrolyzer, obtain splitting gas;
(2) under oxidative dehydrogenation condition, lighter hydrocarbons are contacted with the oxy-dehydrogenation catalyst in oxydehydrogenation equipment with the gas of oxygen with containing nitrogen, obtains the oxydehydrogenation logistics being rich in ethene;
(3) oxydehydrogenation logistics step (1) gained splitting gas being rich in ethene through splitting gas house steward, gasoline splitter, water wash column and step (2) gained successively after at least one in splitting gas house steward, gasoline splitter, water wash column together with Separation and Recovery, obtain the circulation lighter hydrocarbons containing ethane and/or propane and low-carbon alkene product.
Compared with the method for existing Ethylene vapor cracking system producing light olefins, the preparation method of low-carbon alkene provided by the invention, when not losing yield of ethene, significantly reduces energy consumption and the cost of whole existing Ethylene vapor cracking system.Such as, relative to comparative example 1, the yield of ethene of the ethane cracking furnace in the ratio comparative example 1 of the oxydehydrogenation equipment in embodiment 1 improves 8%; And the temperature of reaction of oxydehydrogenation system is down to 400 DEG C by 855 DEG C of light hydrocarbon cracking stove, the energy consumption of the oxydehydrogenation equipment in embodiment 1 is 1689.3MJ/t ethane, be 27.5% of the energy consumption of the ethane cracking furnace in comparative example 1, significantly reduce energy consumption and the cost of steam cracking system, and then improve economic benefit.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the production method schematic flow sheet of low-carbon alkene in steam cracking system in prior art.
Fig. 2 is the schematic flow sheet of low-carbon alkene production method of the present invention.
Description of reference numerals
1 Naphtha solvent pyrolyzer 2 splitting gas house steward
3 Separation and Recovery equipment 4 oxydehydrogenation equipment
The discharge port of the opening for feed 4b oxydehydrogenation equipment of 4a oxydehydrogenation equipment
5 ngl pipeline 6 gasoline splitters
7 water wash column 8 light hydrocarbon cracking stoves
The quenching boiler of the quenching boiler 80 light hydrocarbon cracking stove of 10 Naphtha solvent pyrolyzer
100 Naphtha solvents 200 contain the circulation lighter hydrocarbons of ethane and/or propane
The gas of the oxygenous and nitrogen of 300 lighter hydrocarbons 400
The 500 oxydehydrogenation logistics being rich in ethene
Embodiment
According to the production method of low-carbon alkene of the present invention, the method comprises the following steps:
(1) Naphtha solvent is carried out steam cracking, obtain splitting gas;
(2) under oxidative dehydrogenation condition, lighter hydrocarbons are contacted with oxy-dehydrogenation catalyst with the gas of oxygen with containing nitrogen, obtains the oxydehydrogenation logistics being rich in ethene;
(3) Separation and Recovery together with oxydehydrogenation logistics step (1) gained splitting gas and step (2) gained being rich in ethene, obtains the circulation lighter hydrocarbons and the low-carbon alkene product that contain ethane and/or propane.
According to the production method of low-carbon alkene of the present invention, preferably, step (2) described lighter hydrocarbons are the circulation lighter hydrocarbons that step (3) gained contains ethane and/or propane at least partly.
According to the production method of low-carbon alkene of the present invention, the method is carried out in Ethylene vapor cracking system, described Ethylene vapor cracking system comprises at least one the Naphtha solvent pyrolyzer be communicated with successively according to flow direction of material, splitting gas house steward, gasoline splitter, water wash column and Separation and Recovery equipment, wherein, this cracking system also comprises at least one the oxydehydrogenation equipment be arranged at outside Naphtha solvent pyrolyzer body of heater, the discharge port of described oxydehydrogenation equipment and splitting gas house steward, gasoline splitter, water wash column is connected with at least one in Separation and Recovery equipment, said method comprising the steps of:
(1) Naphtha solvent is carried out steam cracking in Naphtha solvent pyrolyzer, obtain splitting gas;
(2) under oxidative dehydrogenation condition, lighter hydrocarbons are contacted with the oxy-dehydrogenation catalyst in oxydehydrogenation equipment with the gas of oxygen with containing nitrogen, obtains the oxydehydrogenation logistics being rich in ethene;
(3) oxydehydrogenation logistics step (1) gained splitting gas being rich in ethene through splitting gas house steward, gasoline splitter, water wash column and step (2) gained successively after at least one in splitting gas house steward, gasoline splitter, water wash column together with Separation and Recovery, obtain the circulation lighter hydrocarbons containing ethane and/or propane and low-carbon alkene product.
According to the production method of low-carbon alkene of the present invention, preferably, the opening for feed of described oxydehydrogenation equipment is connected by ngl pipeline with Separation and Recovery equipment, and step (2) described lighter hydrocarbons are the circulation lighter hydrocarbons that step (3) gained contains ethane and/or propane at least partly.
Relative to the technique of existing Ethylene vapor cracking low-carbon alkene product, main contributions of the present invention is that the splitting gas that existing Naphtha solvent steam cracking can obtain by discovery and lighter hydrocarbons can be sent in the Separation and Recovery equipment of existing Ethylene vapor cracking system by the products therefrom after oxidative dehydrogenation process together, carry out follow-up process for separating and recovering, thus oxydehydrogenation equipment replacement gaseous light hydrocarbons pyrolyzer wherein can be adopted on the basis of existing Ethylene vapor cracking system, the integrated of the high-temperature steam cracking of Naphtha solvent and the oxidative dehydrogenation process of gaseous light hydrocarbons can be realized, thus greatly reduce the energy consumption of Ethylene vapor cracking technology.
As can be seen here, the production technique of low-carbon alkene provided by the invention is mainly improved and is that the high-temperature steam cracking oxidative dehydrogenation process by gaseous light hydrocarbons replaces, such as, and the Pintsch process technique of Naphtha solvent and Separation and Recovery thereof obtain low-carbon alkene product and can carry out with reference to prior art containing the technique of the circulation lighter hydrocarbons of ethane and/or propane and the oxidative dehydrogenation process of lighter hydrocarbons itself and the oxy-dehydrogenation catalyst that uses, can carry out with reference to the content of above-mentioned background technology description.
Such as, described Separation and Recovery generally comprises material to be separated that (the steam cracking gas of step (1) and/or the oxydehydrogenation logistics being rich in ethene of step (2) are sent in the Separation and Recovery equipment 3 of Fig. 1, obtain low-carbon alkene product and the circulation lighter hydrocarbons containing ethane and/or propane.
In the present invention, the lighter hydrocarbons of step (2) all can come from the circulation lighter hydrocarbons that step (3) Separation and Recovery obtains, also the circulation lighter hydrocarbons that step (3) Separation and Recovery obtains can partly be come from, remainder is provided by the external world, specifically depending on the production capacity of oxydehydrogenation equipment used in step (2).
In the present invention, term " lighter hydrocarbons " refers to that carbonatoms is the alkane of 2-4." splitting gas " refers to the product that cracking stock produces through the radiation section Pintsch process of pyrolyzer, and containing split product and cracking by product, the definition of described cracking stock is existing in the preceding article to be described, and does not repeat them here.Split product is usually containing Pyrolysis fuel oil PFO, cracking solar oil, pyrolysis gasoline, carbon two product etc.; The mixture of cracking by product usually containing the low-carbon alkanes such as ethane and/or propane." circulation lighter hydrocarbons " refer in steam cracking system, the lighter hydrocarbons that the by product low-carbon alkanes in the splitting gas that pyrolyzer produces obtains through Separation and Recovery, are generally pure ethane, propane and butane, also can be the mixture of ethane, propane and butane.
According to the production method of low-carbon alkene of the present invention, in the gas of described oxygenous and nitrogen, the content of oxygen is preferably not less than 15 volume %, and can be purity oxygen, also can be air, can also be the mixed gas of air and oxygen.
According to method of the present invention, lighter hydrocarbons logistics can be the oxydehydrogenation equipment mixed with oxygenous and nitrogen in advance described in rear feeding, also without being pre-mixed, can send into oxydehydrogenation equipment individually.
According to the production method of low-carbon alkene of the present invention, the present invention has no particular limits described oxy-dehydrogenation catalyst.Oxy-dehydrogenation catalyst of the prior art may be used to method of the present invention.Under a kind of preferable case, described oxy-dehydrogenation catalyst is heterozygosis molybdate catalyst, is preferably MoVTeNbO heterozygosis metal oxide catalyst.When adopting MoVTeNbO heterozygosis metal oxide to be oxy-dehydrogenation catalyst, described in described step (2), oxidative dehydrogenation condition comprises: lighter hydrocarbons/containing the volume ratio of the oxygen in the gas of nitrogen and oxygen are 0.8-4, are preferably 1-3; Described Contact Temperature is 300-500 DEG C, is preferably 340-460 DEG C; Reaction pressure is 0.07-0.5MPa, is preferably 0.1-0.2MPa; Reaction volume air speed is 400-2000h
-1, be preferably 800-1200h
-1.
Under the second preferable case, described oxy-dehydrogenation catalyst is base metal catalysts, is preferably Li/MgO catalyzer.When adopting Li/MgO catalyzer to be oxy-dehydrogenation catalyst, described in step (3), oxidative dehydrogenation condition comprises: in the gas of lighter hydrocarbons/oxygenous and nitrogen, the volume ratio of oxygen can be 0.8-4, is preferably 1-2; Described Contact Temperature is 500-700 DEG C, is preferably 600-650 DEG C; Reaction pressure is 0.07-0.5MPa, is preferably 0.1-0.2MPa; Reaction volume air speed is 1000-5000h
-1, be preferably 1500-3600h
-1.
Under the third preferable case, described oxy-dehydrogenation catalyst is and the rare-earth oxide of basic metal and/or alkaline-earth metal compound and/or oxychlorination thing catalyzer, is preferably alkali-metal rare earth metal oxychlorination thing catalyzer.When adopting alkali-metal rare earth metal oxychlorination thing to be oxy-dehydrogenation catalyst, described in step (2), oxidative dehydrogenation condition comprises: lighter hydrocarbons/containing the volume ratio of the oxygen in the gas of nitrogen and oxygen can be 0.8-4, are preferably 1.2-2.5; Described Contact Temperature is 500-700 DEG C, is preferably 600-650 DEG C; Reaction pressure is 0.07-0.5MPa, is preferably 0.1-0.2MPa; Reaction volume air speed is 2000-20000h
-1, be preferably 4000-10000h
-1.
Under preferable case, when carbon monoxide, sour gas, oxygen and a nitrogen content are higher in the oxydehydrogenation logistics of ethene for being rich in of obtaining of step (2), low-carbon alkene production method provided by the invention also comprises the step being rich at least part of carbon monoxide, sour gas, oxygen and nitrogen in the oxydehydrogenation logistics of ethene removing step (2) and obtain, and carries out Separation and Recovery by being removed to small part carbon monoxide, sour gas, oxygen and the logistics after nitrogen together with step (1) gained steam cracking product.
The step of above-mentioned removal of carbon monoxide, sour gas, oxygen and nitrogen generally can be realized by carbon monoxide cleanup device, acid gas removal plants, device for deoxidizing and nitrogen rejection facility.Preferred removal of carbon monoxide, sour gas, oxygen and nitrogen successively.The degree removed preferably make carbon monoxide volume content preferably lower than 400ppm, sour gas volume content preferably lower than the volume content of 1ppm, oxygen lower than the volume content of 1ppm, nitrogen preferably lower than 1ppm.Remove the method for above-mentioned gas and concrete operations and condition for conventionally known to one of skill in the art, in prior art, the method for removal of carbon monoxide may be used to method of the present invention.Preferably, described carbon monoxide cleanup method can be changed and/or low temperature shift method for middle temperature transformation method, and more preferably, described carbon monoxide cleanup method adopts middle temperature transformation method to change and low temperature shift method.
According to method of the present invention, the present invention has no particular limits the described method removing sour gas.The method removing sour gas in prior art may be used to method of the present invention.Preferably, the present invention is girbotol process and/or alkali absorb method to the described method removing sour gas, is preferably girbotol process and alkali absorb method.
In the present invention, the method removing oxygen is had no particular limits.The method removing oxygen in prior art may be used to method of the present invention.Preferably, the present invention to the described method removing oxygen is: under deoxygenation conditions, under the existence of dehydrogenation catalyst, the oxydehydrogenation logistics being rich in ethene is contacted with dehydrogenation catalyst.The present invention is not particularly limited described dehydrogenation catalyst, and in prior art, dehydrogenation catalyst all can realize goal of the invention, preferably, and the load type palladium catalyst of described dehydrogenation catalyst to be activated alumina be carrier.The present invention is not particularly limited described deoxygenation conditions, and in prior art, the condition of deoxygenation all can realize goal of the invention, preferably, and volume space velocity 300-10000h
-1, preferred 500-2000h
-1.Deoxidation temperature is 25 DEG C to 180 DEG C, is preferably 120-160 DEG C.
According to method of the present invention, the present invention has no particular limits the described method removing nitrogen.The method removing nitrogen in prior art may be used to method of the present invention.Preferably, described in remove nitrogen method be one or more in condensed detachment, pressure swing adsorption process, oil-absorption process, be preferably condensed detachment and pressure swing adsorption process.According to the production method of low-carbon alkene of the present invention, the gaseous fraction being rich in the oxydehydrogenation logistics of ethene due to removal of carbon monoxide, sour gas, oxygen and nitrogen can make it enter at least one of splitting gas house steward, gasoline splitter, water wash column and Separation and Recovery equipment, preferably, the method can comprise at least one oxydehydrogenation logistics being rich in ethene through removal of carbon monoxide, sour gas, oxygen and nitrogen simultaneously sent in splitting gas house steward, gasoline splitter, water wash column and Separation and Recovery equipment.Adopt the method, fully can excavate the production potential of the splitting gas house steward of existing Ethylene vapor cracking system, gasoline splitter, water wash column and Separation and Recovery equipment.
According to Ethylene vapor cracking system of the present invention, as shown in Figure 2, described Ethylene vapor cracking system comprises the Naphtha solvent pyrolyzer 1 be communicated with successively according to flow direction of material, the quenching boiler 10 of Naphtha solvent pyrolyzer, splitting gas house steward 2, gasoline splitter 6, water wash column 7 and Separation and Recovery equipment 3, wherein, this cracking system also comprises oxydehydrogenation equipment 4, the opening for feed 4a of described oxydehydrogenation equipment 4 is connected with Separation and Recovery equipment 3 by ngl pipeline 5, the discharge port 4b of oxydehydrogenation equipment 4 and splitting gas house steward 2, gasoline splitter 6, water wash column 7 is directly communicated with at least one in Separation and Recovery equipment 3, thus realize Separation and Recovery equipment 3 pairs of oxydehydrogenation equipment 4 circulation lighter hydrocarbons 200 are provided, oxydehydrogenation equipment 4 couples of splitting gas house stewards 2 provide the oxydehydrogenation logistics being rich in ethene.
Preferably, this system also comprises the carbon monoxide cleanup device, acid gas removal plants, device for deoxidizing and the nitrogen rejection facility that connect successively by flow direction of material, the opening for feed of described carbon monoxide cleanup device is communicated with the discharge port 4b of described oxydehydrogenation equipment 4, and the discharge port of described nitrogen rejection facility is communicated with at least one in Separation and Recovery equipment 3 with splitting gas house steward 2, gasoline splitter 6, water wash column 7.
Be described in detail below in conjunction with a kind of preferred implementation of the Ethylene vapor cracking system shown in Fig. 2 to the technical process of low-carbon alkene production method provided by the invention.As shown in Figure 2, the splitting gas that Naphtha solvent 100 produces after Naphtha solvent pyrolyzer 1 cracking sends into splitting gas house steward 2 through quenching boiler 10, then sends into Separation and Recovery equipment 3 and be separated through gasoline splitter 6, water wash column 7 the circulation lighter hydrocarbons 200 obtaining ethene, propylene product and contain ethane and/or propane.Circulation lighter hydrocarbons 200 containing ethane and/or propane are sent into oxydehydrogenation equipment 4 through ngl pipeline 5 by the opening for feed 4a of oxydehydrogenation equipment, when the feed rate of circulation lighter hydrocarbons 200 is not enough, also oxydehydrogenation equipment can be sent from extraneous lighter hydrocarbons 300 into, in oxydehydrogenation equipment 4, pass into oxygenous and gas 400 that is nitrogen simultaneously, generate the oxydehydrogenation logistics 500 being rich in ethene, the oxydehydrogenation logistics 500 being rich in ethene through the outlet 4b of oxydehydrogenation equipment 4 successively through carbon monoxide cleanup device, acid gas removal plants, device for deoxidizing, after nitrogen rejection facility, send into gasoline splitter 6, at least one in water wash column 7 and Separation and Recovery equipment 3, with produce after Naphtha solvent pyrolyzer 1 cracking successively through splitting gas house steward 2, gasoline splitter 6, water wash column 7 splitting gas in Separation and Recovery equipment 3, carry out Separation and Recovery together, obtain low-carbon alkene.
By following examples, the present invention will be described in more detail.Scope of the present invention does not limit by these embodiments.In the embodiment of the present invention, yield of ethene refers to weight × 100% of the weight/lighter hydrocarbons that feed intake of the ethene obtained, and other yields are similar.
Comparative example 1
This comparative example 1 is the production method of existing Ethylene vapor cracking system low-carbon alkene.
Ethylene vapor cracking system produces the production method of low-carbon alkene as shown in Figure 1, and this Ethylene vapor cracking system comprises liquid petroleum pyrolyzer and ethane cracking furnace.The year charging capacity of liquid petroleum pyrolyzer is 36.32 ten thousand tons of petroleum naphthas, and the year charging capacity of ethane cracking furnace is 19.35 ten thousand tons of cycle ethanes.
(1) by petroleum naphtha (density 0.7076g/cm
3, boiling range scope 35 ~ 153 DEG C, normal paraffin content be 28.34 % by weight, isoparaffin content is 30.31 % by weight, naphthenic hydrocarbon is 32.52 % by weight, aromaticity content is 8.79 % by weight) pass into naphtha cracking stove with the charging capacity of 45.4 tons/hour and water vapour with weight ratio 1: 0.5, the gauge pressure of the entrance of naphtha cracking stove is 0.22MPa, the gauge pressure of outlet is 0.07MPa, pyrolyzer is 590 DEG C across section temperature (XOT), and pyrolyzer temperature out (COT) is 835 DEG C.
(2) cracking of ethane cracking furnace
Ethane is sent into ethane cracking furnace with the inlet amount of 24.1875 tons/hour, ethane cracking furnace be 613 DEG C across section temperature (XOT), temperature out (COT) is 855 DEG C, and the gauge pressure of the entrance of ethane cracking furnace is 0.19MPa, and the gauge pressure of outlet is 0.13MPa.
In this comparative example, the yield of ethene of ethane cracking furnace is 47.96 % by weight, and wherein, the energy consumption of ethane cracking furnace is 6144.81MJ/t ethane.
Embodiment 1
Adopt the low-carbon alkene production method shown in Fig. 2, the light hydrocarbon cracking stove being to use oxydehydrogenation equipment 4 to replace in comparative example 1 with the difference of the production method of low-carbon alkene shown in Fig. 1, and embodiment 1 equipment identical with comparative example 1 adopts identical operational condition, the operational condition of oxydehydrogenation equipment 4 and follow-up removal of carbon monoxide, sour gas, oxygen and nitrogen is as follows.
(1) by lighter hydrocarbons/oxygen/nitrogen be 3/3/4 feeding oxydehydrogenation equipment 4 by volume, the inlet amount of lighter hydrocarbons is 24.1875 tons/hour.Temperature of reaction is 400 DEG C, and reaction pressure (gauge pressure) is 0.15MPa, and volume space velocity is 800h
-1, generate the oxydehydrogenation logistics being rich in ethene, wherein, ethylene content is 20.0 % by weight, CO content is 4.40 % by weight, CO
2content be 5.02 % by weight, oxy-dehydrogenation catalyst is MoVTeNbO heterozygosis metal oxide, and the mol ratio of Mo-V-Te-Nb atom is 1: 0.15: 0.16: 0.17 (being prepared according to the preparation method of the catalyzer in document Journal of Catalysis.225 (2004) 428-138);
(2) carbon monoxide conversion device is delivered in the oxydehydrogenation logistics being rich in ethene, carbon monoxide conversion device comprises middle temperature transformation unit and low temperature shift unit, be rich in the oxydehydrogenation logistics of ethene successively by middle temperature transformation unit and low temperature shift unit, remove most carbon monoxide, obtain logistics a.In middle temperature transformation unit, the catalyzer of removal of carbon monoxide take ferric oxide as Primary Catalysts, chromium sesquioxide is promotor (B116 type), temperature of reaction in middle temperature transformation unit is 350-550 DEG C, the carbon monoxide containing 2-4 % by weight after conversion; In low temperature shift unit, the catalyzer of removal of carbon monoxide is copper oxide catalyst (B203 type), and the temperature of reaction in low temperature shift unit is 180-260 DEG C, and the carbon monoxide content in logistics a is 200-400ppm.
(3) logistics a is delivered to acid gas removal plants, remove the sour gas such as most carbon monoxide and sulfur monoxide, obtain the logistics b removing wherein most of sour gas.Acid gas removal workshop section comprises absorption tower and soda-wash tower, and logistics a order enters absorption tower and soda-wash tower.Wherein absorption tower adopts thanomin to absorb sour gas, and the temperature on absorption tower is 45 DEG C, and behind absorption tower, content of acid gas is down to below 30-50ppm.Controlling the temperature of soda-wash tower is 42-49 DEG C, and pressure is 0.97-1.55MPa, and the sodium hydroxide solution of to be concentration the be 10-12 % by weight of the alkali lye in soda-wash tower, through soda-wash tower, sour gas is down to below 1ppm.
(4) logistics b is delivered to device for deoxidizing, remove most oxygen, be converted into logistics c.The load type palladium catalyst (Dalian Ke Lian Technew SA, 506GQ type) of to be activated alumina the be carrier of the catalyzer in device for deoxidizing, the temperature of deoxidation is 150 DEG C, and reaction volume air speed is 800h
-1.Through device for deoxidizing, the oxygen in logistics c is down to 1ppm.
(5) logistics c is delivered to nitrogen rejection facility, remove most nitrogen.Nitrogen rejection facility comprises the method for compression separating unit and psa unit, and wherein, the pressure of compression separating unit is 1.3MPa; Pressure in psa unit is 1.2MPa, and nitrogen can take off to 0.1ppm.
(6) the logistics c that step (5) obtains is sent in the splitting gas pipeline of the cracking gas compressor in the splitting gas manifold assembly of steam cracking system, gasoline splitter, water wash column and Separation and Recovery equipment simultaneously, in Separation and Recovery equipment 3, obtain ethene, propylene product through Separation and Recovery together with the splitting gas that naphtha cracking stove produces.
Can be calculated by the state of arts in embodiment 1, the year charging capacity of oxydehydrogenation equipment 4 is 19.35 ten thousand tons of cycle ethanes, and the yield of ethene of oxydehydrogenation equipment 4 reaches 64.0 % by weight.Relative to comparative example 1, the yield of ethene in the present embodiment increases, and the temperature of reaction of oxydehydrogenation equipment 4 is 400 DEG C of COT lower than gas pyrolyzer (855 DEG C).The energy consumption of oxydehydrogenation equipment 4 is 1689.3MJ/t ethane, and 27.5% of the ethane cracking furnace system energy consumption just in comparative example 1, effectively reduces energy consumption and the cost of steam cracking device, and then improve economic benefit.
Embodiment 2
Ethene is produced according to the method for embodiment 1, unlike, the operational condition of oxydehydrogenation equipment 4 is as follows.
(1) oxydehydrogenation equipment 4 is sent in lighter hydrocarbons logistics, in oxydehydrogenation equipment 4, pass into oxygen and nitrogen, the volume ratio of lighter hydrocarbons/oxygen is 2/1/9, and the inlet amount of lighter hydrocarbons is 24.1875 tons/hour simultaneously.Temperature of reaction is 620 DEG C, and reaction pressure (gauge pressure) is 0.10MPa, and volume space velocity is 1640h
-1, in oxydehydrogenation equipment 1, oxidative dehydrogenation occurs containing the circulation lighter hydrocarbons 200 of ethane and/or propane, generate the oxydehydrogenation logistics being rich in ethene, wherein ethylene content is 10.07 % by weight, CO content is 0.728 % by weight, CO
2content be 1.76 % by weight, oxy-dehydrogenation catalyst is Li/MgO System Catalyst (preparation method see petrochemical complex, 1993 (22): 590-593).
Can be calculated by the state of arts in the present embodiment 2, the year charging capacity of oxydehydrogenation equipment 4 is 19.35 ten thousand tons of cycle ethanes, and the yield of ethene of oxydehydrogenation equipment 4 reaches 61.8 % by weight.Relative to comparative example 1, the yield of ethene that in the present embodiment, oxydehydrogenation produces increases relative to the yield of ethene of the ethane cracking furnace of comparative example 1, and the temperature of reaction of oxydehydrogenation equipment 4 is 620 DEG C of COT lower than ethane cracking furnace (855 DEG C).The energy consumption of oxydehydrogenation equipment 4 is 4527.6MJ/t ethane, is 73.7% of the ethane cracking furnace energy consumption in comparative example 1, effectively reduces energy consumption and the cost of steam cracking device, and then improves economic benefit.
Embodiment 3
Ethene is produced according to the method for embodiment 1, unlike, the operational condition of oxydehydrogenation equipment 4 is as follows.
Oxydehydrogenation equipment 4 is sent in lighter hydrocarbons logistics, and in oxydehydrogenation equipment 4, pass into oxygen and nitrogen, the volume ratio of lighter hydrocarbons/oxygen is 2/1/3.7, and the inlet amount of lighter hydrocarbons is 24.1875 tons/hour simultaneously.Temperature of reaction is 660 DEG C, and reaction pressure (gauge pressure) is 0.10MPa, and volume space velocity is 6000h
-1, generate the oxydehydrogenation logistics being rich in ethene, wherein ethylene content is 16.70 % by weight, COx content is 6.61 % by weight.Oxy-dehydrogenation catalyst is La
0.6sr
0.4feO
3-0.103cl
0.164.(adopt pickling process preparation, preparation method see document Journal of Catalysis, 2000, the preparation method of the catalyzer in 189 (1): 52-62 preparation).
Can be calculated by the state of arts in the present embodiment 3, the year charging capacity of oxydehydrogenation equipment 4 is 19.35 ten thousand tons of cycle ethanes, and the yield of ethene of oxydehydrogenation equipment 4 reaches 57.7 % by weight.Relative to the ethane cracking furnace of comparative example 1, the yield of ethene in the present embodiment increases, and the temperature of reaction of oxydehydrogenation equipment 4 is 660 DEG C of COT lower than ethane cracking furnace (855 DEG C).The energy consumption of oxydehydrogenation system, device 4 is 3278.3MJ/t ethane, is 53.4% of the ethane cracking furnace system energy consumption in comparative example 1, effectively reduces energy consumption and the cost of steam cracking device, and then improves economic benefit.
Claims (24)
1. the production method of a low-carbon alkene, the method is carried out in Ethylene vapor cracking system, described Ethylene vapor cracking system comprises at least one the Naphtha solvent pyrolyzer be communicated with successively according to flow direction of material, splitting gas house steward, gasoline splitter, water wash column and Separation and Recovery equipment, it is characterized in that, this cracking system also comprises at least one the oxydehydrogenation equipment be arranged at outside Naphtha solvent pyrolyzer body of heater, the discharge port of described oxydehydrogenation equipment and splitting gas house steward, gasoline splitter, water wash column is connected with at least one in Separation and Recovery equipment, said method comprising the steps of:
(1) Naphtha solvent is carried out steam cracking in Naphtha solvent pyrolyzer, obtain splitting gas;
(2) under oxidative dehydrogenation condition, lighter hydrocarbons are contacted with the oxy-dehydrogenation catalyst in oxydehydrogenation equipment with the gas of oxygen with containing nitrogen, obtains the oxydehydrogenation logistics being rich in ethene;
(3) oxydehydrogenation logistics step (1) gained splitting gas being rich in ethene through splitting gas house steward, gasoline splitter, water wash column and step (2) gained successively after at least one in splitting gas house steward, gasoline splitter, water wash column together with Separation and Recovery, obtain the circulation lighter hydrocarbons containing ethane and/or propane and low-carbon alkene product;
Described in step (2), oxy-dehydrogenation catalyst is Mo-V System Catalyst; Described in step (2), oxidative dehydrogenation condition comprises: lighter hydrocarbons/containing the volume ratio of the oxygen in the gas of nitrogen and oxygen are 0.8-4, described temperature of reaction is 300-500 DEG C, reaction pressure is 0.07-0.5MPa, and reaction volume air speed is 400-2000h
-1.
2. method according to claim 1, wherein, the opening for feed of described oxydehydrogenation equipment is connected by ngl pipeline with Separation and Recovery equipment, and step (2) described lighter hydrocarbons are the circulation lighter hydrocarbons that step (3) gained contains ethane and/or propane at least partly.
3. method according to claim 1, wherein, oxy-dehydrogenation catalyst described in step (2) is MoVTeNbO heterozygosis metal oxide catalyst.
4. method according to claim 1, wherein, described in step (2), oxidative dehydrogenation condition comprises: lighter hydrocarbons/containing the volume ratio of the oxygen in the gas of nitrogen and oxygen are 1-3, described temperature of reaction is 340-460 DEG C, reaction pressure is 0.1-0.2MPa, and reaction volume air speed is 800-1200h
-1.
5. method according to claim 1, wherein, the method is also included in the oxydehydrogenation logistics removal of carbon monoxide being rich in ethene that step (2) obtained before step (3) after step (2) to wherein carbon monoxide volume content lower than 400ppm.
6. method according to claim 5, wherein, the method also comprises carbon monoxide volume content is removed the volume content of sour gas to sour gas lower than 1ppm lower than the oxydehydrogenation logistics being rich in ethene of 400ppm.
7. method according to claim 6, wherein, the method also comprises the volume content of sour gas is removed the volume content of oxygen to oxygen lower than 1ppm lower than the oxydehydrogenation logistics being rich in ethene of 1ppm.
8. method according to claim 7, wherein, the method also comprises the volume content of oxygen is removed the volume content of nitrogen to nitrogen lower than 1ppm lower than the oxydehydrogenation logistics being rich in ethene of 1ppm, sends in splitting gas house steward, gasoline splitter, water wash column and Separation and Recovery equipment afterwards more simultaneously.
9. the production method of a low-carbon alkene, the method is carried out in Ethylene vapor cracking system, described Ethylene vapor cracking system comprises at least one the Naphtha solvent pyrolyzer be communicated with successively according to flow direction of material, splitting gas house steward, gasoline splitter, water wash column and Separation and Recovery equipment, it is characterized in that, this cracking system also comprises at least one the oxydehydrogenation equipment be arranged at outside Naphtha solvent pyrolyzer body of heater, the discharge port of described oxydehydrogenation equipment and splitting gas house steward, gasoline splitter, water wash column is connected with at least one in Separation and Recovery equipment, said method comprising the steps of:
(1) Naphtha solvent is carried out steam cracking in Naphtha solvent pyrolyzer, obtain splitting gas;
(2) under oxidative dehydrogenation condition, lighter hydrocarbons are contacted with the oxy-dehydrogenation catalyst in oxydehydrogenation equipment with the gas of oxygen with containing nitrogen, obtains the oxydehydrogenation logistics being rich in ethene;
(3) oxydehydrogenation logistics step (1) gained splitting gas being rich in ethene through splitting gas house steward, gasoline splitter, water wash column and step (2) gained successively after at least one in splitting gas house steward, gasoline splitter, water wash column together with Separation and Recovery, obtain the circulation lighter hydrocarbons containing ethane and/or propane and low-carbon alkene product;
Described in step (2), oxy-dehydrogenation catalyst is base metal catalysts; Described in step (2), oxidative dehydrogenation condition comprises: lighter hydrocarbons/containing the volume ratio of the oxygen in the gas of nitrogen and oxygen are 0.8-4, described temperature of reaction is 500-700 DEG C, reaction pressure is 0.07-0.5MPa, and reaction volume air speed is 1000-5000h
-1.
10. method according to claim 9, wherein, the opening for feed of described oxydehydrogenation equipment is connected by ngl pipeline with Separation and Recovery equipment, and step (2) described lighter hydrocarbons are the circulation lighter hydrocarbons that step (3) gained contains ethane and/or propane at least partly.
11. methods according to claim 9, wherein, described in step (2), oxy-dehydrogenation catalyst is Li/MgO catalyzer.
12. methods according to claim 9, wherein, described in step (2), oxidative dehydrogenation condition comprises: lighter hydrocarbons/containing the volume ratio of the oxygen in the gas of nitrogen and oxygen are 1-2, described temperature of reaction is 600-650 DEG C, reaction pressure is 0.1-0.2MPa, and reaction volume air speed is 1500-3600h
-1.
13. methods according to claim 9, wherein, the method is also included in the oxydehydrogenation logistics removal of carbon monoxide being rich in ethene that step (2) obtained before step (3) after step (2) to wherein carbon monoxide volume content lower than 400ppm.
14. methods according to claim 13, wherein, the method also comprises carbon monoxide volume content is removed the volume content of sour gas to sour gas lower than 1ppm lower than the oxydehydrogenation logistics being rich in ethene of 400ppm.
15. methods according to claim 14, wherein, the method also comprises the volume content of sour gas is removed the volume content of oxygen to oxygen lower than 1ppm lower than the oxydehydrogenation logistics being rich in ethene of 1ppm.
16. methods according to claim 15, wherein, the method also comprises the volume content of oxygen is removed the volume content of nitrogen to nitrogen lower than 1ppm lower than the oxydehydrogenation logistics being rich in ethene of 1ppm, sends in splitting gas house steward, gasoline splitter, water wash column and Separation and Recovery equipment afterwards more simultaneously.
The production method of 17. 1 kinds of low-carbon alkenes, the method is carried out in Ethylene vapor cracking system, described Ethylene vapor cracking system comprises at least one the Naphtha solvent pyrolyzer be communicated with successively according to flow direction of material, splitting gas house steward, gasoline splitter, water wash column and Separation and Recovery equipment, it is characterized in that, this cracking system also comprises at least one the oxydehydrogenation equipment be arranged at outside Naphtha solvent pyrolyzer body of heater, the discharge port of described oxydehydrogenation equipment and splitting gas house steward, gasoline splitter, water wash column is connected with at least one in Separation and Recovery equipment, said method comprising the steps of:
(1) Naphtha solvent is carried out steam cracking in Naphtha solvent pyrolyzer, obtain splitting gas;
(2) under oxidative dehydrogenation condition, lighter hydrocarbons are contacted with the oxy-dehydrogenation catalyst in oxydehydrogenation equipment with the gas of oxygen with containing nitrogen, obtains the oxydehydrogenation logistics being rich in ethene;
(3) oxydehydrogenation logistics step (1) gained splitting gas being rich in ethene through splitting gas house steward, gasoline splitter, water wash column and step (2) gained successively after at least one in splitting gas house steward, gasoline splitter, water wash column together with Separation and Recovery, obtain the circulation lighter hydrocarbons containing ethane and/or propane and low-carbon alkene product;
Oxy-dehydrogenation catalyst described in step (2) is and the rare-earth oxide of basic metal and/or alkaline-earth metal compound and/or oxychlorination thing catalyzer; Described in step (2), oxidative dehydrogenation condition comprises: lighter hydrocarbons/containing the volume ratio of the oxygen in the gas of nitrogen and oxygen are 0.8-4, described temperature of reaction is 500-700 DEG C, reaction pressure is 0.07-0.5MPa, and reaction volume air speed is 2000-20000h
-1.
18. methods according to claim 17, wherein, the opening for feed of described oxydehydrogenation equipment is connected by ngl pipeline with Separation and Recovery equipment, and step (2) described lighter hydrocarbons are the circulation lighter hydrocarbons that step (3) gained contains ethane and/or propane at least partly.
19. methods according to claim 17, wherein, oxy-dehydrogenation catalyst described in step (2) is alkali-metal rare earth metal oxychlorination thing catalyzer.
20. methods according to claim 17, wherein, described in step (2), oxidative dehydrogenation condition comprises: lighter hydrocarbons/containing the volume ratio of the oxygen in the gas of nitrogen and oxygen are 1.2-2.5, described temperature of reaction is 600-660 DEG C, reaction pressure is 0.1-0.2MPa, and reaction volume air speed is 4000-10000h
-1.
21. methods according to claim 17, wherein, the method is also included in the oxydehydrogenation logistics removal of carbon monoxide being rich in ethene that step (2) obtained before step (3) after step (2) to wherein carbon monoxide volume content lower than 400ppm.
22. methods according to claim 21, wherein, the method also comprises carbon monoxide volume content is removed the volume content of sour gas to sour gas lower than 1ppm lower than the oxydehydrogenation logistics being rich in ethene of 400ppm.
23. methods according to claim 22, wherein, the method also comprises the volume content of sour gas is removed the volume content of oxygen to oxygen lower than 1ppm lower than the oxydehydrogenation logistics being rich in ethene of 1ppm.
24. methods according to claim 23, wherein, the method also comprises the volume content of oxygen is removed the volume content of nitrogen to nitrogen lower than 1ppm lower than the oxydehydrogenation logistics being rich in ethene of 1ppm, sends in splitting gas house steward, gasoline splitter, water wash column and Separation and Recovery equipment afterwards more simultaneously.
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| MX2019000809A (en) * | 2016-08-02 | 2019-09-09 | Shell Int Research | Ethylene production process and chemical complex. |
| AU2019356977B2 (en) | 2018-11-02 | 2021-10-07 | Shell Internationale Research Maatschappij B.V. | Separation of ethane oxidative dehydrogenation effluent |
| CN112142547A (en) * | 2019-06-27 | 2020-12-29 | 惠生工程（中国）有限公司 | Method for removing residual oxygen in product stream of ethylene preparation by catalytic oxidative dehydrogenation of ethane |
| CN110819377B (en) * | 2019-11-05 | 2021-09-03 | 辽宁北方华锦五洲化工工程设计有限公司 | Process method for improving light hydrocarbon feeding of ethylene unit cracking furnace |
| CN112831348B (en) * | 2020-12-30 | 2022-07-19 | 宁夏宝利科技设计研究院有限公司 | Mixed light hydrocarbon modification process method and system |
| WO2023104963A1 (en) | 2021-12-08 | 2023-06-15 | Linde Gmbh | Process and plant for producing one or more hydrocarbons |
| WO2023104962A1 (en) | 2021-12-08 | 2023-06-15 | Linde Gmbh | Process and system for producing one or more hydrocarbons |
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