CN106608804A - Method for removing oxygen from oxygen-containing light hydrocarbons - Google Patents
Method for removing oxygen from oxygen-containing light hydrocarbons Download PDFInfo
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- CN106608804A CN106608804A CN201510691446.8A CN201510691446A CN106608804A CN 106608804 A CN106608804 A CN 106608804A CN 201510691446 A CN201510691446 A CN 201510691446A CN 106608804 A CN106608804 A CN 106608804A
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- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
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Abstract
The invention relates to a method for removing oxygen from oxygen-containing light hydrocarbons. The method comprises the following step: conveying the oxygen-containing light hydrocarbons and absorbents into an absorbing column and carrying out contacting so as to obtain a column reactor material and oxygen-rich gas which is not absorbed at the top of the column, wherein the absorbents are C4 distillates and/or C5 distillates. In the method, by using the C4 distillates and the C5 distillates as the absorbents of the oxygen-containing light hydrocarbons instead of a deoxidizing catalyst, deoxidizing capacity is greatly increased. Besides, the method is simple in technology, does not need to use ethylene and propylene refrigerators or expanders, and reduces investment and consumption.
Description
Technical field
The present invention relates to lighter hydrocarbons manufacture field, in particular it relates to a kind of side for removing oxygen in oxygen-containing lighter hydrocarbons
Method.
Background technology
Lighter hydrocarbons are valuable ethylene, the propylene raw material of industry and chemical resource, are with big compared with high added value
Ancestor's chemicals.The lighter hydrocarbons gas (such as ethylene, propylene) of many commercial plant outputs all contains many oxygen
Gas.This oxygen-containing lighter hydrocarbons gas has huge potential safety hazard in manufacture of polyolefins industry.In addition, lighter hydrocarbons
The presence of oxygen in gas can not only reduce activity, selectivity and the yield of polyene hydrocarbon reaction effective catalyst,
And can affect to produce the performance of polymer.Therefore, the deoxidizing purification of lighter hydrocarbons gas is processed for downstream
Manufacture of polyolefins is most important.
It is logical in Patents documents and commercial production at present for the deoxidizing purification of light hydrocarbon gas is processed
Cross dehydrogenation catalyst realization.Dehydrogenation catalyst is broadly divided into two big class, and a class is the catalysis of carried noble metal
Hydrogenation deoxidation agent.This deoxidizer activity is higher, and deoxidation capacity is big, but expensive, is susceptible to add
Hydrogen side reaction, using less.An also class is chemisorbed type deoxidizer, and such deoxidizer does not have pair
Reaction, but it is restricted to unstripped gas oxygen content, and deoxidation capacity is little, needs frequent regeneration, in commercial production
In often have the shortcomings that to need to design double tower switching technique.It is light that Current Domestic is used for ethylene, propylene etc.
The catalyst of hydrocarbon gas deoxidizing purification is mainly Equations of The Second Kind chemisorbed type deoxidizer.But this kind of deoxidizer can only
Meet the loss of essence oxygen of light hydrocarbon gas of the oxygen content less than 100ppm, and for oxygen content is higher than 500ppm
Or even the light hydrocarbon gas of 5000ppm are unable to reach deoxidation requirement.
CN 102850159A disclose a kind of Nano titanium dioxide of employing modification by alkali metal
It is higher for the deoxidation depth under the dehydrogenation catalyst of carrier, room temperature, but preparation section is complicated, and alkene gas
Body oxygen content is unsuitable too high.
It is to help activity that CN 101745391A propose one kind active component, Ag, Au etc. based on Pd
The dehydrogenation catalyst of agent component, strong with poison resistance, bed is difficult the advantage of temperature runaway.But it is this de-
VPO catalysts can cause in use the loss of light hydrocarbon gas 0.5-1.7%.
CN 101165030A disclose Mn-Ag double activated composite deoxidation catalyst, and deoxidation effect is preferable.
But the mixture carrier for being used needs to calcine 3-8h more than 1000 DEG C, then crushes again, sieves.
Dehydrogenation catalyst is relatively costly, and the specific surface of carrier is low, and unit interval deoxidation amount is relatively low, also can increase
Cost.
In sum, existing lighter hydrocarbons QI prostration oxygen is realized by dehydrogenation catalyst, there is catalysis
Agent cost intensive, light hydrocarbon gas have been lost the problem low with deoxidation capacity.
It is also increasing for the demand of lighter hydrocarbons QI prostration oxygen with the swift and violent growth of China's lighter hydrocarbons production capacity.Pin
To present dehydrogenation catalyst yield and the deficiency of performance, studying new lighter hydrocarbons gas deoxy technology has huge
Potential value and wide application prospect.
The content of the invention
It is an object of the invention to overcome the above-mentioned technical problem of prior art, contain so as to provide a kind of removing
The method of oxygen in oxygen lighter hydrocarbons.
The invention provides a kind of method for removing oxygen in oxygen-containing lighter hydrocarbons, wherein, the method includes：Will
Oxygen-containing lighter hydrocarbons and absorbent are delivered in absorption tower and contacted, and obtain kettle material and tower top is unabsorbed
Oxygen rich air, wherein, the absorbent is C-4-fraction and/or C5 fraction；
Wherein, on the basis of the gross weight of the C-4-fraction, the C-4-fraction contains 10-50 weight %
Normal butane, the iso-butane of 10-30 weight %, the 1-butylene of 1-10 weight %, 15-35 weight % it is anti-
The cis-2-butene of -2-butylene and 15-25 weight %；
On the basis of the gross weight of the C5 fraction, the C5 fraction contains the different of 0.2-9 weight %
Pentane, the pentane of 30-60 weight %, the Pentamethylene. of 10-20 weight %, the 2- first of 10-30 weight %
The normal hexane of base pentane, the 2,3- dimethylbutanes of 5-15 weight % and 5-15 weight %；
The oxygen-containing lighter hydrocarbons contain monoolefines more than 60 weight %.
In the method for the present invention, dehydrogenation catalyst is replaced as oxygen-containing with the C-4-fraction, C5 fraction
The absorbent of lighter hydrocarbons, greatly improved deoxidation capacity, and the method process is simple, without using ethylene,
Propylene refrigeration machine and decompressor, reduce investment and consume.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with
Detailed description below is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is the flow chart for removing oxygen in oxygen-containing lighter hydrocarbons according to one embodiment of the present invention.
Description of reference numerals
The oxygen-containing lighter hydrocarbons gas of 1-；2- absorbent；3- oxygen rich airs；4- non-interactive gases；5- carrier gas；6-
Lighter hydrocarbons gas；The absorbent that 7- is supplemented；8- compressors；9- coolers；10- absorption towers；11- desorbers；12-
Cooler；13- kettle materials.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method for removing oxygen in oxygen-containing lighter hydrocarbons, wherein, the method includes：Will
Oxygen-containing lighter hydrocarbons and absorbent are delivered in absorption tower and contacted, and obtain kettle material and tower top is unabsorbed
Oxygen rich air, wherein, the absorbent is C-4-fraction and/or C5 fraction；
Wherein, on the basis of the gross weight of the C-4-fraction, the C-4-fraction contains 10-50 weight %
Normal butane, the iso-butane of 10-30 weight %, the 1-butylene of 1-10 weight %, 15-35 weight % it is anti-
The cis-2-butene of -2-butylene and 15-25 weight %；
On the basis of the gross weight of the C5 fraction, the C5 fraction contains the different of 0.2-9 weight %
Pentane, the pentane of 30-60 weight %, the Pentamethylene. of 10-20 weight %, the 2- first of 10-30 weight %
The normal hexane of base pentane, the 2,3- dimethylbutanes of 5-15 weight % and 5-15 weight %；
The oxygen-containing lighter hydrocarbons contain monoolefines more than 60 weight %.
In the present invention, the oxygen-containing lighter hydrocarbons can be from refinery's commercial plant (for example catalytic cracking, coking,
The commercial plants such as hydrogen peroxide legal system expoxy propane) reclaim containing monoolefines more than 60 weight %
The gaseous mixture of C2-C4 hydro carbons, its monoolefine mainly includes ethylene and/or propylene, C2-C4 hydro carbons other
Composition includes：One or more in ethane and propane etc..It is well known in the art that, due to production technology
Restriction, the hydro carbons of the C2-C4 inevitably contains oxygen, and the presence of oxygen can be in follow-up alkene
There is the huge potential safety hazard of such as blast in hydrocarbon production industry, therefore, it is necessary to remove the hydro carbons
In oxygen.
According to the present invention, the oxygen-containing lighter hydrocarbons contain monoolefines more than 60 weight %, are meeting this
Under part, under preferable case, on the basis of the gross weight of the oxygen-containing lighter hydrocarbons, in the oxygen-containing lighter hydrocarbons, C2-C4
The content of monoolefine be 60-95 weight %, the content of the alkane of C2-C4 is 1-25 weight %, oxygen
Content be 1 weight % more than (preferred 3-10 weight %).Further, it is also possible to contain nitrogen, dioxy
Change one or more (as balance gas) in carbon, the alcohol of C1-C3, alkane of C4-C5 etc..
In the case where above range is met, for example, on the basis of the gross weight of the oxygen-containing lighter hydrocarbons, institute
In stating oxygen-containing lighter hydrocarbons, the content of ethylene is 40-60 weight %, and the content of propylene is 15-25 weight %,
The content of ethane is 10-15 weight %, and the content of propane is 2-7 weight %, and oxygen content is 3-5 weight %,
One or more in balance of nitrogen, carbon dioxide, the alcohol of C1-C3, alkane of C4-C5 etc..
Again for example, on the basis of the gross weight of the oxygen-containing lighter hydrocarbons, in the oxygen-containing lighter hydrocarbons, propylene contains
Measure as 80-95 weight %, the content of propane is 2-10 weight %, oxygen content is 3-5 weight %, first
The content of alcohol is balance of nitrogen, carbon dioxide, the alcohol of C2-C3, C4-C5 below 2 weight %
One or more in alkane etc..
Well known in the art to be, the oxygen-containing lighter hydrocarbons are at normal temperatures and pressures gas.For the ease of description,
The oxygen-containing lighter hydrocarbons of gaseous state are referred to as into oxygen-containing lighter hydrocarbons gas below of the invention.Similarly, deoxidation is obtained
The lighter hydrocarbons of gaseous state are referred to as lighter hydrocarbons gas.
In the present invention, in order that the oxygen-containing lighter hydrocarbons gas further meets the process needs of absorption tower apparatus simultaneously
The usage amount of absorbent is reduced, the oxygen-containing lighter hydrocarbons is delivered to before absorption tower, it is preferable that methods described
Also include for the oxygen-containing lighter hydrocarbons carrying out shallow cold treatment, it is highly preferred that the shallow cold process includes：Will
The pressure boil down to 3-6MPa of the oxygen-containing lighter hydrocarbons, then by compression after oxygen-containing lighter hydrocarbons be cooled to
5-20℃.The compression can be carried out on the compressor, generally required and improve step by step pressure, and the present invention is to pressure
The hop count of contracting is not particularly limited, it is preferred to use three sections of compressions.Method of deoxidation of the invention, it is described
Cooling need not adopt ethylene commonly used in the art, propylene refrigeration machine and decompressor, can select by bromine
The cooling water for changing 5 DEG C or so that lithium-absorbing formula refrigeration machine is provided is cold-producing medium, and the lithium bromide refrigerator can
With the waste hot steam or hot water of factory as thermal source, to have the advantages that energy consumption is low.Therefore, the present invention's is cold
But the cooler for preferably using is lithium-bromide absorption-type refrigerating machine.
According to the present invention, the C-4-fraction can be derived from the C-4-fraction after refinery's etherification reaction.It is preferred that
In the case of, on the basis of the gross weight of the C-4-fraction, the C-4-fraction contains 20-30 weight %
Normal butane, the iso-butane of 10-20 weight %, the 1-butylene of 6-9 weight %, the trans- 2- of 25-30 weight %
The cis-2-butene of butylene and 15-20 weight %.
In the present invention, the C5 fraction can be derived from pentane oil.Under preferable case, evaporated with the carbon five
On the basis of the gross weight divided, the C5 fraction contains the isopentane of 0.2-5 weight %, 30-40 weight %
Pentane, the Pentamethylene. of 15-20 weight %, the 2- methylpentanes of 20-30 weight %, 5-10 weight %
2,3- dimethylbutanes and 5-15 weight % normal hexane.
According to the present invention, the temperature on the absorption tower can be selected according to the species of absorbent and consumption
Select, from the angle for improving assimilation effect and reducing energy consumption, it is preferable that the tower top temperature on the absorption tower
Spend for 5-60 DEG C (preferably 10-20 DEG C), bottom temperature is 80-200 DEG C (preferably 95-160 DEG C).
In absorption tower, the absorbent absorbs lighter hydrocarbons and more heavy constituent that may be present in oxygen-containing lighter hydrocarbons, obtains
To kettle material, and unabsorbed lighter enter tower top containing nitrogen oxygen rich air.
The present invention is not particularly limited to the number of theoretical plate and operating pressure on the absorption tower, generally with reason
By the number of plates, the raising of operating pressure, deoxidation effect is better.In order to ensure deoxidation effect while,
Reducing energy consumption, the preferably operating pressure on the absorption tower are 3-5MPa, and theoretical cam curve is 40-50.
In the present invention, unabsorbed light hydrocarbon component is inevitably contained in the oxygen rich air, in order to contract
The concentration of the little oxygen and lighter hydrocarbons, further to reduce explosive range, preferred methods described also includes：
The oxygen rich air is diluted with non-interactive gas.The non-interactive gas can be normal for this area
Rule not with or do not promote oxygen and lighter hydrocarbons that any gas of chemical reaction occurs.From the angle that raw material is easy to get
Set out, preferably the non-interactive gas is nitrogen.The present invention does not have to the consumption of the non-interactive gas
There is special restriction, after the non-interactive gas mixes with the oxygen rich air, in the carrier gas for obtaining
Oxygen concentration is the smaller the better.
According to the present invention, the method can also include：The kettle material is delivered to into Analytic Tower to be parsed,
From the lighter hydrocarbons that tower top is recycled, the kettle material can be relied between the absorption tower and desorber
Pressure reduction is entered in the Analytic Tower, and without the need for additionally applying pressure.In by controlling the Analytic Tower
The kettle material can be separated into absorbent and lighter hydrocarbons by condition, and tower top obtains lighter hydrocarbons gas, and tower reactor is suction
Receive agent.
The present invention is not particularly limited to the condition in the Analytic Tower, as long as can be by absorbent and lighter hydrocarbons point
From.Preferably, the tower top temperature of the Analytic Tower be 5-60 DEG C (preferably 20-50 DEG C), tower reactor
Temperature is 80-200 DEG C (preferably 100-160 DEG C).The separating effect of both collateral securities and reducing energy consumption
Angle is set out, it is highly preferred that the operating pressure of the Analytic Tower is 1-2.5MPa (preferably 1.2-2MPa),
Theoretical cam curve is 25-35.
With the method for the invention it is preferred to methods described also includes：Analytically the tower reactor of tower reclaims absorbent,
And recycle.But it is able to obtain higher oxygen removing effect, can be with to the tower of Analytic Tower
Kettle and/or absorption tower supplement without the fresh absorbent for absorbing link so that absorbent is enough to be used in
The absorption to oxygen-containing lighter hydrocarbons gas is completed, such as in the mass flow of the fresh absorbent for supplementing and absorption tower
The mass flow ratio of the absorbent of addition is 1：500-2000.The absorbent of the supplement is also the carbon four
Fraction and/or C5 fraction, supplementary C-4-fraction and/or the composition of C5 fraction can with adopt before
Absorbent composition it is identical or different.
Oxygen-containing lighter hydrocarbons are entered by a preferred embodiment of the invention using flow process as shown in Figure 1
Row deoxidation.Wherein, will pressure is increased to through compressor 8 from the oxygen-containing lighter hydrocarbons gas 1 of commercial plant
3-6MPa；Then Jing coolers 9 are cooled to 5-20 DEG C, and deliver in absorption tower 10.By absorbent 2
Spray into from the tower top on absorption tower 10, to absorb oxygen-containing lighter hydrocarbons gas 1 in lighter hydrocarbons and more heavy constituent, obtain
Kettle material 13 and the unabsorbed oxygen rich air 3 of tower top.The oxygen rich air 3 is mixed to get with nitrogen 4
Carrier gas 5, carrier gas 5 is discharged from tower top.Kettle material 13 is delivered to into desorber 11 by pressure reduction
Processed, from tower top the lighter hydrocarbons gas 6 after deoxidizing purification is obtained, and discharged it；Tower reactor obtains lean suction
Agent is received, the cooling of Jing coolers 12 returns to absorption tower and recycles.According to the composition of lean receipts agent, optionally exist
The tower reactor of desorber 11 adds supplementary absorbent 7.
According to the present invention, the flow for entering into the oxygen-containing lighter hydrocarbons on the absorption tower can setting according to absorption tower
Meter and type selecting are selected.In this case, it is preferable to the quality stream of the oxygen-containing lighter hydrocarbons and the absorbent
The ratio of amount is 1:1-5, more preferably 1:3-5.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
The present embodiment is used for the method for deoxidation of the oxygen-containing lighter hydrocarbons for illustrating the present invention.
What the present embodiment was processed is the oxygen-containing lighter hydrocarbons gas that hydrogen peroxide legal system expoxy propane commercial plant is produced, and is contained
The composition of oxygen lighter hydrocarbons gas and the absorbent of carbon four is shown in Table 1.
Table 1
| Quality constitutes (weight %) | Oxygen-containing lighter hydrocarbons gas | The absorbent of carbon four |
| Nitrogen | 0.24 | - |
| Oxygen | 4.34 | - |
| Carbon dioxide | 0.48 | - |
| Ethane | 14.58 | - |
| Ethylene | 56.78 | - |
| Propane | 5.37 | - |
| Propylene | 18.15 | - |
| Normal butane | 0.06 | 27.91 |
| Iso-butane | - | 15.59 |
| 1-butylene | - | 7.72 |
| Isobutene. | - | 0.04 |
| Trans-2-butene | - | 28.44 |
| Cis-2-butene | - | 20.23 |
| Water | - | 0.01 |
| Dimethyl ether | - | 0.06 |
Oxygen-containing lighter hydrocarbons are carried out by deoxidation using flow process as shown in Figure 1, except for the difference that, not including Analytic Tower
Part：By oxygen-containing lighter hydrocarbons pneumatic transmission of the pressure shown in the table 1 of 1MPa to compressor 8, pressure is improved
To 5MPa.Oxygen-containing lighter hydrocarbons gas Jing coolers 9 after supercharging are cooled to 13 DEG C, then with 2613.56kg/h
Send in absorption tower 10, and the absorbent of carbon four is sprayed into from tower top with 8000kg/h, absorb oxygen-containing lighter hydrocarbons
Lighter hydrocarbons and heavier component in gas.The number of theoretical plate on absorption tower 10 is 40, and operating pressure is 4.5MPa,
Tower top temperature is 16.6 DEG C, and bottom temperature is 99.9 DEG C, obtains kettle material and the unabsorbed richness of tower top
Oxygen.Oxygen rich air is mixed with the nitrogen of 400kg//h, carrier gas is obtained, with 536.84kg/h from tower top
Discharge.Wherein, the composition of carrier gas and kettle material is as shown in table 2.
Table 2
| Quality constitutes (weight %) | Carrier gas | Kettle material |
| Nitrogen | 75.67 | - |
| Oxygen | 21.11 | 1ppm |
| Carbon dioxide | - | 0.12 |
| Ethane | - | 3.64 |
| Ethylene | - | 14.16 |
| Propane | - | 1.34 |
| Propylene | - | 4.53 |
| Normal butane | 0.86 | 21.28 |
| Iso-butane | 0.68 | 11.87 |
| 1-butylene | 0.28 | 5.88 |
| Isobutene. | - | 0.03 |
| Trans-2-butene | 0.84 | 21.68 |
| Cis-2-butene | 0.55 | 15.42 |
| Water | 0.01 | - |
| Dimethyl ether | - | 0.05 |
Embodiment 2
The present embodiment is used for the method for deoxidation of the oxygen-containing lighter hydrocarbons for illustrating the present invention.
What the present embodiment was processed is the oxygen-containing lighter hydrocarbons gas that hydrogen peroxide legal system expoxy propane commercial plant is produced, and is contained
The composition of oxygen lighter hydrocarbons gas and the absorbent of carbon five is as shown in table 3.
Table 3
| Quality constitutes (weight %) | Oxygen-containing lighter hydrocarbons gas | The absorbent of carbon five |
| Nitrogen | 0.36 | - |
| Oxygen | 4.39 | - |
| Carbon dioxide | 0.23 | - |
| Methanol | 1.04 | - |
| Propane | 4.78 | 0.02 |
| Propylene | 89.13 | 0.26 |
| Normal butane | 0.07 | 0.01 |
| Isopentane | - | 0.63 |
| Pentane | - | 34.03 |
| Pentamethylene. | - | 17.05 |
| 2,3- dimethylbutanes | - | 8.83 |
| 2- methylpentanes | - | 27.42 |
| Normal hexane | - | 11.76 |
Oxygen-containing lighter hydrocarbons are carried out by deoxidation using flow process as shown in Figure 1：By pressure for 1MPa the institute of table 3
The oxygen-containing lighter hydrocarbons pneumatic transmission for showing pressure is increased to 3.3MPa to compressor 8.Oxygen-containing lighter hydrocarbons gas after supercharging
Jing coolers 9 are cooled to 13 DEG C, then are sent in absorption tower 10 with 2382.17kg/h, and carbon five is absorbed
Agent, with 10316.16kg/h penetratings, absorbs the lighter hydrocarbons and heavier component in oxygen-containing lighter hydrocarbons gas from tower top.Inhale
The number of theoretical plate for receiving tower 10 is 40, and operating pressure is 3MPa, and tower top temperature is 14.1 DEG C, tower reactor temperature
Spend for 154.7 DEG C, obtain kettle material and the unabsorbed oxygen rich air of tower top.By oxygen rich air and 400kg//h
Nitrogen mixing, obtain carrier gas, with 517.88kg/h from tower top discharge.
The kettle material on absorption tower is delivered to into desorber 11 with 12580.46kg/h by pressure reduction to process.Solution
The number of theoretical plate for inhaling tower 11 is 31, and operating pressure is 1.2MPa, and tower top temperature is 27 DEG C, tower reactor temperature
Spend for 150.9 DEG C.The lighter hydrocarbons gas after deoxidizing purification is obtained from tower top, with 2274.16kg/h discharges；Tower reactor
Lean absorbent is obtained, 13 DEG C are cooled to, absorption tower 10 is returned to and is recycled, and in desorber
Kettle supplements 10kg/h C5 fractions.The composition of carrier gas and lighter hydrocarbons gas is as shown in table 4.
Table 4
| Quality constitutes (weight %) | Carrier gas | Lighter hydrocarbons gas |
| Nitrogen | 78.89 | - |
| Oxygen | 20.2 | 3ppm |
| Carbon dioxide | - | 0.24 |
| Methanol | - | 1.09 |
| Propane | - | 5.01 |
| Propylene | 0.05 | 93.35 |
| Normal butane | 0.07 | |
| Isopentane | 0.01 | 0.06 |
| Pentane | 0.44 | 0.17 |
| Pentamethylene. | 0.15 | - |
| 2,3- dimethylbutanes | 0.05 | - |
| 2- methylpentanes | 0.15 | - |
| Normal hexane | 0.04 | - |
Embodiment 3
The present embodiment is used for the method for deoxidation of the oxygen-containing lighter hydrocarbons for illustrating the present invention.
What the present embodiment was processed is the oxygen-containing lighter hydrocarbons gas that hydrogen peroxide legal system expoxy propane commercial plant is produced, and is contained
The composition of oxygen lighter hydrocarbons gas and the absorbent of carbon four is shown in Table 5.
Table 5
| Quality constitutes (weight %) | Oxygen-containing lighter hydrocarbons gas | The absorbent of carbon four |
| Nitrogen | 0.24 | - |
| Oxygen | 3.21 | - |
| Carbon dioxide | 0.31 | - |
| Methanol | 1.33 | - |
| Propane | 1.91 | - |
| Propylene | 92.94 | - |
| Normal butane | 0.06 | 27.91 |
| Iso-butane | - | 15.59 |
| 1-butylene | - | 7.72 |
| Isobutene. | - | 0.04 |
| Trans-2-butene | - | 28.44 |
| Cis-2-butene | - | 20.23 |
| Water | - | 0.01 |
| Dimethyl ether | - | 0.06 |
Oxygen-containing lighter hydrocarbons are carried out by deoxidation using flow process as shown in Figure 1：By the table 5 that pressure is 1.5MPa
Shown oxygen-containing lighter hydrocarbons pneumatic transmission pressure is increased to 3.6MPa to compressor 8.Oxygen-containing lighter hydrocarbons after supercharging
Gas Jing coolers 9 are cooled to 13 DEG C, then are sent in absorption tower 10 with 2543.92kg/h, and carbon four is inhaled
Agent is received from tower top with 7980.45kg/h penetratings, the lighter hydrocarbons and heavier component in oxygen-containing lighter hydrocarbons gas are absorbed.
The number of theoretical plate on absorption tower 10 is 40, and operating pressure is 3.4MPa, and tower top temperature is 15.3 DEG C, tower reactor
Temperature is 122.3 DEG C, obtains kettle material and the unabsorbed oxygen rich air of tower top.By oxygen rich air with
400kg//h nitrogen mixes, and obtains carrier gas, is discharged from tower top with 500.9kg/h.
Kettle material is processed with 10423.48kg/h from the top feeding of desorber 11 by pressure reduction.Solution
The number of theoretical plate for inhaling tower is 31, and operating pressure is 1.7MPa, and tower top temperature is 40.9 DEG C, bottom temperature
For 106.7 DEG C.The lighter hydrocarbons gas after deoxidizing purification is obtained from tower top, with 2547.15kg/h discharges；Tower reactor is obtained
To lean absorbent, 13 DEG C are cooled to, return to absorption tower 10 and recycle.In desorbing tower reactor with 10
Kg/h supplements C-4-fraction.The composition of carrier gas and lighter hydrocarbons gas is as shown in table 6.
Table 6
| Quality constitutes (weight %) | Carrier gas | Lighter hydrocarbons gas |
| Nitrogen | 81.06 | - |
| Oxygen | 16.31 | 3ppm |
| Carbon dioxide | - | 0.32 |
| Methanol | - | 1.37 |
| Propane | - | 1.98 |
| Propylene | 0.03 | 96.23 |
| Normal butane | 1.08 | 0.02 |
| Iso-butane | 0.09 | 0.05 |
| 1-butylene | 0.07 | 0.02 |
| Isobutene. | - | - |
| Trans-2-butene | 0.77 | 0.01 |
| Cis-2-butene | 0.59 | - |
Comparative example 1
Method according to embodiment 2, except that, using C-4-fraction as absorbent, institute
Using C-4-fraction it is as shown in table 7：
Table 7
| Quality constitutes (weight %) | C-4-fraction |
| Normal butane | 29.56 |
| Iso-butane | 0.14 |
| 1-butylene | 11.86 |
| Trans-2-butene | 33.25 |
| Cis-2-butene | 24.23 |
| The hydro carbons of more than C5 | 1 |
The composition of carrier gas and lighter hydrocarbons gas is as shown in table 8：
Table 8
| Quality constitutes (weight %) | Carrier gas | Lighter hydrocarbons gas |
| Nitrogen | 80.71 | - |
| Oxygen | 16.24 | 10ppm |
| Carbon dioxide | - | 0.29 |
| Methanol | - | 1.25 |
| Propane | 0.02 | 1.82 |
| Propylene | 0.65 | 88.33 |
| Normal butane | 0.75 | 3.01 |
| Iso-butane | - | - |
| 1-butylene | 0.01 | 0.09 |
| Trans-2-butene | 0.73 | 2.9 |
| Cis-2-butene | 0.85 | 2.3 |
| The hydro carbons of more than C5 | 0.02 | - |
Comparative example 2
Method according to embodiment 2, except that, the C5 fraction of employing is shown in Table 9：
Table 9
| Quality constitutes (weight %) | C5 fraction |
| Isopentane | 10 |
| Pentane | 20.1 |
| Iso-amylene | 28.9 |
| N-pentene | 14.7 |
| 2- amylenes | 26.3 |
The composition of carrier gas and lighter hydrocarbons gas is as shown in table 10：
Table 10
| Quality constitutes (weight %) | Carrier gas | Lighter hydrocarbons gas |
| Nitrogen | 78.39 | - |
| Oxygen | 20.07 | 9ppm |
| Carbon dioxide | - | 0.23 |
| Methanol | - | 1.02 |
| Propane | - | 4.71 |
| Propylene | - | 87.79 |
| Normal butane | - | 0.04 |
| Isopentane | 0.65 | 3.29 |
| Pentane | - | - |
| Iso-amylene | 0.89 | 2.92 |
| N-pentene | - | - |
| 2- amylenes | - | - |
Embodiment 1-3 and comparative example 1-2 by more than can be seen that the lighter hydrocarbons of method of the present invention recovery
Oxygen content is in below 3ppm in gas, and deoxidation capacity is high, and lighter hydrocarbons are not lost substantially.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible compound modes.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. in a kind of oxygen-containing lighter hydrocarbons of removing oxygen method, it is characterised in that the method includes：To contain
Oxygen lighter hydrocarbons and absorbent are delivered in absorption tower and contacted, and obtain kettle material and the unabsorbed richness of tower top
Oxygen, wherein, the absorbent is C-4-fraction and/or C5 fraction；
Wherein, on the basis of the gross weight of the C-4-fraction, the C-4-fraction contains 10-50 weight %
Normal butane, the iso-butane of 10-30 weight %, the 1-butylene of 1-10 weight %, 15-35 weight % it is anti-
The cis-2-butene of -2-butylene and 15-25 weight %；
On the basis of the gross weight of the C5 fraction, the C5 fraction contains the different of 0.2-9 weight %
Pentane, the pentane of 30-60 weight %, the Pentamethylene. of 10-20 weight %, the 2- first of 10-30 weight %
The normal hexane of base pentane, the 2,3- dimethylbutanes of 5-15 weight % and 5-15 weight %；
The oxygen-containing lighter hydrocarbons contain monoolefines more than 60 weight %.
2. method according to claim 1, wherein, methods described also includes：Will be described oxygen-containing
Lighter hydrocarbons are delivered to before absorption tower, by the pressure boil down to 3-6MPa of the oxygen-containing lighter hydrocarbons, then will compression
Oxygen-containing lighter hydrocarbons afterwards are cooled to 5-20 DEG C.
3. method according to claim 1 and 2, wherein, with the gross weight of the C-4-fraction
On the basis of, the C-4-fraction contain the normal butane of 20-30 weight %, the iso-butane of 10-20 weight %,
The cis-2-butene of the 1-butylene, the Trans-2-butene of 25-30 weight % and 15-20 weight % of 6-9 weight %.
4. the method according to any one in claim 1-3, wherein, with the C5 fraction
Gross weight on the basis of, the C5 fraction contains the isopentane of 0.2-5 weight %, 30-40 weight %
Pentane, the Pentamethylene. of 15-20 weight %, the 2- methylpentanes of 20-30 weight %, 5-10 weight %
The normal hexane of 2,3- dimethylbutanes and 5-15 weight %.
5. the method according to any one in claim 1-4, wherein, the tower on the absorption tower
Top temperature is 5-60 DEG C, and bottom temperature is 80-200 DEG C.
6. method according to claim 5, wherein, the operating pressure on the absorption tower is 3-5MPa,
Theoretical cam curve is 40-50.
7. the method according to any one in claim 1-6, wherein, the method also includes：
The kettle material is delivered to into Analytic Tower to be parsed, from the lighter hydrocarbons that tower top is recycled, wherein, it is described
The tower top temperature of Analytic Tower is 5-60 DEG C, and bottom temperature is 80-200 DEG C；
Preferably, the operating pressure of the Analytic Tower is 1-2.5MPa, and theoretical cam curve is 25-35.
8. the method according to any one in claim 1-7, wherein, the oxygen-containing lighter hydrocarbons with
The ratio of the mass flow of the absorbent is 1:1-5.
9. the method according to any one in claim 1-8 wherein, wherein, methods described is also
Including：Analytically the tower reactor of tower reclaims absorbent, and recycles.
10. the method according to any one in claim 1-9 wherein, wherein, methods described is also
Including：The oxygen rich air is diluted with non-interactive gas.
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