CN107986933A - The device and method of carbon two is recycled in a kind of aromatic hydrocarbons by-product dry gas from methanol - Google Patents
The device and method of carbon two is recycled in a kind of aromatic hydrocarbons by-product dry gas from methanol Download PDFInfo
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- CN107986933A CN107986933A CN201610949747.0A CN201610949747A CN107986933A CN 107986933 A CN107986933 A CN 107986933A CN 201610949747 A CN201610949747 A CN 201610949747A CN 107986933 A CN107986933 A CN 107986933A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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 present invention relates to gas organic matter recycling field, disclose the device and method that carbon two is recycled in a kind of aromatic hydrocarbons by-product dry gas from methanol, the device includes sequentially connected raw sorbent feed unit, lightness-removing column, four desorber of gasoline stabilizer, four absorption tower of carbon and carbon, and the lightness-removing column and gasoline stabilizer are used for the carbon four in the raw sorbent that purifier absorption agent raw material feed unit provides；This method includes carrying out raw sorbent de- light, to slough light component of the carbon below three, raw sorbent after taking off gently is subjected to the first rectifying with isolated carbon four and aromatic hydrocarbons, is contacted with obtained carbon four with methanol aromatic hydrocarbons by-product dry gas to absorb the heavy constituent of carbon more than two in dry gas；Obtained carbon four and the mixture of the heavy constituent of carbon more than two are subjected to the second rectifying with isolated carbon two and carbon four.By apparatus and method of the present invention, other various impurity and metal ion will not be introduced outside MTA devices, so as to improve organic efficiency and product quality.
Description
Technical field
The present invention relates to gas organic matter recycling field, and in particular, to a kind of from methanol aromatic hydrocarbons by-product (MTA) dry gas
The device and method of middle recycling carbon two.
Background technology
MTA dry gas comes from methanol aromatic device, wherein usually containing substantial amounts of ethene, ethane and aromatic component, no
Preferably sell, and utilization is more difficult.If two component of carbon in MTA dry gas recycled, return to methanol aromatic device and do raw material,
The production cost of aromatic hydrocarbons can be reduced, its economic benefit and social benefit are all fairly obvious.
Recycling ethane, the method for ethylene component from dry gas at present mainly has separation by deep refrigeration, pressure swing adsorption method and shallow cold
Oil-absorption process etc., various methods all have the characteristics that respective.Separation by deep refrigeration technical maturity, Recovery rate of ethylene is high, but invests greatly,
It is higher for dilute ethylene recovery energy consumption；Pressure swing adsorption method is easy to operate, and energy consumption is relatively low, but product purity is low, and Recovery rate of ethylene is low,
Take up a large area.
Shallow cold oil absorption process mainly utilizes absorbent to the different solubility of each component in gas to separate gas mixing
Thing, generally absorbs the heavy constituent of carbon two and carbon more than two first with absorbent, isolates the fixed gases such as methane, hydrogen, then with smart
Evaporate each component in method separate absorbent agent.This method has carbon two, three rate of recovery height of carbon, production safety, reliable and to original
Expect gas it is adaptable the features such as, be one of current competitive technology.But there is a small amount of carbon in shallow cold oil absorption technique
Four absorbents and gasoline absorbent can send out battery limit (BL) with methane, hydrogen body, in order to ensure four absorbent of carbon and gasoline absorbent
Dosage is circulated, generally requires from the external world and introduces one four absorbent of carbon and one gasoline absorbent respectively as supplement.Supplement carbon
Four absorbents and/or gasoline absorbent are needed based on carbon four and/or gasoline component, avoid influencing carbon four and/or gasoline absorbs
The product design of the two concentrate gas of assimilation effect and carbon of agent.But the not logistics based on four component of carbon in MTA devices, only
Carbon containing three, the mixture flow of carbon four and aromatic hydrocarbons, introduces four absorbent of carbon and/or gasoline absorbent, Ke Nengsui such as outside MTA devices
The various impurity of introducing and metal ion, so as to influence dry-gas recovery device product gas specification.
CN103087772A discloses a kind of device and method of oil-absorption process separation dry gas, this method absorbs by carbon four,
Carbon four desorbs, gasoline absorb and etc. composition, absorbent be used as using carbon four, carbon two, C3 fraction in recycling dry gas.Adopt again
The carbon four in tail gas is recycled with gasoline absorbent.The technique Recovery rate of ethylene is high, and the loss of four absorbent of carbon is few, but need to be outside battery limit (BL)
Introduce one four absorbent of carbon and one gasoline absorbent.Four absorbent of carbon may be selected from after refinery's mixing carbon four, ether carbon four or its
His C-4-fraction, gasoline absorbent often use gasoline for refinery.
CN101759516A discloses a kind of method of oily absorption and separation plant catalytic dry gas, uses the light dydrocarbon comprising pentane
Hydrocarbon is absorbed in main absorption tower and sent through two component of carbon in overcompression, catalysis drying gas after cooling, tower reactor logistics as absorbent
Enter desorber and desorb two concentrate gas of carbon, the light dydrocarbon absorbent of main absorbing tower top gas entrainment is recycled using reabsorber.The work
It is preferably refinery's raw gasoline that skill, which needs to supplement light dydrocarbon absorbent and gasoline absorbent, gasoline absorbent outside battery limit (BL),.
CN104557387A discloses a kind of refinery's mixing dry gas recovery system, including absorption tower, desorber, purification dress
Put, crude tower, naphtha scrubber and gasoline desorber.The technique is absorbed-desorbed by a set of carbon four to recycle the carbon in dry gas
Two components, then recycle by a set of gasoline absorption-desorption four absorbent of carbon of entrainment.The technique can recycle carbon four and inhale
Agent and gasoline absorbent are received, absorbent dosage is few, and loss is few, but four absorbent of carbon and gasoline absorbent still can be by methane hydrogen fuels
Gas takes away a part, therefore still needs and four absorbent of carbon and gasoline absorbent are supplemented outside battery limit (BL).Four absorbent of carbon of supplement
For C-4-fraction, saturation liquefied gas or C5 fraction etc..The gasoline fraction of supplement is stable gasoline, heavy naphtha or aromatic hydrocarbons raffinate
Oil etc..
In conclusion the technique of two component of carbon is, it is necessary to supplement carbon four (or light dydrocarbon) absorption in existing separation and recovery dry gas
Agent and gasoline absorbent, available supplement carbon four (or light dydrocarbon) absorbent come from material of the refinery based on carbon four (or light dydrocarbon)；
Available supplement gasoline absorbent comes from oil refinery gasoline/heavy naphtha/and the product such as raffinates oil.Obviously, if drawn outside MTA devices
Enter four absorbent of carbon or gasoline absorbent, various impurity and metal ion may be introduced therewith, so as to influence product quality.
The content of the invention
The purpose of the present invention is overcoming that four absorbent of carbon or gasoline absorbent need to be introduced outside MTA devices in the prior art,
Various impurity and metal ion may be introduced therewith, so that the defects of influencing product quality, there is provided one kind is suitable for using only MTA
The device and method of the recycling carbon two from methanol aromatic hydrocarbons by-product dry gas is completed in the case of device interior air-flow.
To achieve these goals, on the one hand, recycle carbon from methanol aromatic hydrocarbons by-product dry gas the present invention provides one kind
Two device, the device include sequentially connected raw sorbent feed unit, lightness-removing column, gasoline stabilizer, four absorption tower of carbon
With four desorber of carbon, the lightness-removing column and gasoline stabilizer are used for the raw sorbent that purifier absorption agent raw material feed unit provides
In carbon four.
On the other hand, present invention also offers a kind of method that carbon two is recycled in aromatic hydrocarbons by-product dry gas from methanol, the party
Method comprises the following steps：
(1) raw sorbent take off gently, to slough light component of the carbon below three；
(2) raw sorbent after taking off gently is subjected to the first rectifying with isolated carbon four and aromatic hydrocarbons；
(3) contacted with the carbon four obtained in step (2) with methanol aromatic hydrocarbons by-product dry gas to absorb carbon more than two in dry gas
Heavy constituent；
(4) carbon four obtained in step (3) and the mixture of the heavy constituent of carbon more than two are subjected to the second rectifying to separate
Obtain carbon two and carbon four.
Carbon two is recycled from MTA dry gas by apparatus and method of the present invention, carbon four can not be introduced outside MTA devices and inhaled
Agent or gasoline absorbent are received, so that other various impurity and metal ion will not be introduced, improves the efficiency and product of recycling
Quality.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the structure diagram according to a kind of device of preferred embodiment of the present invention.
Description of reference numerals
1 MTA dry gas feed unit, 2 residue gas compressor
3 dry gas cooler, 4 carbon, four absorption tower
5 carbon, four desorber, 6 naphtha scrubber
7 gasoline stabilizer, 8 raw sorbent cooler
9 raw sorbent gas-liquid separator, 10 raw sorbent pumps
11 lightness-removing column, 12 carbon, four circulating pump
13 carbon, four cooler, 14 gasoline circulating pump
15 aromatic hydrocarbons discharge port, 16 methane hydrogen discharge port
17 carbon, three discharge port, 18 carbon, two discharge port
19 carbon, four feed inlet, 20 aromatic feed mouth
21 carbon, four discharge port, 22 raw sorbent feed unit
23 fixed gas discharge ports
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 endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In the present invention, in the case where not making conversely explanation, " carbon two " refers to that carbon number is two to the term used
The general designation of a hydrocarbon compound (mainly including ethene, ethane)；" carbon three " refers to the hydro carbons that carbon number is three to term
The general designation of compound (mainly including propylene, propane)；" carbon four " refers to that the hydrocarbon compound that carbon number is four is (main to term
Will include butylene, butane) general designation；Term " aromatic hydrocarbons " refers to the hydrocarbon compound containing phenyl ring that carbon number is six and seven
The general designation of (mainly including benzene, toluene).
The present invention provides the device that carbon two is recycled in a kind of aromatic hydrocarbons by-product dry gas from methanol, described device is included successively
Raw sorbent feed unit 22, lightness-removing column 11, four desorber 5 of gasoline stabilizer 7, four absorption tower 4 of carbon and carbon of connection, it is described
Lightness-removing column 11 and gasoline stabilizer 7 are used for the carbon four in the raw sorbent that purifier absorption agent raw material feed unit 22 provides.
Wherein, raw sorbent can be the gaseous mixture of carbon containing three, carbon four and aromatic hydrocarbons in methanol aromatic hydrocarbons, carbon after purification
Four can be used as absorbent, and the heavy constituent of the carbon more than two in MTA dry gas is absorbed in four absorption tower 4 of carbon, and be desorbed in carbon four
Rectifying separates in tower 5, for purifying and recycling the carbon two in MTA dry gas.
According to the present invention it is possible to the raw sorbent for being introduced into lightness-removing column 11 is pre-processed.Preferably, described device
Further include the raw sorbent cooler 8 being arranged between raw sorbent feed unit 22 and lightness-removing column 11 and raw sorbent
Gas-liquid separator 9 so that raw sorbent is through cooling down and being entered back into after gas-liquid separation in lightness-removing column 11.
According to the present invention, described device can also include the MTA dry gas feed unit 1 being connected with four absorption tower 4 of carbon,
And the MTA dry gas for being introduced into four absorption tower 4 of carbon can also be pre-processed.It is preferred that described device further includes setting
Residue gas compressor 2 and dry gas cooler 3 between four absorption tower 4 of MTA dry gas feed unit 1 and carbon so that methanol aromatic hydrocarbons
By-product dry gas is compressed and is entered back into after cooling down in four absorption tower 4 of carbon.
According to the present invention, the carbon four that rectifying is isolated in four desorber 5 of carbon can be used as the part or all of reuse of absorbent
In four absorption tower 4 of carbon, it is preferable that the bottom of towe of four desorber 5 of carbon is connected with four absorption tower 4 of carbon so that four desorber 5 of carbon
The carbon four that middle rectifying is isolated can enter in four absorption tower 4 of carbon.
According to the present invention, the carbon four in order to be carried secretly in the overhead product on four absorption tower 4 of reuse carbon, it is preferable that described
Device further includes naphtha scrubber 6, and the naphtha scrubber 6 is connected with four absorption tower 4 of carbon and gasoline stabilizer 7 respectively, with from
Carbon containing four material is recycled in the overhead product on four absorption tower 4 of carbon and is sent into gasoline stabilizer 7 and is used to carbon four be further purified,
And the tower bottom product in gasoline stabilizer 7 is introduced naphtha scrubber 6 and be used to absorb carbon four.
In addition, as shown in Figure 1, the device of the invention can also include some equipment commonly used in the art or component, for example,
Raw sorbent pump 10 is provided between raw sorbent gas-liquid separator 9 and lightness-removing column 11, for by raw sorbent gas-liquid
The liquid phase obtained in separator 9 is pressurizeed and is sent into lightness-removing column 11.
For example, it is provided with four circulating pump 12 of carbon and four cooler of carbon between four absorption tower 4 of four desorber of carbon, 5 bottom of towe and carbon
13, it is used to be pressurizeed, cooled down and be back to carbon by carbon four isolated in four absorption tower 5 of carbon and gasoline stabilizer 7 successively
Four absorption towers 4.
For example, gasoline circulating pump 14, aromatic hydrocarbons discharge port 15 are provided between 7 bottom of towe of gasoline stabilizer and naphtha scrubber 6
With aromatic feed mouth 20, it is used to pressurize the tower bottom product of gasoline stabilizer 7 successively, and make part from aromatic hydrocarbons discharge port 15
Discharger, partly enters naphtha scrubber 6 from aromatic feed mouth 20.
For example, 9 tower top of raw sorbent gas-liquid separator is provided with three discharge port 17 of carbon, for will be obtained after gas-liquid separation
Carbon three (gas phase portion) outflow；7 tower top of gasoline stabilizer is provided with four discharge port 21 of carbon and fixed gas discharge port 23, uses respectively
Flowed out in by the separated carbon four of 7 tower top of gasoline stabilizer and fixed gas；6 tower top of naphtha scrubber is provided with methane hydrogen discharge port
16, for light component product outflow by naphtha scrubber 6, etc..
In actual use, raw sorbent can be introduced raw sorbent feed unit 22, by raw sorbent
After the cooling and gas-liquid separation of cooler 8 and raw sorbent knockout drum 9, gained liquid phase enters in lightness-removing column 11, sloughs
Carbon light component below three, heavy constituent enter in gasoline stabilizer 7, and by the first distillation separation C four and aromatic hydrocarbons, gained carbon four is used
Absorbent is used as in four absorption tower 4 of carbon, in addition, MTA dry gas feed unit 1 provides MTA dry gas, MTA dry gas passes through MTA dry gas
After the compression and cooling of compressor 2 and MTA dry gas cooler 3, contacted into four absorption tower 4 of carbon with the carbon four as absorbent,
To absorb the heavy constituent of carbon more than two, desorbed as the carbon four of absorbent and the mixture of heavy constituent of carbon more than two into carbon four
In tower 5, by the second distillation separation C two and carbon four, gained carbon four is back in four absorption tower 4 of carbon, and in four absorption tower 4 of carbon
Unabsorbed light component enters in naphtha scrubber 6, is contacted with the aromatic hydrocarbons obtained in gasoline stabilizer 7, to absorb this light group
Divide the carbon four of middle entrainment, the heavy constituent after being absorbed in naphtha scrubber 6 is re-fed into gasoline stabilizer 7 with separation of carbon four and virtue
Hydrocarbon.
Present invention also offers a kind of method that carbon two is recycled in aromatic hydrocarbons by-product dry gas from methanol, this method includes following
Step：
(1) raw sorbent take off gently, to slough light component of the carbon below three；
(2) raw sorbent after taking off gently is subjected to the first rectifying with isolated carbon four and aromatic hydrocarbons；
(3) contacted with the carbon four obtained in step (2) with methanol aromatic hydrocarbons by-product dry gas to absorb carbon more than two in dry gas
Heavy constituent；
(4) carbon four obtained in step (3) and the mixture of the heavy constituent of carbon more than two are subjected to the second rectifying to separate
Obtain carbon two and carbon four.
According to the present invention, had no particular limits for the source of raw sorbent, it is various in order to avoid being introduced from the external world
Impurity and metal ion, influence the quality of dry-gas recovery, it is preferable that the raw sorbent be methanol aromatic hydrocarbons in carbon containing three,
The gaseous mixture of carbon four and aromatic hydrocarbons.Wherein, carbon containing 10-70mol% three, 10-70mol% carbon four and 5- in raw sorbent
20mol% aromatic hydrocarbons.
According to the present invention, had no particular limits for taking off light condition in step (1), as long as carbon can be sloughed below three
Light component.Preferably, the de- light condition includes：Number of theoretical plate is 10-40, pressure 0.4-2MPaG, tower top temperature
Spend for 10-50 DEG C, column bottom temperature is 55-120 DEG C.Wherein, units MPa G refers to the pressure unit of gauge pressure, i.e. 1MPaG refers to
It is that gauge pressure is 1MPa.
According to the present invention it is possible to pre-processed to not taking off light raw sorbent.Preferably, the method further includes：
Before taking off gently, (gas-liquid separation) collection liquid phase after the raw sorbent is cooled to 0-20 DEG C.
According to the present invention, had no particular limits for the condition of the first rectifying in step (2), as long as being capable of separation of carbon four
With aromatic hydrocarbons.Preferably, the condition of first rectifying includes：Number of theoretical plate is 10-60, pressure 0.4-2MPaG, tower top
Temperature is 50-100 DEG C, and column bottom temperature is 120-200 DEG C.
According to the present invention, had no particular limits for carbon four in step (3) with the condition that MTA dry gas contacts, as long as energy
Enough so that carbon four absorbs the heavy constituent of carbon more than two in dry gas.Preferably, the condition that carbon four is contacted with dry gas includes：It is theoretical
Plate number is 25-50, and pressure 3-5MPaG, tower top temperature is 10-40 DEG C, and column bottom temperature is 90-160 DEG C.Relative to first per ton
Alcohol aromatic hydrocarbons by-product dry gas, the dosage of carbon four can be 50-200kg.
According to the present invention, had no particular limits for the condition of the second rectifying in step (4), as long as being capable of separation of carbon two
With carbon four.Preferably, the condition of second rectifying includes：Number of theoretical plate is 20-50, pressure 1.5-2.8MPaG, tower
It is 15-70 DEG C to push up temperature, and column bottom temperature is 100-160 DEG C.
According to the invention, it is further possible to the MTA dry gas before pair being contacted with carbon four pre-processes.Preferably, the method is also
Including：Before being contacted with carbon four, the MTA dry gas is compressed and cooled down.It is highly preferred that the MTA dry gas compression and cooling
Pressure and temperature afterwards is respectively 3-5MPaG and 0-20 DEG C.Wherein, in order to avoid occurring excessive temperature in compression process,
Compression can use sectional compression, be preferably two sections of compressions or three sections of compressions.The species of refrigerant to being used during cooling does not have
There is special limitation, can be the cold water of propylene or 5 DEG C or so, can be provided by lithium-bromide absorption-type refrigerating machine, or use
Other cryogens such as ammonia refrigeration, are preferably propylene refrigerant.
According to the present invention, in order to improve utilization rate of the carbon four as absorbent, it is preferable that the carbon that will be obtained in step (4)
Four are partly or entirely back in step (2).
According to the present invention, in order to utilizing the carbon four carried secretly in the light component of methanol aromatic hydrocarbons by-product dry gas, it is preferable that
This method, which further includes, connects the aromatic hydrocarbons in step (2) and the unabsorbed light component of methanol aromatic hydrocarbons by-product dry gas in step (3)
Touch, to absorb the carbon four carried secretly in light component, then first will be carried out in the mixture return to step (2) of obtained carbon four and aromatic hydrocarbons
Rectifying.
According to the present invention, the condition contacted to aromatic hydrocarbons with light component has no particular limits, as long as enabling to aromatic hydrocarbons to inhale
Receive the carbon four carried secretly in light component.Preferably, the condition that aromatic hydrocarbons is contacted with light component includes：Number of theoretical plate is 15-30, pressure
Power is 2.5-4.5MPaG, and tower top temperature is 10-40 DEG C, and column bottom temperature is 20-60 DEG C.
In accordance with the present invention it is preferred that this method carries out in foregoing device.Specifically, step (1) can be in lightness-removing column
Carried out in 11, step (2) can carry out in gasoline stabilizer 7, and step (3) can carry out in four absorption tower of carbon, step (4)
It can be carried out in four desorber of carbon.In addition, replenishers raw material takes off gently preceding cooling and gas-liquid separation can be respectively in replenishers
Carried out in feed cooler 8 and replenishers raw material gas-liquid separator 9, MTA dry gas contacted with carbon four before compression and cooling can be with
Carried out in MTA residue gas compressors 2 and MTA dry gas cooler 3, the contact of aromatic hydrocarbons and the light component of MTA dry gas can be in gasoline
(application method for being specifically referred to aforementioned means) is carried out in absorption tower 6.
The present invention will be described in detail by way of examples below.
In following embodiments, the composition and parameter of MTA dry gas and raw sorbent are shown in Table 1, from methanol aromatics production
In technique.
Table 1
In following embodiments, the method for carbon two is recycled from MTA dry gas to be included：
(1) raw sorbent take off gently, to slough light component of the carbon below three；
(2) raw sorbent after taking off gently is subjected to the first rectifying with isolated carbon four and aromatic hydrocarbons；
(3) contacted with the carbon four obtained in step (2) with methanol aromatic hydrocarbons by-product dry gas to absorb carbon more than two in dry gas
Heavy constituent；
(4) aromatic hydrocarbons in step (2) and the unabsorbed light component of methanol aromatic hydrocarbons by-product dry gas in step (3) are connect
Touch, to absorb the carbon four carried secretly in light component, then first will be carried out in the mixture return to step (2) of obtained carbon four and aromatic hydrocarbons
Rectifying；
(5) carbon four obtained in step (3) and the mixture of the heavy constituent of carbon more than two are subjected to the second rectifying to separate
Carbon two and carbon four are obtained, obtained four fully recovering of carbon is in step (2).
The detection method of each component content is ASTM D1945 in raw material and product；The computational methods of two rate of recovery of carbon
For：The weight of weight/MTA dry gas (ethene+ethane) of the overhead product (ethene+ethane) of the rectifying of two rate of recovery of carbon=second ×
100%.
Embodiment 1
Raw sorbent is cooled to after 8 DEG C and collects liquid phase, then take off gently, taking off light condition includes：Number of theoretical plate is
15, pressure 0.6MPaG, tower top temperature are 17 DEG C, and column bottom temperature is 70 DEG C；The condition of first rectifying includes：Number of theoretical plate is
40, pressure 0.5MPaG, tower top temperature are 51 DEG C, and column bottom temperature is 160 DEG C；Two sections of MTA dry gas is compressed to 4MPaG and cold
But to 15 DEG C, then contact with carbon four, carbon four includes with the condition that MTA dry gas contacts：Number of theoretical plate is 40, pressure 3.8MPaG,
Tower top temperature is 23 DEG C, and column bottom temperature is 110 DEG C；The condition of second rectifying includes：Number of theoretical plate is 40, pressure 2.1MPaG,
Tower top temperature is 67 DEG C, and column bottom temperature is 120 DEG C；The condition of the light component of aromatic hydrocarbons and MTA dry gas contact includes：Number of theoretical plate is
20, pressure 3.5MPaG, tower top temperature are 29 DEG C, and column bottom temperature is 42 DEG C.The overhead product of the second rectifying is collected, and is detected
Component and parameter therein, the results are shown in Table 2, calculate the rate of recovery of carbon two is 93.90 weight %.
Embodiment 2
Raw sorbent is cooled to after 20 DEG C and collects liquid phase, then take off gently, taking off light condition includes：Number of theoretical plate is
35, pressure 1.6MPaG, tower top temperature are 50 DEG C, and column bottom temperature is 113 DEG C；The condition of first rectifying includes：Number of theoretical plate is
15, pressure 1.5MPaG, tower top temperature are 94 DEG C, and column bottom temperature is 190 DEG C；Two sections of MTA dry gas is compressed to 5MPaG and cold
But to 5 DEG C, then contact with carbon four, carbon four includes with the condition that MTA dry gas contacts：Number of theoretical plate is 25, pressure 4.8MPaG,
Tower top temperature is 22 DEG C, and column bottom temperature is 140 DEG C；The condition of second rectifying includes：Number of theoretical plate is 20, pressure 2.7MPaG,
Tower top temperature is 31 DEG C, and column bottom temperature is 132 DEG C；The condition of the light component of aromatic hydrocarbons and MTA dry gas contact includes：Number of theoretical plate is
27, pressure 4.5MPaG, tower top temperature are 23 DEG C, and column bottom temperature is 34 DEG C.The overhead product of the second rectifying is collected, and is detected
Component and parameter therein, the results are shown in Table 2, calculate the rate of recovery of carbon two is 95.85 weight %.
Embodiment 3
Raw sorbent is cooled to after 4 DEG C and collects liquid phase, then take off gently, taking off light condition includes：Number of theoretical plate is
15, pressure 0.4MPaG, tower top temperature are 27 DEG C, and column bottom temperature is 57 DEG C；The condition of first rectifying includes：Number of theoretical plate is
57, pressure 0.5MPaG, tower top temperature are 54 DEG C, and column bottom temperature is 120 DEG C；Two sections of MTA dry gas is compressed to 3MPaG and cold
But to 18 DEG C, then contact with carbon four, carbon four includes with the condition that MTA dry gas contacts：Number of theoretical plate is 50, pressure 3.2MPaG,
Tower top temperature is 23 DEG C, and column bottom temperature is 99 DEG C；The condition of second rectifying includes：Number of theoretical plate is 50, pressure 1.7MPaG,
Tower top temperature is 46 DEG C, and column bottom temperature is 106 DEG C；The condition of the light component of aromatic hydrocarbons and MTA dry gas contact includes：Number of theoretical plate is
15, pressure 2.5MPaG, tower top temperature are 23 DEG C, and column bottom temperature is 39 DEG C.The overhead product of the second rectifying is collected, and is detected
Component and parameter therein, the results are shown in Table 2, calculate the rate of recovery of carbon two is 93.71 weight %.
Comparative example 1
MTA dry gas is compressed and cooled down according to the condition of embodiment 1, then it is (miscellaneous with four air-flow of pure carbon of external world's introducing
The content of matter hydrogen sulfide is 5ppm) contact, and the second rectifying is carried out, the condition of contact and the second rectifying is also same as Example 1.
Collect the overhead product of the second rectifying, and detect component therein and hydrogen sulfide content, the results are shown in Table 2, calculate carbon two return
Yield is 92.89 weight %.
Table 2
| Composition and parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Temperature, DEG C | 13 | 13 | 13 | 13 |
| Pressure, MPaG | 2.1 | 2.7 | 1.7 | 2.1 |
| Mass flow, t/h | 16 | 16 | 16 | 16 |
| H2, mol% | 0.0 | 0.0 | 0.0 | 0.0 |
| CH4, mol% | 0.7 | 2.1 | 2.1 | 0.7 |
| C2H6, mol% | 68.7 | 72.6 | 71.2 | 68.7 |
| C2H4, mol% | 14.3 | 17.2 | 13.7 | 14.3 |
| C3H8, mol% | 9.4 | 6.5 | 6.8 | 9.4 |
| C3H6, mol% | 1.0 | 0.7 | 0.8 | 1.0 |
| C4H10, mol% | 5.8 | 0.9 | 5.3 | 5.8 |
| C4H8, mol% | 0.1 | 0.0 | 0.1 | 0.1 |
| H2O, mol% | 0.0 | 0.0 | 0.0 | 0.0 |
| H2S, ppm | 0.0 | 0.0 | 0.0 | 20.0 |
Can be seen that from embodiment 1-3 can effectively recycle carbon two, production using the method for the present invention from MTA dry gas
Quality is high；Especially, the method for the present invention is can be seen that from embodiment 1 and comparative example 1 without introducing absorbent from the external world,
So as to avoid other various impurity (such as hydrogen sulfide) are introduced outside MTA devices, so as to improve the efficiency and product of recycling
Quality.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
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, 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 (14)
1. the device of carbon two is recycled in a kind of aromatic hydrocarbons by-product dry gas from methanol, it is characterised in that the device includes being sequentially connected
Raw sorbent feed unit (22), lightness-removing column (11), four desorber of gasoline stabilizer (7), four absorption tower of carbon (4) and carbon
(5), it is former to be used for the absorbent that purifier absorption agent raw material feed unit (22) provides for the lightness-removing column (11) and gasoline stabilizer (7)
Carbon four in material.
2. device according to claim 1, wherein, described device, which further includes, is arranged at raw sorbent feed unit (22)
Raw sorbent cooler (8) and raw sorbent gas-liquid separator (9) between lightness-removing column (11) so that raw sorbent
Through cooling down and being entered back into after gas-liquid separation in lightness-removing column (11).
3. device according to claim 1 or 2, wherein, described device further includes naphtha scrubber (6), and the gasoline is inhaled
Receive tower (6) respectively with four absorption tower of carbon (4) and gasoline stabilizer (7) to be connected, to return from the overhead product on four absorption tower of carbon (4)
Receive carbon containing four material and be sent into gasoline stabilizer (7) and be used to carbon four be further purified, and make the tower in gasoline stabilizer (7)
Bottom product introduces naphtha scrubber (6) and is used to absorb carbon four.
4. the method for carbon two is recycled in a kind of aromatic hydrocarbons by-product dry gas from methanol, it is characterised in that this method comprises the following steps：
(1) raw sorbent take off gently, to slough light component of the carbon below three；
(2) raw sorbent after taking off gently is subjected to the first rectifying with isolated carbon four and aromatic hydrocarbons；
(3) contacted with the carbon four obtained in step (2) with methanol aromatic hydrocarbons by-product dry gas to absorb the weight of carbon more than two in dry gas
Component；
(4) carbon four obtained in step (3) and the mixture of the heavy constituent of carbon more than two are subjected to the second rectifying with isolated
Carbon two and carbon four.
5. according to the method described in claim 4, wherein, the raw sorbent is carbon containing three, four and of carbon in methanol aromatic hydrocarbons
The gaseous mixture of aromatic hydrocarbons.
6. according to the method described in claim 4, wherein, the de- light condition includes：Number of theoretical plate is 10-40, and pressure is
0.4-2MPaG, tower top temperature are 10-50 DEG C, and column bottom temperature is 55-120 DEG C.
7. according to the method described in claim 4, wherein, the method further includes：Before taking off gently, the raw sorbent is cooled down
Liquid phase is collected after to 0-20 DEG C.
8. according to the method described in claim 4, wherein, the condition of first rectifying includes：Number of theoretical plate is 10-60, pressure
Power is 0.4-2MPaG, and tower top temperature is 50-100 DEG C, and column bottom temperature is 120-200 DEG C.
9. according to the method described in claim 4, wherein, the condition that carbon four is contacted with dry gas includes：Number of theoretical plate is 25-50,
Pressure is 3-5MPaG, and tower top temperature is 10-40 DEG C, and column bottom temperature is 90-160 DEG C.
10. according to the method described in claim 4, wherein, the condition of second rectifying includes：Number of theoretical plate is 20-50, pressure
Power is 1.5-2.8MPaG, and tower top temperature is 15-70 DEG C, and column bottom temperature is 100-160 DEG C.
11. according to the method described in claim 4, wherein, the carbon four obtained in step (4) is partly or entirely back to step
(2) in.
12. according to the method described in claim 4, wherein, this method is further included in the aromatic hydrocarbons in step (2) and step (3)
The unabsorbed light component contact of methanol aromatic hydrocarbons by-product dry gas, to absorb the carbon four carried secretly in light component, then the carbon that will be obtained
Four and aromatic hydrocarbons mixture return to step (2) in carry out the first rectifying.
13. according to the method for claim 12, wherein, the condition that aromatic hydrocarbons is contacted with light component includes：Number of theoretical plate is 15-
30, pressure 2.5-4.5MPaG, tower top temperature are 10-40 DEG C, and column bottom temperature is 20-60 DEG C.
14. according to the method described in any one in claim 4-13, wherein, this method is any one in claim 1-3
Carried out in device described in.
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| CN201610949747.0A CN107986933B (en) | 2016-10-26 | 2016-10-26 | Device and method for recycling carbon dioxide from byproduct dry gas generated in preparation of aromatic hydrocarbon from methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087772A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Device and method for separating refinery dry gas through oil absorption |
| CN104557387A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Refinery mixed dry gas recovery system and recovery method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087772A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Device and method for separating refinery dry gas through oil absorption |
| CN104557387A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Refinery mixed dry gas recovery system and recovery method |
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