CN107082733B - The method for separating carbon dioxide in methanol to propylene reaction gas - Google Patents
The method for separating carbon dioxide in methanol to propylene reaction gas Download PDFInfo
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- CN107082733B CN107082733B CN201710431420.9A CN201710431420A CN107082733B CN 107082733 B CN107082733 B CN 107082733B CN 201710431420 A CN201710431420 A CN 201710431420A CN 107082733 B CN107082733 B CN 107082733B
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Abstract
The present invention relates to a kind of method of carbon dioxide in separation methanol to propylene reaction gas, mainly solves the problems, such as to exist in the prior art that carbon dioxide eliminating rate is low, residual carbon dioxide content height, product gas quality dissatisfaction in MTP purified gas.The present invention is by using a kind of method for separating carbon dioxide in methanol to propylene reaction gas, carbon dioxide in 1 group of absorbing unit removing MTP reaction gas is composed in series using absorption-three sections of absorption-absorption, and 2~3 groups of absorbing units in parallel are set by MTP production scale, wherein 1~2 group of adsorption operations, remaining 1 group of regenerative operation, to keep MTP commercial industrial device continuous operation at full capacity, make carbon dioxide≤2ppm in MTP purified gas, reach polymer grade ethylene, the technical solution of the quality standard of polymerization-grade propylene preferably solves the above problem, it can be used in separation removal methanol to propylene reaction gas in carbon dioxide.
Description
Technical field
The present invention relates to a kind of methods of carbon dioxide in separation preparing propylene from methanol (MTP) reaction gas, are applied to extensive
Commercialization MTP device is prepared in the industrial production of propylene.
Background technique
Preparing propylene from methanol MTP technology has the application prospect than broader heavy industrialization, meets China
Using energy source Strategic Policy.Wherein: German Lucci corporation is successfully to develop MTP technology at present in the world and realized industrialization
One of company.The said firm uses the molecular sieve catalyst and fixed bed reactors provided by South Chemical Company, operation
Temperature is 380~480 DEG C, and reaction pressure is 0.13~0.16MPa.Its technical process is as follows: reaction raw materials methanol is anti-first
The outlet material of device is answered to be preheated to 250~350 DEG C, then methanol dehydration generates dimethyl ether and water, the reaction in pre-reactor
Conversion ratio nearly reaches the degree of thermodynamical equilibrium.After methanol, water and the fractional condensation of dimethyl ether material, gas phase is directly entered reactor,
Liquid phase enters reactor control reaction temperature as temperature control medium via flow quantity control instrument.The outlet material of reactor is first by portion
Divide heat to be transmitted to recirculated water and generate steam, then by the methanol of the pre- hot feed of heat, finally uses air and be water-cooled to cohesion
It send after point and is separated into separator.Gas-phase product removes water, CO2After dimethyl ether, its further rectifying is obtained into polymer grade third
Alkene.Remaining by-product includes: that light component fuel gas, ethylene, butylene, liquefied petroleum gas, high-knock rating gasoline etc. are sent outside.
Number of patent application in the prior art is the separating technology of CN201410568431.8 preparing propylene from methanol product gas, public
The method that methanol prepares carbon dioxide in propylene MTP device removing MTP reaction gas is opened, by the pretreated MTP of quenching unit
Reaction gas material is sent into one section of suction tank of reaction gas compressor of separative unit, since this burst of logistics contains a small amount of carbon dioxide etc.
Acid impurities after entering before continuous separation and purification unit, need to carry out alkali cleaning/washing process by caustic wash tower and water scrubber,
By this partial CO 2 impurity removal.Generated spent lye and hydrocarbonaceous waste water need to carry out harmless treatment, qualified discharge,
Once otherwise these spent lyes and hydrocarbonaceous waste water direct emission will seriously pollute environment, therefore consider other carbon dioxide removals
Method.
Number of patent application in the prior art is the suction that CN03135127.1 removes ethylene, carbon dioxide from mixed gas
Attached partition method discloses and carries out pressure-variable adsorption, solution using at least one of active carbon, aluminium oxide, silica gel, molecular sieve adsorbent
Suction regeneration and etc., it by the ethylene and carbon dioxide separation in mixed gas and removes, to be purified gas.It can be by dioxy
Carbon dioxide is obtained after the technical method adsorbing separation processing that the gaseous mixture for changing carbon content 1%~10% passes through the patent of invention to contain
The purified gas of amount 0.005%~0.3%.Number of patent application is the processing of CN201180027276.3 hydrocarbon gas, open
One kind, using cooling, expansion, condensation, fractionation, is gone the method for removing carbon dioxide and is set from hydrocarbon fuel streams
It is standby.By the technical method deep cooling condensation fractionation separation of the patent of invention, carbon dioxide content is reduced to from 38.5% (mole)
13.5% (mole).Number of patent application is a kind of raising associated gas separative efficiency of CN201410526096.5 and recycles dioxy
The method for changing carbon is disclosed and is purified respectively to lighter hydrocarbons in fixed gas and carbon dioxide using double membrane separators, in same dress
Interior realization is set to improve lighter hydrocarbons recovery efficiency, reduce carbon dioxide bring device operational load and three kinds of decarburization works of natural gas realization
With light hydrocarbon yield can reach 30% or more, and natural gas gas concentration lwevel is down to 2% hereinafter, natural gas loss late is less than
0.5%.
CN03135127.1 uses adsorbing separation carbon dioxide removal, and CN201180027276.3 is using deep cooling fractionation removing
Carbon dioxide, CN201410526096.5 using double UF membrane carbon dioxide removals, although avoid using alkali cleaning with it is water washed
Journey generates the deficiency of waste liquor contamination environment, but carbon dioxide content exists in the purified gas after these technology carbon dioxide removals
Between 0.005%~13.5%, the requirement of carbon dioxide content≤0.0002% (2ppm) far can not be reached, there are titanium dioxides
The problem of carbon removal efficiency is low, residual carbon dioxide content is high in MTP purified gas, product gas quality dissatisfaction
Summary of the invention
The technical problem to be solved by the present invention is to exist in the prior art, carbon dioxide eliminating rate is low, in MTP purified gas
The problem of residual carbon dioxide content height, product gas quality dissatisfaction, provide a kind of new separation methanol to propylene reaction gas
The method of middle carbon dioxide.Residual carbon dioxide content is low in high, MTP purified gas with carbon dioxide eliminating rate for this method, produces
Product gaseous mass advantage up to standard.
To solve the above problems, The technical solution adopted by the invention is as follows: two in a kind of separation methanol to propylene reaction gas
The carbon dioxide in mode separation removal MTP reaction gas is connected in series using absorption-three sections of absorption-absorption in the method for carbonoxide,
Methanol prepares carbonated reaction gas in propylene MTP device and first passes around the preliminary absorption carbon dioxide of absorber progress
Operation, then by chemical absorber carry out chemical absorbing carbon dioxide operation, finally by second adsorption device carry out most
The carbon dioxide eliminating in MTP device reaction gas is made the carbon dioxide content in reaction gas by the operation of absorption carbon dioxide eventually
Reach the quality standard of polymer grade ethylene, polymerization-grade propylene；The absorber, chemical absorber, second adsorption device are
It is connected in series and is formed one group of absorbing unit, according to the production scale of MTP device, 2~3 groups of absorbing units in parallel are set,
In 1~2 group of absorbing unit carry out absorption absorption operation, remaining 1 group of absorbing unit carries out desorption and regeneration operation, to keep MTP big
Continuous and stable is run scale commercial chemical industry process units at full capacity；Wherein, the technique ginseng of an absorber absorption absorption operation
Number are as follows: operation temperature is 10~40 DEG C, and operating pressure is 2.6~4.2MPaA；The technique ginseng of absorber desorption and regeneration operation
Number are as follows: operation temperature is 295~345 DEG C, and operating pressure is 0.20~0.50MPaA；Absorber primary parameters of test apparatus are as follows:
Draw ratio is 2.0~4.0:1；Adsorbent uses A type molecular sieve, and aperture is 0.6~0.8nm；Chemical absorber absorption absorbs
The technological parameter of operation are as follows: operation temperature is 10~40 DEG C, and operating pressure is 2.5~4.1MPaA；Chemical absorber without desorption again
Raw operation；Chemical absorber primary parameters of test apparatus are as follows: draw ratio is 0.6~1.4:1；Chemical absorbent is calcium oxide CaO particle
With the alkaline mixt of sodium hydroxide NaOH particle, the mass ratio of calcium oxide and sodium hydroxide is CaO:NaOH=1.8~4.8:
1；Second adsorption device absorption absorption operation technological parameter are as follows: operation temperature be 10~40 DEG C, operating pressure be 2.4~
4.0MPaA；The technological parameter of second adsorption device desorption and regeneration operation are as follows: operation temperature is 295~345 DEG C, and operating pressure is
0.10~0.40MPaA；Second adsorption device primary parameters of test apparatus are as follows: draw ratio is 1.0~3.0:1；Adsorbent uses X-type molecule
Sieve, aperture are 0.3~0.5nm.
In above-mentioned technical proposal, it is preferable that the technological parameter of an absorber absorption absorption operation are as follows: operation temperature 15
~35 DEG C, operating pressure is 2.8~4.0MPaA；The technological parameter of absorber desorption and regeneration operation are as follows: operation temperature is
305~335 DEG C, operating pressure is 0.25~0.45MPaA；Absorber primary parameters of test apparatus are as follows: draw ratio be 2.2~
3.8:1；Adsorbent use silica alumina ratio for 2 A type molecular sieve.
In above-mentioned technical proposal, it is preferable that the technological parameter of chemical absorber absorption absorption operation are as follows: operation temperature 15
~35 DEG C, operating pressure is 2.7~3.9MPaA；Chemical absorber primary parameters of test apparatus are as follows: draw ratio is 0.7~1.3:1.
In above-mentioned technical proposal, it is preferable that the technological parameter of second adsorption device absorption absorption operation are as follows: operation temperature 15
~35 DEG C, operating pressure is 2.6~3.8MPaA；The technological parameter of second adsorption device desorption and regeneration operation are as follows: operation temperature is
305~335 DEG C, operating pressure is 0.15~0.35MPaA；Second adsorption device primary parameters of test apparatus are as follows: draw ratio be 1.2~
2.8:1；Adsorbent use silica alumina ratio for 3 X-type molecular sieve.
In above-mentioned technical proposal, it is highly preferred that the technological parameter of absorber absorption absorption operation are as follows: operation temperature is
20~30 DEG C；Operating pressure is 3.0~3.8MpaA；The technological parameter of absorber desorption and regeneration operation are as follows: operation temperature is
315~325 DEG C；Operating pressure is 0.30~0.40MPaA；Absorber primary parameters of test apparatus are as follows: draw ratio be 2.4~
3.6:1.
In above-mentioned technical proposal, it is highly preferred that the technological parameter of chemical absorber absorption absorption operation are as follows: operation temperature is
20~30 DEG C；Operating pressure is 2.9~3.7MPaA；Chemical absorber primary parameters of test apparatus are as follows: draw ratio is 0.8~1.2:1.
In above-mentioned technical proposal, it is highly preferred that the technological parameter of second adsorption device absorption absorption operation are as follows: operation temperature is
20~30 DEG C；Operating pressure is 2.8~3.6MPaA；The technological parameter of second adsorption device desorption and regeneration operation are as follows: operation temperature is
315~325 DEG C；Operating pressure is 0.20~0.30MPaA；Second adsorption device primary parameters of test apparatus are as follows: draw ratio be 1.4~
2.6:1.
In above-mentioned technical proposal, it is preferable that chemical absorbent volume is the 70~90% of chemical absorber volume.
In above-mentioned technical proposal, it is preferable that A type molecular sieve volume is the 70~90% of an adsorber volume.
In above-mentioned technical proposal, it is preferable that X-type molecular sieve volume is the 70~90% of second adsorption body product.
Present invention separation removal MTP in such a way that absorption-three sections of absorption-absorption series connection forms 1 group of absorbing unit
Carbon dioxide in device reaction gas, and 2~3 group absorbing units in parallel by the setting of MTP device production scale, wherein 1~2 group of suction
Attached operation, remaining 1 group of regenerative operation make MTP to keep MTP large-scale commercial industrial production equipment continuous operation at full capacity
Carbon dioxide content≤0.0002% (2ppm) in purified gas reaches the quality standard of polymer grade ethylene, polymerization-grade propylene, obtains
Preferable technical effect.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the invention.
In Fig. 1,1 group of absorbing unit, parallel connection 2 are formed with an absorber, chemical absorber, the series connection of second adsorption device
For group absorbing unit.
(1), (4) are an absorber；(2), (5) are chemical absorber；(3), (6) are second adsorption device；It (7) is MTP
Reaction gas charging；(8) it discharges for MTP purified gas；(9) it is fed for desorption and regeneration gas；(10) it discharges for desorption and regeneration gas；(11),
It (15) is A type molecular sieve adsorbent；(12), (16) are alkali electroless absorbent；(13), (17) are stainless steel wire web filter；
(14), (18) are X-type molecular sieve adsorbent；(101)~(118) are stop valve.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
[embodiment 1]
A method of carbon dioxide in separation methanol to propylene reaction gas, as shown in Figure 1, with absorber, a chemistry
Absorber, second adsorption device, which are connected in series, forms 1 group of absorbing unit, for 2 groups of absorbing units in parallel.Absorber (1) is changed
Learn absorber (2), second adsorption device (3) forms one group of absorbing unit and carries out absorption absorption operation, an absorber (4), chemistry
Absorber (5), second adsorption device (6) form one group of absorbing unit and carry out desorption and regeneration operation.
Stop valve (101), stop valve (102) are opened, and the MTP reaction gas charging (7) out-of-bounds inputted enters an absorber
(1) and by A type molecular sieve adsorbent (11) operation of preliminary absorption carbon dioxide is carried out.Stop valve (108) is closed, and is prevented
MTP reaction gas feeds (7) and enters an absorber (4)；Stop valve (115) is closed, and prevents desorption and regeneration gas charging (9) from entering one
Secondary absorber (1).
Stop valve (103), stop valve (105) are opened, and the MTP reaction gas by tentatively adsorbing carbon dioxide enters chemical suction
It receives device (2) and chemical suction is carried out by the chemical absorbent (12) of alkaline oxygenated calcium CaO and sodium hydroxide NaOH granulate mixture
Receive the operation of carbon dioxide.Alkali grain enters subsequent facility in order to prevent, and stainless steel is arranged below in chemical absorbent (12)
Wire gauzee filter (13) enters stainless steel wire web filter (13) by the MTP reaction gas of chemical absorbing carbon dioxide and carries out gas
Gu alkali grain is filtered in separation.Stop valve (104) is closed, and prevents MTP reaction gas from flowing through by by-pass line " short circuit ".
Stop valve (106), stop valve (107) are opened, and enter secondary suction by the MTP reaction gas of chemical absorbing carbon dioxide
Adnexa (3) and the operation that final absorption carbon dioxide is carried out by X-type molecular sieve adsorbent (14), MTP purified gas discharging (8) are defeated
It arrives out out-of-bounds.Stop valve (114) is closed, desorption and regeneration gas discharging (10) outflow for preventing second adsorption device (6) from flowing out；Stop valve
(117) it closes, prevents MTP purified gas discharging (8) outflow.
Stop valve (116), stop valve (109) are opened, and the desorption and regeneration gas charging (9) out-of-bounds inputted enters an absorber
(4) and by A type molecular sieve adsorbent (15) desorption and regeneration operation is carried out.Stop valve (110), (112) are closed, chemical absorber
(5) it is operated without desorption and regeneration；Stop valve (111) is opened, and desorption and regeneration gas is flowed through by by-pass line " short circuit ".Stop valve
(113), (118) are opened, and desorption and regeneration gas enters second adsorption device (6) and desorbed by X-type molecular sieve adsorbent (18)
Regenerative operation, desorption and regeneration gas discharging (10) are output to out-of-bounds.
Again relevant stop valve is opened and closed to operate with regard to achievable 2 groups of absorbing units absorption absorption operation in parallel and desorption and regeneration
Switching, make an absorber (4), chemical absorber (5), second adsorption device (6) composition 1 group of absorbing unit carry out absorption suction
Bring drill to an end work, an absorber (1), chemical absorber (2), second adsorption device (3) composition 1 group of absorbing unit carry out desorption and regeneration
Operation, to keep MTP large-scale commercial industrial production equipment, continuous and stable is run at full capacity.
Chemical absorber is operated without desorption and regeneration, when the alkalinity of calcium oxide CaO particle and sodium hydroxide NaOH particle
It when mixture chemical absorbent will fail, needs for chemical absorber to be switched out, replaces alkaline mixt chemical absorbent.
Since 2 groups of absorbing units in parallel are arranged in the present invention, the operation of replacement alkaline mixt chemical absorbent can be carried out online, to protect
Holding MTP large-scale commercial industrial production equipment, continuous and stable is run at full capacity.
Using the method for carbon dioxide in molecular sieve adsorbing separation MTP reaction gas of the present invention, the nominal of MTP device produces energy
Power is 1,800,000 tons/year of methanol, and the reaction gas into separative unit forms, and is shown in Table 1.
Table 1
According to production scale described in MTP device, 2 groups of absorbing units in parallel are set, wherein 1 group of absorbing unit is inhaled
Attached absorption operation, remaining 1 group of absorbing unit carries out desorption and regeneration operation, to keep MTP large-scale commercial industrial production equipment
Continuous and stable is run at full capacity.The technological parameter that the present invention adsorbs absorption operation is as follows: an adsorber works temperature is 20 DEG C,
Operating pressure is 3.0MPaA, and an absorber equipment draw ratio is 2.7:1；Chemical absorber operation temperature is 20 DEG C, operation pressure
Power is 2.9MPaA, and chemical absorber equipment draw ratio is 0.9:1, and chemical absorbent CaO:NaOH mass ratio is 2.9:1；It is secondary
Adsorber works temperature is 20 DEG C, operating pressure 2.8MPaA, and second adsorption device equipment draw ratio is 1.8:1.Desorption and regeneration behaviour
The technological parameter of work is as follows: an adsorber works temperature is 305 DEG C, operating pressure 0.25MPaA；The operation of second adsorption device
Temperature is 305 DEG C, operating pressure 0.15MPaA.Chemical absorbent volume is 75.8%, the A type molecule of chemical absorber volume
Sieve nest product is the 82.1% of an adsorber volume, and X-type molecular sieve volume is the 83.6% of second adsorption body product.
Thus after MTP reaction gas is by absorption-three sections of absorption-absorption series connection carbon dioxide removal processing, in MTP purified gas
Carbon dioxide content is 0.00019% (1.9ppm)；MTP purified gas further separation and purification, obtains polymer grade ethylene product
With polymerization-grade propylene product, purity >=99.95mol% of polymer grade ethylene product, the purity of polymerization-grade propylene product >=
99.6mol%.
[embodiment 2]
According to condition described in embodiment 1 and step, only forms and change into the reaction gas of separative unit, be shown in Table 2.
Table 2
The technological parameter that the present invention adsorbs absorption operation is as follows: one time adsorber works temperature is 26 DEG C, and operating pressure is
3.2MPaA, an absorber equipment draw ratio are 2.9:1；Chemical absorber operation temperature is 26 DEG C, and operating pressure is
3.1MPaA, chemical absorber equipment draw ratio are 1.0:1, and chemical absorbent CaO:NaOH mass ratio is 3.2:1；Second adsorption
Device operation temperature is 26 DEG C, operating pressure 3.0MPaA, and second adsorption device equipment draw ratio is 1.9:1.Desorption and regeneration operation
Technological parameter is as follows: an adsorber works temperature is 318 DEG C, operating pressure 0.29MPaA；Second adsorption device operation temperature
It is 318 DEG C, operating pressure 0.19MPaA.Chemical absorbent volume is the 78.6% of chemical absorber volume, A type molecular sieve body
Product is the 83.2% of an adsorber volume, and X-type molecular sieve volume is the 84.1% of second adsorption body product.
Thus after MTP reaction gas is by absorption-three sections of absorption-absorption series connection carbon dioxide removal processing, in MTP purified gas
Carbon dioxide content is 0.00017% (1.7ppm)；MTP purified gas further separation and purification, obtains polymer grade ethylene product
With polymerization-grade propylene product, purity >=99.95mol% of polymer grade ethylene product, the purity of polymerization-grade propylene product >=
99.6mol%.
[embodiment 3]
According to condition described in embodiment 1 and step, only forms and change into the reaction gas of separative unit, be shown in Table 3.
Table 3
The technological parameter that the present invention adsorbs absorption operation is as follows: one time adsorber works temperature is 33 DEG C, and operating pressure is
3.7MPaA, an absorber equipment draw ratio are 3.5:1；Chemical absorber operation temperature is 33 DEG C, and operating pressure is
3.6MPaA, chemical absorber equipment draw ratio are 1.2:1, and chemical absorbent CaO:NaOH mass ratio is 4.1:1；Second adsorption
Device operation temperature is 33 DEG C, operating pressure 3.5MPaA, and second adsorption device equipment draw ratio is 2.2:1.Desorption and regeneration operation
Technological parameter is as follows: an adsorber works temperature is 339 DEG C, operating pressure 0.42MPaA；Second adsorption device operation temperature
It is 339 DEG C, operating pressure 0.32MPaA.Chemical absorbent volume is the 79.7% of chemical absorber volume, A type molecular sieve body
Product is the 84.6% of an adsorber volume, and X-type molecular sieve volume is the 85.8% of second adsorption body product.
Thus after MTP reaction gas is by absorption-three sections of absorption-absorption series connection carbon dioxide removal processing, in MTP purified gas
Carbon dioxide content is 0.00016% (1.6ppm)；MTP purified gas further separation and purification, obtains polymer grade ethylene product
With polymerization-grade propylene product, purity >=99.95mol% of polymer grade ethylene product, the purity of polymerization-grade propylene product >=
99.6mol%.
[embodiment 4]
According to condition described in embodiment 1 and step, only technological parameter changes, the technique that the present invention adsorbs absorption operation
Parameter is as follows: an adsorber works temperature is 10 DEG C, and operating pressure 2.6MPaA, one time absorber equipment draw ratio is
2.0:1；Chemical absorber operation temperature is 10 DEG C, operating pressure 2.5MPaA, and chemical absorber equipment draw ratio is 0.6:1,
Chemical absorbent CaO:NaOH mass ratio is 1.8:1；Second adsorption device operation temperature is 10 DEG C, operating pressure 2.4MPaA, two
Secondary absorber equipment draw ratio is 1.0:1.The technological parameter of desorption and regeneration operation is as follows: an adsorber works temperature is 295
DEG C, operating pressure 0.20MPaA；Second adsorption device operation temperature is 295 DEG C, operating pressure 0.10MPaA.Chemical absorbent
Volume is the 70.0% of chemical absorber volume, and A type molecular sieve volume is the 70.0% of an adsorber volume, X-type molecular sieve
Volume is the 70.0% of second adsorption body product.
Thus after MTP reaction gas is by absorption-three sections of absorption-absorption series connection carbon dioxide removal processing, in MTP purified gas
Carbon dioxide content is 0.00020% (2.0ppm)；MTP purified gas further separation and purification, obtains polymer grade ethylene product
With polymerization-grade propylene product, purity >=99.95mol% of polymer grade ethylene product, the purity of polymerization-grade propylene product >=
99.6mol%.
[embodiment 5]
According to condition described in embodiment 1 and step, only technological parameter changes, the technique that the present invention adsorbs absorption operation
Parameter is as follows: an adsorber works temperature is 40 DEG C, and operating pressure 4.2MPaA, one time absorber equipment draw ratio is
4.0:1；Chemical absorber operation temperature is 40 DEG C, operating pressure 4.1MPaA, and chemical absorber equipment draw ratio is 1.4:1,
Chemical absorbent CaO:NaOH mass ratio is 4.8:1；Second adsorption device operation temperature is 40 DEG C, operating pressure 4.0MPaA, two
Secondary absorber equipment draw ratio is 3.0:1.The technological parameter of desorption and regeneration operation is as follows: an adsorber works temperature is 345
DEG C, operating pressure 0.50MPaA；Second adsorption device operation temperature is 345 DEG C, operating pressure 0.40MPaA.Chemical absorbent
Volume is the 90.0% of chemical absorber volume, and A type molecular sieve volume is the 90.0% of an adsorber volume, X-type molecular sieve
Volume is the 90.0% of second adsorption body product.
Thus after MTP reaction gas is by absorption-three sections of absorption-absorption series connection carbon dioxide removal processing, in MTP purified gas
Carbon dioxide content is 0.00015% (1.5ppm)；MTP purified gas further separation and purification, obtains polymer grade ethylene product
With polymerization-grade propylene product, purity >=99.95mol% of polymer grade ethylene product, the purity of polymerization-grade propylene product >=
99.6mol%.
[embodiment 6]
According to condition described in embodiment 1 and step, only the nominal production capacity of MTP device expands as 3,600,000 tons/year
According to the nominal production capacity of MTP device 3 groups of absorbing units in parallel are arranged, every group of absorbing unit is by absorption-absorption-in methanol
Three sections of series connection compositions are adsorbed, wherein 2 groups of absorbing units carry out absorption absorption operation, remaining 1 group of absorbing unit is desorbed
Regenerative operation.
The technological parameter that the present invention adsorbs absorption operation is as follows: one time adsorber works temperature is 20 DEG C, and operating pressure is
3.0MPaA, an absorber equipment draw ratio are 2.7:1；Chemical absorber operation temperature is 20 DEG C, and operating pressure is
2.9MPaA, chemical absorber equipment draw ratio are 0.9:1, and chemical absorbent CaO:NaOH mass ratio is 2.9:1；Second adsorption
Device operation temperature is 20 DEG C, operating pressure 2.8MPaA, and second adsorption device equipment draw ratio is 1.8:1.Desorption and regeneration operation
Technological parameter is as follows: an adsorber works temperature is 305 DEG C, operating pressure 0.25MPaA；Second adsorption device operation temperature
It is 305 DEG C, operating pressure 0.15MPaA.Chemical absorbent volume is the 75.8% of chemical absorber volume, A type molecular sieve body
Product is the 82.1% of an adsorber volume, and X-type molecular sieve volume is the 83.6% of second adsorption body product.
Thus after MTP reaction gas is by absorption-three sections of absorption-absorption series connection carbon dioxide removal processing, in MTP purified gas
Carbon dioxide content is 0.00019% (1.9ppm)；MTP purified gas further separation and purification, obtains polymer grade ethylene product
With polymerization-grade propylene product, purity >=99.95mol% of polymer grade ethylene product, the purity of polymerization-grade propylene product >=
99.6mol%.
[comparative example 1]
The prior art either uses adsorbing separation carbon dioxide removal, or is fractionated carbon dioxide removal using deep cooling,
Or double UF membrane carbon dioxide removals are used, carbon dioxide content exists in the purified gas after these technology carbon dioxide removals
Between 0.005%~13.5%, product quality is not up to standard.And alkali cleaning-washing method is used, although MTP reaction can be removed
Carbon dioxide in gas keeps product quality up to standard；But in alkaline cleaning procedure, spent lye and butter can be generated, these spent lyes
After with butter needing that environmental protection administration is sent to carry out special harmless treatment, qualified discharge thereby increases the operation of process unit
Cost.
Claims (10)
1. the method for carbon dioxide, is connected in series using absorption-three sections of absorption-absorption in a kind of separation methanol to propylene reaction gas
Carbon dioxide in mode separation removal MTP reaction gas, methanol prepare in propylene MTP device carbonated reaction gas first
The operation that preliminary absorption carbon dioxide is carried out by an absorber, then carries out chemical absorbing titanium dioxide by chemical absorber
The operation of carbon finally carries out the operation of final absorption carbon dioxide, by the dioxy in MTP device reaction gas by second adsorption device
Change carbon removing, the carbon dioxide content in reaction gas is made to reach the quality standard of polymer grade ethylene, polymerization-grade propylene；Described one
Secondary absorber, chemical absorber, second adsorption device are to be connected in series and form one group of absorbing unit, according to the production of MTP device
2~3 groups of absorbing units in parallel are arranged in scale, wherein 1~2 group of absorbing unit carries out absorption absorption operation, remaining 1 group of absorption
Unit carries out desorption and regeneration operation, and to keep MTP large-scale commercial industrial production equipment, continuous and stable is run at full capacity；Its
In, the technological parameter of absorber absorption absorption operation are as follows: operation temperature is 10~40 DEG C, operating pressure is 2.6~
4.2MPaA；The technological parameter of absorber desorption and regeneration operation are as follows: operation temperature is 295~345 DEG C, and operating pressure is
0.20~0.50MPaA；Absorber primary parameters of test apparatus are as follows: draw ratio is 2.0~4.0:1；Adsorbent uses A type molecule
Sieve, aperture are 0.6~0.8nm；The technological parameter of chemical absorber absorption absorption operation are as follows: operation temperature is 10~40 DEG C,
Operating pressure is 2.5~4.1MPaA；Chemical absorber is operated without desorption and regeneration；Chemical absorber primary parameters of test apparatus are as follows: major diameter
Than for 0.6~1.4:1；Chemical absorbent is the alkaline mixt of calcium oxide CaO particle and sodium hydroxide NaOH particle, calcium oxide
Mass ratio with sodium hydroxide is CaO:NaOH=1.8~4.8:1；The technological parameter of second adsorption device absorption absorption operation are as follows:
Operation temperature is 10~40 DEG C, and operating pressure is 2.4~4.0MPaA；The technological parameter of second adsorption device desorption and regeneration operation are as follows:
Operation temperature is 295~345 DEG C, and operating pressure is 0.10~0.40MPaA；Second adsorption device primary parameters of test apparatus are as follows: draw ratio
For 1.0~3.0:1；Adsorbent uses X-type molecular sieve, and aperture is 0.3~0.5nm.
2. separating the method for carbon dioxide in methanol to propylene reaction gas according to claim 1, it is characterised in that primary to inhale
The technological parameter of adnexa absorption absorption operation are as follows: operation temperature is 15~35 DEG C, and operating pressure is 2.8~4.0MPaA；It is primary to inhale
The technological parameter of adnexa desorption and regeneration operation are as follows: operation temperature is 305~335 DEG C, and operating pressure is 0.25~0.45MPaA；One
Secondary absorber primary parameters of test apparatus are as follows: draw ratio is 2.2~3.8:1；Adsorbent use silica alumina ratio for 2 A type molecular sieve.
3. separating the method for carbon dioxide in methanol to propylene reaction gas according to claim 1, it is characterised in that chemistry is inhaled
Receive the technological parameter of device absorption absorption operation are as follows: operation temperature is 15~35 DEG C, and operating pressure is 2.7~3.9MPaA；Chemistry is inhaled
Receive device primary parameters of test apparatus are as follows: draw ratio is 0.7~1.3:1.
4. separating the method for carbon dioxide in methanol to propylene reaction gas according to claim 1, it is characterised in that secondary suction
The technological parameter of adnexa absorption absorption operation are as follows: operation temperature is 15~35 DEG C, and operating pressure is 2.6~3.8MPaA；Secondary suction
The technological parameter of adnexa desorption and regeneration operation are as follows: operation temperature is 305~335 DEG C, and operating pressure is 0.15~0.35MPaA；Two
Secondary absorber primary parameters of test apparatus are as follows: draw ratio is 1.2~2.8:1；Adsorbent use silica alumina ratio for 3 X-type molecular sieve.
5. separating the method for carbon dioxide in methanol to propylene reaction gas according to claim 2, it is characterised in that primary to inhale
The technological parameter of adnexa absorption absorption operation are as follows: operation temperature is 20~30 DEG C；Operating pressure is 3.0~3.8MpaA；It is primary to inhale
The technological parameter of adnexa desorption and regeneration operation are as follows: operation temperature is 315~325 DEG C；Operating pressure is 0.30~0.40MPaA；One
Secondary absorber primary parameters of test apparatus are as follows: draw ratio is 2.4~3.6:1.
6. separating the method for carbon dioxide in methanol to propylene reaction gas according to claim 3, it is characterised in that chemistry is inhaled
Receive the technological parameter of device absorption absorption operation are as follows: operation temperature is 20~30 DEG C；Operating pressure is 2.9~3.7MPaA；Chemistry is inhaled
Receive device primary parameters of test apparatus are as follows: draw ratio is 0.8~1.2:1.
7. separating the method for carbon dioxide in methanol to propylene reaction gas according to claim 4, it is characterised in that secondary suction
The technological parameter of adnexa absorption absorption operation are as follows: operation temperature is 20~30 DEG C；Operating pressure is 2.8~3.6MPaA；Secondary suction
The technological parameter of adnexa desorption and regeneration operation are as follows: operation temperature is 315~325 DEG C；Operating pressure is 0.20~0.30MPaA；Two
Secondary absorber primary parameters of test apparatus are as follows: draw ratio is 1.4~2.6:1.
8. separating the method for carbon dioxide in methanol to propylene reaction gas according to claim 1, it is characterised in that chemistry is inhaled
Receive 70~90% that agent volume is chemical absorber volume.
9. separating the method for carbon dioxide in methanol to propylene reaction gas according to claim 1, it is characterised in that A type molecule
Sieve nest product is the 70~90% of an adsorber volume.
10. separating the method for carbon dioxide in methanol to propylene reaction gas according to claim 1, it is characterised in that X-type point
Sub- sieve nest product is the 70~90% of second adsorption body product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6444869B2 (en) * | 1999-10-04 | 2002-09-03 | Uop Llc | Process for producing ethylene |
| CN101072742A (en) * | 2004-12-06 | 2007-11-14 | 埃克森美孚化学专利公司 | Carbon dioxide removal from oxygenate to olefin reaction effluents |
| CN103827062A (en) * | 2011-07-28 | 2014-05-28 | 道达尔研究技术弗吕公司 | Process for removing oxygenated contaminants from an ethylene stream |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6444869B2 (en) * | 1999-10-04 | 2002-09-03 | Uop Llc | Process for producing ethylene |
| CN101072742A (en) * | 2004-12-06 | 2007-11-14 | 埃克森美孚化学专利公司 | Carbon dioxide removal from oxygenate to olefin reaction effluents |
| CN103827062A (en) * | 2011-07-28 | 2014-05-28 | 道达尔研究技术弗吕公司 | Process for removing oxygenated contaminants from an ethylene stream |
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