CN118005478A - Method and device for removing carbon dioxide from MTO product gas - Google Patents
Method and device for removing carbon dioxide from MTO product gas Download PDFInfo
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- CN118005478A CN118005478A CN202410024396.7A CN202410024396A CN118005478A CN 118005478 A CN118005478 A CN 118005478A CN 202410024396 A CN202410024396 A CN 202410024396A CN 118005478 A CN118005478 A CN 118005478A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 112
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 claims abstract description 196
- 239000003463 adsorbent Substances 0.000 claims description 50
- 230000008929 regeneration Effects 0.000 claims description 27
- 238000011069 regeneration method Methods 0.000 claims description 27
- 238000007906 compression Methods 0.000 claims description 19
- 230000006835 compression Effects 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000005056 compaction Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 137
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000012535 impurity Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- -1 alcohol amine Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000002274 desiccant Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 235000014121 butter Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000001447 compensatory effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The application relates to the technical field of carbon dioxide removal in methanol-to-olefin product gas, in particular to a method and a device for removing carbon dioxide from MTO product gas. The method includes introducing a product gas comprising carbon dioxide into an input of an adsorption unit such that the product gas undergoes a plurality of process steps formed from top to bottom such that at least a portion of the carbon dioxide is adsorbed by the adsorption unit and such that carbon dioxide in the product gas output from an output of the adsorption unit is reduced, the plurality of process steps including at least one cryogenic process step and at least one carbon dioxide adsorption step, and the product gas undergoes the cryogenic process step followed by the carbon dioxide adsorption step. The method and the device can remove the acid gas (100 ppm-400 ppm) of the MTO product, the CO 2 content in the purified MTO product gas can be as low as 0.04ppm, and the polymerization grade propylene product with the purity more than or equal to 99.6mol percent can be obtained.
Description
Technical Field
The application relates to the technical field of carbon dioxide removal in methanol-to-olefin product gas, in particular to a method and a device for removing carbon dioxide from MTO product gas.
Background
In the olefin product gas obtained by the reaction of preparing olefin (MTO) from methanol, acid gas impurities such as carbon dioxide usually exist, the content of the carbon dioxide is generally 100-400 ppm, the content of the acid impurities in the product gas needs to be reduced to below 1ppm based on the technical requirements of products of MTO chemical devices, and all the current industrial methods for removing the product gas are an alkaline washing method or an alcohol amine method.
CN1822017B discloses a process for purifying product gas from MTO reaction systems which uses a caustic medium to remove most of the carbon dioxide to bring the product gas to the requirements of polymerization grade ethylene and polymerization grade propylene. The alkaline washing method is adopted to remove acidic impurities, and most of the acidic impurities can be removed, but the requirement of 1ppm is not met in actual production, and meanwhile, water is added into the product gas, so that the operation burden of a downstream dryer is increased. The alkaline residue treatment cost generated by the alkaline washing method is high, and the treatment process is accompanied with safety and environmental protection risks. CN102039172B discloses a method for removing acidic impurities by using a complex amine aqueous solution, which uses a complex amine solution to remove carbon dioxide from gas, and when the partial pressure of carbon dioxide in the gas is less than 0.1MPa and the carbon dioxide is to be deeply removed, the method is used for decarbonizing, and has the characteristics of large carbon dioxide absorption capacity, high purification degree, low energy consumption and the like. The composite amine aqueous solution is also used for removing acidic impurities by a liquid phase method, the carbon dioxide content of the purified mixed gas is only reduced to 0.03-0.80 vol%, water is also added into the product gas, and the operation burden of a downstream dryer is increased.
Disclosure of Invention
In view of the above, the embodiment of the application discloses a method and a device for removing carbon dioxide from MTO product gas, which solve one of the above technical problems to a certain extent. Therefore, the embodiment of the application at least discloses the following technical scheme:
In one aspect, embodiments of the present application provide a process for removing carbon dioxide from an MTO product gas comprising:
S100: introducing a product gas comprising carbon dioxide into an input of an adsorption unit such that the product gas is subjected to a plurality of treatment steps formed from top to bottom such that at least a portion of the carbon dioxide is adsorbed by the adsorption unit and such that carbon dioxide in the product gas output from an output of the adsorption unit is reduced; the plurality of treatment steps includes at least one low temperature treatment step and at least one carbon dioxide adsorption step, and the product gas is subjected to the low temperature treatment step and then to the carbon dioxide adsorption step;
S200: stopping inputting the product gas into the adsorption unit before the carbon dioxide concentration of the output end reaches the turning point;
s300: providing a cold source required by the low-temperature treatment step;
In another aspect, embodiments of the present application disclose an apparatus for removing carbon dioxide from an MTO product gas, the apparatus comprising:
Each adsorption unit comprises at least two adsorption towers which are sequentially communicated from top to bottom, and a low-temperature area and an adsorbent bed formed by adsorption materials are formed in each adsorption tower from bottom to top; and
A pipeline connecting the plurality of adsorption units and the plurality of adsorption towers;
Wherein, the adsorption tower includes:
A tower body;
a support grid and a compaction grid transversely arranged in the tower body;
An adsorbent packed between the support grid and the compaction grid to form the adsorbent bed;
The input pipe extends downwards from the top end of the tower body and is inserted into the adsorbent bed;
the first output pipe is abutted from the upper end of the adsorbent bed to extend out of the tower body;
the second output pipe extends from the lower part of the adsorbent bed to the outside of the tower body;
and the cooling pipe is coiled below the adsorbent bed of the tower body so as to form the low-temperature area.
The method and the device for removing carbon dioxide in the MTO product gas can remove the acid gas (100 ppm-400 ppm) of the MTO product, the CO 2 content in the purified MTO product gas can be as low as 0.04ppm, and the polymerization grade propylene product with the purity more than or equal to 99.6mol% can be obtained. In addition, the method and the device for removing the carbon dioxide in the MTO product gas can avoid the problems of safety of an alkaline washing incineration system for treating the carbon dioxide by adopting conventional alkali liquor, large butter production of an alkaline washing tower, long alcohol amine method process flow and the like. Compared with the prior art, the method and the device provided by the embodiment of the application can not generate waste lye, waste amine liquid and butter, and the shutdown waste lye incineration system or alcohol amine impurity removal system reduces the running cost and the safety and environmental protection risks.
Drawings
FIG. 1 is a schematic flow chart of a method for removing carbon dioxide from MTO product gas according to an embodiment of the present application.
Fig. 2 is a specific flowchart of step S100 according to an embodiment of the present application.
Fig. 3 is a specific flowchart of step S100 according to another embodiment of the present application.
Fig. 4 is a specific flowchart of step S300 provided in the embodiment of the present application.
Fig. 5 is a schematic flow chart of a method for removing carbon dioxide from MTO product gas according to an embodiment of the present application.
Fig. 6 is a specific flowchart of step S400 according to an embodiment of the present application.
Fig. 7 is a schematic diagram of an apparatus for removing carbon dioxide from MTO product gas according to an embodiment of the present application.
Fig. 8 is a schematic diagram of an apparatus for an adsorption tower according to an embodiment of the present application.
Fig. 9 is a schematic diagram of an apparatus for an adsorption tower according to an embodiment of the present application.
Fig. 10 is a schematic diagram of an apparatus for an adsorption tower according to an embodiment of the present application.
The adsorption unit 1, the adsorption tower 10, the low temperature zone 10a, the adsorbent bed 10b, the tower body 101, the support grid 102, the compression grid 103, the adsorbent 104, the input pipe 105, the first output pipe 106, the second output pipe 107, the cooling pipe 108, the membrane module 109, the regeneration system 2, the regeneration gas feed heater 21, the regeneration gas discharge collector 22, the compression system 3, the compressor 31, the cooler 32, the scrubber 33, the dryer 34, the recovery system 4, the second discharge filter 41, the second product tank 42, the first discharge filter 43, the first product tank 44.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be described in further detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application. The reagents not specifically and individually described in the present application are all conventional reagents and are commercially available; methods which are not specifically described in detail are all routine experimental methods and are known from the prior art.
It should be noted that, the terms "first," "second," and the like in the description and the claims of the present application and the above drawings are used for distinguishing similar objects, and are not necessarily used for describing a particular sequence or order, nor do they substantially limit the technical features that follow. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the application described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The term "adsorption" as used herein includes physical adsorption, chemisorption, and condensation on solid supports, adsorption on solid support liquids, chemisorption on solid support liquids, and combinations thereof.
The term "turning point" as used herein refers to the point at which the product gas exiting the adsorbent bed exceeds the target specification for the contaminant component. At the turning point, the adsorbent bed may be considered "spent" and thus any significant further operation by the spent adsorbent bed alone will result in off-spec product gas. As used herein, a "turning point" may generally coincide with a "adsorption front", i.e., the adsorption front is generally located at the end of the adsorbent bed when a turning point is detected at the outlet of the adsorbent bed.
In one aspect, embodiments of the present application provide a process for removing carbon dioxide from an MTO product gas, as shown in fig. 1, comprising:
S100: introducing a product gas comprising carbon dioxide into an input of an adsorption unit such that the product gas is subjected to a plurality of treatment steps formed from top to bottom such that at least a portion of the carbon dioxide is adsorbed by the adsorption unit and such that carbon dioxide in the product gas output from an output of the adsorption unit is reduced; the plurality of treatment steps includes at least one low temperature treatment step and at least one carbon dioxide adsorption step, and the product gas is subjected to the low temperature treatment step and then to the carbon dioxide adsorption step;
S200: stopping inputting the product gas into the adsorption unit before the carbon dioxide concentration of the output end reaches the turning point;
s300: providing a cold source required by the low-temperature treatment step;
S400: recovering a product gas or stream from the output after the plurality of processing steps;
S500: and desorbing the carbon dioxide from the adsorption unit.
In some embodiments, as shown in fig. 2, the step S100 specifically includes:
S101: introducing a product gas comprising carbon dioxide into an input of an adsorption unit; wherein, the adsorption units are provided with at least two, each adsorption unit comprises at least two adsorption towers, and each adsorption tower sequentially executes the low-temperature treatment step and the carbon dioxide adsorption step;
S102: the product gas comprising dioxide is subjected to at least two of the cryogenic treatment steps and at least two of the oxidation adsorption steps via each adsorption unit;
S103: the top gas stream obtained after passing through each adsorption unit is incorporated into the input of the next adsorption unit in series.
In some embodiments, as shown in fig. 3, the step S100 specifically includes:
S101: introducing a product gas comprising carbon dioxide into an input of an adsorption unit; wherein, the adsorption units are provided with at least two adsorption towers, each adsorption unit comprises at least two adsorption towers, and each adsorption tower sequentially executes a low-temperature treatment step, a carbon dioxide adsorption step and at least one carbon dioxide filtering step; the carbon dioxide filtering step is capable of amplifying other gas molecules to prevent the passage of carbon dioxide;
S102: the product gas comprising carbon dioxide is subjected to at least two of the cryogenic treatment steps, at least two of the dioxygenation adsorption steps and at least two of the carbon dioxide filtration steps via each adsorption unit;
S103: the top gas stream obtained after passing through each adsorption unit is incorporated into the input of the next adsorption unit in series.
In some embodiments, the adsorption unit has a plurality of adsorption columns, each adsorption column performing the same adsorption operation cycle in a compensatory manner. The cycle typically includes an adsorption period and a regeneration period. During the adsorption period, the corresponding adsorption tower is contacted with the gas mixture and adsorbs impurities. During the regeneration period, the adsorption tower is contacted with the regeneration gas and desorbs the previously adsorbed impurities. In this embodiment, the adsorption column may be subjected to depressurization and repressurization steps as well as steps of paralleling the adsorbent beds. During this time, the total treated gas stream is obtained by treating the first gas stream with at least one adsorption column ending its adsorption period and treating the second gas stream to be treated with at least one other adsorption column starting its adsorption period. The parallel connection is generally used to prevent the pressure of the gas stream being treated in production from building up on the way from one adsorption column to another, in particular in order to take account of the operating time of the valves that are operated in parallel.
In an embodiment of the application, where N adsorption units are used, where N is greater than or equal to 2, each being subjected to the same cycle of time T in a compensating manner, during which there is a succession of an adsorption period and a regeneration period with regeneration gas, and where at the beginning of the period and/or at the beginning of the use of regeneration gas, each adsorption unit is in contact with only a part of the nominal flow of the gas mixture to be treated, or with only a part of the nominal flow of regeneration gas, until said adsorption unit is substantially saturated with, or substantially unloaded from, at least one main component to be produced, while at least one other adsorption unit is kept in the adsorption period.
In some embodiments, the temperature of a plurality of the cryogenic treatment steps is reduced in each adsorption unit in turn. For example, the temperature at the previous said low temperature treatment step is higher than the temperature at the next said low temperature treatment step, and the temperature at the last said low temperature treatment step in the adsorption unit is the lowest, for example, the temperature thereof is-40 to-30 ℃, more preferably-40 to 37.7 ℃. In this context, the terms "preceding" and "following" are used to distinguish between the sequential passes through the adsorption tower treatment sequences in each adsorption unit.
In some embodiments, as shown in fig. 4, the step S300 specifically includes:
S301: the cold source gas flow is subjected to at least one stage of compression step, so that the pressure of the cold source gas is increased;
s302: subjecting the cold source gas stream having an elevated pressure to at least one stage of cooling such that the temperature of the cold source gas stream is reduced;
s303: passing the cold source gas having an elevated pressure and a reduced temperature through a washing step to remove condensed water;
s304: and (3) the cold source air flow with condensed water removed is subjected to a drying step so as to further remove water vapor.
In some embodiments, as shown in fig. 5, the method for removing carbon dioxide from MTO product gas prior to step S100 further comprises:
s601: subjecting a product gas comprising carbon dioxide to at least one stage of compression such that the pressure of the product gas is increased;
S602: subjecting the product gas having an elevated pressure to at least one stage of cooling such that the temperature of the product gas is reduced;
S602: subjecting the product gas having an elevated pressure and a reduced temperature to a washing step to remove condensed water;
S603: the product gas from which the condensed water is removed is subjected to a drying step to further remove water vapour.
In this embodiment, the product gas passes through the steps S601 to S603 before entering each adsorption unit or before entering the adsorption units connected in series.
In some embodiments, as shown in fig. 6, the step S400 specifically includes:
S401: recovering a product gas or stream from the output of each of said adsorption units; or alternatively
S402: product gas or product stream is recovered from the output of a plurality of said adsorption units in series.
In some embodiments, in step S400, a regeneration gas free of carbon dioxide is provided to purge the adsorbent bed, thereby desorbing carbon dioxide from the adsorbent bed.
In another aspect, embodiments of the present application disclose an apparatus for removing carbon dioxide from an MTO product gas, as shown in fig. 7-10, comprising:
A plurality of adsorption units 1, wherein each adsorption unit 1 comprises at least two adsorption towers 10 which are sequentially communicated from top to bottom, and a low-temperature area 10a and an adsorbent bed 10b formed by adsorption materials are formed in each adsorption tower 10 from bottom to top;
A pipeline connecting the plurality of adsorption units and the plurality of adsorption towers;
Wherein the adsorption tower 10 comprises:
A tower 101;
a support grid 102 and a compression grid 103 transversely spaced within the tower body;
an adsorbent 104 filled between the support grid 102 and the compaction grid 103 to form an adsorbent bed 10b;
an input pipe 105, wherein the input pipe 105 extends downwards from the top end of the tower body 101 and is inserted into the adsorbent bed 10 b;
The first output pipe 106, the first output pipe 106 extends out of the tower 101 from the upper end of the adsorbent bed 10 b;
A second output pipe 107, the second output pipe 107 extends outside the column 101 from below the adsorbent bed 10 b;
And a cooling tube 108, the cooling tube 108 being coiled below the adsorbent bed 10b of the column 101 to form the low temperature zone 10a.
For typical plant scale operations, embodiments of the present application provide 2 adsorption units such that at any given time one adsorption unit will be regenerated while the other two adsorption units in parallel will be contacted with an olefin-containing feed stream. With the first adsorption unit in contact with the olefin-containing feed stream saturated with CO 2 (as evidenced by CO 2 in the effluent of the first adsorption unit), the second adsorption unit in reserve will become the primary bed in contact with the olefin-containing feed stream; the newly regenerated adsorption unit will be put into production as a backup and the saturation unit will be treated under suitable regeneration conditions.
In some embodiments, the adsorbent material is selected from the following types of framework structured zeolites ：AFT、AFX、DAC、EMT、EUO、IMF、ITH、ITT、KFI、LAU、MFS、MRE、MTT、MWW、NES、PAU、RRO、SFF、STF、STI、SZR、TER、TON、TSC、TUN、VFI and combinations thereof; the zeolite has a silicon to aluminum element ratio of 100.
In some embodiments, as shown in fig. 9 and 10, the adsorption tower 10 further includes:
The gas flow absorbed by the membrane module 109 via the adsorbent bed 10b is filtered by the membrane module 109, and carbon dioxide can be further blocked in the adsorption tower 10.
In some embodiments, as shown in fig. 10, the membrane assemblies 109 are disposed above and below the adsorbent bed 10b, so that carbon dioxide can be blocked between the two membrane assemblies 109 and concentrated in the adsorbent bed 10b, which is beneficial to fully adsorbing carbon dioxide in the adsorbent bed, improving the adsorption rate of the carbon dioxide, avoiding the carbon dioxide flowing out of the first output pipe 106 or the second output pipe 107, reducing the load of the downstream adsorption process or avoiding the carbon dioxide from being mixed into the product. The membrane module is capable of amplifying other gas molecules while preventing the passage of carbon dioxide, and the gas re-diffusion rate may be a function of the membrane area used and the difference in carbon dioxide concentration along the one or more membranes. The membrane component is made of a material selected from polydimethylsiloxane, poly 3-methyl-1-pentene or polyethersulfone or polyimide.
In each adsorption tower 10 of one adsorption unit 1, the product gas containing carbon dioxide is directly fed into the adsorbent bed 10b via the input pipe 105, so that the flow path of the product gas is reduced, the carbon dioxide is directly absorbed by the adsorption material, and the adsorption efficiency is improved. Through the diffusion of the product gas, the main component thereof enters the low temperature region at the bottom through the diffusion, and is advantageously adsorbed in the adsorbent bed 10b of the next stage of the adsorption tower 10 of the same adsorption unit. Engineering experiments show that the aspect ratio of the adsorbent bed 10b provided by the embodiment of the application is 2-3.5:1, the operating temperature is-20-100 ℃, and the operating pressure is 0.4-2.0 MPa; the adsorption towers 10b of each adsorption unit are connected in series upstream and downstream, and preferably the number of the adsorption towers in each adsorption unit is 2. And in each adsorption unit, the temperature of the low temperature region of the adsorption tower 10 is sequentially lowered, for example, the temperature of the low temperature region of the adsorption tower 10 of the first stage is controlled to-25 to 0 ℃, the temperature of the low temperature region of the adsorption tower 10 of the middle stage is controlled to-25 to 35 ℃, and the temperature of the low temperature region of the adsorption tower 10 of the last stage is controlled to-50 to-40 ℃, more preferably-50 to 47.7 ℃.
In each adsorption tower 10 of one adsorption unit 1, after the product gas containing carbon dioxide is adsorbed by the multi-stage adsorbent bed 10, the carbon dioxide is adsorbed or blocked by the membrane module 109. And the top gas flow flowing out of the second output pipe 107 is combined into the next adsorption unit 1, so that part of carbon dioxide in the top gas flow is adsorbed or blocked again, and the carbon dioxide is fully removed.
In some embodiments, to prevent the top gas stream exiting the second output conduit 107 from exiting, the exiting line may be passed through one or more heat exchangers so that it becomes gaseous, thereby facilitating its flow.
In some embodiments, as shown in fig. 7, an embodiment of the present application discloses an apparatus for removing carbon dioxide from MTO product gas further comprising: a regeneration system 2 that provides a regeneration gas free of carbon dioxide to purge the adsorbent bed, thereby desorbing carbon dioxide from the adsorbent bed. The regeneration system provides a nitrogen flow with an operating pressure of 0.2-0.8 MPa.
In some embodiments, as shown in fig. 7, the regeneration system 2 includes a regeneration gas feed heater 21, a regeneration gas discharge collector 22, and a pipeline through which the hot carbon dioxide-free regeneration gas withdrawn by the regeneration gas feed heater 21 flows into the bottom end of the adsorbent bed 10b, flows out of the top end of the adsorbent bed 10b, and then is collected into the regeneration gas discharge collector 22. Wherein, the operation temperature of the inlet of the regenerated gas feeding heater is 24 ℃, the operation temperature of the outlet is 294 ℃, and the operation pressure is 0.24MPaA; the regeneration gas discharge collector had an inlet operating temperature of 294 c, an outlet operating temperature of 24 c, and an operating pressure of 0.04MPaA c.
In some embodiments, as shown in fig. 7, an embodiment of the present application discloses an apparatus for removing carbon dioxide from MTO product gas further comprising: a compression system 3 for compressing and cooling the product gas or the gas stream flowing out of each adsorption tower or providing a required cold source for the low temperature region. Specifically, compression system 3 includes one or more compressors 31, coolers 32, scrubbers 33, and dryers 34. Such multiple compressors 31 may achieve multiple stages of compression of the product such that it enters the adsorption column 10 to form a low temperature feed. In addition, after each stage of compression, the gas leaving the compressor 31 may be further cooled by a cooler 32, where the temperature produced may depend on the type of cooler, the temperature of the heat exchange medium, or other factors such as the ambient temperature.
After each stage of compression and cooling, condensed water may be removed from the gas in scrubber 33. The scrubber 32 may be equipped with, for example, a mist eliminator or other device to separate water droplets entrained in the gas stream. This water may be recovered from scrubber 33 via an outlet and, in some embodiments, may be discharged into a wastewater treatment system.
In some embodiments, as shown in fig. 8-10, after compressing the system 3, the resulting compressed gas stream may flow into the adsorption unit 1, specifically into the adsorption column 10, via a flow line to form the low temperature zone 10a.
In some embodiments, the product gas comprising carbon dioxide may be treated and compressed via parallel piping or parallel compression system 3 such that it forms a low temperature, higher pressure, and dry product gas. In these embodiments, the product gas treated by the compression system 3 is capable of removing moisture therefrom. This is removed from the compressed gas in the flow line by passing the gas through a solid desiccant contained in the dryer 34. The desiccant may include other desiccants known in the art, such as type 2A molecular sieves.
The dried compressed gas stream may be recovered from dryer 34 via a flow line. In some embodiments, the compressed gas recovered from dryer 34 may have less than 200ppm by volume of water; less than 100ppm by volume in another embodiment, and less than 40ppm by volume in yet another embodiment. A dust filter may be provided at the outlet of the dryer 34 to remove any fines carried by the air stream from the desiccant.
In some embodiments, the low temperature, higher pressure, and dried product gas may have a pressure of at least 30 bar; in another embodiment the compressed gas stream may have a pressure of from 30 to 60 bar; in another embodiment from 32 to 44bar; and in yet another embodiment 36 to 42bar, for example about 39bar.
In some embodiments, the product gas after being treated by the compression system 3 is fed via a flow line to the adsorption unit 1, the low temperature, higher pressure and temperature of the dried product gas may be cooled to a temperature of-20 ℃ to-24 ℃, such as for example a temperature of about-22 ℃.
In some embodiments, to provide a cold source to the cooling tubes in the adsorption column 10, the compression system 3 may deliver the compressed cold source to the cooling tubes 108 through parallel piping so that the cooling tubes 108 form the low temperature zone 10a in the adsorption column 10.
In some embodiments, the apparatus for removing carbon dioxide from MTO product gas disclosed in the embodiments of the present application further comprises: and the recovery system 4 is connected with the second output pipe 107 through a flow pipeline, filters the product at the bottom of the adsorption tower through the second discharging filter 41, and recovers the product into the second product tank 42 through heat exchange or cooling by a cooler. In some embodiments, the recovery system 4 is further connected to the first output pipe 106 via a flow line, for example, the product gas flowing out of the first output pipe 106 connected to the last stage of the plurality of adsorption units 1 is filtered by the first discharging filter 43, cooled by heat exchange or a cooler, and recovered to the first product tank 44.
In some embodiments, the refrigerant used for indirect heat exchange is propane to provide a cold source in cooling tube 108; other refrigerants or refrigerant mixtures may also be used. Propane may circulate in a refrigeration circuit, i.e. a circuit formed by the compression system 3. In some embodiments, compression system 3 may also include an accumulator and an economizer. Vapor from the economizer may be recycled to the suction of the second stage compressor and the liquid may be fed to a heat exchanger to cool the compressed feed to a temperature below about-22 c, such as to a temperature range of about-24 c to about-30 c. The flash propane from the heat exchanger may be fed to the scrubber via a flow line and then to the compressor.
Example 1
The MTO unit has a nominal capacity of 200 ten thousand tons/year of methanol and the MTO product gas flow required to remove carbon dioxide is 31200 kg/hour. The composition of the product gas is as follows: methane 0.003%, ethylene 98.622%, ethane 1.188%, propylene 0.022% and carbon dioxide 0.142%. By adopting the method and the device for removing carbon dioxide from the MTO product gas, which are provided by the embodiment of the application, carbon dioxide removal and product gas refining are carried out.
According to the production scale of the MTO device, 2 groups of adsorption units are required to be arranged in parallel, wherein 1 group of adsorption units carry out adsorption and absorption operations, and the rest 1 group of adsorption units carry out desorption and regeneration operations so as to keep full-load continuous and stable operation of the large-scale commercial MTO industrial production device. Wherein, the adsorption unit 1 is provided with three stages of adsorption towers 10, and the structure of the adsorption towers 10 is shown in fig. 8. In the three-stage adsorption tower 10, the height-to-diameter ratio of the adsorbent bed 10b is 3.5:1, the operating temperature is-10 ℃, and the operating pressure is 1.5MPa. In the three-stage adsorption tower 10, the temperature of the low temperature region of the uppermost stage is about-10 ℃, the temperature of the low temperature region of the middle stage is controlled to be about-30 ℃, and the temperature of the low temperature region of the last stage is controlled to be about-50 ℃.
Thus, after the MTO product gas is treated by the method and the device for removing the carbon dioxide from the MTO product gas, the CO 2 content in the purified MTO product gas is 0.8ppm; further separating and refining the MTO product gas to obtain a polymer grade ethylene product with the purity of more than or equal to 99.94mol percent and a polymer grade propylene product with the purity of more than or equal to 99.6mol percent.
Example 2
The MTO unit has a nominal capacity of 200 ten thousand tons/year of methanol and the MTO product gas flow required to remove carbon dioxide is 31200 kg/hour. The composition of the product gas is as follows: methane 0.003%, ethylene 98.622%, ethane 1.188%, propylene 0.022% and carbon dioxide 0.142%. By adopting the method and the device for removing carbon dioxide from the MTO product gas, which are provided by the embodiment of the application, carbon dioxide removal and product gas refining are carried out.
According to the production scale of the MTO device, 2 groups of adsorption units are required to be arranged in parallel, wherein 1 group of adsorption units carry out adsorption and absorption operations, and the rest 1 group of adsorption units carry out desorption and regeneration operations so as to keep full-load continuous and stable operation of the large-scale commercial MTO industrial production device. Wherein the adsorption unit 1 is provided with three stages of adsorption towers 10, and the structure of the adsorption towers 10 is shown in fig. 9. In the three-stage adsorption tower 10, the height-to-diameter ratio of the adsorbent bed 10b is 3.5:1, the operating temperature is-10 ℃, and the operating pressure is 1.5MPa. In the three-stage adsorption tower 10, the temperature of the low temperature region of the uppermost stage is about-10 ℃, the temperature of the low temperature region of the middle stage is controlled to be about-30 ℃, and the temperature of the low temperature region of the last stage is controlled to be about-50 ℃.
Thus, after the MTO product gas is treated by the method and the device for removing the carbon dioxide from the MTO product gas, the CO 2 content in the purified MTO product gas is 0.08ppm; further separating and refining the MTO product gas to obtain a polymer grade ethylene product with the purity of more than or equal to 99.96mol percent and a polymer grade propylene product with the purity of more than or equal to 99.4mol percent.
Example 3
The MTO unit has a nominal capacity of 200 ten thousand tons/year of methanol and the MTO product gas flow required to remove carbon dioxide is 31200 kg/hour. The composition of the product gas is as follows: methane 0.003%, ethylene 98.622%, ethane 1.188%, propylene 0.022% and carbon dioxide 0.142%. By adopting the method and the device for removing carbon dioxide from the MTO product gas, which are provided by the embodiment of the application, carbon dioxide removal and product gas refining are carried out.
According to the production scale of the MTO device, 2 groups of adsorption units are required to be arranged in parallel, wherein 1 group of adsorption units carry out adsorption and absorption operations, and the rest 1 group of adsorption units carry out desorption and regeneration operations so as to keep full-load continuous and stable operation of the large-scale commercial MTO industrial production device. Wherein, the adsorption unit 1 is provided with three stages of adsorption towers 10, and the structure of the adsorption towers 10 is shown in fig. 10. In the three-stage adsorption tower 10, the height-to-diameter ratio of the adsorbent bed 10b is 3.5:1, the operating temperature is-10 ℃, and the operating pressure is 1.5MPa. In the three-stage adsorption tower 10, the temperature of the low temperature region of the uppermost stage is about-10 ℃, the temperature of the low temperature region of the middle stage is controlled to be about-30 ℃, and the temperature of the low temperature region of the last stage is controlled to be about-50 ℃.
Thus, after the MTO product gas is treated by the method and the device for removing the carbon dioxide from the MTO product gas, the CO 2 content in the purified MTO product gas is 0.04ppm; further separating and refining the MTO product gas to obtain a polymer grade ethylene product with the purity of more than or equal to 99.96mol percent and a polymer grade propylene product with the purity of more than or equal to 99.5mol percent.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application.
Claims (10)
1. A process for removing carbon dioxide from an MTO product gas comprising:
S100: introducing a product gas comprising carbon dioxide into an input of an adsorption unit such that the product gas is subjected to a plurality of treatment steps formed from top to bottom such that at least a portion of the carbon dioxide is adsorbed by the adsorption unit and such that carbon dioxide in the product gas output from an output of the adsorption unit is reduced; the plurality of treatment steps includes at least one low temperature treatment step and at least one carbon dioxide adsorption step, and the product gas is subjected to the low temperature treatment step and then to the carbon dioxide adsorption step;
S200: stopping inputting the product gas into the adsorption unit before the carbon dioxide concentration of the output end reaches the turning point;
s300: providing a cold source required by the low-temperature treatment step;
S400: recovering a product gas or stream from the output after the plurality of processing steps;
S500: and desorbing the carbon dioxide from the adsorption unit.
2. The method according to claim 1, wherein the step S100 specifically comprises:
S101: introducing a product gas comprising carbon dioxide into an input of an adsorption unit; wherein, the adsorption units are provided with at least two, each adsorption unit comprises at least two adsorption towers, and each adsorption tower sequentially executes the low-temperature treatment step and the carbon dioxide adsorption step;
S102: the product gas comprising dioxide is subjected to at least two of the cryogenic treatment steps and at least two of the oxidation adsorption steps via each adsorption unit;
S103: the top gas stream obtained after passing through each adsorption unit is incorporated into the input of the next adsorption unit in series.
3. The method according to claim 1 or 2, wherein the step S100 specifically comprises:
S101: introducing a product gas comprising carbon dioxide into an input of an adsorption unit; wherein, the adsorption units are provided with at least two adsorption towers, each adsorption unit comprises at least two adsorption towers, and each adsorption tower sequentially executes a low-temperature treatment step, a carbon dioxide adsorption step and at least one carbon dioxide filtering step; the carbon dioxide filtering step is capable of amplifying other gas molecules to prevent the passage of carbon dioxide;
s102: the product gas comprising dioxide is subjected to at least two of the cryogenic treatment steps, at least two of the oxidation adsorption steps and at least two of the carbon dioxide filtration steps via each adsorption unit;
S103: the top gas stream obtained after passing through each adsorption unit is incorporated into the input of the next adsorption unit in series.
4. A method according to any one of claims 1-3, characterized in that step S300 comprises in particular:
S301: the cold source gas flow is subjected to at least one stage of compression step, so that the pressure of the cold source gas is increased;
s302: subjecting the cold source gas stream having an elevated pressure to at least one stage of cooling such that the temperature of the cold source gas stream is reduced;
s303: passing the cold source gas having an elevated pressure and a reduced temperature through a washing step to remove condensed water;
s304: and (3) the cold source air flow with condensed water removed is subjected to a drying step so as to further remove water vapor.
5. The method of any one of claims 1-4, wherein prior to step S100, the method of removing carbon dioxide from MTO product gas further comprises:
s601: subjecting a product gas comprising carbon dioxide to at least one stage of compression such that the pressure of the product gas is increased;
S602: subjecting the product gas having an elevated pressure to at least one stage of cooling such that the temperature of the product gas is reduced;
S602: subjecting the product gas having an elevated pressure and a reduced temperature to a washing step to remove condensed water;
S603: the product gas from which the condensed water is removed is subjected to a drying step to further remove water vapour.
6. The method according to any one of claims 1 to 5, wherein the step S400 specifically comprises:
S401: recovering a product gas or stream from the output of each of said adsorption units; or alternatively
S402: product gas or product stream is recovered from the output of a plurality of said adsorption units in series.
7. An apparatus for removing carbon dioxide from MTO product gas, comprising:
Each adsorption unit comprises at least two adsorption towers which are sequentially communicated from top to bottom, and a low-temperature area and an adsorbent bed formed by adsorption materials are formed in each adsorption tower from bottom to top; and
A pipeline connecting the plurality of adsorption units and the plurality of adsorption towers;
Wherein, the adsorption tower includes:
A tower body;
a support grid and a compaction grid transversely arranged in the tower body;
An adsorbent packed between the support grid and the compaction grid to form the adsorbent bed;
The input pipe extends downwards from the top end of the tower body and is inserted into the adsorbent bed;
the first output pipe is abutted from the upper end of the adsorbent bed to extend out of the tower body;
the second output pipe extends from the lower part of the adsorbent bed to the outside of the tower body;
and the cooling pipe is coiled below the adsorbent bed of the tower body so as to form the low-temperature area.
8. The apparatus of claim 7, wherein the adsorption column further comprises:
and the gas flow absorbed by the adsorbent bed is filtered by the membrane component.
9. The apparatus of claim 8, wherein the apparatus further comprises:
A regeneration system providing a regeneration gas free of carbon dioxide to purge the adsorbent bed, thereby desorbing carbon dioxide from the adsorbent bed;
A compression system for compressing and cooling the product gas or the gas stream exiting each adsorption column or providing a source of cooling for the low temperature zone.
10. The apparatus according to any one of claims 7-9, wherein the apparatus further comprises:
the recovery system comprises a second discharging filter and a second product tank which are connected with the second output pipe through a flow pipeline, and a first discharging filter and a first product tank which are connected with the first output pipe through the flow pipeline.
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