CN115197038A - CO using methanol as intermediate 2 Method for preparing low-carbon olefin by hydrogenation - Google Patents
CO using methanol as intermediate 2 Method for preparing low-carbon olefin by hydrogenation Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 301
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 53
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 53
- 150000001336 alkenes Chemical class 0.000 claims abstract description 45
- 238000007670 refining Methods 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 54
- 238000000926 separation method Methods 0.000 claims description 48
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 38
- 239000005977 Ethylene Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910001868 water Inorganic materials 0.000 claims description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 25
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 24
- 239000001294 propane Substances 0.000 claims description 23
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 22
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 17
- 239000006227 byproduct Substances 0.000 claims description 14
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 13
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- -1 ethylene, propylene Chemical group 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- 238000011144 upstream manufacturing Methods 0.000 claims 2
- 239000001273 butane Substances 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 230000006837 decompression Effects 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 25
- 239000007789 gas Substances 0.000 description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000004172 quinoline yellow Substances 0.000 description 2
- 239000002151 riboflavin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000004229 Alkannin Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004230 Fast Yellow AB Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004234 Yellow 2G Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1512—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses CO taking methanol as an intermediate 2 The process method for preparing the low-carbon olefin by hydrogenation mainly comprises a methanol synthesis unit, an olefin synthesis unit and an olefin refining unit. Compared with the traditional coal-made low-carbon olefinDifferent in process, the invention utilizes CO in the factory waste gas 2 The methanol is synthesized through hydrogenation reaction, and the low-carbon olefin is prepared by taking the methanol as an intermediate, so that the dependence on fossil energy is reduced, and the cyclic utilization of carbon resources is realized. In addition, the present invention focuses on CO 2 The design of a process system for preparing the low-carbon olefin by hydrogenation provides important reference for large-scale industrial application. In CO 2 The output of the low-carbon olefin is 1278.53 tons/h, the yield of the low-carbon olefin is 91.12 percent and the CO content is 4.4 tons/h 2 The energy utilization rate of the whole process of the low-carbon olefin preparation process by hydrogenation is 58.47 percent, and the net CO is 2 The reduction rate is 65.22%.
Description
Technical Field
The invention belongs to the technical field of low-carbon olefin production, and particularly relates to CO taking methanol as an intermediate 2 A method for preparing low-carbon olefin by hydrogenation.
Background
The low-carbon olefin including ethylene, propylene and butylene is an important basic raw material in modern chemical industry and is widely applied to the production of important chemical products such as polyethylene, polypropylene, allyl alcohol, synthetic rubber and the like, wherein the ethylene yield is a very important mark for measuring the petrochemical industry development level of a country or a region. From the domestic market, the low-carbon olefins are widely applied and have large demand, but the self-sufficiency of the low-carbon olefins is not realized yet, the traditional production process of the low-carbon olefins mainly comprises the steps of carrying out catalytic cracking, thermal cracking and the like on naphtha or light diesel oil and the like through a fluidized bed reactor, but the process is seriously dependent on petroleum resources, so that the price of the low-carbon olefins is greatly influenced by the international crude oil price. In view of the energy characteristics of "rich coal, lean oil and low gas" in China, in recent years, a process for preparing intermediate methanol from coal as a raw material and producing low-carbon olefins by a Methanol To Olefin (MTO) technology has received wide attention from the industry. However, in both the coal-to-olefin and petroleum-to-olefin processes, a large amount of CO is produced 2 Emissions, in turn, contribute to global warming. Therefore, to reduce CO 2 The invention provides an ambitious goal of discharging and realizing carbon neutralization, and provides a method for utilizing CO in industrial waste gas 2 The process route of synthesizing intermediate methanol through hydrogenation reaction and preparing low-carbon olefin through MTO technology converts waste carbon resources into low-carbon olefin with high added value, not only realizes the recycling of the carbon resources, but also provides a new way for the production of the low-carbon olefin, relieves the serious dependence of the production process of the low-carbon olefin on fossil energy, and has important significance for maintaining the national energy safety and relieving the resource environmental constraint. In addition, most of the patents currently granted or published are focused on CO 2 The design of catalyst for hydrogenation to prepare low-carbon olefinEmphasis is placed on CO 2 The design of a process system for preparing the low-carbon olefin by hydrogenation is expected to provide important reference for future large-scale industrial application.
Disclosure of Invention
The invention provides CO taking methanol as an intermediate 2 A process route for preparing low-carbon olefin by hydrogenation, which is to remove CO in industrial waste gas 2 Synthesizing intermediate methanol through hydrogenation reaction, and preparing low-carbon olefin through a methanol-to-olefin technology, wherein the yield of the low-carbon olefin is 91.15%, the energy efficiency and the net CO are high 2 The reduction rates are 58.47% and 65.22%, respectively.
In order to achieve the above object, the present invention adopts the following technical solutions.
Raw material gas CO 2 And H 2 Preheated and pressurized, then sent to a methanol synthesis reactor, and passed through CO 2 Hydrogenation reaction to obtain high-temperature crude methanol mixture. The high-temperature crude methanol mixture contains unreacted CO 2 、CO、H 2 And by-product H 2 And O. The high-temperature crude methanol mixture is cooled and then subjected to two-stage flash evaporation to remove unreacted CO in the high-temperature crude methanol mixture 2 CO and H 2 And is recycled to the methanol synthesis reactor after being pressurized and preheated. Rectifying water-containing crude methanol to remove water, pressurizing and preheating, sending to an olefin synthesis reactor, preparing low-carbon olefin through the reaction of preparing olefin from methanol, and simultaneously generating CO 2 、CO、 H 2 、H 2 O, methane, ethane, propane, and pentene. The crude product obtained from the olefin synthesis reactor is sequentially passed through equipment such as a pentene separation tower, an alkaline washing tower, a dryer, a methane separation tower, a carbon dioxide separation tower, an ethylene separation tower, a propylene separation tower, a butene separation tower and the like to obtain polymerization-grade ethylene with the purity of more than 99.8 percent (mass fraction), industrial-grade propylene with the purity of more than 99.6 percent (mass fraction) and industrial-grade butene with the purity of more than 99 percent (mass fraction). And by-products such as methane, ethane, propane, pentene and the like generated in the olefin synthesis process are respectively sent to corresponding storage tanks.
Description of the drawings:
FIG. 1 is CO with methanol as an intermediate 2 The process flow chart of dimethyl ether preparation by hydrogenation comprises the following steps:
wherein the figures include the following reference numerals:
r101-methanol synthesis reactor; r102-olefin synthesizer; m101 — first mixer; m102-a second mixer; m103-a third mixer; c101-first compressor; c102-a second compressor; c103-third compressor; e101-a first heat exchanger; e102-a second heat exchanger; e103-a third heat exchanger; e104-a fourth heat exchanger; e105-a fifth heat exchanger; e106-a sixth heat exchanger; e107-a seventh heat exchanger; t101-a first rectification column; t102-a second rectification column; t103-a third rectifying tower; t104-a fourth rectifying tower; t105-a fifth rectifying column; t106-a sixth rectifying tower; t107-a seventh rectifying column; v101-first flash tank; v102 — second flash tank; v103-an alkaline washing tower; d101-a first dryer; d102-a second dryer; p101-first booster pump; a VALVE-relief VALVE; 101-hydrogen; 102-carbon dioxide; 141-ethylene; 144-propene; 146-butene;
this method will be described in more detail below.
And (3) preparing crude methanol.
H 2 [101]And CO 2 [102]Mixing in a first mixer M101, mixing the gas mixture [103]Compressed to 5-8MPa by a first compressor C101, and the pressurized mixed gas [104 ]]Preheating to 180-250 ℃ after passing through a first heat exchanger E101 and a second heat exchanger E102 so as to meet the feeding condition of a methanol synthesis reactor R101, and feeding gas [107 ] under the action of a copper-based catalyst]By CO in the methanol Synthesis reactor R101 2 Hydrogenation reaction to convert into high-temperature crude methanol [108 ]]High temperature crude methanol [108 ]]Exchanging heat with the raw material gas entering the methanol synthesis reactor R101 in a first heat exchanger E101, then cooling to 20-60 ℃ through a third heat exchanger E103, sending to a first flash tank V101, and extracting water-containing crude methanol [112 ] from the bottom of the first flash tank V101]Considering that part of CO is still dissolved in crude methanol containing water 2 Affecting the subsequent methanol purity, thus reducing the aqueous methanol [112 ]]Reducing the pressure to 0.1-0.5MPa by a pressure reducing VALVE VALVE, sending to a second flash tank V102, and obtaining CO at the top of the second flash tank 2 [114]Compressed to 5-8MPa by a second compressor C102 and unreacted CO extracted from the top of a first flash tank V101 2 CO and H 2 [111]In the first placeMixing in a three-mixer M103, and mixing with the pressurized raw material gas [104 ]]Mixed in a second mixer M102, preheated and sent to a methanol synthesis reactor R101.
And (3) preparing crude olefin.
Aqueous methanol [117 ] taken from the bottom of the second flash tank V102]The methanol is sent to a first rectifying tower T101 for separating and purifying the methanol, the number of tower plates of the first rectifying tower T101 is controlled to be 20-30, the feeding position is the feeding at the middle lower part of the tower, the pressure at the top of the tower is controlled to be 0.1-0.5MPa, the temperature at the bottom of the tower is controlled to be 100-150 ℃, the recovery rate of the methanol is more than 99.99 percent (mass fraction), and the purity of the high-purity liquid phase methanol [119 ] extracted at the top of the first rectifying tower T101 is more than 99 percent (mass fraction)]The tower bottom discharges waste water [118 ]]Sending to a wastewater tank, wherein the content of methanol in wastewater is lower than 0.01% (mass fraction), and liquid-phase methanol [119 ] is extracted from the top of a first rectifying tower T101]Pressurizing to 0.1-0.5MPa by a first pressurizing pump P101, preheating to 400-500 ℃ by a fourth heat exchanger E104 and a fifth heat exchanger E105 so as to meet the feeding condition of an olefin synthesis reactor R102, and reacting high-purity gas-phase methanol [119 ] under the action of a specific catalyst]In addition to the conversion into low carbon olefins such as ethylene, propylene and butylene, CO is also generated in the olefin synthesis reactor R102 2 、CO、H 2 、H 2 O, methane, ethane, propane, pentene, and the like. High temperature gas [123 ] at the outlet of the olefin synthesis reactor R102]Is mixed with feed gas [120 ] in a fourth heat exchanger E104]Heat exchange is carried out and then sent to an olefin refining unit.
And (4) refining the olefin.
Outlet product of olefin synthesis reactor R102 [124 ]]First sent to a first dryer D101 for removing moisture [125 ]]Then the mixture is sent to a second rectifying tower T102, wherein the number of tower plates of the second rectifying tower is controlled to be 10-20, the feeding position is the feeding position at the lower part of the tower, the pressure at the top of the tower is controlled to be 0.1-0.5MPa, the condensation temperature at the top of the tower is controlled to be-20 to-60 ℃, the recovery rate of the amylene is more than 99.9 percent (mass fraction), and the liquid-phase amylene (127) with the purity more than 99 percent (mass fraction) is extracted from the bottom of the second rectifying tower]The low-carbon olefin and CO are obtained at the top of the second rectifying tower 2 、CO、H 2 Mixture of methane, ethane and propane [128 ]]Mixing the mixture [128 ]]Preheated by a sixth heat exchanger E106Then sent to an alkaline washing tower V103 to remove impurity CO 2 [132]Obtaining low-carbon olefin, CO and H from the top of the alkaline washing tower V103 2 、H 2 Mixture of O, methane, ethane and propane [133 ]]Sent to a second dryer D102 for removing water [134 ]]Dried mixture [135 ]]Compressing to 1-5MPa by a third compressor C103, cooling by a seventh heat exchanger E107, and delivering to a third rectifying tower T103, wherein the number of tower plates of the third rectifying tower T103 is controlled at 20-40, the feeding position is the middle part of the tower, the pressure at the top of the tower is controlled at 1-5MPa, the condensing temperature at the top of the tower is controlled at-50 to-150 ℃, and methane, CO and H are extracted from the top of the third rectifying tower T103 2 [138]And methane, CO and H 2 The recovery rate is more than 99.9 percent (mass fraction), and the mixture of ethylene, ethane, propylene, propane and butylene [139 ] is extracted from the tower bottom of the third rectifying tower]Feeding the mixture into a fourth rectifying tower T104 to realize the separation of ethylene/ethane and propylene/propane/butylene, controlling the number of plates of the fourth rectifying tower T104 between 30 and 60, feeding the materials from the middle upper part of the tower at the feeding position, controlling the pressure at the top of the tower between 1 and 5MPa, controlling the condensation temperature at the top of the tower between minus 10 and minus 30 ℃, and mixing the ethylene/ethane mixture (140) obtained at the top of the fourth rectifying tower with ethylene/ethane]Feeding the mixture to a fifth rectifying tower T105 to separate ethylene and ethane, wherein the number of plates of the fifth rectifying tower T105 is controlled to be 80-150, the feeding position is the feeding position at the middle upper part of the tower, the pressure at the top of the tower is controlled to be 1-5MPa, the condensing temperature at the top of the tower is controlled to be-10 to-30 ℃, the recovery rate of the ethylene is more than 99.9 percent (mass fraction), and the top of the fifth rectifying tower T105 obtains polymerization grade ethylene [141 with the purity of more than 99.99 percent (mass fraction)]The fifth rectifying tower T105 obtains industrial grade ethane with the purity of more than 99.9 percent (mass fraction) [142 ]]Sending the propylene/propane/butylene mixture obtained from the tower bottom of the fourth rectifying tower to a sixth rectifying tower T106 to realize the separation of propylene, controlling the number of tower plates of the sixth rectifying tower T106 to be 150-250, feeding the propylene at the middle upper part of the tower at a feeding position, controlling the pressure at the tower top to be 1-5MPa, controlling the condensation temperature at the tower top to be 10-30 ℃, controlling the recovery rate of the propylene to be more than 99.9 percent (mass fraction), and obtaining the industrial-grade propylene (144 mass fraction) with the purity of more than 99.6 percent at the tower top of the sixth rectifying tower T106]The sixth rectifying tower T106 obtains a mixture of propane and butylene [145 ]]Then sent to a seventh rectifying column T107 to effect propane andseparating the butylene, controlling the number of trays of a seventh rectifying tower T107 to be 15-35, controlling the pressure at the top of the tower to be 1-5MPa, controlling the condensation temperature at the top of the tower to be 10-30 ℃, controlling the recovery rates of the butylene and the pentane to be more than 99.9 percent (mass fraction), and obtaining the butylene [146 ] with the purity of more than 99 percent (mass fraction) at the bottom of the seventh rectifying tower]The tower top of the seventh rectifying tower obtains propane with the purity of more than 99 percent (mass fraction 147)]。
Examples
The following examples are for illustrative purposes only and are not meant to limit the present invention.
Example 1
Raw material gas CO 2 And H 2 Preheated and pressurized, then sent to a methanol synthesis reactor, and passed through CO 2 Hydrogenation reaction to obtain high-temperature crude methanol mixture. The high-temperature crude methanol mixture contains unreacted CO 2 、CO、H 2 And by-product H 2 And O. The high-temperature crude methanol mixture is cooled and then subjected to two-stage flash evaporation to remove unreacted CO in the mixture 2 CO and H 2 And is recycled to the methanol synthesis reactor after being pressurized and preheated. The water-containing crude alcohol is rectified to remove water, pressurized and preheated, and then is sent to an olefin synthesis reactor, low-carbon olefin is prepared through the reaction of preparing olefin from methanol, and byproducts such as carbon dioxide, carbon monoxide, hydrogen, water, methane, ethane, propane, pentene and the like are generated at the same time. The crude product obtained from the olefin synthesis reactor is sequentially passed through equipment such as a pentene separation tower, an alkaline washing tower, a dryer, a methane separation tower, a carbon dioxide separation tower, an ethylene separation tower, a propylene separation tower, a butene separation tower and the like to obtain polymerization-grade ethylene with the purity of more than 99.8 percent (mass fraction), industrial-grade propylene with the purity of more than 99.6 percent (mass fraction) and industrial-grade butene with the purity of more than 99 percent (mass fraction). Unlike the above process, this example does not consider the comprehensive utilization of the energy inside the system, i.e., the high temperature outlet gases of the methanol synthesis reactor and the olefin synthesis reactor do not preheat the respective feed gases, the energy efficiency of the process is 53.28%, net CO 2 The emission reduction rate was 48.56%.
Example 2
Raw material gas CO 2 And H 2 By preheating and addingAfter pressing, the mixture is sent to a methanol synthesis reactor and passes through CO 2 Hydrogenation reaction to obtain high-temperature crude methanol mixture. The high-temperature crude methanol mixture contains unreacted CO 2 、CO、H 2 And by-product H 2 And O. The high-temperature crude methanol mixture is cooled and then subjected to two-stage flash evaporation to remove unreacted CO in the mixture 2 CO and H 2 And is recycled to the methanol synthesis reactor after being pressurized and preheated. The water-containing crude alcohol is rectified to remove water, pressurized and preheated, and then is sent to an olefin synthesis reactor, low-carbon olefin is prepared through the reaction of preparing olefin from methanol, and byproducts such as carbon dioxide, carbon monoxide, hydrogen, water, methane, ethane, propane, pentene and the like are generated at the same time. The crude product obtained from the olefin synthesis reactor sequentially passes through equipment such as a pentene separation tower, an alkaline washing tower, a dryer, a methane separation tower, a carbon dioxide separation tower, an ethylene separation tower, a propylene separation tower, a butene separation tower and the like to obtain polymerization-grade ethylene with the purity of more than 99.8 percent (mass fraction), industrial-grade propylene with the purity of more than 99.6 percent (mass fraction) and industrial-grade butene with the purity of more than 99 percent (mass fraction). Unlike the above process, the electric energy consumed by the compressor, the booster pump and the like in the present embodiment is generated from a coal-fired power plant, and the process has net CO 2 The reduction rate was 29.41%.
Example 3
Raw material gas CO 2 And H 2 Preheated and pressurized, then sent to a methanol synthesis reactor, and passed through CO 2 Hydrogenation reaction to obtain high-temperature crude methanol mixture. The high-temperature crude methanol mixture contains unreacted CO 2 、CO、H 2 And by-product H 2 And (O). The high-temperature crude methanol mixture is cooled and then subjected to two-stage flash evaporation to remove unreacted CO in the mixture 2 CO and H 2 And is recycled to the methanol synthesis reactor after being pressurized and preheated. The water-containing crude alcohol is rectified to remove water, pressurized and preheated, and then is sent to an olefin synthesis reactor, low-carbon olefin is prepared through the reaction of preparing olefin from methanol, and byproducts such as carbon dioxide, carbon monoxide, hydrogen, water, methane, ethane, propane, pentene and the like are generated at the same time. The crude product obtained from the olefin synthesis reactor sequentially passes through a pentene separation tower, an alkaline washing tower, a drier and a methane separation towerThe device comprises a carbon dioxide hydrocarbon separation tower, an ethylene separation tower, a propylene separation tower, a butylene separation tower and the like, so as to obtain polymerization-grade ethylene with the purity of more than 99.8 percent (mass fraction), industrial-grade propylene with the purity of more than 99.6 percent (mass fraction) and industrial-grade butylene with the purity of more than 99 percent (mass fraction). Unlike the above process, the electrical energy consumed by the compressor and booster pumps in this embodiment is derived from natural gas power plant power generation, the net CO of the process 2 The emission reduction rate was 35.75%.
Example 4
Raw material gas CO 2 And H 2 Preheated and pressurized, then sent to a methanol synthesis reactor, and passed through CO 2 Hydrogenation reaction to obtain high-temperature crude methanol mixture. The high-temperature crude methanol mixture contains unreacted CO 2 、CO、H 2 And by-product H 2 And O. The high-temperature crude methanol mixture is cooled and then subjected to two-stage flash evaporation to remove unreacted CO in the mixture 2 CO and H 2 And is recycled to the methanol synthesis reactor after being pressurized and preheated. The water-containing crude alcohol is rectified to remove water, pressurized and preheated, and then is sent to an olefin synthesis reactor, low-carbon olefin is prepared through the reaction of preparing olefin from methanol, and byproducts such as carbon dioxide, carbon monoxide, hydrogen, water, methane, ethane, propane, pentene and the like are generated at the same time. The crude product obtained from the olefin synthesis reactor is sequentially passed through equipment such as a pentene separation tower, an alkaline washing tower, a dryer, a methane separation tower, a carbon dioxide separation tower, an ethylene separation tower, a propylene separation tower, a butene separation tower and the like to obtain polymerization-grade ethylene with the purity of more than 99.8 percent (mass fraction), industrial-grade propylene with the purity of more than 99.6 percent (mass fraction) and industrial-grade butene with the purity of more than 99 percent (mass fraction). Unlike the above process, in which the electrical energy consumed by the compressor and booster pump, etc. is from photovoltaic power generation, the process has net CO 2 The reduction rate is 63.53%.
Example 5
Raw material gas CO 2 And H 2 Preheated and pressurized, then sent to a methanol synthesis reactor, and passed through CO 2 Hydrogenation reaction to obtain high-temperature crude methanol mixture. The high-temperature crude methanol mixture contains unreacted CO 2 、CO、H 2 Andby-product H 2 And (O). The high-temperature crude methanol mixture is cooled and then subjected to two-stage flash evaporation to remove unreacted CO in the mixture 2 CO and H 2 And is recycled to the methanol synthesis reactor after being pressurized and preheated. The water-containing crude alcohol is rectified to remove water, pressurized and preheated, and then is sent to an olefin synthesis reactor, low-carbon olefin is prepared through the reaction of preparing olefin from methanol, and byproducts such as carbon dioxide, carbon monoxide, hydrogen, water, methane, ethane, propane, pentene and the like are generated at the same time. The crude product obtained from the olefin synthesis reactor is sequentially passed through equipment such as a pentene separation tower, an alkaline washing tower, a dryer, a methane separation tower, a carbon dioxide separation tower, an ethylene separation tower, a propylene separation tower, a butene separation tower and the like to obtain polymerization-grade ethylene with the purity of more than 99.8 percent (mass fraction), industrial-grade propylene with the purity of more than 99.6 percent (mass fraction) and industrial-grade butene with the purity of more than 99 percent (mass fraction). Unlike the above process, in which the electrical energy consumed by the compressor and booster pump, etc. is derived from hydroelectric power, the process has net CO 2 The reduction rate is 64.34%.
Example 6
Raw material gas CO 2 And H 2 Preheated and pressurized, then sent to a methanol synthesis reactor, and passed through CO 2 Hydrogenation reaction to obtain high-temperature crude methanol mixture. The high-temperature crude methanol mixture contains unreacted CO 2 、CO、H 2 And by-product H 2 And (O). The high-temperature crude methanol mixture is cooled and then subjected to two-stage flash evaporation to remove unreacted CO in the mixture 2 CO and H 2 And is recycled to the methanol synthesis reactor after being pressurized and preheated. The water-containing crude alcohol is rectified to remove water, pressurized and preheated, then is sent to an olefin synthesis reactor, and is used for preparing low-carbon olefin through the reaction of preparing olefin from methanol, and simultaneously generates byproducts such as carbon dioxide, carbon monoxide, hydrogen, water, methane, ethane, propane, pentene and the like. The crude product obtained from the olefin synthesis reactor is sequentially passed through equipment such as a pentene separation tower, an alkaline washing tower, a dryer, a methane separation tower, a carbon dioxide separation tower, an ethylene separation tower, a propylene separation tower, a butene separation tower and the like to obtain polymerization-grade ethylene with the purity of more than 99.8 percent (mass fraction) and industrial ethylene with the purity of more than 99.6 percent (mass fraction)Grade propylene and technical grade butene with purity more than 99 percent (mass fraction). Unlike the above process, in which the electrical energy consumed by the compressor and booster pumps is derived from nuclear power generation, the process has net CO 2 The emission reduction rate is 65.15%.
Industrial applicability
The invention provides CO taking methanol as an intermediate 2 The technological route for preparing low-carbon olefin by hydrogenation utilizes CO in flue gas from coal-fired power plant, iron and steel plant and cement plant 2 And green hydrogen produced by electrolysis of water using renewable energy sources, by CO 2 The methanol is synthesized by hydrogenation reaction, and then the low-carbon olefin with high added value is prepared by taking the methanol as an intermediate, the yield of the low-carbon olefin is 91.15 percent, the energy efficiency and the net CO are improved 2 The reduction rates are 58.47% and 65.22%, respectively. Compared with the prior industrially mature technology for preparing low-carbon olefins and olefins from coal by naphtha cracking, the process not only reduces the over dependence of fossil energy and relieves the resource and environment constraints, but also realizes CO 2 Effective utilization of (b) is an important technical route to achieve carbon neutralization.
Claims (8)
1. CO using methanol as intermediate 2 The method for preparing the low-carbon olefin by hydrogenation comprises the following steps:
the first step is as follows: CO 2 2 And H 2 By CO in a methanol synthesis reactor R101 containing a catalyst 2 Preparing crude methanol by hydrogenation reaction;
the second step is that: after the crude methanol is rectified to remove water, the low-carbon olefin is prepared in an olefin synthesis reactor R102 through a methanol-to-olefin reaction.
2. The process according to claim 1, wherein in the first step the operating temperature of the methanol synthesis reactor R101 is between 180 and 250 ℃ and the operating pressure of the methanol synthesis reactor R101 is between 5 and 8MPa; in the second step, the operating temperature of the olefin synthesis reactor R102 is 400 to 500 ℃, and the operating pressure of the olefin synthesis reactor R102 is 0.1 to 0.5MPa.
3. The method of claim 1In the first step, the high-temperature crude methanol contains unreacted CO 2 、CO、H 2 And by-product H 2 Cooling to 20-60 deg.C, sending to the first flash tank, separating by flash evaporation to obtain unreacted CO at the top 2 CO and H 2 The bottom part is dissolved with a small amount of CO 2 The aqueous methanol solution is sent to a second flash tank for decompression flash evaporation, and CO obtained from the top of the second flash tank 2 After being pressurized by a second compressor, the CO obtained from the top of the first flash tank 2 CO and H 2 Mixed in a third mixer, and then the mixed gas is mixed with the raw gas CO pressurized by the first compressor 2 And H 2 Mixing in a second mixer, preheating and sending to a methanol synthesis reactor.
4. The method according to claim 3, wherein the high-temperature crude methanol is subjected to at least two-stage heat exchange in the cooling process, the high-temperature crude methanol exchanges heat with the feed of the methanol synthesis reactor in a first heat exchanger, wherein the first heat exchanger is positioned at the downstream of the first mixer and at the upstream of the second heat exchanger, and the high-temperature crude methanol is cooled to 20-60 ℃ by a third heat exchanger after being cooled by the first heat exchanger so as to achieve the feeding condition of the first flash tank.
5. The method of claim 1, wherein in the second step, the hydrous methanol from the bottom of the second flash tank is sent to a first rectifying tower for separating and purifying the methanol, wherein the number of plates of the first rectifying tower is controlled to be 20-30, the feeding position is the feeding position of the middle lower part of the tower, the pressure of the tower top is controlled to be 0.1-0.5MPa, the temperature of the tower bottom is controlled to be 100-150 ℃, the methanol with the purity of more than 99% (mass fraction) is obtained at the tower top of the first rectifying tower, the waste water is discharged from the tower bottom, and the content of the methanol in the waste water is less than 0.01% (mass fraction).
6. The method as claimed in claim 1 and claim 5, wherein in the second step, the high purity methanol from the top of the first rectifying tower is pressurized, preheated and fed into the olefin synthesis reactor, and the products of methanol-to-olefin are obtained except for the lower olefins such as ethylene, propylene and butyleneIn addition, it also includes CO 2 、CO、H 2 、H 2 O, methane, ethane, propane, and pentene. Therefore, the product of the methanol-to-olefin is required to be sent to an olefin refining unit for further separation and purification.
7. The process of claim 6, wherein the pressurized high purity methanol is subjected to at least two heat exchange stages during the preheating process, and the mixed gas exchanges heat with the high temperature outlet gas of the olefin synthesis reactor in a fourth heat exchanger, wherein the fourth heat exchanger is located downstream of the first pressurizing pump and upstream of the fifth heat exchanger, and the mixed gas is preheated to 400-500 ℃ through the fifth heat exchanger after exchanging heat with the fourth heat exchanger, so as to achieve the feeding condition of the olefin synthesis reactor.
8. The method as claimed in claim 6, wherein (1) the product of methanol to olefins is dried to remove water, and then sent to a second rectification column to remove amylene, wherein the number of plates of the second rectification column is controlled to be 10-20, the feeding position is the feeding position at the lower part of the column, the pressure at the top of the column is controlled to be 0.1-0.5MPa, the condensation temperature at the top of the column is controlled to be-20-60 ℃, the recovery rate of amylene is more than 99.9% (mass fraction), industrial-grade amylene with the purity of more than 99% (mass fraction) is obtained at the bottom of the second rectification column, and (2) low-carbon olefins, methane, ethane, propane, CO, are obtained at the top of the second rectification column 2 CO and H 2 Preheating the waste water by a sixth heat exchanger and sending the waste water to an alkaline washing tower to remove CO impurities 2 Then drying to remove water to obtain the product containing low-carbon olefin, methane, ethane, propane, CO and H 2 The crude product in the distillation tower is sent to a third compressor to be pressurized to 1-5MPa, and enters a third rectifying tower to remove methane, CO and H 2 Wherein, the number of the tower plates of the third rectifying tower is controlled to be 20-40, the feeding position is the middle part of the tower for feeding, the pressure of the tower top is controlled to be 1-5MPa, the condensing temperature of the tower top is controlled to be-50 to-150 ℃, and methane, CO and H are extracted from the tower top of the third rectifying tower 2 And methane, CO and H 2 The recovery rate is more than 99.9 percent (mass fraction), (3) the third rectifying tower bottom produces C2 and the alkene and alkane with more than C2, and the alkene and the alkane are sent to a fourth rectifying tower to realize the separation of C2 hydrocarbon and C3 and the hydrocarbon with more than C3, and the fourth rectifying towerControlling the number of tower plates of the rectifying tower to be 30-60, feeding C2 hydrocarbon obtained at the top of the fourth rectifying tower to a fifth rectifying tower to separate ethylene and ethane, wherein the pressure at the top of the tower is controlled to be 1-5MPa, the condensing temperature at the top of the tower is controlled to be-10 to-30 ℃, the number of tower plates of the fifth rectifying tower is controlled to be 80-150, feeding C2 hydrocarbon obtained at the top of the tower is controlled to be-10 to-30 ℃, the condensing temperature at the top of the tower is controlled to be-10 to-30 ℃, the recovery rate of ethylene is more than 99.9 percent (mass fraction), the top of the fifth rectifying tower obtains polymerization grade ethylene with the purity of more than 99.99 percent (mass fraction), and the bottom of the fifth rectifying tower obtains industrial grade ethane with the purity of more than 99.9 percent (mass fraction), (5) C3 and hydrocarbons with more than 3 carbon atoms obtained from the tower bottom of the fourth rectifying tower are sent to a sixth rectifying tower to realize the separation of propylene, the number of tower plates of the sixth rectifying tower is controlled to be 150-250, the feeding position is the feeding of the middle upper part of the tower, the pressure of the tower top is controlled to be 1-5MPa, the condensation temperature of the tower top is controlled to be 10-30 ℃, and the recovery rate of propylene is more than 99.9 percent (mass fraction), the tower top of the sixth rectifying tower obtains industrial grade propylene with the purity of more than 99.6 percent (mass fraction), (6) the tower bottom of the sixth rectifying tower obtains the mixture of propane and butylene, and then the mixture is sent to a seventh rectifying tower to realize the separation of propane and butylene, the number of tower plates of the seventh rectifying tower is controlled to be 15-35, the pressure of the tower top is controlled to be 1-5MPa, the condensation temperature of the tower top is controlled to be 10-30 ℃, and the average recovery rate of the butylene and the propane is more than 99.9 percent (mass fraction), and obtaining the industrial grade butene with the purity of more than 99 percent (mass fraction) at the tower bottom of the seventh rectifying tower, and obtaining the industrial grade butane with the purity of more than 99 percent (mass fraction) at the tower top of the seventh rectifying tower.
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| CN104098419A (en) * | 2014-07-28 | 2014-10-15 | 神华集团有限责任公司 | System and method for preparing low-carbon olefin through adopting coal, natural gas and methyl alcohol |
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| CN101500975A (en) * | 2006-08-10 | 2009-08-05 | 南加利福尼亚大学 | Method for producing methanol, dimethyl ether, derived synthetic hydrocarbons and their products from carbon dioxide and water(moisture) of the air as sole source material |
| CN104098419A (en) * | 2014-07-28 | 2014-10-15 | 神华集团有限责任公司 | System and method for preparing low-carbon olefin through adopting coal, natural gas and methyl alcohol |
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